WO2013028307A1

WO2013028307A1 - Derivatives of hydrocarbon terpenes

Info

Publication number: WO2013028307A1
Application number: PCT/US2012/048203
Authority: WO
Inventors: Frank X. Woolard; Derek James Mcphee
Original assignee: Amyris, Inc.
Priority date: 2011-08-24
Filing date: 2012-07-25
Publication date: 2013-02-28

Abstract

This application relates to derivatives of hydrocarbon terpenes (e.g., myrcene or farnesene), to methods of making the derivatives, and to the use of the derivatives as oils, solvents, lubricants, additives or base oils for lubricant compositions, surfactants, plasticizers, and/or as monomers, cross-linking agents, curing agents or reactive diluents for use in making oligomers or polymers.

Description

DERIVATIVES OF HYDROCARBON TERPENES

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of and priority to U.S. provisional patent application

61/527,041 filed August 24, 2011, U.S. provisional patent application 61/543,747 filed October 5, 2011, U.S. provisional patent application 61/544,257 filed October 6, 2011, and U.S. provisional patent application 61/590,321 filed January 24, 2012, each of which is incorporated herein by reference in its entirety as if put forth fully below.

STATEMENT REGARDING FEDERALLY FUNDED RESEARCH

[0002] Some of the work described herein was funded by Award No. DE-EE0002869 awarded by the U.S. Department of Energy. Accordingly, the Government may have rights to some embodiments of this invention.

FIELD

[0003] This application relates to derivatives of hydrocarbon terpenes comprising at least one conjugated diene moiety (e.g. , myrcene or farnesene), methods of making the derivatives, and the use of the derivatives in various applications such as use as oils, lubricants, additives or base oils for lubricant compositions, surfactants, plasticizers, and/or as monomers, cross-linking agents, curing agents, or reactive diluents for use in making oligomers or polymers.

BACKGROUND

[0004] Conjugated terpenes such as myrcene and the sesquiterpene β -farnesene can be synthesized via biological routes. For example, myrcene and β -farnesene can be produced in high yield from modified yeast, as described in U.S. Patent Nos. 7,399,323 and 7,659,097, each of which is incorporated herein by reference in its entirety, as if put forth fully below.

[0005] A need exists for oils, lubricants, additives or base oils for lubricant compositions, surfactants, plasticizers, and/or monomers, cross-linking agents or reactive diluents for use in making oligomers or polymers that are made at least in part from renewable carbon sources such as sugars and biomass, other than conventional oleochemicals derived from petroleum-based carbon sources.

SUMMARY

[0006] Described herein are Diels-Alder adducts between a hydrocarbon terpene comprising a conjugated diene (e.g., myrcene, β-farnesene, or a-farnesene) and a dienophile, and derivatives of such adducts, methods of making the adducts, methods for derivatizing the adducts, and to the use of the adducts and their derivatives as oils, solvents, lubricants, additives or base oils for lubricant

compositions, surfactants, plasticizers, and/or as monomers, cross-linking agents, curing agents or reactive diluents for use in making oligomers or polymers. [0007] In some embodiments, described herein are compounds comprising a Diels-Alder adduct of a hydrocarbon terpene comprising a conjugated diene and a dienophile. The compounds can be adapted for use, for example, as additives to modify at least one physical property of one or more polymers, or as monomers, cross-linking agents, or reactive diluents for making one or more polymers, or as lubricants or components of a lubricant formulations, or as oils, solvents, or surfactants. In some variations, the hydrocarbon terpene is β-farnesene. In some variations, the dienophile is selected from maleic anhydride and substituted maleic anhydrides, citraconic anhydride and substituted citraconic anhydrides, fumaric acid, itaconic acid and substituted itaconic acids, itaconic anhydride and substituted itaconic anhydrides, acrolein and substituted acroleins, crotonaldehyde and substituted crotonaldehydes, monoalkyl or dialkyl maleates, monoalkyl or dialkyl fumarates, monoalkyl or dialkyl itaconates, acrylic acid esters, methacrylic acid esters, cinnamic acid esters, mesityl oxide and substituted mesityl oxides, hydroxyalkyl acrylates, carboxyalkyl acrylates, (dialkylamino)alkyl acrylates, monoalkyl or dialkyl acetylene dicarboxylates, vinyl ketones, maleimide and substituted maleimides, dialkyl

azidocarboxylates, acetylene dicarboxylic acid, 1 ,4-benzoquinone and substituted 1 ,4-benzoquinones, 1 ,2-benzoquinone and substituted 1 ,2-benzoquinones, sulfur dioxide, vinyl sulfonates, vinyl sulfonates, vinyl sulfoxides, naphthoquinones, phosphorus trihalide, and combinations thereof.

[0008] In some variations, the Diels-Alder adduct is chemically modified, e.g., by oxidizing the adduct, reducing the adduct, and/or by reacting the adduct with one or more reactants. In some variations, a Diels-Alder adduct or its derivative is hydrogenated. In some cases, a Diels-Alder adduct is hydrogenated before chemical modification, and in some cases, a Diels-Alder adduct is hydrogenated after chemical modification.

[0009] In some variations, the Diels-Alder adduct is physically blended with a polymer. In some variations, the Diels-Alder adduct is chemically reacted with a polymer.

[0010] The Diels-Alder adducts and their derivatives as described herein may be used to modify any suitable type of polymer. In some variations, a Diels-Alder adduct or its derivative is used to modify a condensation polymer. In some variations, a Diels-Alder adduct or its derivative is used to modify a thermoplastic. In some variations, a Diels-Alder adduct or its derivative is used to modify a thermoset.

[0011] In some variations, a Diels-Alder adduct or its derivative is used as a monomer, cross- linking agent, or reactive diluent to make a polymer. In some variations, a Diels-Alder adduct or its derivative may be used to make an alkyd resin. In some variations, a Diels-Alder adduct or its derivative as described herein may be used to make a polyester. In some variations, a Diels-Alder adduct or its derivative as described herein may be used to make a polyamide.

[0012] In some variations, a Diels-Alder adduct or its derivative as described herein may be used to make a lubricant, a base oil, or a component of a lubricant formulation. In certain variations, a dienophile used to make a Diels-Alder adduct that has utility in a lubricant application is selected from maleic anhydride and substituted maleic anhydrides, citraconic anhydride and substituted citraconic anhydrides, fumaric acid, itaconic acid and substituted itaconic acids, itaconic anhydride and substituted itaconic anhydrides, acrolein and substituted acroleins, crotonaldehyde and substituted crotonaldehydes, monoalkyl or dialkyl maleates, monoalkyl or dialkyl fumarates, monoalkyl or dialkyl itaconates, acrylic acid esters, methacrylic acid esters, cinnamic acid esters, hydroxyalkyl acrylates, (dialkylamino)alkyl acrylates, monoalkyl or dialkyl acetylene dicarboxylates, vinyl ketons, maleamide and substituted maleamides, maleimide and substituted maleimides, dialkyl azidocarboxylates, acetylene dicarboxylic acid, 1 ,4-benzoquinone and substituted 1 ,4-benzoquinones, 1 ,2-benzoquinone, substituted 1 ,2- benzoquinones, napthoquinones, sulfur dioxide, vinyl sulfonates, vinyl sulfinates, vinyl sulfoxides, phosphorus trihalides, and any combination of two or more of the foregoing. In some variations, the adduct or its derivative is adapted for use as a viscosity index improver in a lubricant composition. In some variations, the adduct or its derivative is adapted for use as a base oil in a lubricant composition. In some variations, the adduct or its derivative is adapted for use as a pour point modifier in a lubricant composition. In some variations, the adduct or its derivative is adapted for use as a cutting oil.

[0013] In some variations, the hydrocarbon terpenes (e.g., β-farnesene) or the Diels-Alder adducts derived from the hydrocarbon terpenes comprise at least one epoxy group. In some variations, the hydrocarbon terpenes (e.g., β-farnesene) or the Diels-Alder adducts comprise one epoxy group. In some variations, the hydrocarbon terpenes (e.g., β-farnesene) or the Diels-Alder adducts comprise two epoxy groups. In some variations, the hydrocarbon terpenes (e.g., β-farnesene) or the Diels-Alder adducts comprise more than two epoxy groups. In certain variations, the epoxidized hydrocarbon terpenes and/or the epoxidized Diels-Alder adducts are adapted for use as monomers or as cross-linking agents, or as curing agents to make a polymer. In certain variations, at least one epoxy group may be hydrolyzed.

[0014] In some variations, a Diels-Alder adduct or its derivative as described herein may be used to make a surfactant. The surfactants derived from the Diels-Alder adducts may be nonionic in some variations. For example, the Diels-Alder adduct may be an alcohol (e.g., a primary alcohol), or a polyol (e.g., a diol). In some cases, a nonionic surfactant is an alkoxylated alcohol (which may be a primary alcohol or end-capped with a terminal group such as a methyl group). In some cases, a nonionic surfactant comprises at least one glucoside group, at least one glucamide group, at least one amine group, or at least one alkanolamide group. In some cases, the Diels-Alder adducts are adapted for use as anionic surfactants. For example, a Diels-Alder adduct may comprise a carboxylate salt, a sulfonate salt, a sulfate salt, or a phosphate salt. In some cases, the Diels-Alder adducts are adapted for use as cationic surfactants. For example, a Diels-Alder adduct may comprises a quaternary ammonium ion. In some cases, the Diels-Alder adducts may be adapted for use as zwitterionic surfactants. For example, a Diels- Alder adduct may comprise an amine-oxide group, or may be a betaine. In some variations, the surfactants are derived from Diels-Alder adducts comprising alcohol or aldehyde functionality. In some variations, the surfactants are derived by reacting a Diels-Alder adduct comprising at least one alcohol group with an alkylene oxide such as ethylene oxide and/or propylene oxide.

[0015] In some variations, a Diels-Alder adduct or its derivative as described herein may be used to make a solvent. In some variations, the hydrocarbon terpene used to make the Diels-Alder adduct is β-farnesene. The hydrophobicity and/or hydrophilicity of the solvent may be tuned by selection of the hydrocarbon terpene and the dienophile, as well as by subsequent chemical modification of the Diels- Alder adduct. In some variations, the solvent is a reactive solvent that undergoes a chemical reaction with one or more co-solvents or with one or more solutes.

[0016] In some variations, the hydrocarbon terpene used to make the Diels-Alder adduct is derived from a simple sugar by a microorganism. In some variations, β-farnesene that is derived from a simple sugar by a microorganism is used to make the Diels-Alder adduct.

[0017] In some variations, at least about 25%, at least about 30%, at least about 40%, at least about 50%), at least about 60%, at least about 70%, at least about 80%, at least about 90%, or about 100%) of the carbon atoms in the Diels-Alder adducts are derived from readily renewable, non-petroleum carbon sources, such as a sugar or biomass.

BRIEF DESCRIPTION OF DRAWINGS

[0018] FIGURE 1 shows weight loss with heat aging for Example 22, Comparative Examples

CE 7-CE 9, and neat PVC.

[0019] FIGURE 2 shows toughness for Examples 21 and 22, Comparative Examples CE 4-CE

9, and neat PVC measured according to ASTM D638 using a pull rate of 50mm/min.

[0020] FIGURE 3 shows Young's modulus for Examples 21 and 22 and Comparative Examples

CE 4-CE 9 measured according to ASTM D638 using a pull rate of 50mm/min.

[0021] FIGURE 4 shows engineering strain (%> elongation) at failure for Examples 21 and 22,

Comparative Examples CE 4-CE 9, and neat PVC, measured according to ASTM D638 using a pull rate of 50mm/min.

[0022] FIGURE 5 shows displacement at break for Examples 21 and 22, Comparative Examples

CE 4-CE 9, and neat PVC, measured according to ASTM D638 using a pull rate of 50mm/min.

[0023] FIGURE 6 shows load at break for Examples 21 and 22, Comparative Examples CE 4-

CE 9, and neat PVC, measured according to ASTM D638 using a pull rate of 50mm/min.

[0024] FIGURE 7 shows stress at break for Examples 21 and 22, Comparative Examples CE 4-

CE 9, and neat PVC, measured according to ASTM D638 using a pull rate of 50mm/min. [0025] FIGURE 8 shows energy to yield point for Examples 21 and 22, Comparative Examples

[0026] FIGURE 9 shows ^lB NMR spectrum of (E)-dimethyl 4-(4,8-dimethylnona-3,7- dienyl)cyclohex-4-ene-l,2-dicarboxylate of Example 30.

[0027] FIGURE 10 shows ^lH NMR spectrum of dimethyl 4-(4,8-dimethylnonyl)cyclohexane-

1 ,2-dicarboxylate of Example 31.

[0028] FIGURE 11 shows ^lH NMR spectrum of (4-(4,8-dimethylnonyl)cyclohexane-l ,2- diyl)dimethanol of Example 32.

[0029] FIGURE 12A and FIGURE 12B show ¹³C NMR spectra of (4-(4,8- dimethylnonyl)cyclohexane-l,2-diyl)dimethanol of Example 32.

[0030] FIGURE 13 shows ^lH NMR spectrum of a mixture of (E)-3-(4,8-dimethylnona-3,7- dienyl)cyclohex-3-enecarbaldehyde and (E)-4-(4,8-dimethylnona-3,7-dienyl)cyclohex-3- enecarbaldehyde of Example 33.

[0031] FIGURE 14A and 14B show GC/MS spectra of a mixture of (E)-3-(4,8-dimethylnona-

3,7-dienyl)cyclohex-3-enecarbaldehyde and (E)-4-(4,8-dimethylnona-3,7-dienyl)cyclohex-3- enecarbaldehyde of Example 33.

[0032] FIGURE 15 shows ^lH NMR spectrum of a mixture of (3-(4,8- dimethylnonyl)cyclohexyl)methanol and (4-(4,8-dimethylnonyl)cyclohexyl)methanol of Example 34.

[0033] FIGURES 16A-16C show ^lB NMR spectra of a mixture of l-(4,8-dimethyl-nonyl)- cyclohexane-3-pentaethylene glycol and l-(4,8-dimethyl-nonyl)-cyclohexane-4-pentaethylene glycol of Example 35.

[0034] FIGURES 16D-16F show ¹³C NMR spectra of a mixture of l-(4,8-dimethyl-nonyl)- cyclohexane-3-pentaethylene glycol and l-(4,8-dimethyl-nonyl)-cyclohexane-4-pentaethylene glycol of Example 35.

[0035] FIGURES 17A-17C show ^lB NMR spectra of a mixture of l-(4,8-dimethyl-nonyl)- cyclohexane-3-decaethylene glycol and l-(4,8-dimethyl-nonyl)-cyclohexane-4-decaethylene glycol of Example 36.

[0036] FIGURES 17D-17F show ¹³C NMR spectra of a mixture of l-(4,8-dimethyl-nonyl)- cyclohexane-3-decaethylene glycol and l-(4,8-dimethyl-nonyl)-cyclohexane-4-decaethylene glycol of Example 36. [0037] FIGURES 18A-18C show ^lB NMR spectra of a mixture of l-(4,8-dimethyl-nonyl)- cyclohexane-3-pentadecaethylene glycol and 1 -(4,8-dimethyl-nonyl)-cyclohexane-4-pentadecaethylene glycol of Example 37.

[0038] FIGURES 18D-18F show ¹³C NMR spectra of a mixture of l-(4,8-dimethyl-nonyl)- cyclohexane-3-pentadecaethylene glycol and 1 -(4,8-dimethyl-nonyl)-cyclohexane-4-pentadecaethylene glycol of Example 37.

[0039] FIGURES 19A-19C show ^lB NMR spectra of l-(4,8-dimethyl-nonyl)-cyclohexane-3,4- bis(methyl-pentaethylene glycol) of Example 38.

[0040] FIGURES 19D-19F show ¹³C NMR spectra of a mixture of l-(4,8-dimethyl-nonyl)- cyclohexane-3,4-bis(methyl-pentaethylene glycol) of Example 38.

[0041] FIGURES 20A-20C show ^lB NMR spectra of 1 -(4,8-dimethyl-nonyl)-cyclohexane-3,4- bis(methyl-decaethylene glycol) of Example 39.

[0042] FIGURES 20D-20F show ¹³C NMR spectra of a mixture of 1 -(4,8-dimethyl-nonyl)- cyclohexane-3,4-bis(methyl-decaethylene glycol) of Example 39.

[0043] FIGURES 21A-21C show ^lB NMR spectra of l-(4,8-dimethyl-nonyl)-cyclohexane-3,4- bis(methyl-decapentaethylene glycol) of Example 40.

[0044] FIGURES 21D-21F show ¹³C NMR spectra of a mixture of l-(4,8-dimethyl-nonyl)- cyclohexane-3,4-bis(methyl-decapentaethylene glycol) of Example 40.

[0045] FIGURE 22 shows correlation of durometer hardness A with Hansen solubility parameters using durometer hardness A values from Table 64 and Hansen solubility parameters from Table 5.

[0046] FIGURE 23 shows correlation of durometer hardness A with tensile properties for data shown in Table 64.

[0047] FIGURE 24 shows DMA results for Example 78.

[0048] FIGURE 25A shows a plot of surface tension (mN/m) vs. logi₀(surfactant concentration in ppm) for the surfactant of Example 37.

[0049] FIGURE 25B shows a plot of surface tension (mN/m) vs. logi₀(surfactant concentration in ppm) for the surfactant of Example 38.

[0050] FIGURE 25C shows a plot of surface tension (mN/m) vs. logi₀(surfactant concentration in ppm) for the surfactant of Example 39. [0051] FIGURE 25D shows a plot of surface tension (mN/m) vs. logio(surfactant concentration in ppm) for the surfactant of Example 40.

DETAILED DESCRIPTION

A) Definitions

[0052] In the following description, all numbers disclosed herein are approximate values, regardless whether the word "about" or "approximate" is used in connection therewith. Numbers may vary by 1 percent, 2 percent, 5 percent, or, sometimes, 10 to 20 percent. Whenever a numerical range with a lower limit, R^L, and an upper limit, R^u, is disclosed, any number falling within the range is specifically disclosed. In particular, the following numbers within the range are specifically disclosed: R=R^L+k*(R^u-R^L), wherein k is a variable ranging from 1 percent to 100 percent with a 1 percent increment, i.e., k is 1 percent, 2 percent, 3 percent, 4 percent, 5 percent,..., 50 percent, 51 percent, 52 percent,..., 95 percent, 96 percent, 97 percent, 98 percent, 99 percent or 100 percent. Moreover, any numerical range defined by two R numbers as defined in the above is also specifically disclosed.

[0053] "Terpene" as used hereinis a compound that is capable of being derived from isopentyl pyrophosphate (IPP) or dimethylallyl pyrophosphate (DMAPP), and the term terpene encompasses hemiterpenes, monoterpenes, sesquiterpenes, diterpenes, sesterterpenes, triterpenes, tetraterpenes and polyterpenes. A hydrocarbon terpene contains only hydrogen and carbon atoms and no heteroatoms such as oxygen, and in some embodiments has the general formula (C₅H₈)_n, where n is 1 or greater. A "conjugated terpene" or "conjugated hydrocarbon terpene" as used herein refers to a hydrocarbon terpene comprising at least one conjugated diene moiety, but is not part of an aromatic ring. A conjugated hydrocarbon termpene may contain a conjugated diene at a terminal position (e.g., myrcene, farnesene) or the conjugated diene may be at an internal position (e.g., isodehydrosqualene or isosqualane precursor I or II). It should be noted that the conjugated diene moiety of a conjugated terpene may have any stereochemistry {e.g., cis or trans) and may be part of a longer conjugated segment of a terpene, e.g., the conjugated diene moiety may be part of a conjugated triene moiety. It should be understood that hydrocarbon terpenes as used herein also encompasses monoterpenoids, sesquiterpenoids, diterpenoids, triterpenoids, tetraterpenoids and polyterpenoids that exhibit the same carbon skeleton as the corresponding terpene but have either fewer or additional hydrogen atoms than the corresponding terpene, e.g., terpenoids having 2 fewer, 4 fewer, or 6 fewer hydrogen atoms than the corresponding terpene, or terpenoids having 2 additional, 4 additional or 6 additional hydrogen atoms than the corresponding terpene. Some non-limiting examples of conjugated hydrocarbon terpenes include isoprene, myrcene, a-ocimene, β-ocimene, a-farnesene, β -farnesene, β-springene, geranylfarnesene, neophytadiene, d,y-phyta-l,3-diene, ira¾y-phyta-l,3-diene, isodehydrosqualene, isosqualane precursor I, and isosqualane precursor II. [0054] Terpenes or isoprenoid compounds are a large and varied class of organic molecules that can be produced by a wide variety of plants and some insects. Some terpenes or isoprenoid compounds can also be made from organic compounds such as sugars by microorganisms, including bioengineered microorganisms. Because terpenes or isoprenoid compounds can be obtained from various renewable carbon sources, they are useful monomers for making eco-friendly and renewable chemicals. In certain embodiments, the conjugated hydrocarbon terpenes as described herein are derived from microorganisms using a renewable carbon source, such as a sugar or biomass that can be replenished in a matter of months or a few years unlike fossil fuels.

[0055] "Isoprene" refers to a compound having the following structure:

or a stereoisomer thereof.

[0056] "Myrcene" refers to a compound having the following structure:

or a stereoisomer thereof.

[0057] "Ocimene" refers to a-ocimene, β-ocimene or a mixture thereof.

[0058] "a-ocimene" refers to a compound having the following formula:

or a stereoisomer (e.g., s-cis isomer) thereof.

[0059] "β -ocimene" refers to a compound having the following formula:

or a stereoisomer (e.g., s-cis isomer) thereof.

[0060] "Farnesene" as used herein refers to a-farnesene, β-farnesene or a mixture thereof.

[0061] "a-Farnesene" refers to a compound having the following structure:

or a stereoisomer (e.g., s-cis isomer) thereof. In some embodiments, a-farnesene comprises a substantially pure stereoisomer of a-farnesene. In some embodiments, a-farnesene comprises a mixture of stereoisomers, such as s-cis and s-trans isomers. In some embodiments, the amount of each of the stereoisomers in an a-farnesene mixture is independently from about 0.1 wt.% to about 99.9 wt.%, from about 0.5 wt.%) to about 99.5 wt.%, from about 1 wt.% to about 99 wt.%, from about 5 wt.% to about 95 wt.%), from about 10 wt.% to about 90 wt.% or from about 20 wt.% to about 80 wt.%, based on the total weight of the a-farnesene mixture of stereoisomers.

[0062] "β-farnesene" refers to a compound having the following structure:

or a stereoisomer thereof (e.g., s-cis isomer). In some embodiments, β-farnesene comprises a substantially pure stereoisomer of β-farnesene. Substantially pure β-farnesene refers to compositions comprising at least 80%, at least 90%, at least 95%, at least 97%, at least 98% or at least 99% β- farnesene by weight, based on total weight of the farnesene. In other embodiments, β-farnesene comprises a mixture of stereoisomers, such as s-cis and s-trans isomers. In some embodiments, the amount of each of the stereoisomers in a β-farnesene mixture is independently from about 0.1 wt.% to about 99.9 wt.%, from about 0.5 wt.% to about 99.5 wt.%, from about 1 wt.% to about 99 wt.%, from about 5 wt.%) to about 95 wt.%, from about 10 wt.% to about 90 wt.%, or from about 20 wt.% to about 80 wt.%), based on the total weight of the β-farnesene mixture of stereoisomers.

[0063] "Farnesane" refers to a compound having the following structure:

or a stereoisomer thereof.

[0064] "β-springene" or "springene" refers to a compound having the following structure:

or a stereoisomer (e.g. , s-cis isomer) thereof.

[0065] "Geranylfarnesene" refers to a compound having the following structure:

or a stereoisomer (e.g. , s-cis isomer) thereof.

[0066] "Neophytadiene" refers to a compound having the following structure:

stereoisomer (e.g. , s-cis isomer) thereof. [0067] "rra¾y-phyta-l,3-diene" refers to a compound having the following structure:

or a stereoisomer (e.g., s-cis isomer) thereof.

[0068] "Q,y-phyta-l,3-diene" refers to a compound having the following structure:

or a stereoisomer (e.g., s-cis isomer) thereof.

[0069] "Isodehydrosqualene" refers to a compound having the following structure:

or a stereoisomer thereof.

[0070] "Isosqualane precursor I" or "2,6,18,22-tetramethyl-10-methylene-14-vinyltricosa-

2,6,11,17,21 -pentaene" refers to a compound having the following structure:

or a stereoisomer thereof.

[0071] "Isosqualane precursor Π" or "2,6, 14,18,22-pentamethyl- 10-vinyltricosa-

2,6, 10, 14, 17,21 -pentaene" refers to a compound having the following structure:

or a stereoisomer thereof.

[0072] "Farnesol" refers to a compound having the following structure:

or a stereoisomer thereof.

[0073] "Nerolidol" refers to a compound having the following structure:

or a stereoisomer thereof. [0074] Farnesol or nerolidol may be converted into a-farnesene or β-farnesene, or a combination thereof by dehydration with a dehydrating agent or an acid catalyst. Any suitable dehydrating agent or acid catalyst that can convert an alcohol into an alkene may be used. Non-limiting examples of suitable dehydrating agents or acid catalysts include phosphoryl chloride, anhydrous zinc chloride, phosphoric acid, and sulfuric acid.

[001] A "polymer" refers to any kind of synthetic or natural oligomer or polymer having two or more repeat units, including thermoplastics, thermosets, elastomers, polymer blends, polymer composites, synthetic rubbers, and natural rubbers. A synthetic oligomer or polymer can be prepared by polymerizing monomers, whether of the same or a different type. The generic term "polymer" embraces the terms "homopolymer," "copolymer," "terpolymer" as well as "interpolymer."

[002] "Interpolymer" refers to a polymer prepared by the polymerization of at least two different types of monomers. The generic term "interpolymer" includes the term "copolymer" (which generally refers to a polymer prepared from two different monomers) as well as the term "terpolymer" (which generally refers to a polymer prepared from three different types of monomers). Interpolymer also encompasses polymers made by polymerizing four or more types of monomers.

[0075] "Hydrocarbyl" refers to a group containing one or more carbon atom backbones and hydrogen atoms, and the group may optionally contain one or more heteroatoms. Where the hydrocarbyl group contains heteroatoms, the heteroatoms may form one or more functional groups known to one of skill in the art. Hydrocarbyl groups may contain cycloaliphatic, aliphatic, aromatic, or any combination thereof. Aliphatic segments may be straight or branched. Aliphatic and cycloaliphatic groups may include one or more double and/or triple carbon-carbon bonds. Included in hydrocarbyl groups are alkyl, alkenyl, alkynyl, aryl, cyclalkyl, cycloalkenyl, alkaryl and aralkyl groups. Cycloaliphatic groups may contain both cyclic moieties and noncyclic portions. In some embodiments, the hydrocarbyl group is a saturated or unsaturated, cyclic or acyclic, unsubstituted or substituted Ci-C₃₀ hydrocarbyl group (e.g., Ci-C₂o alkyl, C₁-C₂₀ alkenyl, C₁-C₂₀ alkynyl, cycloalkyl, aryl, aralkyl and alkaryl).

[0076] "Alkyl" refers to a group having the general formula C_nH_2n+i derived from a saturated, straight chain or branched aliphatic hydrocarbon, where n is an integer. In certain embodiments, n is from 1 to about 30, from 1 to about 20, or from 1 to about 10. Non- limiting examples of alkyl groups include CpCg alkyl groups such as methyl, ethyl, propyl, isopropyl, 2-methylpropyl, 2-methylbutyl, 3- methylbutyl, 2,2,-dimethylpropyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2-2-dimethylbutyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-butyl, isobutyl, tert-butyl, isopentyl, n-pentyl, neopentyl, n-hexyl, isohexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, n-nonyl, isononyl, n-decyl and isodecyl. An alkyl group may be unsubstituted, or may be substituted. In some embodiments, the alkyl group is straight chain having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbons. In some embodiments, the alkyl group is branched having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbons. [0077] "Cycloaliphatic" encompasses "cycloalkyl" and "cycloalkenyl." Cycloaliphatic groups may be monocyclic or polycyclic. A cycloaliphatic group can be unsubstituted or substituted with one or more suitable substituents.

[0078] "Cycloalkyl" refers to a saturated carbocyclic mono- or bicyclic (fused or bridged) ring of 3-12 (e.g., 5-12) carbon atoms. Non-limiting examples of cycloalkyl include C₃-C₈ cycloalkyl groups, e.g., cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups and saturated cyclic and bicyclic terpenes. Cycloalkyl groups may be unsubstituted or substituted.

[0079] "Cycloalkenyl" refers to a non-aromatic carbocyclic mono- or bicyclic ring of 3 to 12

(e.g., 4 to 8) carbon atoms having one or more double bonds. Non-limiting examples of cycloalkenyl include C3-C8 cycloalkenyl groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, and unsaturated cyclic and bicyclic terpenes. Cycloalkenyl groups may be unsubstituted or substituted.

[0080] "Aryl" refers to an organic radical derived from a monocyclic or polycyclic aromatic hydrocarbon by removing a hydrogen atom. Non-limiting examples of the aryl group include phenyl, naphthyl, benzyl, or tolanyl group, sexiphenylene, phenanthrenyl, anthracenyl, coronenyl, and tolanylphenyl. An aryl group can be unsubstituted or substituted with one or more suitable substituents. Furthermore, the aryl group can be monocyclic or polycyclic. In some embodiments, the aryl group contains at least 6, 7, 8, 9, or 10 carbon atoms. As used herein, one or more dashed bonds in a structure independently represents a bond that may or may not be present. For example, the dashed bond in the structure indicates a bond that may be present to result in a double bond, or may not be present to result in a single bond.

[0081] "Isoprenoid" and "isoprenoid compound" are used interchangeably herein and refer to a compound derivable from isopentenyl diphosphate.

[0082] A substituted group or compound refers to a group or compound in which at least one hydrogen atom is replaced with a substituent chemical moiety. A substituent chemical moiety may be any suitable substituent that imparts desired properties to the compound or group. Non-limiting examples of substituents include halo, alkyl, heteroalkyl, alkenyl, alkynyl, aryl, heteroayrl, hydroxyl, alkoxyl, amino, nitro, thiol, thioether, imine, cyano, amido, phosphonato, phosphine, carbosyl, thiocarbonyl, sulfonyl, sulfonamide, carbonyl, formyl, carbonyloxy, oxo, haloalkyl (e.g. , trifluoromethyl or trichloromethyl), carbocyclic cycloalkyl (which may be monocyclic, or fused or non-fused polycyclic) such as cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, or a heterocycloalkyl (which may be monocyclic, or fused or nonfused polycyclic such as pyrrolidinyl, piperidinyl, piperazinyl, morpholinyl or thiazinyl), carbocyclic or heterocyclic, monocyclic or fused or nonfused polycyclic aryl (e.g. , phenyl, naphthyl, pyrrolyl, idolyl, furanyl, thiopenyl, imidazolyl, oxazolyl, isoxazolyl, thiazolyl, trizolyl, tetrazolyl, pyrazolyl, pyridinyl, quinolinyl, benzothiophenyl, or benzofuranyl); amino (primary, secondary or tertiary): -CONH₂; -OCH₂CONH₂; -NH₂; -S0₂NH₂; -OCHF₂; CF₃, -CC1₃; -OCF₃; -NH₂; - NH(alkyl); -N(alkyl)₂; -NH(aryl); -N(alkyl)(aryl); -N(aryl)₂; -CHO; -CO(alkyl); -CO(aryl); - (OCH₂CH₂0)_n-, where n is from 1 to about 30 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20); -(OCH₂CH(CH₃)0)_m-, where m is from 1 to about 30 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20); -CI, -Br, or -I; and -C0₂(alkyl) (e.g., -C0₂CH₃ or -C0₂CH₂CH₃; - C0₂(aryl)). In certain embodiments, the substituents disclosed herein may be further substituted with one or more substituents.

[0083] As used herein, "detergent" refers to an agent or composition that is useful for cleaning surfaces or articles. A detergent may lift or remove soil, food, oil, grease and the like from a surface (e.g., fabric or a hard surface) and/or disperse or solubilize particles in a medium (e.g., disperse or suspend oil particles in an aqueous solution). A detergent can be in any form such as liquid, paste, gel or solid (e.g., powder, a granular solid, a bar or tablet).

B) Source of Conjugated Hydrocarbon Terpenes

[0084] The conjugated terpenes disclosed herein may be obtained from any suitable source. In some embodiments, the conjugated terpene is obtained from naturally occurring plants or marine species. For example, farnesene can be obtained or derived from naturally occurring terpenes that can be produced by a variety of plants, such as Copaifera langsdorfii, conifers, and spurges; or by insects, such as swallowtail butterflies, leaf beetles, termites, or pine sawflies; and marine organisms, such as algae, sponges, corals, mollusks, and fish. Terpene oils can also be obtained from conifers and spurges.

Conifers belong to the plant division Pinophya or Coniferae and are generally cone-bearing seed plants with vascular tissue. Conifers may be trees or shrubs. Non-limiting examples of suitable conifers include cedar, cypress, douglas fir, fir, juniper, kauris, larch, pine, redwood, spruce and yew. Spurges, also known as Euphorbia, are a diverse worldwide genus of plants belonging to the spurge family (euphorbiaceae). Farnesene is a sesquiterpene, a member of the terpene family, and can be derived or isolated from terpene oils for use as described herein. In some embodiments, a conjugated terpene is derived from a fossil fuel (petroleum or coal), for example, by fractional distillation of petroleum or coal tar. In some embodiments, a conjugated terpene is made by chemical synthesis. For example, one non- limiting example of suitable chemical synthesis of farnesene includes dehydrating nerolidol with phosphoryl chloride in pyridine as described in the article by Anet E.F.L.J., "Synthesis of (Ε,Ζ)-α-, and (Z)-P-farnesene, Aust. J. Chem. 23(10), 2101-2108, which is incorporated herein by reference in its entirety.

[0085] In some embodiments, a conjugated terpene is obtained using genetically modified organisms that are grown using renewable carbon sources (e.g., sugar cane). In certain embodiments, a conjugated terpene is prepared by contacting a cell capable of making a conjugated terpene with a suitable carbon source under conditions suitable for making a conjugated terpene. Non-limiting examples conjugated terpenes obtained using genetically modified organisms are provided in U.S. Pat. No. 7,399,323, U.S. Pat. Publ. Nos. 2008/0274523 and 2009/0137014, and International Patent

Publication WO 2007/140339, and International Patent Publication WO 2007/139924, each of which is incorporated herein by reference in its entirety. Any carbon source that can be converted into one or more isoprenoid compounds can be used herein. In some embodiments, the carbon source is a fermentable carbon source (e.g., sugars), a nonfermentable carbon source or a combination thereof. A non-fermentable carbon source is a carbon source that cannot be converted by an organism into ethanol. Non-limiting examples of suitable non-fermentable carbon sources include acetate, glycerol, lactate and ethanol.

[0086] The sugar can be any sugar known to one of skill in the art. For example, in some embodiments, the sugar is a monosaccharide, disaccharide, polysaccharide or a combination thereof. In certain embodiments, the sugar is a simple sugar (a monosaccharide or a disaccharide). Some non- limiting examples of suitable monosaccharides include glucose, galactose, mannose, fructose, ribose and combinations thereof. Some non-limiting examples of suitable disaccharides include sucrose, lactose, maltose, trehalose, cellobiose, and combinations thereof. In some embodiments, the sugar is sucrose. In certain embodiments, the carbon source is a polysaccharide. Non-limiting examples of suitable polysaccharides include starch, glycogen, cellulose, chitin, and combinations thereof.

[0087] The sugar suitable for making a conjugated terpene can be obtained from a variety of crops or sources. Non-limiting examples of suitable crops or sources include sugar cane, bagasse, miscanthus, sugar beet, sorghum, grain sorghum, switchgrass, barley, hemp, kenaf, potato, sweet potato, cassava, sunflower, fruit, molasses, whey, skim milk, corn, stover, grain, wheat, wood, paper, straw, cotton, cellulose waste, and other biomass. In certain embodiments, suitable crops or sources include sugar cane, sugar beet and corn. In some embodiments, the sugar source is cane juice or molasses.

[0088] In certain embodiments, a conjugated terpene can be prepared in a facility capable of biological manufacture of isoprenoids. For example, for making a Ci₅ isoprenoid, the facility may comprise any structure useful for preparing C_i5 isoprenoids (e.g., a-farnesene, β-farnesene, nerolidol or farnesol) using a microorganism capable of making the Ci₅ isoprenoids with a suitable carbon source under conditions suitable for making the Ci₅ isoprenoids. In some embodiments, the biological facility comprises a cell culture comprising a desired isoprenoid (e.g., a Cio, a Ci₅, a C₂₀, or a C25 isoprenoid) in an amount of at least about 1 wt.%, at least about 5 wt.%, at least about 10 wt.%, at least about 20 wt.%, or at least about 30 wt.%, based on the total weight of the cell culture. In certain embodiments, the biological facility comprises a fermentor comprising one or more cells capable of generating a desired isoprenoid. Any fermentor that can provide for cells or bacteria a stable and optimal environment in which they can grow or reproduce may be used herein. In some embodiments, the fermentor comprises a culture comprising one or more cells capable of generating a desired isoprenoid (e.g., a C_w, a Ci₅, a C₂o, or a C25 isoprenoid). In some embodiments, the fermentor comprises a cell culture capable of biologically manufacturing farnesyl pyrophosphate (FPP). In certain embodiments, the fermentor comprises a cell culture capable of biologically manufacturing isopentenyl diphosphate (IPP). In some embodiments, the fermentor comprises a cell culture comprising a desired isoprenoid (e.g., a C₁₀, a Ci₅, a C₂₀, or a C25 isoprenoid) in an amount of at least about 1 wt.%, at least about 5 wt.%, at least about 10 wt.%, at least about 20 wt.%, or at least about 30 wt.%, based on the total weight of the cell culture.

[0089] The facility may further comprise any structure capable of manufacturing a chemical derivative from the desired isoprenoid (e.g., a C₁₀, a Ci₅, a C₂₀, or a C25 isoprenoid). In some embodiments, a facility comprises a reactor for dehydrating nerolidol or farnesol to a-farnesene or β- farnesene or a combination thereof. In certain embodiments, a facility comprises a reactor for dehydrating linalool to myrcene or ocimene or a combination thereof. Any reactor that can be used to convert an alcohol into an alkene under conditions known to skilled artisans may be used. In some embodiments, the reactor comprises a dehydrating catalyst.

C) Formation of Diels-Alder Adducts

[0090] Described herein are Diels-Alder adducts of conjugated terpenes and a dienophile, and derivatives of such Diels-Alder adducts. In a Diels-Alder reaction between a conjugated terpene and a dienophile, a [2π + 4π] cycloaddition reaction between the conjugated diene moiety of the conjugated terpene and the dienophile occurs. In some cases, the stereochemistry of the resulting compounds can be reliably predicted using orbital symmetry rules.

[0091] The hydrocarbon terpene is selected to have a stereochemistry amenable to Diels-Alder reactions. That is, the conjugated diene is able to adopt an s-cis conformer. For a hydrocarbon terpene to undergo Diels-Alder cycloaddition reaction, the double bonds exist in an s-cis conformation or conformational rotation around the single bond between the double bonds so that an s-cis conformation of the diene is adoptable. In many conjugated dienes, the s-trans conformer population is in rapid equilibrium with s-cis conformers. In some cases, steric effects due to substituents on the conjugated diene may impede a Diels-Alder reaction. The hydrocarbon terpene and a dienophile in a Diels-Alder reaction may each demonstrate stereoisomerism. Stereoisomerism of the reactants is preserved in the Diels-Alder adduct, and the relative orientation of the substituents on the reactants is preserved in the Diels-Alder adduct. For example, fumaric acid and fumaric acid esters (fumarate) exist as trans -isomers, so if a fumaric acid ester is used a dienophile, the carboxylate groups in the Diels-Alder adduct have a 1 ,2-anti- (also referred to as trans-) orientation relative to each other. The carboxylate groups (or anhydride) of maleic anhydride, maleic acid, and maleic acid esters (maleates) have a cis- orientation, so that the carboxylate groups in the Diels-Alder adduct have a \ ,2-syn- (also referred to as cis-) orientation relative to each other. [0092] In certain embodiments, a Diels-Alder reaction between a conjugated terpene and a dienophile is thermally driven, without the need for a catalyst. In some embodiments, a Diels-Alder reaction occurs at a temperature in a range from about 50 °C to about 100 °C, or from about 50 °C to about 130 °C. In other embodiments, a catalyst is used, e.g., to increase reaction rate, to increase reactivity of weak dienophiles or sterically hindered reactants, or to increase selectivity of certain adducts or isomers. For example, a Lewis acid may be used in some variations. In some embodiments, a Diels- Alder reaction is run without solvent. In certain embodiments, reaction conditions (e.g., temperature, pressure, catalyst (if present), solvent (if present), reactant purities, reactant concentrations relative to each other, reactant concentrations relative to a solvent (if present), reaction times and/or reaction atmosphere are selected so that formation of dimers, higher oligomers and/or polymers of the conjugated terpene is suppressed or minimized. Reaction conditions (e.g., temperature, pressure, catalyst (if present), solvent (if present), reactant purities, reactant concentrations relative to each other, reactant concentrations relative to a solvent (if present), reaction times and/or reaction atmosphere may be selected so that formation of dimers, higher oligomers and/or polymers of the diene is suppressed or minimized. In some embodiments, the reaction conditions (e.g., temperature, catalyst (if present), solvent (if present), reactant purities, reactant concentrations, reaction times, reaction atmosphere and/or reaction pressure are selected to produce a desired adduct or isomer. More detailed descriptions of the Diels-Alder reaction and reaction conditions for the Diels-Alder reaction are disclosed in the book by Fringuelli et al., titled "The Diels-Alder Reaction: Selected Practical Methods," 1st edition, John Wiley & Sons, Ltd., New York (2002), which is incorporated by reference herein in its entirety. Non-limiting Diels-Alder reactions using β-farnesene to produce pheromones are provided in U.S. Patent No.

4,546,110, which is incorporated herein by reference in its entirety. In some variations, trans- β-farnesene [(6E)-7,1 l-dimethyl-3-methylidenedodeca-l,6,10-triene] is selected to be reacted with a suitable dienophile to form Diels-Alder adducts described herein.

[0093] A variety of electron deficient dienophiles may effectively undergo the Diels-Alder reaction with conjugated terpenes to produce cyclic compounds that have utility as described herein. Any dienophile that can undergo the Diels-Alder reaction with one or more dienes may be used herein. Some non-limiting examples of suitable dienophiles are disclosed in Fringuelli et al., titled "The Diels- Alder Reaction: Selected Practical Methods " 1 st edition, John Wiley & Sons, Ltd., New York, pages 3- 5 (2002), which is incorporated herein. Other non-limiting examples of dienophiles are provided in Section D below. Any conjugated terpene described herein or otherwise known may undergo Diels- Alder reaction with a dienophile to provide a Diels-Alder adduct having utility as described herein. Some non-limiting examples of conjugated terpenes that may be used to make the Diels-Alder adducts are provided in Section E below and include myrcene, ocimene, a-farnesene, β-farnesene, β-springene, geranylfamesene, isodehydrosqualene, isosqualane precursor I, and isosqualane precursor II. Some non- limiting examples of Diels-Alder adducts are provided in Section G below. D) Dienophiles

[0094] The dienophile used herein can be any dienophile that undergoes a Diels-Alder reaction with a diene on the conjugated hydrocarbon terpene to form the corresponding cyclic compound. In certain embodiments, the dienophile has formula (I), (II) or (III):

wherein each of R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷ and R¹⁸ is independently H, a saturated or unsaturated, cyclic or acyclic, unsubstituted or substituted C₁-C30 hydrocarbyl group (e.g., C₁-C₂0 alkyl, C₁-C₂0 alkenyl, C₁-C₂₀ alkynyl, cycloalkyl, aryl, aralkyl and alkaryl), hydroxyalkyl (e.g., -CH₂OH), aminoalkyl (e.g., -CH₂NH₂), carboxylalkyl (e.g., -CH₂C0₂H), thioalkyl (e.g., -CH₂SH), epoxyalkyl (e.g., glycidyl), hydroxyaryl, aminoaryl, carboxylaryl, thioaryl, hydroxyl, amino, halo, cyano, nitro, sulfonate, sulfmate, sulfoxide, acyl (e.g., formyl and acetyl), -C0₂R¹⁹, -(CH₂)_nC0₂R²⁰, -COOTVI^, -(CH₂)_mCOCnVi₂ ⁺, - C(=0)NR²¹R²², -OR²³ or -C(=0)X where X is halo; or R¹¹ and R¹² together or R¹³ and R¹⁴ together form a -C(=0)-0-C(=0)- group, a -C(=0)-S-C(=0)- group, a -C(=0)-NR²⁴-C(=0)- group, a -C(=0)- CR²⁵=CR²⁶-C(=0)- group, or a -C(=0)-C(=0)-CR²⁷=CR²⁸- group; or R¹¹ and R¹³ together or R¹² and R¹⁴ together form a -CH₂-C(=0)-0-C(=0)- group, where each of and M₂ ⁺ is independently a monovalent cation such as Fr⁺, Cs⁺, Rb⁺, K⁺, Na⁺, Li⁺, Ag⁺, Au⁺, Cu⁺, NH₄ ⁺, primary ammonium, secondary ammonium, tertiary ammonium, or quaternary ammonium; each of R 19 , R 20 , R 21 , R 22 , R 23 , R 24 ,

R 25 , R 26 , R 27 and R 28 is independently H, hydrocarbyl, hydroxyalkyl, aminoalkyl, carboxylalkyl, thioalkyl, epoxyalkyl, hydroxyaryl, aminoaryl, carboxylaryl, thioaryl, hydroxyl, amino, halo, cyano, nitro or acyl, or R 25 and R 26 together or R 27 and R 28 together form a benzo ring or a substituted or

unsubstituted -CH₂(CH₂)_kCH₂- group; and each of m, n and k is independently an integer from 1 to 20 or from 1 to 12, with the proviso that at least one of R¹¹, R¹², R¹³ and R¹⁴ is not H, and the proviso that at least one of R¹⁵ and R¹⁶ is not H, and the proviso that at least one of R¹⁷ and R¹⁸ is not H.

[0095] In some embodiments, a dienophile has formula (Al), (A2), (A3), (A4), (A5), (A6), or

(A7):

(A5), RA¹⁴-C≡C-RA¹³ (_A6), or (A7), wherein QA¹ may be O, S, or NRA¹⁹; each of QA², QA³ and QA⁴ may independently be a halo substituent (e.g., chloro or bromo), NRA²⁰RA²¹ or ORA²²; QA⁵ may be a halo substituent (e.g., chloro or bromo), a cyano group or ORA²³; and each of RA¹, RA², RA³, RA⁴, RA⁵, RA⁶, RA⁷, RA⁸, RA⁹, RA¹⁰, RA¹¹, RA¹², RA¹³, RA¹⁴, RA¹⁵, RA¹⁶, RA¹⁷, RA¹⁸, RA¹⁹, RA²⁰, RA²¹, RA²² and RA²³ is independently H, C₁-C₂₀ alkyl, C₁-C₂₀ alkenyl, C₁-C₂₀ alkynyl, cycloalkyl, aryl, aralkyl, alkaryl, OH, NH₂, carboxyl, epoxy or glycidyl.

[0096] In some embodiments, the dienophile comprises an unsaturated carbon-carbon bond with one or more electron withdrawing groups attached to a carbon of the unsaturated bond. Non-limiting examples of electron withdrawing groups that may be attached to an unsaturated carbon-carbon bond in a dienophile include: one or more substituted carbonyl groups such as one or more ester groups represented as -COOR, one or more aldehyde groups represented as -CHO, one or more ketone groups represented as -COR, one or more carboxyl groups represented as -COOH, one or more amide groups represented as - CONRR', one or more imide groups represented as -CONRCOR', one or more aryloxycarbonyl groups such as a phenoxycarbonyl group, one or more carbonyloxycarbonyl groups, or a one or more carbonyliminocarbonyl groups, wherein each of R and R' is independently H or any Ci-C₃₀ aliphatic, aromatic, linear, branched, cyclic or acyclic, substituted or unsubstituted, saturated or unsaturated hydrocarbyl group, and may include one or more heteroatoms such as nitrogen, oxygen, phosphorus, sulfur, or chloride. In some embodiments, the dienophile comprises a vinyl sulfonate, vinyl sulfinate, or vinyl sulfoxide.

[0097] In certain embodiments, the dienophile comprises sulfur dioxide, or a sulfone SO₂RR', where R and R' may independently be any Ci-C₃₀ hydrocarbyl group.

[0098] Some non-limiting examples of suitable dienophiles that can form Diels-Alder adducts with conjugated terpenes (e.g., farnesene or myrcene) include acrylate esters, vinyl ketones, monoalkyl or dialkyl maleates, maleic anhydride, maleimides and substituted maleimides, acetylene dicarboxylic acids and their monoesters or diesters, and quinones.

[0099] Some non-limiting specific examples of dienophiles that can react with a conjugated terpene (e.g., farnesene or myrcene) to produce a compound useful as described herein include dienophiles in groups (A)-(Y) below:

(A) maleic anhydride and substituted maleic anhydrides;

(B) citraconic anhydride and substituted citraconic anhydrides;

(C) itaconic acid and substituted itaconic acids;

(D) itaconic anhydride and substituted itaconic anhydrides;

(E) acrolein and substituted acroleins; (F) crotonaldehyde and substituted crotonaldehydes;

(G) monoalkyl or dialkyl maleates or monoalkyl or dialkyl fumarates (e.g., linear or branched, cyclic or acyclic, C₁-C30 dialkyl maleates or dialkyl fumarates such as dimethyl maleate, dimethyl fumarate, diethyl maleate, diethyl fumarate, di-n-propyl maleate, di-n-propyl fumarate, di-isopropyl maleate, diisopropyl fumarate, di-n-butyl maleate, di-n-butyl fumarate, diisobutyl maleate, di(isobutyl) fumarate, di-tert-butyl maleate, di-tert-butyl fumarate, di-n-pentyl maleate, di-n-pentyl fumarate, diisopentyl maleate, diisopentyl fumarate, di-n-hexyl maleate, di-n-hexyl fumarate, bis(2-ethylhexyl) maleate, bis(2- ethylhexyl) fumarate, diisohexyl maleate, diisohexyl fumarate, di-n-heptyl maleate, di-n-heptyl fumarate, diisoheptyl) maleate, diisoheptyl fumarate, di-n-octyl maleate, di-n-octyl fumarate, diisooctyl maleate, diisooctyl fumarate, di-n-nonyl maleate, di-n-nonyl fumarate, diisononyl maleate, diisononyl fumarate, di-n-decyl maleate, di-n-decyl fumarate, diisodecyl maleate, and diisodecyl fumarate, or fumaric acid;

(H) monoalkyl or dialkyl itaconates (e.g., linear or branched, cyclic or acyclic, Ci-C₃₀ dialkyl itaconates such as dimethyl itaconate, diethyl itaconate, di-n-propyl itaconate, diisopropyl itaconate, di-n-butyl itaconate, diisobutyl itaconate, di-tert-butyl itaconate, di-n-pentyl itaconate, diisopentyl itaconate, di-n- hexyl itaconate, bis(2-ethylhexyl) itaconate, diisohexyl itaconate, di-n-heptyl itaconate, diisoheptyl itaconate, di-n-octyl itaconate, diisooctyl itaconate, di-n-nonyl itaconate, diisononyl itaconate, di-n-decyl itaconate and diisodecyl itaconate);

(I) acrylic acid esters (e.g., linear or branched, cyclic or acyclic, Ci-C₃₀ alkyl acrylates, such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-pentyl acrylate, isopentyl acrylate, n-hexyl acrylate, isohexyl acrylate, 2-ethylhexyl acrylate, n-heptyl acrylate, isoheptyl acrylate, n-octyl acrylate, isooctyl acrylate, n-nonyl acrylate, isononyl acrylate, n-decyl acrylate, isodecyl acrylate, 2-propylheptyl acrylate, n-undecyl acrylate, isoundecyl acrylate, n-dodecyl acrylate, isododecyl acrylate, n-tridecyl acrylate, n-tetradecyl acrylate, n- pentadecyl acrylate, n-hexadecyl acrylate, n-heptadecyl acrylate, n-octadecyl acrylate, n-nonadecyl acrylate, n-eicosyl acrylate, and n-tricosyl acrylate);

(J) methacrylic acid esters (e.g., linear or branched, cyclic or acyclic, C₁-C30 alkyl methacrylates, such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-pentyl methacrylate, isopentyl methacrylate, n-hexyl methacrylate, isohexyl methacrylate, 2-ethylhexyl methacrylate, n-heptyl methacrylate, isoheptyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, n-nonyl methacrylate, isononyl methacrylate, n-decyl methacrylate, isodecyl methacrylate, 2-propylheptyl methacrylate, n- undecyl methacrylate, isoundecyl methacrylate, n-dodecyl methacrylate, isododecyl methacrylate, n- tridecyl methacrylate, n-tetradecyl methacrylate, n-pentadecyl methacrylate, n-hexadecyl methacrylate, n-heptadecyl methacrylate, n-octadecyl methacrylate, n-nonadecyl methacrylate, n-eicosyl methacrylate, and n-tricosyl methacrylate); (K) cinnamic acid and cinnamic acid esters (e.g., linear or branched, cyclic or acyclic, Ci-C₃₀ alkyl cinnamate, such as methyl cinnamate and ethyl cinnamate);

(L) mesityl oxide and substituted mesityl oxides;

(M)hydroxyalkyl acrylates (e.g., 2-hydroxymethyl acrylate and 2 -hydroxy ethyl acrylate);

(N) carboxyalkyl acrylates (e.g., 2-carboxy ethyl acrylate);

(O) (dialkylamino)alkyl acrylates (e.g., 2-(diethylamino)ethyl acrylate);

[00100] (P) monoalkyl and dialkyl acetylene dicarboxylates (e.g., linear or branched, cyclic or acyclic, C₁-C30 dialkyl acetylene dicarboxylates such as dimethyl acetylene dicarboxylate, diethyl acetylene dicarboxylate, di-n-propyl acetylene dicarboxylate, diisopropyl acetylene dicarboxylate, di-n- butyl acetylene dicarboxylate, diisobutyl) acetylene dicarboxylate, di(tert-butyl) acetylene dicarboxylate, di-n-pentyl acetylene dicarboxylate, diisopentyl acetylene dicarboxylate, di-n-hexyl acetylene dicarboxylate, bis(2-ethylhexyl) acetylene dicarboxylate, diisohexyl acetylene dicarboxylate, di-n-heptyl acetylene dicarboxylate, di(isoheptyl) acetylene dicarboxylate, di-n-octyl acetylene dicarboxylate, diisooctyl acetylene dicarboxylate, di-n-decyl acetylene dicarboxylate, diisodecyl acetylene

dicarboxylate), an alkyl propiolate (e.g., an alkyl propiolate incorporating any C₁-C₂₀ alkyl group such as methyl propiolate, ethyl propiolate, or butyl propiolate), an alkyl 2-butynoate, an alkyl 2-pentynoate, an alkyl 2-hexynoate, 2-butynoic acid, and 2-pentynoic acid; an alkyl 2-butynoate, e.g., an alkyl 2-butynoate incorporating any C₁-C₂₀ alkyl group such as methyl 2-butynoate, ethyl 2-butynoate, propyl 2-butynoate, or propyl 2-butynoate; an alkyl 2-pentynoate, e.g., an alkyl 2-pentynoate incorporating any C ₁-C₂₀ alkyl group such as methyl 2-pentyne, ethyl 2-pentanoate, propyl 2-pentynoate or butyl 2-pentynoate; an alkyl 2-hexynoate, e.g., an alkyl 2-hexynoate incorporating any C₁-C₂₀ alkyl group such as methyl 2- hexynanoate, ethyl 2-hexynoate, propyl 2-hexynoate or butyl 2-hexynoate; 2-butynoic acid; 2-pentynoic acid; 2-hexynoic acid; dicyanoacetylene; and cyanoacetylene;

(Q) vinyl ketones (e.g., linear or branched, cyclic or acyclic, aliphatic or aromatic, C₁-C30 vinyl ketones, such as methyl vinyl ketone, ethyl vinyl ketone, n-propyl vinyl ketone, n-butyl vinyl ketone, isobutyl vinyl ketone, tert-butyl vinyl ketone, n-pentyl vinyl ketone, n-hexyl vinyl ketone, 2-ethylhexyl vinyl ketone, n-heptyl vinyl ketone, n-octyl vinyl ketone, n-nonyl vinyl ketone, n-decyl vinyl ketone, n-undecyl vinyl ketone, n-dodecyl vinyl ketone, n-tridecyl vinyl ketone, n-tetradecyl vinyl ketone, n-pentadecyl vinyl ketone, n-hexadecyl vinyl ketone, n-heptadecyl vinyl ketone, n-octadecyl vinyl ketone, n-nonadecyl vinyl ketone, n-eicosyl vinyl ketone, and n-tricosyl vinyl ketone);

(R) maleamides, fumaramides, maleimide and substituted maleimides (e.g., maleic acid diamide, or C_r C₃₀ alkyl or aryl N- or Ν,Ν'- substituted maleamides such as N-methyl maleamide, N-ethyl maleamide, N-n-butyl maleamide, Ν,Ν'-dimethyl maleamide, Ν,Ν'-methyl ethyl maleamide, or N,N'-tetramethyl maleamide; fumaramide, or Ci-C₃₀ alkyl or aryl N- or Ν,Ν'- substituted fumaramides such as N-methyl fumaramide, N-isopropyl fumaramide, Ν,Ν'-diethyl fumaramide, N,N'-di-n-butyl fumaramide, Ν,Ν'- tetraethyl fumaramide; linear or branched, cyclic or acyclic, C₁-C30 alkyl or aryl N-substituted maleimides, such as N-methylmaleimide, N-ethyl maleimide, N-n-propyl maleimide, N-isopropyl maleimide, N-n-butyl maleimide, N-tert-butyl maleimide, N-n-pentyl maleimide, N-isopentyl maleimide, N-n-hexyl maleimide, N-isohexyl maleimide, N-(2-ethylhexyl) maleimide, N-n-heptyl maleimide, N-n- octyl maleimide, N-n-decyl maleimide, N-n-undecyl maleimide, N-n-dodecyl maleimide, N-n-tridecyl maleimide, N-n-tetradecyl maleimide, N-n-pentadecyl maleimide, N-n-hexadecyl maleimide, N-n- heptadecyl maleimide, N-n-octadecyl maleimide, N-n-nonadecyl maleimide, N-n-eicosyl maleimide, and maleimides in which the nitrogen is substituted with -COOR, where R represents any linear or branched, cyclic or acyclic C₁-C30 alkyl group, for example, N-methoxycarbonylmaleimide);

(S) dialkyl azidocarboxylates, e.g. linear or branched, cyclic or acyclic, Ci-C₃₀ dialkyl

azidocarboxylates, such as dimethyl azidocarboxylate, and diethyl azidocarboxylate;

(T) azidocarboxylic acid and azidodicarboxylic acid diesters containing two ester groups which may be the same or different ester groups;

(U) sulfur dioxide;

(V) 1 ,4-benzoquinone and substituted 1 ,4-benzoquinones (e.g., 2-(3-methyl-2-butenyl)benzo-l,4- quinone), 1 ,2-benzoquinone and substituted 1,2-benzoquinones;

(W)naphthoquinones such as 1 ,4-naphthoquinone, 1 ,2-naphthoquinone, plumbagin

;

(X) phosphorus trihalide (e.g., phosphorus tribromide); and

(Y) vinyl sulfonates, vinyl sulfinates, or vinyl sulfoxides.

E) Conjugated Hydrocarbon Terpenes

[00101] The conjugated hydrocarbon terpene used herein can be any conjugated hydrocarbon terpene having a diene group that undergoes a Diels-Alder reaction with a dienophile to form the corresponding cyclic compound. In certain embodiments, the conjugated hydrocarbon terpene has formula (IV):

wherein each of RB¹, RB², RB³ and RB⁴ is independently H, a saturated or unsaturated, cyclic or acyclic, unsubstituted or substituted Ci-C₃₀ hydrocarbyl group, with the proviso that at least one of RB¹, RB², RB and RB⁴ is not hydrogen.

[00102] The hydrocarbon terpene is selected to have a stereochemistry amenable to Diels-Alder reactions, That is, the conjugated diene is able to adopt an s-cis conformer. For a hydrocarbon terpene to undergo a Diels-Alder cycloaddition reaction, the double bonds exist in an s-cis conformation or conformational rotation around the single bond between the double bonds so that an s-cis conformation of the diene is adoptable. In many conjugated dienes, the s-trans conformer population is in rapid equilibrium with s-cis conformers. In some cases, steric effects due to substituents on the conjugated diene and/or dienophile may impede a Diels-Alder reaction. In some casaes, hydrocarbon terpenes having terminal conjugated diene groups are selected, i.e., hydrocarbon terpenes in which RB¹, RB², and RB³ are each H, but RB⁴ is not H. In some cases, RB¹ is H, but RB², RB³ and RB⁴ are not H. In some cases^B¹ and RB² are H, but RB³ and RB⁴ are not H.

[00103] In some embodiments, the conjugated hydrocarbon terpene has formula (IV) where each of RB¹, RB³ and RB⁴ is independently H; and RB² has formula (V):

wherein n is 1, 2, 3 or 4. In other embodiments, the conjugated hydrocarbon terpene has formula (AI):

wherein n is 1, 2, 3 or 4.

[00104] In certain embodiments, the conjugated hydrocarbon terpene is myrcene which has formula (AI) where n is 1. In some embodiments, the conjugated hydrocarbon terpene is β-farnesene which has formula (AI) where n is 2. In certain embodiments, the conjugated hydrocarbon terpene is β- springene which has formula (AI) where n is 3. In some embodiments, the conjugated hydrocarbon terpene is geranylfarnesene which has formula (AI) where n is 4.

[00105] In certain embodiments, the conjugated hydrocarbon terpene has formula (IV) where each of RB³ and RB⁴ is H; RB² is methyl; and RB¹ has formula (VI):

(VI), wherein m is 1, 2, 3 or 4. The dashed bond in formula (VI) represents a bond that may be present to result in a double bond, or may not be present to result in a single bond. In other embodiments, the conjugated hydrocarbon terpene has formula (All):

wherein m is 1, 2, 3 or 4.

[00106] In certain embodiments, the conjugated hydrocarbon terpene is β-ocimene which has formula (All) where m is 1. In some embodiments, the conjugated hydrocarbon terpene is a-farnesene which has formula (All) where m is 2.

[00107] In some embodiments, the conjugated hydrocarbon terpene that can react with a dienophile disclosed herein is isodehydrosqualene. In certain embodiments, the conjugated hydrocarbon terpene is isosqualane precursor I. In some embodiments, the hydrocarbon terpene is isosqualane precursor II.

F) Diels-Alder Adducts

[00108] Diels-Alder adducts can be prepared by reacting a dienophile disclosed herein with one or more conjugated hydrocarbon terpene under suitable Diels-Alder reaction conditions with or without the presence of a catalyst. The hydrocarbon terpene and a dienophile in a Diels-Alder reaction may each demonstrate stereoisomerism. Stereoisomerism of the reactants is preserved in the Diels-Alder adduct, and the relative orientation of the substituents on the reacts is preserved in the Diels-Alder adduct. For example, fumaric acid and fumaric acid esters (fumarates) exist as trans-isomers, so if a fumaric acid ester is used as a dienophile, the carboxylate groups in the Diels-Alder adduct have a 1 ,2-anti- (also referred to as trans-) orientation relative to each other. The carboxylate groups (or anhydride) of maleic anhydride, maleic acid, and maleic acid esters (maleates) have a cis- orientation, so that the carboxylate groups in the Diels-Alder adduct have a 1 ,2-syn- (also referred to as a cis-) orientation relative to each other. In some embodiments, a conjugated hydrocarbon terpene of formula (IV) reacts with a dienophile of formula (I) to provide the Diels-Alder adduct having formula (VIIA) or (VIIB) or a mixture thereof:

wherein RB¹, RB², RB³, RB⁴, R¹¹, R¹², R¹³ and R¹⁴ are as defined herein. [00109] In some embodiments, the Diels-Alder adduct of formula (VIIA) and (VIIB) can be hydrogenated or reduced by any reduction reaction known to a skilled artisan to form a hydrogenated adduct having formula (VIIA') and (VIIB') respectively:

wherein RB¹, RB², RB³, RB⁴, R¹¹, R¹², R¹³ and R¹⁴ are as defined herein.

[00110] In certain embodiments, a conjugated hydrocarbon terpene of formula (IV) reacts with a dienophile of formula (II) to provide the Diels-Alder adduct having formula (VIIIA) or (VIIIB) or a mixture thereof:

(VIIIB) wherein RB¹, RB², RB³, RB⁴, R¹⁵ and R¹⁶ are as defined herein. In some embodiments, the Diels-Alder adduct of formula (VIIA) and (VIIB) can be oxidized by any oxidation reaction known to a skilled artisan to form an oxidized adduct having formula (VIIIA") and (VIIIB"), respectively.

[00111] In some embodiments, the Diels-Alder adduct of formula (VIIIA) and (VIIIB) can be hydrogenated or reduced by any reduction reaction known to a skilled artisan to form a hydrogenated adduct having formula (VIIIA') and (VIIIB') respectively:

(VIIIB'), wherein RB¹, RB², RB³, RB⁴, R¹⁵ and R¹⁶ are as defined herein.

[00112] In some embodiments, the Diels-Alder adduct of formula (VIIIA) and (VIIIB) or of formula (VIIA) and (VIIB) can be oxidized by any oxidation reaction known to a skilled artisan to form an oxidized adduct having formula (VIIIA") and (VIIIB"), respectively:

(VIIIA"), or (VIIIB"),

wherein RB¹, RB², RB³, RB⁴, R¹⁵ and R¹ 1⁶6 are as defined herein.

[00113] In certain embodiments, a conjugated hydrocarbon terpene of formula (IV) reacts with a dienophile of formula (III) to provide the Diels-Alder adduct having formula (IXA) or (IXB) or a mixture thereof:

wherein RB¹, RB², RB³, RB⁴, R¹⁷ and R¹⁸ are as defined herein.

[00114] In some embodiments, the Diels-Alder adduct of formula (IXA) and (IXB) can be hydrogenated or reduced by any reduction reaction known to a skilled artisan to form a hydrogenated adduct having formula (ΙΧΑ') and (ΙΧΒ') respectively:

wherein RB¹, RB², RB³, RB⁴, R¹⁷ and R¹⁸ are as defined herein.

[00115] In some embodiments, each of RB¹, RB³ and RB⁴ of the adduct of formula (VILA),

(VILA'), (VLLB), (VIIB'), (VIIIA), (VIIIA'), (VIIIA"), (VIIIB), (VIIIB'), (VIIIB"), (IXA), (ΙΧΑ'), (IXB) or (ΙΧΒ') is independently H; and RB² has formula (X):

wherein n is 1, 2, 3 or 4. In certain embodiments, n is 1. In some embodiments, n is 2. In certain embodiments, n is 3. In some embodiments, n is 4. [00116] In some embodiments, RB having formula (X) in the adducts disclosed herein can be hydrogenated or reduced by any reduction reaction known to a skilled artisan to form the corresponding alkyl group having formula (XI):

wherein n is 1, 2, 3 or 4. In certain embodiments, n is 1. In some embodiments, n is 2. In certain embodiments, n is 3. In some embodiments, n is 4.

[00117] In some embodiments, RB² having formula (X) in the adducts disclosed herein can be epoxidized by any epoxidation reaction known to a skilled artisan to form the corresponding epoxy group having formula (XII):

[00118] In certain embodiments, each of RB³ and RB⁴ of the adduct of formula (VIIA), (VILA.'),

(VIIB), (VIIB'), (VILLA), (VILLA'), (VILLA"), (VIIIB), (VIIIB'), (VIIIB"), (IXA), (ΙΧΑ'), (IXB) or (ΙΧΒ') is independently is H; RB² is methyl; and RB¹ has formula (XIII):

wherein m is 1, 2, 3 or 4. In certain embodiments, m is 1. In some embodiments, m is 2. In certain embodiments, m is 3. In some embodiments, m is 4.

[00119] In some embodiments, RB¹ having formula (XIII) in the adducts disclosed herein can be hydrogenated or reduced by any reduction reaction known to a skilled artisan to form the corresponding alkyl group having formula (XLV):

wherein m is 1, 2, 3 or 4. In certain embodiments, m is 1. In some embodiments, m is 2. In certain embodiments, m is 3. In some embodiments, m is 4. [00120] In some embodiments, RB having formula (XIII) in the adducts disclosed herein can be epoxidized by any epoxidation reaction known to a skilled artisan to form the corresponding epoxy group having formula (XV):

[00121] In some embodiments, the Diels-Alder adduct between a conjugated hydrocarbon terpene and a dienophile is represented by formula (Bl):

where RB¹, RB², RB³ and RB⁴ represent the substituents of the conjugated diene of the conjugated terpene and may each independently be H or a Ci-C₃₀ saturated or unsaturated, cyclic or acyclic, hydrocarbyl group, with the proviso that one of RB¹, RB², RB³ and RB⁴ is not hydrogen. In certain embodiments, QB¹ and QB² represent the residue of the dienophile directly following the Diels-Alder reaction. In some embodiments, QB ¹ and QB² represent the residue following Diels-Alder reaction that has undergone subsequent chemical modification. In certain embodiments, a 6-membered ring adduct is formed by the Diels-Alder reaction. In some embodiments, the Diels-Alder adduct formed comprises a 5-membered ring so that QB¹ and QB² are the same. Each of the dashed bonds in formula (Bl) independently represents a bond that may be present to result in a double bond, or may not be present to result in a single bond. In some embodiments, the Diels-Alder adduct is derived form a dienophile containing a double bond and therefore, the bond between QB ¹ and QB² is single and the bond between RB² and RB³ is double. In certain embodiments, the Diels-Alder adduct is derived form a dienophile containing a triple bond, and therefore, the bond between QB ¹ and QB² is double and the bond between RB² and RB³ is double. In some embodiments, the Diels-Alder adduct is derived form a dienophile containing a double bond and is hydrogenated to saturate the double bond between RB² and RB³ to form a single bond. In some embodiments, the Diels-Alder adduct is hydrogenated to saturate all or some of the unsaturated bonds in the ring and/or in one or more of the RB¹, RB², RB³, RB⁴, QB¹ and QB² groups. It should be noted that in some embodiments, a cyclohexenyl ring may be oxidized to form a cyclohexadienyl ring. In other embodiments, a cyclohexenyl or a cyclohexadienyl ring may be oxidized so that the ring is aromatic. [00122] In some embodiments, the Diels-Alder adduct is formed between a conjugated hydrocarbon terpene having formula (AI) and a dienoph herein and the adduct has formula

(Bl), where each of RB¹, RB³ and RB⁴ is H; and RB² is , where n is 1 , 2, 3 or 4, as represented by formula (B2) or (B3) or a mixture thereof:

[00123] When the conjugated terpene is β-farnesene, the Diels-Alder adduct may be represented by formula (B2), (B3) or a mixture thereof, wherein n is 2. When the conjugated terpene is myrcene, the Diels-Alder adduct may be represented by formula (B2), (B3) or a mixture thereof, wherein n is 1.

[00124] In some embodiments, the Diels-Alder adduct is formed between a conjugated hydrocarbon terpene having formula (All) and a dienophile disclosed herein and the adduct has formula

(Bl) where each of RB³ and RB⁴ is H; RB² is methyl; and RB¹ is

where m is 1, 2, 3 or 4, as represented by formula (B4), (B5), or a mixture thereof:

[00125] When the conjugated terpene is a-farnesene, the Diels-Alder adduct may be represented by formula (B4), (B5) or a mixture thereof where m is 2. When the conjugated terpene is β-ocimene, the Diels-Alder adduct may be represented by formula (B4), (B5) or a mixture thereof where m is 1.

[00126] Table 1 shows RB¹, RB², RB³ and RB⁴ for exemplary conjugated terpenes, where dashed lines indicate unsaturated olefinic bonds originating from the conjugated terpene that may in some embodiments be completely or partially hydrogenated prior to or subsequent to the Diels-Alder reaction. Table 2 shows QB¹ and QB² for some exemplary dienophiles. For both Tables 1 and 2, it should be noted that isomers may be formed in which RB¹ is reversed with RB⁴, RB² is reversed with RB³, and/or QB¹ is reversed with QB². The Diels-Alder adduct having formula (Bl) may include any combination of RB¹, RB², RB³ and RB⁴ shown in Table 1 with any combination of QB¹ and QB² shown in Table 2. For the compounds in Table 1 and Table 2, RB¹, RB², RB³ and RB⁴ are as defined herein, and RB¹ , RB² , RB^3', and RB^4' are defined as RB¹, RB², RB³ and RB⁴. Table 1. Some exemplary conjugated terpenes for making Diels-Alder adducts having formula (Bl).

TABLE 2. SOME EXEMPLARY DIENOPHILES AND DIELS-ALDER ADDUCTS.

different

[00127] In some embodiments, a Diels-Alder adduct is formed in which two conjugated terpene molecules react with a single dienophile (e.g., a dienophile comprising an acetylenic moiety). Some non- limiting examples are shown as entries 11, 12, 13, 14, 16 and 17 in Table 2. It should be noted that the two conjugated terpenes that react with a single dienophile may be the same or different. For example, the following combinations of conjugated terpenes may react with a single dienophile: 2 myrcene; 2 a- farnesene; 2 β-farnesene; 1 a-farnesene and 1 β-farnesene; 1 myrcene and 1 a-farnesene, 1 myrcene and 1 β-farnesene. In certain embodiments, a Diels-Alder adduct is formed in which one conjugated terpene molecule (e.g., myrcene, α-farnesene, or β-farnesene) and one substituted or unsubstituted conjugated diene molecules (e.g., 1,3 -butadiene) is reacted with a single dienophile (e.g., a dienophile comprising an acetylenic moiety).

[00128] Also described herein are Diels-Alder adducts between oligomers (e.g., dimers and trimers) of conjugated terpenes and a dienophile. For example, β-farnesene can be dimerized (e.g., to form isodehydrosqualene, isosqualane precursor I or isosqualane precursor II), trimerized, or oligomerized as described in U.S. Patent Application No. 13/ US 13/112,991, filed May 20, 2011, and U.S. Patent Application No. 12/552278, filed Sept. 1, 2009, or to form cyclic dimers, as described in U.S. Patent Nos. 7,691,792 and 7,592,295, all of which are incorporated herein by reference in their entireties. The dimers, trimers and oligomers so formed may contain a conjugated diene, which can undergo Diels- Alder reaction with a dienophile.

G) Chemical Modification Of Diels-Alder Adducts

[00129] In some embodiments, a Diels-Alder adduct between one or more conjugated terpenes and a dienophile as described herein may be chemically modified following the Diels-Alder reaction. The chemical modifications may be selected to tune the applicability to the modified Diels-Alder reaction for use as oils, lubricants, additives or base oils for lubricant compositions, surfactants, plasticizers, and/or as monomers, cross-linking agents, curing agents or reactive diluents for use in making oligomers or polymers.

[00130] For example, any one of or any suitable combination of the following chemical modifications in any suitable order may be made to a Diels-Alder adduct: i) an alkoxycarbonyl group may be reduced to a hydroxymethyl or methyl group; ii) one or more ester groups may be hydrolyzed to a carboxylic acid or a salt thereof; iii) one or more carboxyl groups may be decarboxylated to a hydrogen; iv) an anhydride group may be opened to yield the dicarboxylic acid compound or a salt thereof; v) an anhydride group may be opened with an amine to produce a compound having a carboxylic acid group and an amide group on adjacent carbons; vi) reduction of amides to amines; vii) opening of anhydrides with hydrogen peroxide; viii) one or more ester groups on a Diels Alder adduct may undergo

transesterification with an alcohol (e.g. a methyl ester may undergo transesterification with a C₈ or longer primary alcohol); ix) a formyl group may be reduced to a methyloyl group; x) a hydroxyl substituent may be alkoxylated to form an alkoxylated substituent (e.g., ethoxylated or propoxylated); xi) one or more double bonds originating from the conjugated terpene can be oxidized (e.g., epoxidized); xii) one or more double bonds originating from the conjugated terpene may be halogenated; xiii) a hydroxyl or ester group may undergo a condensation reaction; xiv) a hydroxyl group or amide group may undergo a condensation reaction; xv) a hydroxyl group or ester group may be sulfated; xvi) an alcohol may be converted to an alkyl halide; xvii) an alkyl halide may be reacted with sodium sulfite to form a sulfoante; xviii) an amine group may be converted to an ammonium ion (e.g., a quaternary ammonium ion) or an aine-oxide; and xix) a reverse Diels-Alder reaction may occur to yield desired products.

[00131] In certain embodiments, a Diels-Alder adduct between a conjugated terpene and a dienophile as described herein is hydrogenated so as to completely or partially hydrogenate aliphatic portions of the Diels-Alder adduct. Such hydrogenated Diels-Alder adducts (and derivatives thereof) may in certain circumstances exhibit improved thermo-oxidative stability in use. [00132] In certain embodiments, a ring formed in the Diels-Alder adduct is oxidized. For example, a cyclohexenyl ring may be oxidized to a cyclohexadienyl ring or to an aromatic 6-membered ring, or a cyclohexadienyl ring may be oxidized to an aromatic 6-membered ring.

[00133] In some embodiments, at least one carbon-carbon double bond remains in the aliphatic tail originating from the conjugated terpene in the Diels-Alder adduct. The unsaturated tail provides a reactive site that may have a variety of functions. For example, the unsaturated tail may be oxidized as described in more detail herein, may provide scavenging functionality, may provide a site for oligomerization or polymerization, and/or may provide a site for cross-linking into a matrix. The unsaturated bond may undergo oxidation, e.g., to form a polyol.

[00134] Table 3 illustrates some non-limiting examples of chemical modifications of Diels-Alder adducts between conjugated terpenes and dienophiles.

Table 3. Some exemplary chemical modifications of Diels-Alder adducts.

(oxidation)

[00135] In some embodiments, one or more carbon-carbon double bonds of a conjugated terpene

Diels-Alder adduct as described herein is oxidized (e.g., epoxidized). Such oxidized (e.g., epoxidized) hydrocarbon terpene derivatives may be useful in a variety of applications. For example, oxidized farnesene derivatives may exhibit increased compatibility or solubility with relatively polar polymers or solvents. In some embodiments, an epoxidized farnesene derivative may be useful as a reactive diluent in a resin and/or as a cross-linking agent. Any suitable oxidation technique known to oxidize carbon- carbon double bonds may be used. For example, any suitable oxidant such as peroxides, peracetic acid, meta chloroperoxybenzoic acid, enzymes, or peroxide complexes such as urea-peroxide complexes (e.g., Novozyme-435™ urea-peroxide complex) may be used. In some embodiments, the oxidation (e.g., epoxidation) conditions are adjusted to oxidize only one carbon-carbon double bond, e.g., one carbon- carbon double bond that originated in the conjugated terpene starting material. In some embodiments, the oxidation (e.g., epoxidation) conditions are adjusted to oxidize two carbon-carbon double bonds, e.g., two carbon-carbon double bonds that originated in the conjugated terpene starting material. In some embodiments, oxidation (e.g., epoxidation) conditions are adjusted to oxidize three or more carbon- carbon double bonds, e.g., three or more carbon-carbon double bonds that originated in the conjugated terpene starting material. In some embodiments, oxidation (e.g. , epoxidation) conditions are adjusted to oxidize substantially all carbon-carbon double bonds originating in the conjugated terpene starting material. A molar ratio of oxidan conjugated terpene may be lower than the number of unsaturated carbon-carbon bonds to produce compositions in which not all carbon-carbon double bonds are oxidized (e.g., epoxidized). A molar ratio of oxidant:conjugated terpene may be about 5: 1 or less for farnesene- based compounds, such as about 5: 1, 4: 1, 3: 1, 2: 1, 1 : 1 or 0.5: 1.

[00136] Alcohols and polyols may be derived from epoxidized hydrocarbon terpene Diels-Alder adducts using any known technique that allows for reaction of epoxy groups to form hydroxyl groups. For example, an epoxy group can be reduced to form a single hydroxyl group, or an epoxy group can be hydrolyzed to form two hydroxyl groups. In some varaitions, the hydroxyl groups may be subsequently acetylated to form a compound that may have use as described herein.

[00137] In some variations, the alcohols and diols disclosed herein have utility as solvents, emollients (e.g., cosmetics), or surfactants.

[00138] In some embodiments, one or more carbon-carbon double bonds of a conjugated terpene

Diels-Alder adduct as described herein is halogenated, e.g., with chlorine where one chlorine atom is added to each double bond using a reagent such as HC1, or where two chlorine atoms are added to each double bond using a reagent such as chlorine gas. Such chloride containing hydrocarbon conjugated terpene derivatives may for example exhibit increased compatibility or solubility with relatively polar polymers or solvents. In some embodiments, the reaction conditions are adjusted such only one carbon- carbon double bond is chlorinated, e.g. , one carbon-carbon double bond that originated in the conjugated terpene starting material. In some embodiments, the reaction conditions are adjusted so that two carbon- carbon double bonds are halogenated (e.g., chlorinated), e.g., two carbon-carbon double bonds that originated in the conjugated terpene starting material. In some embodiments, reaction conditions are adjusted such that three or more carbon-carbon double bonds are halogenated (e.g., chlorinated), e.g., three or more carbon-carbon double bonds that originated in the conjugated terpene starting material. In some embodiments, substantially all carbon-carbon double bonds originating from the conjugated terpene are halogenated (e.g., chlorinated).

H) Non-Limiting Examples of Farnesene-Based Diels-Alder Adducts

[00139] Described below in Sections (H-I) - (H-XII) are some non-limiting specific examples of

Diels-Alder adducts made using β-farnesene or a-farnesene as the conjugated hydrocarbon terpene. It should be understood that analogs of these examples of Diels-Alder adducts are contemplated in which conjugated terpenes other than a-farnesene or β-farnesene are used.

(H-I) Acrylate Ester Dienophiles

[00140] In some embodiments, a Diels-Alder adduct is formed between β-farnesene and acrylic

O O acid, "OH , or an acrylate ester, ^"OR¹ _s where R¹ is as described below in connection with formula (H-IA) and (H-IB). An oil, solvent, lubricant, additive or base oil for a lubricant formulation, a surfactant, a plasticizer, or a monomer, cross-linking agent or reactive diluent for use in making oligomers or polymers may be derived from a Diels-Alder adduct between β-farnesene and acrylic acid or an acrylate ester. Diels-Alder adducts formed between β-farnesene and an acrylate ester can be represented by formula (H-IA), (H-IB), and/or an isomer thereof, or a mixture thereof:

where R¹ may be H, or a linear or branched, cyclic or acyclic, saturated or unsaturated, substituted or unsubstituted substituent, e.g., Ci-C₃₀ hydrocarbyl. In some embodiments, R¹ is an aliphatic Ci-C₃₀ substituent. In some embodiments, R¹ is a linear saturated or unsaturated Ci-C₃₀ hydrocarbyl group (e.g., Ci, C2, C3, C4, C₅, C , C7, Cg, C9, Cio, C11, C12, Ci₃, Ci₄, Ci₅, C_\ , Cn, Qg, C19, C20 or C21-C30

hydrocarbyl), or a branched saturated or unsaturated Ci-C₃₀ hydrocarbyl group (e.g., C C₂, C₃, C₄, C₅, C₆, C₇, Cg, C₉, Cio, Cn, C12, Ci3, CM, C15, C_l6, Cn, Cig, C_l9, C₂₀ or C₂i-C₃₀ hydrocarbyl). In some embodiments, R¹ is methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, 2-ethylhexyl, 3-ethylhexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, methyloctyl, ethyloctyl, n-nonyl, isononyl, methylnonyl, ethylnonyl, n-decyl, isodecyl, 2-propylheptyl, methyldecyl, ethyldecyl, n-undecyl, isoundecyl, methylundecyl, ethylundecyl, n-dodecyl, isododecyl, methyldodecyl, ethyldodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n- octadecyl, n-nonadecyl, n-eicosyl or n-tricosyl. In some embodiments, R¹ is an aromatic substituent, e.g., comprising a phenyl or benzyl group. In some embodiments, R¹ may comprise one or more heteroatoms, e.g., oxygen, phosphorus, sulfur, nitrogen or chloride. In some embodiments, R¹ may comprise a carboxylic acid, an ester, a carbonyl, an ether, an alkoxy or a hydroxyl group. In some embodiments, R¹ is a polyol substituent, e.g., including 2, 3 or 4 hydroxyl groups. In some embodiments, R¹ is a saturated or unsaturated C₈-C₃₀ fatty acid or a saturated or unsaturated C₈-C₃₀ fatty alcohol, e.g., R¹ is cetyl, oleyl or stearyl. In some embodiments, R¹ is a Ci-C₃₀ aliphatic hydrocarbyl group that contains at least one double bond, e.g., one or more internal double bonds and/or a terminal double bond.

[00141] In some embodiments, R¹ is selected to increase the compatibility of the Diels-Alder adduct with an oil, a component of a formulation, or with a selected host polymer. For example, if the host polymer is relatively polar such as PVC, R¹ may be selected to be a relatively short linear or branched aliphatic hydrocarbon chain (e.g., a linear or branched Q-C4 hydrocarbyl), and/or R¹ may be substituted with or include one or more polar moieties (e.g., R¹ may be a Ci-C₃₀ aliphatic hydrocarbon that includes one or more hydroxyl, carboxyl, amino, epoxy, or chloro substituents, or R¹ may include a carbonyl group or an ether group). In some variations, R¹ may be selected to increase solubility in water, or to increase solubility in electrolyte solutions. In some variations, the Diels-Alder adduct is nonionic and R¹ comprises one or more hydroxyl grups such that the adduct is a primary alcohol, an amino group, a primary alcohol including an alkoxylate chain, an alkyl-capped alkoxylate, an amide, an ethanolamide, or one or more glucose groups. In some variations, the Diels-Alder adduct is anionic, e.g., R¹ may comprise a sulfate salt, a sulfonate salt, a carboxylate salt, or a phosphate salt. In some variations, the Diels-Alder adduct is cationic, e.g., R¹ may comprise a quaternary amine. In some variations, the Diels- Alder adduct is zwitterionic, e.g., R¹ may comprise an amine oxide.

[00142] In some embodiments, a Diels-Alder adduct between β-farnesene and acrylic acid or an acrylate ester results in a mixture of compounds having formulae (H-IA) and (HIB) in any relative amount may be used, e.g. , a mixture comprising a ratio of formula (H-IA): formula (H-IB) of about 0.1 :99.9, 1 :99, 5:95, 10:90, 20: 80, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90: 10, 95 :5, 99: 1 , or 99.9:0.1 by weight, by mole, or by volume. In some embodiments, the ratio of formula (H-IA): formula (H-IB) is from about 0. 1 :99.9 to about 99.9:0.1 , from about 1 :99 to about 99: 1 , from about 5 :95 to about 95 :5, from about 10:90 to about 90: 10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight or by volume.

[00143] In some embodiments, a Diels-Alder adduct between β-farnesene and acrylic acid or an acrylate ester is hydrogenated, prior to use, to form a compound having formula (H-IC), or (H-ID) or an corner thereof, or a combination thereof:

where R² may be H, or a linear or branched, cyclic or acyclic, saturated or unsaturated, substituted or unsubstituted substituent, e.g. , C₁-C₃₀. In some embodiments, R² is an aliphatic Ci-C₃o Substituent. In some embodiments, R² is a linear saturated or unsaturated C₁-C₃₀ hydrocarbyl group (e.g. , Ci, C₂, C₃, C₄, C5, Ce, C7, Cs, C9, Cio, C₁₁, C₁₂, Ci3, CM, Ci₅, Ci6, Ci₇, Ci8, Ci9, C₂0 or C₂₁-C30 hydrocarbyl), or a branched saturated or unsaturated Ci-C₃₀ hydrocarbyl group (e.g. , C C₂, C₃, C₄, C₅, C₆, C₇, C₈, C₉, Ci₀, C₁₁, C₁₂, Ci₃, CM, Ci₅, Ci₆, On, Cig, Ci₉, C₂₀ or C₂₁-C₃₀ hydrocarbyl). In some embodiments, R² is methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, 2-ethylhexyl, 3-ethylhexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, methyloctyl, ethyloctyl, n- nonyl, isononyl, methylnonyl, ethylnonyl, n-decyl, isodecyl, methyldecyl, ethyldecyl, n-undecyl, isoundecyl, methylundecyl, ethylundecyl, n-dodecyl, 2-propylheptyl, isododecyl, methyldodecyl, ethyldodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n- nonadecyl, n-eicosyl or n-tricosyl. In some embodiments, R² is an aromatic group, e.g., comprising a phenyl or benzyl group. In some embodiments, R² may comprise one or more heteroatoms, e.g., oxygen, phosphorus, sulfur, nitrogen or chloride. In some embodiments, R² may comprise a carboxylic acid, an ester, a carbonyl, an ether, an alkoxy or polyalkoxylate, a hydroxyl group, an amide group, or an amine group. In some embodiments, R² is a saturated or unsaturated C8-C30 fatty acid or a saturated or unsaturated C8-C30 fatty alcohol, e.g., R² is cetyl, oleyl or stearyl. In some embodiments, R² is a C1-C30 aliphatic hydrocarbyl group that contains at least one double bond, e.g. , one or more internal double bonds and/or a terminal double bond. In some embodiments, R² includes a polyol substituent, e.g., including 2, 3, or 4 hydroxy groups.

[00144] In some embodiments, R² is selected to increase the compatibility of the Diels-Alder adduct with an oil or a host polymer to be modified, to increase solubility in water, or to increase solubility in electrolyte solutions. In some variations, the Diels-Alder adduct is nonionic, e.g., R² may be selected so that the adduct is a primary alcohol, an amine, an alkoxylated alcohol, an alkyl-capped alkoxylate, a carboxylic acid, an amide, an ethanolamide, a glucoside, or a glucamide. In some variations, the surfactant is anionic, e.g., R² may comprise a sulfate salt, a sulfonate salt, a carboxylate salt, or a phosphate salt. In some variations, Diels-Alder adduct is cationic, e.g., R² may comprise a quaternary amine. In some variations, the Diels-Alder adduct is zwitterionic, e.g., R² may comprise an amine oxide.

[00145] In some embodiments, compounds of formula (H-IC) may be derived from compounds of formula (H-IA), and compounds of formula (H-ID) may be derived from compounds of formula (H- IB) by hydrogenation. In some embodiments, hydrogenation occurs so that R² is the same as R¹. In some embodiments, some degree of hydrogenation occurs in the R¹ group so that R² is not the same as R¹. In some embodiments, compounds of formulae (H-IC) and (H-ID) are derived using additional chemical modification of a hydrogenated Diels-Alder adduct between β-farnesene and acrylic acid or an acrylate ester, so that R² is not the same as R¹.

[00146] A mixture of compounds of formulae (H-IC) and (H-ID) in any relative amounts may be used in the applications described herein, e.g., a mixture comprising a ratio of formula (H-IC): formula (H-ID) of about 0.1 :99.9, 1 :99, 5:95, 10:90, 20:80, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90: 10, 95:5, 99: 1, or 99.9:0.1 by weight or by volume. In some embodiments, the ratio of formula (H-IC): formula (H-ID) is from about 0.1 :99.9 to about 99.9:0.1, from about 1 :99 to about 99: 1, from about 5:95 to about 95:5, from about 10:90 to about 90: 10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight, by mole, or by volume. [00147] A possible Diels-Alder adduct between a-farnesene and acrylic acid or an acrylate ester may have formula (H-IE), formula (H-IF), or an isomer thereof, or a mixture thereof:

where R¹ is as described in relation to formula (H-IA) and (H-IB).

[00148] In some embodiments, a Diels-Alder adduct between a-farnesene and acrylic acid or an acrylate ester results in a mixture of compounds having formulae (H-IE) and (H-IF) in any relative amount, e.g., a mixture comprising a ratio of formula (H-IE): formula (H-IF) of about 0.1 :99.9, 1 :99, 5:95, 10:90, 20:80, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90: 10, 95:5, 99: 1, or 99.9:0.1 by weight or by volume. In some embodiments, the ratio of formula (H-IE): formula (H-IF) is from about 0.1 :99.9 to about 99.9:0.1, from about 1 :99 to about 99: 1, from about 5:95 to about 95:5, from about 10:90 to about 90: 10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight, by mole, or by volume.

[00149] Compounds of formulae (H-IG) and (H-IH) may be obtained by hydrogenating formulae

(H-IE) and (H-IF) or by any suitable route.

where R is as described in relation to formulae (H-IC) and (H-ID).

[00150] Any one of or any combination of compounds of formulae (H-IA), (H-IB), (H-IC), (H-

ID), (H-IE), (H-IF), (H-IG), and (H-IH) may be used in any application utilizing esters. In certain embodiments, a compound having formula (H-IA), (H-IB), (H-IC), (H-ID), (H-IE), (H-IF), (H-IG) and (H-IH) or a derivative thereof may have use as oils, solvents, lubricants, additives or base oils for lubricant compositions, surfactants, plasticizers, and/or as monomers, cross-linking agents, curing agents or reactive diluents for use in making oligomers or polymers.

(H-II) Dialkyl Maleate or Dialkyl Fumarate Dienophiles

In some embodiments, a Diels-Alder adduct between β-farnesene and a dialkyl maleate,

in which the carboxylate groups are oriented as a cis-isomer, or a dialkyl

fumarate

or fumaric acid, in which the carboxylate groups are oriented as a trans- isomer, has utility in making the Diels-Alder adducts for the applications described herein, shown by formula (H-IIA):

where R³ and R³ are each independently H or a straight or branched chain, saturated or unsaturated, cyclic or acyclic, substituted or unsubstituted substituents or hydrocarbyl, e.g. Ci-C₃₀. In some embodiments, R³ and R³ are the same. In other embodiments, R³ and R³ are different. In some embodiments, each of R³ and R³ is independently a linear saturated or unsaturated Ci-C₃₀ hydrocarbyl group (e.g., Ci, C2, C3, C₄, C₅, C , C₇, Cg, C₉, C10, Cn, C12, C13, CI₄, CI₅, Ci , Cn, Qg, C19, C20 or C21-C30 hydrocarbyl ), or a branched saturated or unsaturated Ci-C₃₀ hydrocarbyl group (e.g., C C₂, C₃, C₄, C₅, C₆, C₇, Cg, C₉, Cio, Cn, C12, C , CM, C15, C_i6, Cn, Cig, C19, C₂₀ or C21-C30 hydrocarbyl). In some embodiments, each of R³ and R³ is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, 2-ethylhexyl, 3-ethylhexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, methyloctyl, ethyloctyl, n-nonyl, isononyl, methylnonyl, ethylnonyl, n-decyl, isodecyl, 2-propylheptyl, methyldecyl, ethyldecyl, n-undecyl, isoundecyl, methylundecyl, ethylundecyl, n-dodecyl, isododecyl, methyldodecyl, ethyldodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n- heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl or n-tricosyl. In some embodiments, each of R³ and R³ is independently an aromatic group, e.g., comprsing a phenyl or benzyl group. In some embodiments, each of R³ and R³ may independently comprise one or more heteroatoms, e.g. , oxygen, phosphorus, sulfur, nitrogen or chloride. In some embodiments, each of R³ and R³ may independently comprise a carboxylic acid, an ester, a carbonyl, an ether, an alkoxy or polyalkoxylate, a hydroxyl group, an amine, an amide, or one or more glucose groups. In some embodiments, each of R³ and R³ may independently include a polyol substituent, e.g., each of R³ and R³ may independently include 2, 3 or 4 hydroxy groups. In some embodiments, each of R³ and R³ is independently a saturated or unsaturated C₈-C₃o fatty acid or a saturated or unsaturated C8-C30 fatty alcohol, e.g., each of R³ and R³ may independently be cetyl, oleyl or stearyl. In some embodiments, each of R³ and R³ is independently a C₁-C30 aliphatic hydrocarbyl group that contains at least one double bond, e.g., one or more internal double bonds and/or a terminal double bond. It should be noted that the carboxylate substituents on the adduct (H-IIA) have a 1 ,2-syn- orientation relative to each other originating form the cis- orientation of the carboxylate substituents if a maleate is used as a dienophile. If a 1,2-anti- orientation of the carboxylate substituents relative to each other on the adduct is desired, a dialkyl fumarate may be used as dienophile instead of a dialkyl maleate.

[00152] In some embodiments, each of R³ and R³ is independently selected to increase compatibility with an oil or a host polymer to be modified. In some cases, R³ and R³ are independently selected to increase solubility in water or in an electrolyte solution. For example, if the host resin is a relatively polar substance, each of R³ and R³ may independently be selected to be a relatively short linear or branched aliphatic hydrocarbyl (e.g., a linear or branched Q-C4 hydrocarbyl group), or each of R³ and R³ may independently be substituted with or include one or more polar moieties (e.g., each of R³ and R³ is independently Ci-C₃₀ aliphatic hydrocarbyl that includes one or more hydroxyl, carboxyl, amino, epoxy, or chloro substituents, each of R³ and R³ may independently include a carbonyl group, or each of R³ and R³ may independently include an ether group). In some cases, the Diels-Alder adduct is nonionic, e.g., the adduct comprises a primary alcohol (a monoalcohol or a diol), an amine, an alkoxylated alcohol, an alkyl-capped alkoxylate, a carboxylic acid, an amide, or a glucoside. In some variations, the Diels-Alder adduct is anionic, e.g., one or both of R³ and R³ comprises a sulfate salt, a sulfonate salt, a carboxylate salt, or a phosphate salt. In some variations, the Diels-Alder adduct is cationic, e.g., one or both of R³ and R³ comprises a quaternary amine. In some variations, the Diels- Alder adduct is zwitterionic, e.g., one or both of R³ and R³ comprises an amine oxide. In some variations, one of R³ and R³ is a carboxylic acid salt and the other of R³ and R³ is an ammonium ion.

[00153] In some embodiments, a compound having formula (H-IIA) is obtained by derivatizing a

Diels-Alder adduct between β-farnesene and a dienophile. For example, a compound having formula (H- IIA) may be obtained by making a Diels-Alder adduct between β-farnesene and maleic anhydride, hydrolysis of the farnesene-maleic anhydride adduct using known techniques to create a dicarboxylic acid, and esterifying the dicarboxylic acid using known techniques.

[00154] In some embodiments, it is desirable to create a diester Diels-Alder adduct in which the aliphatic tail originating from the β-farnesene is partially hydrogenated, or fully hydrogenated to form a hydrogenated adduct having formula (H-IIB):

where each of R⁴ and R⁴ is independently H or a straight or branched chain, cyclic or acyclic, saturated or unsaturated, substituted or unsubstituted substituents, e.g. C₁-C30. In some embodiments, R⁴ and R⁴ are the same. In other embodiments, R⁴ and R⁴ are different. In some embodiments, each of R⁴ and R⁴ is independently a linear saturated or unsaturated C₁-C30 hydrocarbyl group (e.g. , Ci, C₂, C3, C4, C₅, Ce, C₇, Cg, C₉, Cio, C11, C12, Co, CM, Ci5, Ci6, Ci?, Ci8, Ci9, C₂₀ or C21-C30 hydrocarbyl), or a branched saturated or unsaturated C₁-C30 hydrocarbyl group (e.g. , Ci, C₂, C3, C4, C₅, Ce, C₇, Cg, C9, Cio, Cn, C₁₂, Ci3, CM, Ci₅, Ci6, Cn, Cig, Ci9, C₂0 or C₂₁-C30 hydrocarbyl). In some embodiments, each of R⁴ and R⁴ is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, 2-ethylhexyl, 3-ethylhexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, methyloctyl, ethyloctyl, n-nonyl, isononyl, methylnonyl, ethylnonyl, n-decyl, isodecyl, methyldecyl, ethyldecyl, n-undecyl, isoundecyl, methylundecyl, ethylundecyl, n-dodecyl, isododecyl, 2-propylheptyl, methyldodecyl, ethyldodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n- octadecyl, n-nonadecyl, n-eicosyl or n-tricosyl. In some embodiments, each of R⁴ and R⁴ comprises an aromatic group (e.g., one or both of R⁴ and R⁴ may comprise a phenyl group or one or both of R⁴ and R⁴ may be a benzyl group). In some embodiments, each of R⁴ and R⁴ may independently comprise one or more heteroatoms, e.g. , oxygen, phosphorus, sulfur, nitrogen or chloride. In some embodiments, each of R⁴ and R^4' may independently comprise a carboxylic acid, an ester, a carbonyl, an ether, an alkoxy or a polyalkoxylate, a hydroxyl group, an amide group, an amine group, or one or more glucose groups. In some embodiments, each of R⁴ and R⁴ may independently include a polyol substituent, e.g. , each of R⁴ and R^4' may independently include 2, 3 or 4 hydroxyl groups. In some embodiments, each of R⁴ and/or R⁴ is independently a saturated or unsaturated Cg-C₃o fatty acid or a saturated or unsaturated Cg-C₃o fatty alcohol, e.g. , each of R⁴ and R⁴ may independently be cetyl, oleyl or stearyl. In some embodiments, each of R⁴ and R⁴ is independently a C₁-C₃₀ aliphatic hydrocarbyl group that contains at least one double bond, e.g., one or more internal double bonds and/or a terminal double bond.

[00155] Compounds having formula (H-IIB) can be obtained by a variety of methods using

Diels-Alder reactions. In some embodiments, compounds having formula (H-IIB) are derived by hydrogenating compounds having formula (H-IIA). In some embodiments, R³ and R³ are not affected by the hydrogenation so that R⁴ is the same as R³ and R⁴ is the same asR³ . In other embodiments, R³ and R³ are at least partially hydrogenated so that R⁴ and R⁴ are not the same as R³ and R³ . In some embodiments, compounds having formula (H-IIB) are derived by hydrogenating compounds having formula (H-IIB) with further chemical modification, e.g. , to chemically modify R³ and/or R³ to form R⁴ and/or R⁴ respectively. In some embodiments, compounds having formula (H-IIB) are obtained by making a Diels-Alder adduct between β-farnesene and maleic anhydride, hydrogenating the adduct, and hydrolysis of the hydrogenated farnesene-maleic anhydride adduct using known techniques to create a dicarboxylic acid, and esterifying the dicarboxylic acid using known techniques. It should be noted that if (H-IIB) is derived by hydrogenating (H-IIA) made using a maleate dienophile, the carboxylate groups on (H-IIB) have a 1 ,2-syn- orientation relative to each other originating from the cis- orientatin of the carboxylate substituents on the maleate dienophile, and if (H-IIB) is derived by hydrogenating (H-IIA) made by using a fumarate dienophile, the carboxylate groups on (H-IIB) have a 1 ,2-anti- orientation relative to each other originating from the trans- orientation of the carboxylate substituents on the fumarate dienophile.

[00156] In some embodiments, each of R⁴ and R⁴ is independently selected to increase compatibility with an oil or host polymer to be modified. In some cases, R⁴ and R^4' are independently selected to increase solubility in water or in an electrolyte solution. For example, if the host resin is a relatively polar substance, each of R⁴ and R⁴ may independently be selected to be a relatively short linear or branched aliphatic hydrocarbyl chain (e.g., a linear or branched C₁-C4 hydrocarbyl), or each of R⁴ and R⁴ may independently be substituted with or include one or more polar moieties (e.g., each of R⁴ and R⁴ may independently be a Ci-C₃₀ aliphatic hydrocarbyl that includes one or more hydroxy, carboxy, amino, epoxy, or chloro substituents, each of R⁴ and R⁴ may independently include a carbonyl group, or each of R⁴ and R^4' may independently include an ether group). In some cases, the Diels-Alder adduct is nonionic, e.g., the adduct comprises a primary alcohol (a monoalcohol or a diol), an amine, an alkoxylated alcohol, an alkyl-capped alkoxylate, a carboxylic acid, an amide, or a glucoside. In some variations, the Diels- Alder adduct is anionic, e.g., one or both of R⁴ and R⁴ comprises a sulfate salt, a sulfonate salt, a carboxylate salt, or a phosphate salt. In some variations, the Diels-Alder adduct is cationic, e.g., one or both of R⁴ and R⁴ comprises a quaternary amine. In some variations, the Diels-Alder adduct is zwitterionic, e.g., one or both of R⁴ and R⁴ comprises an amine oxide. In some variations, one of R³ and R³ is a carboxylic acid salt and the other of R⁴ and R⁴ is an ammonium ion.

[00157] In some embodiments, a Diels-Alder adduct between a-farnesene and a dialkyl maleate,

, or maleic acid, or a dialkyl fumarate or fumaric acid has utility the applications described herein, the adduct having formula (H-IIC)

where R3 and R3' are as described in relation to formula (H-IIA). It should be noted that the carboxylate substituents on the adduct (H-IIC) have a 1 ,2-syn- orientation relative to each other originating form the cis- orientation of the carboxylate substituents if a maleate is used as a dienophile. If a 1 ,2-anti- orientation of the carboxylate substituents relative to each other on the adduct is desired, a dialkyl fumarate may be used as dienophile instead of a dialkyl maleate.

[00158] Compounds having formula (H-IID) may be made by hydrogenating compounds of formula (H-IIC), or by any suitable reduction reaction:

where R4 and R4' are as described in relation to formula (H-IIB). It should be noted that if (H-IID) is derived by hydrogenating (H-IIC) made using a maleate dienophile, the carboxylate groups on (H-IID) have a 1 ,2-syn- orientation relative to each other originating from the cis- orientatin of the carboxylate substituents on the maleate dienophile, and if (H-IID) is derived by hydrogenating (H-IIC) made by using a fumarate dienophile, the carboxylate groups on (H-IID) have a 1 ,2-anti- orientation relative to each other originating from the trans- orientation of the carboxylate substituents on the fumarate dienophile.

[00159] Compounds of formulae (H-IIA), (H-IIB), (H-IIC) and (H-IID) may be useful in applications utilizing diesters. In certain embodiments, compounds of formula (H-IIA), (H-IIB), (H-IIC) and (H-IID) or a derivative thereof may have use as oils, solvents, lubricants, additives or base oils for lubricant compositions, surfactants, plasticizers, and/or as monomers, cross-linking agents, curing agents or reactive diluents for use in making oligomers or polymers.

(H-III) Maleic anhydride Dienophiles

[00160] In some embodiments, maleic anhydride is used as a dienophile in a Diels-Alder reaction with farnesene. A reaction product with β-farnesene is shown as compound (H-IIIA):

[00161]

[00162] A proposed Diels-Alder reaction product between a-farnesene and maleic anhydride is shown as Compound (H-IIIC):

[00163] Compound (H-IIIC) can be hydrogenated to form Compound (H-IIID).

[00164] The anhydride compounds (H-IIIA), (H-IIIB), (H-IIIC) and (H-IIID) may have use in any application in which an anhydride is used. In certain embodiments, the anhydride compounds (H- IIIA), (H-IIIB), (H-IIIC) and (H-IIID) or derivatives thereof may be used to make oils, solvents, lubricants, additives or base oils for lubricant compositions, surfactants, plasticizers, and/or as monomers, cross-linking agents, curing agents or reactive diluents for use in making oligomers or polymers. In some embodiments, the anhydride compounds disclosed herein may be use to make polyesters or co-polymers with one or more polyols such as diols and triols.

(H-IV) Diols

[00165] Additional compounds disclosed herein are compounds (H-IVA), (H-IVB), (H-IVC) and

(H-IVD):

[00166] Compounds (H-IVA), (H-IVB), (H-IVC) and (H-IVD) can be made by any suitable method. In some embodiments, a Diels-Alder adduct between β-farnesene and maleic acid, a dialkyl maleate, fumaric acid, or a dialkyl fumarate is reduced using known techniques (e.g. , using lithium aluminum hydride) to form Compound (H-IVA). Compound (H-IVB) may be made by hydrogenating Compound (H-IVA), or alternatively by reducing Compound (H-IIIB) using known techniques. In some embodiments, a Diels-Alder adduct between a-farnesene, maleic acid, a dialkyl maleate, fumaric acid, or a dialkyl fumarate is reduced using known techniques (e.g., using lithium aluminum hydride) to form Compound (H-IVC). Compound (H-IVD) may be made by hydrogenating Compound (H-IVC), or alternatively by reducing a compound having formula (H-IIID) using known techniques.

[00167] The diols of formulae (H-IVA), (H-IVB), (H-IVC) and (H-IVD) may be used in place of any diol. In certain embodiments, the diol of formula (H-IVA), (H-IVB), (H-IVC) or (H-IVD) or a derivative thereof may be used to make an ester or a diester as a plasticizer or as a cross-linking agent or reactive diluent. In some embodiments, the diols disclosed herein may be use as monomers or comonomers for making polyesters, co-polyesters, polyurethanes, polycarbonates and the like. In some embodiments, the diols disclosed herein may be used as surfactants, or may be treated with one or more alkylene oxides to make a surfactant. In some variations, the alcohols and diols disclosed herein have utility as solvents, in cosmetics, or in surfactant formulations (e.g, in personal care formulations such as emollients, shampoos, cleansers, certain cosmetics, and the like; in emulsions; or in detergents and other cleaning formulations). The diols disclosed herein may be used as is in applications or may be treated, alkoxylated, or otherwised derivatized.

(H-V) Maleimide Dienophiles

[00168] Additional compounds disclosed herein are represented by formulae (H-VA), (H-VB),

(H-VC) and (H-VD):

where R⁵ and R⁵ may independently be H, a Ci-C₃₀ saturated or unsaturated, linear or branched chain, cyclic or acyclic, substituted or unsubstituted aliphatic group, or a substituted or unsubsubstituted aromatic group. For example, each of R⁵ and R⁵ may independently be a linear saturated or unsaturated Ci-C₃₀ hydrocarbyl group (e.g., C C₂, C₃, C₄, C₅, C₆, C₇, C₈, C₉, C₁₀, C_u, C₁₂, C₁₃, C₁₄, C₁₅, C₁₆, C₁₇, C₁₈, Ci9, C₂o or C₂₁-C₃₀ hydrocarbyl), or a branched saturated or unsaturated Ci-C₃₀ hydrocarbyl group (e.g., Ci, C₂, C3, C4, C5, C , C7, C%, C9, Cio, Cu, C12, Ci3, CM, C15, Ci , Cn, Cis, C19, C₂0 or C₂₁-C30

hydrocarbyl). In some embodiments, each of R⁵ and R⁵ is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, 2-ethylhexyl, 3- ethylhexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, methyloctyl, ethyloctyl, n-nonyl, isononyl, methylnonyl, ethylnonyl, n-decyl, isodecyl, 2-propylheptyl, methyldecyl, ethyldecyl, n-undecyl, isoundecyl, methylundecyl, ethylundecyl, n-dodecyl, isododecyl, methyldodecyl, ethyldodecyl, n- tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl or n- tricosyl. In some embodiments, each of R⁵ and R⁵ independently comprises an aromatic group, e.g., a phenyl group or a benzyl group. In some cases, R⁵ or R⁵ is a benzyl group. In some embodiments, each of R⁵ and R⁵ may independently comprise one or more heteroatoms, e.g., oxygen, phosphorus, sulfur, nitrogen or chloride. In some embodiments, each of R⁵ and R⁵ may independently comprise a carboxylic acid, an ester, a carbonyl, an ether, an alkoxy or a hydroxyl group. In some embodiments, each of R⁵ and R⁵ is independently a C₁-C30 aliphatic hydrocarbyl group that contains at least one double bond, e.g., one or more internal double bonds and/or a terminal double bond.

[00169] Compounds of formula (H-VA) may be obtained as a Diels-Alder reaction product between β-farnesene and a maleimide. Compounds of formula (H-VC) may be obtained as a Diels-Alder adduct between a-farnesene and a maleimide. In certain embodiments, the Diels-Alder adduct may be subsequently chemically modified to incorporate a desired functionality into the adduct. In some embodiments, a compound having formula (H-VB) may be derived by hydrogenating a compound having formula (H-VA). Similarly, a compound having formula (H-VD) may be derived by

hydrogenating a compound having formula (H-VC). In some embodiments, a compound having formula (H-VB) is obtained by hydrogenating a compound having formula (H-VA), with additional chemical modification. In some embodiments, a compound having formula (H-VD) is obtained by hydrogenating a compound having formula (H-VC), with additional chemical modification.

[00170] The maleimide compounds of formulae (H-VA), (H-VB), (H-VC) and (H-VD) may be used in any application utilizing a maleimide. In certain embodiments, compounds of formulae (H-VA), (H-VB), (H-VC) and (H-VD) or derivatives thereof have utility as oils, solvents, surfactants, additives for plastics or other resins, or monomers, cross-linking agents, curing agents or reactive diluents.

(H-VI) Fumaronitrile Dienophiles

[00171] In some embodiments, fumaronitrile, CN _? undergoes a Diels-Alder reaction with β-farnesene or a-farnesene. The reaction product between β-farnesene and fumaronitrile is Compound (H-VIA) and the proposed reaction product between α-farnesene and fumaronitrile is Compound (H-VIB):

[00172] The cyano groups in the Diels-Alder adducts have a trans- orientation relative to each other oroiginating from the trans- orientation of the fumaronitrile. [00173] Compounds having formula (H-VIA) and (H-VIB) or derivatives thereof may be used to make surfactants, plasticizers, and/or as monomers, cross-linking agents, curing agents or reactive diluents for use in making oligomers or polymers or polymer composition. In some variations, compounds (H-VIA) and (H-VIB) are hydrogenated. The nitrile groups on compounds (H-VIA) and (H- VIB) may undergo hydrolysis under acid or base to form the dicaboxamide or dicarboxylic acid using known techniques. For example, compounds having structure (H-VIC) or (H-VID) may be derived from compound (H-VIA) using hydrolysis:

The trans- orientation of the substituents originating from the fumaronitrile is preserved for modified adducts such as (H-VIC) and (H-VID).

(H-VII) Aldehyde Dienophiles

[00174] In some embodiments, an unsaturated aldehyde is used as a dienophile in a Diels-Alder reaction with farnesene. Some unsaturated aldehydes have the formula

, where R may be

H, a linear or branched hydrocarbyl group or a halo substituent. In some embodiments, R is Ci-C₃₀ alkyl examples of unsaturated aldehydes include acrolein, ⁰ , and crotonaldehyde,

. The reaction product between β -farnesene and acrolein may be Compound (H-VIIA) or (H-VIIB) or a mixture thereof in which Compound (H-VIIA) and Compound (H-VIIB) are present in any relative amounts, e.g., a mixture comprising a ratio of Compound (H-VIIA): Compound (H-VIIB) of about 0.1 :99.9, 1 :99, 5:95, 10:90, 20:80, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90: 10, 95:5, 99:1, or 99.9:0.1 by weight or by volume. In some embodiments, the ratio of Compound (H-VIIA): Compound (H-VIIB) is from about 0.1 :99.9 to about 99.9:0.1, from about 1 :99 to about 99: 1, from about 5:95 to about 95:5, from about 10:90 to about 90: 10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight, by mole, or by volume.

[00175] Proposed reaction products between a-farnesene and acrolein are illustrated by

Compounds (H-VIIC) and (H-VIID), where the reaction product may be (H-VIIC), (H-VIID), or a mixture thereof in which Compounds (H-VIIC) and (H-VIID) are present in any relative amounts, e.g., a ratio of Compound (H-VIIC) Compound (H-VIID) of 0.1 :99.9, 1 :99, 5:95, 10:90, 20:80, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90: 10, 95:5, 99: 1, or 99.9:0.1 by weight or by volume. In some embodiments, the ratio of Compound (H-VIIC) Compound (H-VIID) is from about 0.1 :99.9 to about 99.9:0.1, from about 1 :99 to about 99: 1, from about 5:95 to about 95:5, from about 10:90 to about 90: 10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight, by mole, or by volume.

[00176] Proposed reaction products between β-farnesene and crotonaldehyde are illustrated by

Compounds (H-VIIE) and (H-VIIF), where the reaction product may be (H-VIIE), (H-VIIF), or a mixture thereof in which Compounds (H-VIIE) and (H-VIIF) are present in any relative amounts, e.g., a ratio of Compounds (H-VIIE) Compounds (H-VIIF) of 0.1 :99.9, 1 :99, 5:95, 10:90, 20:80, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90: 10, 95:5, 99: 1, or 99.9:0.1 by weight or by volume. In some embodiments, the ratio of Compound (H-VIIE): Compound (H-VIIF) is from about 0.1 :99.9 to about 99.9:0.1, from about 1 :99 to about 99: 1, from about 5:95 to about 95:5, from about 10:90 to about 90: 10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight, by mole, or by volume.

[00177] Proposed reaction products between a-farnesene and crotonaldehyde are illustrated by

Compounds (H-VIIG) and (H-VIIH), where the reaction product may be Compound (H-VIIG) or (H- VIIH), or a mixture thereof in which Compounds (H-VIIG) and (H-VIIH) are present in any relative amounts, e.g., a ratio of Compound (H-VIIG): Compound (H-VIIH) of 0.1 :99.9, 1 :99, 5:95, 10:90, 20:80, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90: 10, 95:5, 99: 1, or 99.9:0.1 by weight or by volume. In some embodiments, the ratio of Compound (H-VIIG): Compound (H-VIIH) is from about 0.1 :99.9 to about 99.9:0.1, from about 1 :99 to about 99: 1, from about 5:95 to about 95:5, from about 10:90 to about 90: 10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight, by mole, or by volume.

[00178] In certain embodiments, compounds having formulae (H-VIIA), (H-VIIB), (H-VIIC),

(H-VIID), (H-VIIE), (H-VIIF), (H-VIIG), and (H-VIIH), or derivatives thereof may have utility in any of the applications described herein. In some cases, ompounds having formula (H-VIIA), (H-VIIB), (H- VIIC), (H-VIID), (H-VIIE), (H-VIIF), (H-VIIG), or (H-VIIH) may be hydrogenated, and alcohols derived from the aldehydes.

(H-VIII) Itaconate Dienophiles

[00179] In some embodiments, itaconic anhydride ,

, itaconic acid, , or a

dialkyl itaconate,

_s is used as a dienophile in a Diels-Alder reaction with β-farnesene or a- farnesene, where R is any suitable hydrocarbyl group, e.g., a Ci-C₃₀ hydrocarbyl group. Non-limiting examples of dialkyl itaconates that may be used include dimethyl itaconate, diethyl itaconate, di-n-butyl itaconate, di-sec -butyl itaconate, di-tert-butyl itaconate, bis(cyclohexylmethyl) itaconate, dicyclohexyl itaconate, di-isopropyl methyl itaconate, di-n-pentyl itaconate, di-n-hexyl itaconate, di-n-heptyl itaconate, di-n-octyl itaconate, di-n-nonyl itaconate and di-n-decyl itaconate. [00180] The reaction product between β-farnesene and itaconic acid or a dialkyl itaconate is illustrated by formulae (H-VIIIA) and (H-VIIIB) where R is H or any suitable hydrocarbyl group, e.g., a C1-C30 hydrocarbyl group , where the reaction product may have formula (H-VIIIA) or (H-VIIIB), or a mixture thereof in which formula (H-VIIIA) and formula (H-VIIIB) are present in any relative amounts, e.g., a ratio of formula (H-VIIIA): formula (H-VIIIB) of 0.1 :99.9, 1 :99, 5:95, 10:90, 20:80:, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90:10, 95:5, 99:1, or 99.9:0.1 by weight, by mole, or by volume. In some embodiments, the ratio of formula (H-VIIIA): formula (H-VIIIB) is from about 0.1 :99.9 to about 99.9:0.1, from about 1 :99 to about 99:1, from about 5:95 to about 95:5, from about 10:90 to about 90:10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight, by mole, or by volume.

(H-VIIIA), (H-VIIIB).

[00181] The compounds of formulae (H-VIIIA) and (H-VIIIB) can be hydrogenated to form compounds of formulae (H-VIIIC) and (H-VIIID) respectively:

(H-VIIIC), (H-VIIID).

[00182] It should be noted that compounds of formulae (H-VIIIC) and (H-VIIID) may undergo one or more subsequent chemical reactions so that R' is not the same as R. Such a reaction may be conducted prior to or following hydrogenation.

[00183] The reaction product between β-farnesene and itaconic anhydride is shown as

Compounds (H-VIIIE) and (H-VIIIF), where the reaction product may be Compound (H-VIIIE) or (H- VIIIF) or a mixture thereof in which Compound (H-VIIIE) and Compound (H-VIIIF) are present in any relative amounts, e.g., a ratio of Compound (H-VHTE): Compound (H-VIIIF) of 0.1 :99.9, 1 :99, 5:95, 10:90, 20:80:, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90:10, 95:5, 99:1, or 99.9:0.1 by weight, by mole, or by volume. In some embodiments, the ratio of Compound (H-VIIIE): Compound (H-VIIIF) is from about 0.1 :99.9 to about 99.9:0.1, from about 1 :99 to about 99:1, from about 5:95 to about 95:5, from about 10:90 to about 90:10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight, by mole, or by volume.

(H-VIIIE), (H-VIIIF). [00184] Compounds (H-VIIIE) and (H-VIIIF) may be hydrogenated to form Compounds (H-

VIIIG) and (H-VIIIH) respectively:

(H-VIIIG), (H-VIIIH).

[00185] It is contemplated that a-farnesene may undergo Diels-Alder reaction with itaconic anhydride, itaconic acid or a dialkyl itaconate. For example, possible reaction products between a- farnesene and itaconic anhydride are shown as Compounds (H-VIIIJ) and (H-VIIIK). The reaction product may be Compound (H-VIIIJ) or (H-VIIIK) or a mixture thereof, where Compounds (H-VIIIJ) and (H-VIIIK) are present in any relative amounts, e.g., a ratio Compound (H-VIIIJ): Compound (H- VIIIK) of 0.1 :99.9, 1:99, 5:95, 10:90, 20:80:, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90:10, 95:5, 99:1, or 99.9:0.1 by weight or by volume. In some embodiments, the ratio of Compound (H-VIIIJ): Compound (H-VIIIK) is from about 0.1 :99.9 to about 99.9:0.1, from about 1 :99 to about 99:1, from about 5:95 to about 95:5, from about 10:90 to about 90:10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight, by mole, or by volume. Compounds (H-VIIIL) and (H-VIIIM) may be obtained by hydrogenating Compounds (H-VIIIJ) and (H-VIIIK) respectively, or by any suitable route.

[00186] The anhydride compounds of formulae (H-VIIIA), (H-VIIIB), (H-VIIIC) and (H-VIIID), and Compounds (H-VIIIE), (H-VIIIF), (H-VIIIG), (H-VIIIH), (H-VIIIJ), (H-VIIIK), (H-VIIIL) and (H- VIIIM) may be used in any application utilizing an anhydride. In certain embodiments, The anhydride compounds of formulae (H-VIIIA), (H-VIIIB), (H-VIIIC) and (H-VIIID), and Compounds (H-VIIIE), (H-VIIIF), (H-VIIIG), (H-VIIIH), (H-VIIIJ), (H-VIIIK), (H-VIIIL) and (H-VIIIM), and derivatives thereof may have utility as oils, solvents, lubricants, additives or base oils for lubricant compositions, surfactants, plasticizers, and/or as cross-linking agents, curing agents or reactive diluents for use in making oligomers or polymers. In some embodiments, the anhydride compounds disclosed herein can be used as monomers or co-monomers to make polyesters or co-polyesters with polyols such as diols and triols. R or R' may be selected to increase compatibility of the adduct with a host polymer or an oil to be modified, or to increase solubility in water or in an electrolyte solution. For example, the anhydride functionality may be opened up using known techniques to form a diacid, which may be used as is, or further derivatized.

(H-IX) Acetylene Dicarboxylic Acid and Acetylene Dicarboxylic Acid Ester Dienophiles

C0₂H

[00187] In some embodiments, acetylene dicarboxylic acid, H0₂C _{^ or ace}tylene

CONH₂ C0₂R dicarboxamide, ^H2 OC _{^ or an acer}ylene dicarboxylic acid ester, ^R02C _? where R can be H or any suitable hydrocarbyl group (e.g., C₁-C30 hydrocarbyl), is used as a dienophile in a Diels- Alder reaction with farnesene.

[00188] A reaction product between β -farnesene and acetylene dicarboxylic acid is represented by Compounds (H-IXA) and (H-IXB), where the reaction product may be represented by Compound (H- IXA) or (H-IXB), or a mixture thereof, in which Compound (H-IXA) and Compound (H-IXB) are present in any relative amounts, e.g., a ratio of Compound (H-IXA): Compound (H-IXB) of

0.001 :99.999, 0.01 :99:99, 0.1 :99.9, 1 :99, 5:95, 10:90, 20:80:, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90:10, 95:5, 99:1, 99.9:0.1, 99.99:0.01, 99.999:0.001 by weight, by mole, or by volume. In some embodiments, the ratio of Compound (H-IXA): Compound (H-IXB) is from about 0.001 :99.999 to about 99.999:0.001, from about 0.01 :99:99 to about 99.99:0.01; from about 0.1 :99.9 to about 99.9:0.1, from about 1 :99 to about 99:1, from about 5:95 to about 95:5, from about 10:90 to about 90:10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight, by mole, or by volume.

[00189] A reaction product between a-farnesene and acetylene dicarboxylic acid is represented by Compounds (H-IXC) and (H-IXD), where the reaction product may be represented by Compound (H- IXC) or (H-IXD), or a mixture thereof, in which Compound (H-IXC) and Compound (H-IXD) are present in any relative amounts, e.g., a ratio of Compound (H-IXC): Compound (H-IXD) of 0.001:99.999, 0.01 :99:99, 0.1 :99.9, 1:99, 5:95, 10:90, 20:80, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90:10, 95:5, 99:1, 99.9:0.1, 99.99:0.01, 99.999:0.001 by weight or by volume. In some embodiments, the ratio of Compound (H-IXC):Compound (H-IXD) is from about 0.001 :99.999 to about 99.999:0.001 , from about 0.01 :99:99 to about 99.99:0.01 ; from about 0.1 :99.9 to about 99.9:0.1 , from about 1 :99 to about 99: 1 , from about 5:95 to about 95:5, from about 10:90 to about 90: 10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight or by volume.

[00190] A reaction product between β-farnesene and an acetylene dicarboxylic acid ester is represented by formulae (H-IXE) and (H-IXF),where the reaction product may be represented by formula (H-IXE) or (H-IXF), or a mixture thereof, in which formula (H-IXE) and formula (H-IXF) are present in any relative amounts, e.g., a ratio of formula (H-IXE): formula (H-IXF) of 0.001 :99.999, 0.01 :99:99, 0.1 :99.9, 1 :99, 5:95, 10:90, 20:80:, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90: 10, 95:5, 99: 1 , 99.9:0.1 , 99.99:0.01 , 99.999:0.001 by weight or by volume. In some embodiments, the ratio of formula (H- IXE):formula (H-IXF) is from about 0.001 :99.999 to about 99.999:0.001 , from about 0.01 :99:99 to about 99.99:0.01 ; from about 0.1 :99.9 to about 99.9:0.1 , from about 1 :99 to about 99: 1 , from about 5:95 to about 95:5, from about 10:90 to about 90: 10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight or by volume.

where each of R⁶ and R⁶ is independently H, a Ci-C₃₀ saturated or unsaturated, linear or branched chain, cyclic or acyclic, substituted or unsubstituted aliphatic group, or a substituted or unsubstituted aromatic group. For example each of R⁶ and R⁶ may independently be a linear saturated or unsaturated Ci-C₃₀ hydrocarbyl group (e.g., C_b C₂, C₃, C₄, C₅, C₆, C₇, C₈, C₉, C₁₀, C_u, C₁₂, C₁₃, C₁₄, C₁₅, C₁₆, C₁₇, C₁₈, C₁₉, C₂₀ or C₂i-C₃₀ hydrocarbyl), or a branched saturated or unsaturated Ci-C₃₀ hydrocarbyl group (e.g., C C₂, C₃, C4, C5, Ce, C7, Cs, C9, Cio, Cu, C12, Ci₃, C14, C15, Ci6, Cn, Cis, C19, C₂o or C₂i-C₃o hydrocarbyl). In some embodiments, each of R⁶ and R⁶ is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, 2- butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, 2-ethylhexyl, 3-ethylhexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, methyloctyl, ethyloctyl, n-nonyl, isononyl, methylnonyl, ethylnonyl, n-decyl, isodecyl, 2-propylheptyl, methyldecyl, ethyldecyl, n-undecyl, isoundecyl, methylundecyl, ethylundecyl, n-dodecyl, isododecyl, methyldodecyl, ethyldodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl or n-tricosyl. In some embodiments, each of R⁶ and R⁶ is independently aromatic (e.g., one or both of R⁶ and R⁶ may comprise phenyl or benzyl groups). In some cases, R⁶ and/or R⁶ is a benzyl group. In some embodiments, each of R⁶ and R⁶ may independently comprise one or more heteroatoms, e.g., oxygen, phosphorus, sulfur, nitrogen, or chloride. In some embodiments, each of R⁶ and R⁶ may independently comprise a carboxylic acid, an ester, a carbonyl, an ether, an alkoxy, or a hydroxyl group. In some embodiments, each of R⁶ and R⁶ is independently a C1-C30 aliphatic hydrocarbyl group that contains at least one double bond, e.g., one or more internal double bonds and/or a terminal double bond.

[00191] A reaction product between a-farnesene and an acetylene dicarboxylic acid ester is represented by formulae (H-IXG) and (H-IXH), where the reaction product may be represented by formula (H-IXG) or (H-IXH) or a mixture thereof, in which formula (H-IXG) and formula (H-IXH) are present in any relative amounts, e.g., a ratio of formula (H-IXG): formula (H-IXH) of 0.001 :99.999, 0.01 :99:99, 0.1 :99.9, 1:99, 5:95, 10:90, 20:80, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90:10, 95:5, 99:1, 99.9:0.1, 99.99:0.01, 99.999:0.001 by weight, by mole, or by volume. In some embodiments, the ratio of formula (H-IXG): formula (H-IXH) is from about 0.001 :99.999 to about 99.999:0.001, from about 0.01 :99:99 to about 99.99:0.01; from about 0.1 :99.9 to about 99.9:0.1, from about 1 :99 to about 99:1, from about 5:95 to about 95:5, from about 10:90 to about 90:10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight, by mole, or by volume.

where R⁶ and R⁶ are as described in relation to formulae (H-IXE) and (H-IXF).

[00192] Compounds (H-IXA), (H-IXB), (H-IXC) and (H-IXD) and Compounds of formulae (H-

IXE), (H-IXF), (H-IXG), and (H-IXH) may be used in any application that utilizes an unsaturated carboxylic acid or unsaturated carboxylic acid ester. In some embodiments, Compounds (H-IXA) and (H-IXC), and Compounds of formulae (H-IXE) and (H-IXG) may be reacted with another conjugated terpene or conjugated diene. Compounds (H-IXA), (H-IXB), (H-IXC) and (H-IXD) and Compounds of formulae (H-IXE), (H-IXF), (H-IXG) and (H-IXH) and derivatives thereof may have utility as oils, solvents, lubricants, additives or base oils for lubricant compositions, surfactants, plasticizers, and/or as monomers, cross-linking agents, curing agents or reactive diluents for use in making oligomers or polymers.

(H-X) Acetylene diamide or Dicyanoacetylene Dienophiles

[00193] In some embodiments, an acetylene diamide or dicyanoacetylene is used as a dienophile with farnesene in a Diels-Alder reaction. A reaction product between an acetylene diamide and β- farnesene is represented by formulae (H-XA) and (H-XB), where the reaction product may have formula (H-XA) or (H-XB), or a mixture thereof , in which formulae (H-XA) and (H-XB) may be present in any relative amounts, a ratio of formula (H-XA): formula (H-XB) of about 0.001 :99.999, 0.01:99:99, 0.1 :99.9, 1 :99, 5:95, 10:90, 20:80, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90:10, 95:5, 99:1, 99.9:0.1, 99.99:0.01, or 99.999:0.001 by weight or by volume. In some embodiments, the ratio of formula (H- XA):formula (H-XB) is from about 0.001 :99.999 to about 99.999:0.001, from about 0.01 :99:99 to about 99.99:0.01 ; from about 0.1 :99.9 to about 99.9:0.1, from about 1 :99 to about 99: 1, from about 5:95 to about 95:5, from about 10:90 to about 90: 10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight, by mole, or by volume.

[00194] A reaction product between an acetylene diamide and a-farnesene is represented by formulae (H-XC) and H- (XD), where the reaction product may be formula (H-XC) or (H-XD), or a mixture thereof, in which formulae (H-XC) and (H-XD) may be present in any relative amounts, e.g., a ratio of formula (H-XC): formula (H-XD) of about 0.001 :99.999, 0.01 :99:99, 0.1 :99.9, 1 :99, 5:95, 10:90, 20:80, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90: 10, 95:5, 99: 1, 99.9:0.1, 99.99:0.01, or 99.999:0.001 by weight, by mole, or by volume. In some embodiments, the ratio of formula (H-XC): formula (H-XD) is from about 0.001 :99.999 to about 99.999:0.001, from about 0.01 :99:99 to about 99.99:0.01; from about 0.1 :99.9 to about 99.9:0.1, from about 1 :99 to about 99:1, from about 5:95 to about 95:5, from about 10:90 to about 90: 10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight, by mole, or by volume.

[00195] A reaction product between dicyanoacetylene and β-farnesene is shown as Compounds

(H-XE) and (H-XF), where the reaction product may be Compound (H-XE) or (H-XF), or a mixture thereof, in which Compounds (H-XE) and (H-XF) may be present in any relative amounts, e.g., a ratio of Compound (H-XE) Compound (H-XF) of about 0.001 :99.999, 0.01 :99:99, 0.1 :99.9, 1 :99, 5:95, 10:90, 20:80, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90: 10, 95:5, 99: 1, 99.9:0.1, 99.99:0.01, 99.999:0.001by weight, by mole, or by volume. In some embodiments, the ratio of Compound (H-XE): Compound (H- XF) is from about 0.001 :99.999 to about 99.999:0.001, from about 0.01 :99:99 to about 99.99:0.01 ; from about 0.1 :99.9 to about 99.9:0.1, from about 1 :99 to about 99: 1, from about 5:95 to about 95:5, from about 10:90 to about 90: 10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight, by mole, or by volume.

[00196] A reaction product between dicyanoacetylene and a-farnesene is shown as Compounds

(H-XG) and (H-XH), where the reaction product may be Compound (H-XG) or (H-XH), or a mixture thereof, in which Compounds (H-XG) and (H-XH) may be present in any relative amounts, e.g., a ratio of Compound (H-XG): Compound (H-XH) of about 0.001 :99.999, 0.01 :99:99, 0.1 :99.9, 1 :99, 5:95, 10:90, 20:80:, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90: 10, 95:5, 99: 1, 99.9:0.1, 99.99:0.01, 99.999:0.001 by weight, by mole, or by volume. In some embodiments, the ratio of Compound (H-XG): Compound (H- XH) is from about 0.001 :99.999 to about 99.999:0.001, from about 0.01 :99:99 to about 99.99:0.01 ; from about 0.1 :99.9 to about 99.9:0.1, from about 1 :99 to about 99: 1, from about 5:95 to about 95:5, from about 10:90 to about 90: 10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight, by mole, or by volume.

[00197] In some embodiments, dicyanoacetylene is derived from acetylene dicarboxylic acid, following by treatment with ammoniolysis, followed by dehydration with P₂O₅ or the like. In some embodiments, dicyanoacetylene is derived from acetylene diamide, followed by dehydration with P₂0₅ or the like. In some embodiments, a Diels-Alder adduct between β-farnesene and acetylene dicarboxylic acid or acetylene diamide is dehydrated to make Compound (H-XE) or (H-XF) or a mixture thereof, or a Diels-Alder adduct between a-farnesene and acetylene dicarboxylic acid or acetylene diamide is dehydrated to make Compound (H-XG) or (H-XH) or a mixture thereof.

[00198] Compounds of formulae (H-XA), (H-XB), (H-XC) and (H-XD), and Compounds (H-

XE), (H-XF), (H-XG) and (H-XH) may be used in any application that utilizes an unsaturated diamide or saturated dicyanoacetylene. In some embodiments, compounds of formula (H-XA) and (H-XC), and Compounds (H-XE) and (H-XG) may be reacted with another conjugated terpene or conjugated diene (e.g., 1,3-butadiene or a substituted 1,3 -butadiene). Compounds of formula (H-XA), (H-XB), (H-XC) and (H-XD), and Compounds (H-XE), (H-XF), (H-XG) and (H-XH) and derivatives thereof may have utility as surfactants, plasticizers, and/or as monomers, cross-linking agents, curing agents or reactive diluents for use in making oligomers or polymers.

(H-XI) Quinone Dienophiles

[00199] In some embodiments, a benzoquinone or a naphthoquinone is used as a dienophile. For example, Compound (H-XIA), (H-XIB) or (H-XIC) may be made as a Diels-Alder adduct between β- farnesene and 1 ,4-benzoquinone. Compounds (H-XIA), (H-XIB) and (H-XIC) may be hydrogenated to form compounds (H-XID), (H-XIE) and (H-XIF) respectively.

[00200] In some embodiments, only one of Compounds (H-XIA), (H-XIB) and (H-XIC) is produced during a Diels-Alder reaction. For example, the reaction conditions may be slowed or otherwise controlled to produce only Compound (H-XIA). In some embodiments, the reaction conditions may favor formation of a mixture of Compounds (H-XIB) and (H-XIC) in which Compounds (H-XIB) and (H-XIC) are present in any relative amounts, e.g., a ratio of Compound (H-XIB): Compound (H-XIC) of about 0.001 :99.999, 0.01 :99:99, 0.1 :99.9, 1 :99, 5:95, 10:90, 20:80, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90: 10, 95:5, 99: 1, 99.9:0.1, 99.99:0.01, or 99.999:0.001 by weight, by mole, or by volume. In some embodiments, the ratio of Compound (H-XIB): Compound (H-XIC) is from about 0.001 :99.999 to about 99.999:0.001, from about 0.01 :99:99 to about 99.99:0.01 ; from about 0.1 :99.9 to about 99.9:0.1, from about 1 :99 to about 99: 1, from about 5:95 to about 95:5, from about 10:90 to about 90:10, from about 20:80 to about 80:20, from about 30:70 to about 70:30, or from about 40:60 to about 60:40 by weight, by mole, or by volume. In some embodiments, all three of compounds (H-XIA), (H- XIB) and (H-XIC) are present.

[00201] In some embodiments, Compound (H-XIA) may be oxidized to form a benzoquinone having structure (H-XIA' ):

[00202] In some embodiments, Compounds (H-XIB) and/or (H-XIC) may be oxidized to form a benzoquinone having structures (Η-ΧΙΒ') and (H-XIC), respectively:

[00203] In some embodiments, Compounds (H-XIB) and/or (H-XIC) may be oxidized to form an anthraquinone having structures (H-XIB") and (H-XIC") respectively:

[00204] When 1 ,2-benzoquinone is used as the dienophile in a reaction with β-farnesene, one or more of Compounds (H-XID), (H-XIE), (H-XIF), (H-XIG) and (H-XIH) may result:

[00206] a-Famesene may also reacts with 1 ,4-benzoquinone or 1 ,2-benzoquinone in a Diels-

Alder reaction. Possible reaction products with a-farnesene and 1 ,4-benzoquinone are Compounds (H- XIK)-( H-XIM):

[00207] Possible reaction products between a-farnesene and 1 ,2-benzoquinone are Compounds

(H-XIN)-( H-XIR):

A possible reaction product between a-farnesene and 1 ,4-naphthoquinone is Compound

[00209] It should be pointed out that aliphatic portions of any of Compounds (H-XIA)-( H-XIS) may be completely or partially hydrogenated prior to use. Compounds of formulae (H-XIA)-( H-XIS) may be used in any application that utilizes ketones or quinones. In some embodiments, Compounds (H- XIA)-( H-XIS) and derivatives thereof may have utility as oils, solvents, lubricants, additives or base oils for lubricant compositions, surfactants, plasticizers, and/or as monomers, cross-linking agents, curing agents or reactive diluents for use in making oligomers or polymers.

(H-XII) Oxidation of Diels-Alder Adducts

[00210] As described above, one or more unsaturated bonds of a conjugated hydrocarbon terpene may be oxidized (e.g., epoxidized). Non-limiting examples of mono-epoxides, di-epoxides, tri-epoxides, and tetra-epoxides derived from β-farnesene are Compounds (15a), (15b), (16), (17) and (18) as shown below:

[00211] In certain embodiments, one or more unsaturated bonds originating from the conjugated terpene in a Diels-Alder adduct is oxidized (e.g., epoxidized). For example, an epoxidized Diels-Alder adduct having any of structures (H-XIIA)-( H-XIIF) may be formed. Following the epoxidation, one or more remaining double bonds of adducts (H-XIIA)-( H-XIIE) may be hydrogenated to the corresponding Compounds (H-XIIA')-( H-XIIE') as shown below:

where each of R and R' independently represents H or any Ci-C₃₀ linear or branched, cyclic or acyclic, substituted or unsubstituted alkyl group, and R and R' may be the same or different. In some embodiments, each of R and R' independently represents a C₁-C4 linear or branched alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl or t-butyl. In some embodiments, each of R and R' independently represent n-pentyl, isopentyl, n-hexyl, 2-ethylhexyl, isohexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, n-nonyl, isononyl, n-decyl, isodecyl, 2-propylheptyl, n-undecyl, isoundecyl, n-dodecyl, isododecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl or n-tricosyl. In some embodiments, each of R and R' is independently substituted with one or more heteroatoms, e.g., oxygen, nitrogen, or chlorine. In one embodiment, each of R and R' is independently methyl. In certain variations, a polyol may be derived from epoxidized Diels-Alder derivatives using known techniques.

[00212] It should be understood that any suitable Diels-Alder adduct described herein may be oxidized in a similar fashion. Diels-Alder adducts in which unsaturated bonds on the hydrocarbon tail or cyclohexene ring that have been oxidized to form epoxy groups or hydroxyl groups, or derivatives thereof may have utility as oils, surfactants, plasticizers, or monomers, cross-linking agents, curing agents and/or reactive diluents for making oligomers or polymers. In some embodiments, the epoxidized Diels-Alder adducts disclosed herein can be used to prepare epoxy resins or varies epoxidized or epoxy- modified polymers.

[00213] As described above, one or more unsaturated bonds (e.g., in the aliphatic tail originating from the conjugated hydrocarbon terpene) may be halogenated (e.g., chlorinated). Halogenated Diels- Alder adducts or derivatives thereof may have utility as oils, surfactants, plasticizers, or monomers, cross-linking agents, curing agents and/or reactive diluents for making oligomers or polymers.

J) Applications

[00214] The Diels-Alder adducts and derivatives thereof as described herein have a variety of applications. Non-limiting examples of applications which may employ Diels-Alder adducts described herein include: solvents, lubricants (e.g., ester-based lubricants, base oils for lubricants or lubricant additives); surfactants (e.g., nonionic, anionic, cationic, or zwitterionic); plasticizers; and monomers, cross-linking agents, curing agents and/or reactive diluents for making oligomers or polymers.

[00215] As used herein, a "renewable carbon" source refers to a carbon source that is made from modern carbon that can be regenerated within a several months, years or decades rather than a carbon source derived from fossil fuels (e.g., petroleum) that takes typically a million years or more to regenerate. The terms "renewable carbon" and "biobased carbon" are used interchangeably herein. "Atmospheric carbon" refers to carbon atoms from carbon dioxide molecules that have been free in earth's atmosphere recently, in the most recent few decades.

[00216] Renewable carbon content can be measured using any suitable method. For example, renewable carbon content can be measured according to ASTM D6866-11, "Standard Test Methods for Determining the Biobased Content of Solid, Liquid, and Gaseous Samples Using Radiocarbon Analysis," published by ASTM International, which is incorporated herein by reference in its entirety. Some carbon in atmospheric carbon dioxide is the radioactive ¹⁴C isotope, having a half life of about 5730 years.

Atmospheric carbon dioxide is utilized by plants to make organic molecules. The atmospheric ¹⁴C becomes part of biologically produced substances. As the biologically produced organic molecules degrade to produce carbon dioxide into the atmosphere, no net increase of carbon in the atmosphere is produced as a result, which may control or diminish undesired climate effects that may result when molecules produced from fossil fuels degrade to produce carbon dioxide to increase carbon in the atmosphere.

[00217] Isotope fractionation occurs during physical processes and chemical reactions, and is accounted for during radiocarbon measurements. Isotope fractionation results in enrichment of one isotope over another isotope. Exemplary processes that can affect isotope fractionation include diffusion (e.g., thermal diffusion), evaporation, and condensation. In some chemical reactions, certain isotopes may exhibit different equilibrium behaviors than others. In some chemical reactions, kinetic effects may affect isotope ratios. In the carbon cycle of plants, isotope fractionation occurs. During photosynthesis, the relative amounts of different carbon isotopes that are consumed are ¹²C>¹³C>¹⁴C, due to slower processing of heavier isotopes. Plants species exhibit different isotope fractionation due to isotopic discrimination of photosynthetic enzymes and diffusion effects of their stomata. For example C3 plants exhibit different isotope fractionation than C4 plants. The international reference standard for isotope fractionation between ¹³C and ¹²C is PDB (Pee Dee Belemnite standard) or VPDB (Vienna Pee Dee Belemnite standard, replacement for depleted PDB standard). For a given sample, isotope fractionation can be expressed as δ ¹³C (per mil) = {[R(sample)/R(VPDB standard)]- 1 }xl 000 %₀, where

R(sample)=¹³C/¹²C and R(VPDB standard)=¹³C/¹²C for the VPDB standard. Instead of a ¹³C/¹²C ratio, 8^l3C is the relative change of the ¹³C/¹²C ratio for a given sample from that of the VPDB standard.

Carbon isotopic ratios are reported on a scale defined by adopting a 8¹³C value of +0.00195 for NBS-19 limestone (RM 8544) relative to VPDB. "New IUPAC guidelines for the reporting of stable hydrogen, carbon, and oxygen isotope-ratio data," Letter to the Editor, J. Res. Natl. Stand. Technol. 100, 285 (1995). Most naturally occurring materials exhibit negative 8^l3C values. In general, for atmospheric C0₂ 5^l3C ranges between -11 to -6 %₀, for C₃ plants, 5C¹³ varies between -22 and -32 %₀ and for C₄ plants δ C varies between -8 to -18 IQQ. The C fractionation factor can be approximated as the square of the ¹³C fractionation factor. See, e.g., M. Stuiver and S.W. Robinson, Earth and Planetary Science Letters, vol. 23, 87-90.

[00218] ¹⁴C content of a sample can be measured using any suitable method. For example, ¹⁴C content can be measured using Accelerator Mass Spectrometry (AMS), Isotope Ratio Mass Spectrometry (IRMS), Liquid Scintillation Counting (LSC), or a combination of two or more of the foregoing, using known instruments. Activity refers to the number of decays measured per unit time and per unit mass units. To compare activity of a sample with that of a known reference material, isotope fractionation effects can be normalized. If an activity of a sample is measured to be A_s, the sample activity normalized to the reference is A_SN and can be expressed as: A_SN=A_s{[(¹³C/¹²C)reference]/[(¹³C/¹²C)sample]}².

[00219] Radiocarbon measurements are performed relative to a standard having known radioactivity. SRM 4990B is an oxalic acid dehydrate Standard Reference Material provided by the U.S. National Bureau of Standards (now National Institute of Standards and Technology, NIST) in the late 1950s having 8¹³C=-19 %₀ (PDB). SRM 4990B has been depleted so another standard is used, such as SRM 4990C, a second oxalic acid standard from NIST having 8¹³C=-17.8 %₀ (VPDB). Modern carbon, referenced to AD 1950, is 0.95 times ¹⁴C concentration of SRM 4990B, normalized to 8¹³C=-19 %₀ (PDB). The factor 0.95 is used to correct the value to 1950 because by the late 1950s, ¹⁴C in the atmosphere had artificially risen about 5% above natural values due to testing of thermonuclear weapons. Fraction of modern (f_M) refers to a radiocarbon measured compared to modern carbon, referenced to AD 1950. Modern carbon as defined above has f_M=l . For current living plant material not more than a few years old (such as corn), f_M is approximately 1.1. Percent modern carbon (pMC) is f_M x 100%. The AD 1950 standard had 100 pMC. Fresh plant material may exhibit a pMC value of about 107.5.

Biobased carbon content is determined by settingl00% biobased carbon equal to the pMC value of freshly grown plant material (such as corn), and pMC value of zero corresponds to a sample in which all of the carbon is derived from fossil fuel (e.g., petroleum). A sample containing both modern carbon and carbon from fossil fuels will exhibit a biobased carbon content between 0 and 100%. In some cases, a sample that is more than several years old but containing all biobased carbon (such as wood from a mature tree trunk) will exhibit a pMC value to yield a biobased carbon content > 100%.

[00220] Renewable carbon content or biobased carbon content as used herein refers to fraction or percent modern carbon determined by measuring ¹⁴C content, e.g., by any of Method A, Method B, or Method C as described in ASTM D6866-11 "Standard Test Methods for Determining the Biobased Content of Solid, Liquid, and Gaseous Samples Using Radiocarbon Analysis." Counts from ¹⁴C in a sample can be compared directly or through secondary standards to SRM 4990C. A measurement of 0% ¹⁴C relative to the appropriate standard indicates carbon originating entirely from fossils (e.g., petroleum based). A measurement of 100% C indicates carbon originating entirely from modern sources. A measurement of >100% ¹⁴C indicates the source of carbon has an age of more than several years.

[00221] Advantageously, any of the Diels-Alder adducts and derivatives thereof may be made from conjugated terpenes and/or dienophiles that have been derived from renewable carbon sources. In some variations, at least about 25%, at least about 30%, at least about 40%, at least about 50%, at least about 60%), at least about 70%, at least about 80%, at least about 90%, or about 100% of the carbon atoms in the Diels-Alder adducts or derivatives thereof originate from renewable carbon sources. In some variations, the conjugated hydrocarbon terpene (e.g., myrcene, β-farnesene, or a-farnesene) is made by genetically modified microorganisms using renewable carbon sources such as a sugar (e.g. , sugar cane). In some variations, a dienophile is at least partially derived from renewable carbon sources. For example, a dienophile may be derived from ethanol derived from plant sources, e.g. , a dienophile may be derived from renewable ethylene that is derived from renewable ethanol. In some variations, one or more chemicals used to modify the Diels-Alder adducts described herein may be at least partially derived from renewable carbon sources. For example, renewable alcohols or renewable glycols (e.g., ethylene glycol or propylene glycol) may be used to derivatize a Diels-Alder adduct as described herein. The renewable carbon content of a Diels-Alder adduct or its derivatives is measured according to ASTM D6866-11, "Standard Test Methods for Determining the Biobased Content of Solid, Liquid, and Gaseous Samples Using Radiocarbon Analysis," published by ASTM International, which is incorporated herein by reference in its entirety.

[00222] Advantageously, the properties of a Diels-Alder adduct between a conjugated terpene and a dienophile may be tuned, adjusted or modified to accomplish any one of or any combination of two or more of the following: modify hydrophobicity and/or hydophilicity of a portion or the whole of the molecule; modify compatibility with a desired oil; improve solubility in water (e.g., hard water or cold water) in use; improve solubility in electrolytes (e.g., builders); provide a reactive site by which the adduct may react with another component of a composition incorporating the adduct; increase thermal stability; undergo a reverse Diels-Alder reaction to produce desired species; modify molecular weight; modify viscosity, crystallinity, volatility at processing temperatures and/or at use temperatures; modify migration or leaching behavior in operiation; enable the adduct or a composition comprising the adduct to be suitable for use in food grade applications; enable the adduct or a composition comprising the adduct to be suitable for use in medical applications; modify surface properties of the adduct; provide a site for making an anion or cation; tune absorption of a desired portion of the electromagnetic spectrum (e.g., radiofrequency, infrared, visible or ultraviolet); modify critical micelle concentration; modify ability to form a stable emulsion with a specified oil; xviii) provide antistatic properties; provide antimicrobial properties. Such tuning may be accomplished via choice of conjugated terpene and dienophile combination and/or by post-reaction chemical modifications as described herein or otherwise known. [00223] In certain embodiments, the Diels-Alder adducts described herein have a structure X_CHT-

A_DA-Y_DP, in which X_CHT originates or derives from one or more conjugated hydrocarbon terpenes reacted with a dienophile, Y_DP originates or derives from the dienophile, and A_DA comprises one or more cyclic groups resulting from the Diels-Alder reaction between the dienophile and the one or more conjugated hydrocarbon terpenes. In certain embodiments, one conjugated hydrocarbon terpene reacts with a dienophile so that the Diels-Alder adduct has structure X-A-Y, where X represents a tail originating from that conjugated terpene; A represents a cyclic structure (e.g., 6-membered ring); and Y originates from the dienophile. In certain embodiments, two conjugated hydrocarbon terpenes (which may be the same or different) undergo a Diels-Alder reaction with one dienophile so that the Diels-Alder adducts may

have a structure or ^{x — A} Y ^{A — x} , where X refers to a first conjugated terpene and A refers to a cyclic group resulting from the Diels-Alder reaction between the first conjugated terpene and the dienophile, and X² refers to a second conjugated terpene and A₂ refers to a cyclic group resulting from the Diels-Alder reaction between the second conjugated terpene and the dienophile. As used herein, X_CHT may refer to X, X¹ or X²; and Y_Dp may refer to Y, Y¹ or Y².

[00224] X_CHT and/or Y_DP may be selected or chemically modified to make the Diels-Alder adduct suitable for use in certain applications. For example, X_CHT and/or Y_DP may be selected or chemically modified to a Diels-Alder adduct to impart any one of or any combination of two or more of the following properties to the adduct: modify hydrophobicity and/or hydophilicity of a portion or the whole of the molecule, modify compatibility with a desired oil or polymer; improve solubility in water (e.g., hard water or cold water) in use; improve solubility in electrolytes (e.g., builders); provide a reactive site by which the adduct may react with another component of a composition incorporating the adduct; increase thermal stability; undergo a reverse Diels-Alder reaction to produce desired species; modify molecular weight; modify viscosity, crystallinity, volatility at processing temperatures and/or at use temperatures; modify migration or leaching behavior in operiation; enable the adduct or a composition comprising the adduct to be suitable for use in food grade applications; enable the adduct or a composition comprising the adduct to be suitable for use in medical applications; modify surface properties of the adduct; provide a site for making an anion or cation; and tune absorption of a desired portion of the electromagnetic spectrum (e.g., radiofrequency, infrared, visible or ultraviolet); modify critical micelle concentration; modify ability to form a stable emulsion with a specified oil; provide antistatic properties; provide antimicrobial properties. Such tuning may be accomplished via choice of conjugated terpene and dienophile combination and/or by post-reaction chemical modifications as described herein or otherwise known.

[00225] Non-limiting examples of tuning of Diels-Alder adducts for various applications are provided below. (i) Modify hydrophobicity/hydrophilicity of Diels-Alder adduct, or compatibility of Diels-Alder adduct with a polymer or oil

[00226] In certain embodiments, it is desirable for a Diels-Alder adduct to include a nonpolar

(hydrophobic) end and a polar (hydrophilic) end, so that X_CHT provides a hydrophobic end or ends and Y_Dp provides a hydrophilic end. Y_Dp may contain heteroatoms such as O, S, P or N, included in functional groups such as ester, keto, ether, acid, alcohol, amine, amide and thiol.

[00227] The hydrophobicity of X_CHT may be tuned or modified in a variety of ways. X_CHT in general includes methyl substituents originating from the conjugated terpene. In some embodiments, X_CHT is an unsaturated hydrocarbon chain, in other embodiments, X_CHT is a saturated hydrocarbon chain, in some embodiments X_CHT includes one or more nonionic oxygen groups (e.g., epoxy, hydroxy, or keto), and/or one or more nonionic halo substituents (e.g., chloro). Hydrophobicity of X_CHT may be decreased by using a shorter chain conjugated terpene and/or oxidizing or halogenating one or more of the unsaturated carbon bonds of X_CHT-

[00228] Hydrophilicity of Y_Dp may be tuned or modified in a variety of ways. In one example, a dienophile may be selected to vary the number of polar substituents resulting in the Diels-Alder adduct. For example, in some situations a dienophile may be selected that provides only one polar substituent to the cyclic group formed by the Diels-Alder reaction. In other, a dienophile may be selected that provides more than one (e.g., two) polar substituents to the cyclic group formed by the Diels-Alder reaction, e.g., a dienophile that is a diacid, a diester, or a di-cyano may be selected. Alternatively or in addition, a dienophile may be selected or a Diels-Alder adduct may be modified so that Y_DP includes one or more hydrocarbon chains, in which the length and degree of branching in the hydrocarbon chains is varied to tune hydrophobicity of the adduct. In some embodiments, a Diels-Alder adduct is alkoxylated (any number of ethylene oxide or propylene oxide segments are incorporated into the adduct) to tune hydrophobicity properties. In some embodiments, an N-oxide of a Diels-Alder adduct is formed. In some embodiments, a Diels-Alder adduct may be modified so as to form an anionic or cationic compound. For example a Diels-Alder adduct incorporating one or more carboxylic acid salts may be made, a sulfate, a phosphate, or an ammonium ion may be made.

[00229] Non-limiting examples of applications that may utilize the Diels-Alder adducts described herein having a polar end and a nonpolar end include: use as a plasticizer in which compatibility with a polar polymer host is required; use as a surfactant or as positive or negative surface tension modifier; use as an ester-containing base oil additive (e.g., antifriction agent, antiwear agent, or anticorrosion agent) or as an ester-containing base oil; or use as a monomers, cross-linker or reactive diluents for making oligomers and polymers.

[00230] In some variations, a Diels-Alder adduct that is to be used as a plasticizer, surfactant, or solvent for a target substance (e.g., a polymeric resin) is selected based on one or more measured or calculated solubility parameters of the Diels-Alder adduct and of the target substance. For example, a plasticizer for use in PVC may be selected to have solubility parameters close to that of PVC. A solubility parameter is an empirical, calculated or semi-empirical numerical value that indicates relative solubility of a Diels-Alder adduct and a target substance. Any suitable solubility parameter or combination of parameters can be used to evaluate and quantify intermolecular interactions between the Diels-Alder adduct and the target substance to estimate or predict efficacy as a plasticizer, surfactant, or solvent. Non-limiting examples of intermolecular interactions that can be evaluated to incorporate into a solubility parameter include dispersion (van der Waals forces, related to polarizable electrons), dipole moment, hydrogen bonding, and orientation effects. Any scheme or algorithm known in the art to calculate or measure solubility of a Diels-Alder adduct in a target substance can be used to arrive at a solubility parameter. For example, Hildebrand solubility parameters, Hansen solubility parameters, UNIFAC semi-empirical calculations, or a combination thereof can be used to estimate solubility parameters for Diels-Alder/target substance combinations. In some variations, quantum mechanical chemical calculations (e.g., COSMO-RS® software, available from COSMOlogic® GmbH & Co. KG) are used to calculate solubility parameters. Hildebrand solubility parameters do not take into account hydrogen bonding, and may be more relevant for nonpolar systems than for polar systems.

[00231] Hansen solubility parameters include three different parameters: SD (dispersion), δΡ

(dipole moment), and δΗ (hydrogen bonding) and can be used for polar systems in addition to nonpolar systems. The parameters δΌ, δΡ and δΗ are related to δΤοί, the cohesive energy per molar volume for the solvent as follows: δΤοί²⁼δ0²+δΡ²+δΗ². For Hansen solubility parameters, compatibility between a Diels-Alder adduct and a target substance is represented numerically as a distance R_a, calculated as follows: R_a={4[6D_plas-6D_host]²+[6P_pi_as-6P_host]²+[6H_plas-6H_host]²} ^1,2 , where 8D_host is the dispersion parameter for the host resin, 8D_pi_as is the dispersion parameter for the plasticizer, δΡ_¾08ί is the dipole parameter for the host resin, 8P_pi_as is the dipole parameter for the plasticizer, 8H_host is the hydrogen bonding parameter for the host resin, and 8H_plas is the hydrogen bonding parameter for the plasticizer. A smaller value for R_a indicates a greater "likeness" or compatibility between a Diels-Alder adduct and a target substance. The solubility of a target substance in a variety of candidate Diels-Alder adducts can be visualized as a sphere, in which R_a is the radius of the sphere, and the center of the sphere is located at the point (8D_host, 8P_host, §H_host). If R₀ represents a maximum distance for an acceptably compatible interaction between a Diels-Alder adduct and a host resin, then a value R_a/R₀ = Relative Energy Distance (RED) can be calculated. In some cases, a RED value approximately equal to or less than 1 for a particular Diels-Alder adduct/target substance combination indicates that combination is compatible, which will result in a desired effective interaction (e.g., plasticization or solvency). In some cases, a RED value greater than 1 for a particular Diels-Alder/target substance combination indicates an incompatible combination, such that the Diels-Alder adduct is unlikely to be sufficiently compatible with the target substance to provide the desired effect (e.g., effective plasticization or effective solvency). [00232] The parameters δΌ, δΡ, δΗ for the host resin and the plasticizers can be calculated, measured or estimated in any suitable manner or retrieved from existing databases. For example, in some cases Hansen solubility parameters for a substance are determined from empirical solubility data for that substance in about 20 to 30 known solvents. One software package that uses Hansen Solubility parameters to evaluate suitability of particular plasticizers for a desired application is HSPiP, available at www.hansen-solubility.com. The HSPiP package has the capability to read a data table containing chemical name and structure encoded as a SMILES string, and to automatically calculate the HSP of the chemical using the so-called Y-MB fragment-based method. Like all automatic techniques for estimating molecular properties, the results need to be checked for values that may be numerical artifacts. This method is used to calculate those compounds that are not included in the HSP database. In some cases, δϋ, δΡ or δΗ for a substance is obtained from Hansen, C. M., Hansen Solubility Parameters: A User's Handbook, CRC Press, Boca Raton, FL, 1999, Hansen, C. M., Hansen Solubility Parameters: A User's Handbook, Second Ed., CRC Press, Boca Raton, FL, 2007, or Hansen Solubility Parameters in Practice, eBook/software, 1st Ed.2008, 2nd Ed. 2009, with Prof. Stephen Abbott and Dr. Hiroshi Yamamoto available from www.hansen-solubility.com, each of which is incorporated herein by reference in its entirety. A set of solvents is selected to sufficiently characterize solubility or swellability of a substance in a host resin of choice. In some cases, Hansen solubility parameters for a substance are determined by mathematical modeling of the substance. In some cases, mathematical modeling comprises

mathematically dividing the substance into functional groups to facilitate modeling (group contribution methods). For example, a Yamamoto molecular breaking model (Y-MB) or Stefanis-Panayiotou (2008 model) may be used (see, e.g., Hansen Solubility Parameters in Practice, eBook/software, 1st Ed.2008, 2nd Ed. 2009, with Prof. Stephen Abbott and Dr. Hiroshi Yamamoto, available from www.hansen- solubility.com).

[00233] Calculated solubility parameters for various non- limiting examples of Diels-Alder adducts and certain farnesene derivatives that can be used for any application in described herein are shown in Table 5 below. Although calculated Hansen solubility parameters relative to a model PVC having 6D=18.5, δΡ=7.9, δΗ=3.4, and R₀=8 are shown in Table 5, any suitable measured or calculated solubility parameter relative to any desired substance can be used in selecting or tuning the Diels-Alder adducts described herein for a particular application.

TABLE 5: Calculated Hansen Solubility parameters for Diels-Alder adducts in a model PVC system

81

83

84

85

86

88

90 Code Structure 5D δΡ δΗ RED Mvol

10007

6 17.1 6.4 6.2 0.53 608.5

10007

7 16.2 2.8 4.9 0.88 473.2

10007

8 16.3 3 7.2 0.95 522.9

10007

9 16.2 3.1 6.4 0.91 446.4

10008

0 16.1 4.7 6.2 0.80 468

10008

1 16.3 4.9 7.1 0.81 430.9

10008

2 16.1 4.5 7.4 0.89 437.8

Code Structure 5D δΡ δΗ RED Mvol

10008

8 16 2 2 0.98 570.9

10008

9 17.8 6 6.3 0.47 527.4

10009

0 16.5 5.1 3.5 0.61 608.2

10009

1 X, 15.7 1.3 5.5 1.11 718.5

10009

2 16 4.7 2 0.76 816.6

10009

3 15.9 4.6 4.5 0.78 453.6

10009

4 16.7 5.2 4.9 0.59 513.6

95

96

97

99

105

108 (ii) Create an anion or cation

[00234] In some embodiments, a Diels-Alder adduct may be modified so as to form an anionic or cationic compound. For example a Diels-Alder adduct incorporating one or more carboxylic acid salts may be made, a sulfate may be formed (e.g., using standard sulfation techniques such as S0₃/oleum sulfation), a phosphate or phosphite may be formed, or an ammonium ion may be made. Cationic Diels- Alder adducts (e.g., ammonium ions such as quaternary ammonium ions) and anionic Diels-Alder adducts (e.g., sulfates or phosphates) may be useful as surfactants in applications such as soaps, detergents, wetting agents, dispersants, emulsifiers, foaming agents, antistatic agents, corrosion inhibitors and antimicrobials.

[00235] Certain anionic surfactants derived from Diels-Alder adducts may be useful in detergents, soaps, builders and other cleaning agents, emulsifiers and the like. Certain cationic surfactants derived from the Diels-Alder adducts described herein may have use in personal care products. For example, ammonium ions (e.g., quaternary ammonium ions) may have use in hair products such as shampoos, conditioners and the like. Ammonium ions (e.g., quaternary ammonium ions) may be useful as dye sites, antimicrobials, and herbicides. N-oxides formed from the Diels-Alder adducts described herein may have use as surfactants, e.g., for use in personal care products (e.g., shampoos, conditioners, and the like).

(iii) Provide a reactive site by which the adduct may be reacted with another component of a composition incorporating the adduct

[00236] In some embodiments, a Diels-Alder adduct may include a reactive site by which the adduct may be reacted with another component of a composition to incorporate the adduct. In certain applications, a Diels-Alder adduct may be a monomer to be reacted with itself to form an oligomer (e.g., a dimer, trimer, tetramer, etc.) or a homopolymer, or co-polymerized with another monomer to form an oligomer or polymer. In some embodiments, X_CHT is a reactive site. In certain embodiments Y_DP is a reactive site. In some embodiments both X_CHT and Y_DP are reactive sites. Oligomerization and polymerization can proceed by any known route, e.g., using free radical polymerization, anionic polymerization, cationic polymerization, condensation polymerization, polymerization using metallocene or Ziegler Natta catalysts, or hydrovinylation.

[00237] In some embodiments, at least one olefinic bond on X_CHT is left unsaturated, and the one or more unsaturated bonds is used to polymerize the adduct with another like molecule to form a homopolymer or with a co-monomer to form a copolymer. In some embodiments, an unsaturated bond on a X_CHT serves as a cross-linking site. In some embodiments, at least one olefinic bond on X_CHT is epoxidized or halogenated, and the epoxy moiety or halogenated site is used to polymerize the adduct with another like molecule to form a homopolymer or with a co-monomer to form a copolymer. In some embodiments, at least olefinic bond is oxidized to form a hydroxyl group, which can be coupled with another like molecule, or coupled with a co-monomer. In some embodiments, at least one olefin bond on the X_CHT is halogenated, which can serve as a reactive site to couple with another like molecule or a co- monomer. In some embodiments, Y_Dp contains one or more hydroxy, cyano, ester, epoxy, amine, amide, anhydride, or olefinic bonds that can serve as reactive sites to couple to another like molecule, or to a co- monomer. In some embodiments, Y_Dp includes a reactive site that can be used to make an oligomer or polymer. In some embodiments Y_Dp includes a reactive site that can be used to cross-link between polymer chains. In some embodiments, both X_CHT and Y_Dp include one or more reactive sites that can be used to make an oligomer or polymer. In some embodiments, both X_CHT and Y_Dp include one or more reactive sites that can be used to cross-link between polymer chains.

(iv) Increase thermo-oxidative stability

[00238] In some embodiments, X_CHT and/or Y_DP are modified so as to increase thermo-oxidative stability of the adduct. The thermal stability requirements are application dependent, but in some embodiments, thermal stability may be tuned or modified to withstand transient processing temperature (e.g., melt mixing, extruding, molding, soldering, heat treatments, annealing, and the like) and long term use steady state and thermal excursion requirements. As stated above, olefinic bonds may be partially or completely saturated to increase thermal stability. The dienophile may be selected or chemically modified so that the final Diels-Alder adduct does not contain functional groups (e.g., nitrogen containing groups and certain oxygen containing groups) that are susceptible to oxidation in the anticipated processing or use conditions.

(v) Undergo a reverse Diels-Alder reaction to produce desired species

[00239] In some embodiments, a Diels-Alder adduct may formed which subsequently undergoes a reverse Diels-Alder reaction to produce a desired species using known techniques.

(vi) Modify molecular weight

[00240] In some embodiments, the molecular weight of a Diels-Alder adduct may be tuned or modified to make the adduct appropriate for certain applications. For example, if the adduct is to be used as plasticizer dispersed into a polymer, the molecular weight of the adduct may be increased to reduce the amount of migration within the polymer or out of the polymer. The molecular weight of the adduct may be increased by any one of or any combination of the following: reacting two hydrocarbon terpenes with a dienophile, forming dimers or other oligomers, either between like molecules or between different molecules, or by selecting a conjugated terpene with a larger molecular weight, or by functionalizing the adduct with one or more longer hydrocarbon chains, or by alkoxylating the adduct (e.g., ethoxylating or propoxylating).

(vii) Modify volatility at processing temperatures and/or at use temperatures

[00241] Volatility of a Diels-Alder adduct may be tuned or modified to make the adduct more or less volatile in certain applications. For example, to decrease volatility of the neat substance, the Diels- Alder adduct may be functionalized to increase molecular weight and/or increase intermolecular interactions between adduct molecules. To decrease volatility of the adduct in a mixture, the Diels-Alder adduct may be functionalized to increase molecular weight and/or intermolecular interactions between the adduct and its solvent (which may be a liquid or solid).

(viii) and (ix) Enable the adduct or a composition comprising the adduct to be suitable for use in food grade applications and medical applications

[00242] Oils and/or plastics derived from or containing Diels-Alder adducts may be adapted for use in food grade applications, cosmetic applications, or in medical grade applications. Toxicity and biodegradability of the oils and/or plastics incorporating the adducts may be tested according to country- based regulations, local regulations, and/or standards-based tests, and according to anticipated uses (e.g., regulations for substances to come into contact with food to be ingested, substances to be used in food processing equipment, substances to come into contact with the human body, substances to be ingested, or substances to be implanted in the human body).

(x) Tune absorption of a desired portion of the electromagnetic spectrum

[00243] Diels-Alder adducts may be functionalized to tune or modify absorption by the adduct of a desired portion of the electromagnetic spectrum (e.g., infrared, visible or ultraviolet). For example, a Diels-Alder adduct may include one or more conjugated rings so that it absorbs the UV or visible light. Such adducts may function as dyes, UV absorbers or sensitizers. In some embodiments, absorption of the infrared radiation of an adduct may be adjusted, e.g., by tuning the concentration and nature of various infrared absorbing moieties.

[00244] Described below are some non-limiting examples of specific applications in which conjugated terpene Diels-Alder adducts or derivatives there of as described herein may be used: (J-I) in lubricant applications; (J-II) as monomers, cross-linking agents, curing agents, curing agents, or reactive diluents for making polymers; (J-III) as plasticizers or as multi-functional plasticizers; and (J-IV) as surfactants. In some variations, Diels-Alder adducts or derivatives thereof are used as solvents. As described above, hydrophobicity and/or hydrophilicity of the adducts may be tuned to adjust their utility as solvents in a variety of applications. In some variations, the Diels-Alder adducts are reactive diluents or solvents that chemically react with one or more co-solvents or solutes, e.g., by cross-linking, by condensation, by addition, or by transesterification. In one embodiment, farnesene as such (e.g., β- farnesene), or a Diels-Alder adduct as described herein is used as a reactive diluent, e.g., for an alkyd resin, a polyester, a polyurethane, or any other suitable type of resin that may be used as a coating. In some embodiments, a Diels-Alder adduct between β -farnesene and a dienophile is used in any one or more than one of the applications. In some embodiments, Diels-Alder adducts between a-farnesene and dienophiles are used. In some embodiments, Diels-Alder adducts between myrcene and dienophile are used in the applications. It should be understood that the solvents, surfactants, lubricants, plasticizers, monomers, cross-linking agents, curing agents, and reactive diluents may be made from conjugated hydrocarbon terpenes that are not farnesene or myrcene. In some variations, the conjugated terpene used to make a Diels-Alder adduct useful in the applications described herein may for example be any of the C₁₀-C30 conjugated hydrocarbon terpenes described herein, or any other conjugated hydrocarbon terpene otherwise known in the art.

(J-I) Lubricants or Base Oils or Additives for Lubricant Compositions

[00245] In some embodiments, Diels-Alder adducts described herein or derivatives thereof may be designed as lubricants or as components in lubricant compositions. In particular, monoesters or diester Diels-Alder adducts as described herein have utility as base oils or as additives for lubricant compositions. Monoesters and diesters have relatively high dipole moments, causing intermolecular forces to be increased, which may decrease vapor pressure, decrease volatility, and/or increase flash point. These properties may make an ester containing Diels-Alder adduct described herein advantageous for a variety of applications. The polarity of the ester-containing Diels-Alder adduct may increase their compatibility with other polar molecules, which increase their utility as solvents and dispersants for additives and the like. Esters tend to solubilize or disperse oil degradation by-products which may be deposited as sludge in a motor or other lubricated machinery, so that the use of ester-containing Diels- Alder adducts in lubricants may result in increased lubricant lifetime, increased lubricity, and/or improved additive solubility.

[00246] Monoester or diester-containing Diels-Alder adducts may in some instances exhibit relative stability against oxidative and thermal breakdown, but have high biodegradability. In some embodiments, ester-containing Diels-Alder adducts that are hygroscopic are not used in applications in which moisture is present or generated.

[00247] In some variations, a conjugated terpene (e.g., myrcene, β-farnesene or a-farnesene) undergoes a Diels-Alder reaction with acrylic acid, the adduct is hydrogenated to form a saturated adduct, and the saturated adduct is esterified with a polyol (e.g., pentaerythritol, neopentyl glycol, and the like) to obtain a high boiling point ester that is expected to exhibit high viscosity and low pour point due to the methyl-branched hydrocarbon chain originating from the hydrocarbon terpene.

[00248] Monoester or diester-containing Diels-Alder adducts may exhibit increased lubricity in some applications, and may be useful as friction modifiers. The polarity of the ester moiety may be attracted to metal oxide layers formed on metal surfaces, whereas the hydrocarbon tail of the Diels-Alder adduct is solubilized in an oil, which may increase the adducts' utility as boundary lubricants and friction modifiers. In certain embodiments, a monoester or diester-containing Diels-Alder adduct is used in place of all or a portion of a vegetable oil or petroleum-derived monoester, diester (e.g., an adipate), phthalate, dimerate, or trimellitate in a base oil or in a lubricant composition. [00249] In some embodiments, a monoester or diester containing Diels-Alder adduct as described herein is used as a metalworking fluid. In some embodiments, a monoesters or diester containing Diels- Alder adduct as described herein is used as a friction modifier in a lubricant composition.

[00250] In some embodiments, the conjugated terpene and/or alkyl substituent on the ester moiety or moieties that are used to make an ester-containing Diels-Alder adduct are selected to adjust a pour point of a base oil or lubricant formulation comprising the adduct. For example, longer chains may be selected to increase pour point, and shorter or more branched chains may be selected to decrease pour point.

[00251] Diester or mono-ester containing Diels-Alder adducts may be used in place of adipate diesters in some embodiments. In some embodiments, diester or monoester containing Diels-Alder adducts are used in combination with a polyalphaolefin (PAO). In some embodiments, diester or monoester containing Diels-Alder adducts are used in combination with PAOs or mineral oils in compressor oils, gear oils, transmission oils, crankcase oils, or hydraulic fluids. In some embodiments, diester or monoester containing Diels-Alder adducts are used as base oil where biodegradability is desired or low sludge formation is desired (e.g., used as lubricants for textile machines or ovens).

[00252] In some embodiments, the Diels-Alder adducts disclosed herein can be used as base oils or additives in lubricant compositions. In some embodiments, the Diels-Alder adducts disclosed herein are used as additives in lubricant compositions comprising a base oil and optionally other additives. Some Diels-Alder adducts suitable as base oils or additives in lubricant compositions can be prepared by Diels-Alder reaction between β -farnesene and a dienophile, wherein the dienophile is selected from monoalkyl or dialkyl maleates, monoalkyl or dialkyl fumarates, monoalkyl or dialkyl itaconates, acrylic acid esters, methacrylic acid esters, cinnamic acid esters, hydroxyalkyl acrylates, (dialkylamino)alkyl acrylates, dialkyl acetylene dicarboxylates, maleamide or substituted maleamides, fumaramide and substituted fumaramides, maleimide and substituted maleimides, 1 ,4-benzoquinone and substituted 1 ,4- benzoquinones, 1 ,2-benzoquinone, substituted 1 ,2-benzoquinones, and combinations thereof.

[00253] Any base oil known to a person of ordinary skill in the art can be used for preparing the lubricant compositions comprising one or more Diels-Alder adducts disclosed herein. The base oils suitable for preparing lubricant compositions have been described in Mortier et al., "Chemistry and Technology of Lubricants," 2nd Edition, London, Springer, Chapters 1 and 2 (1996), incorporated herein by reference. Generally, the lubricant composition may comprise from about 70 to 99 wt% of the base oil, based on the total weight of the lubricant composition. In some embodiments, the lubricant composition comprises from about 80 to 98 wt% of the base oil, based on the total weight of the lubricant composition.

[00254] In some embodiments, the base oil comprises any of the base stocks in Groups I-V as specified in the American Petroleum Institute (API) Publication 1509, Fourteen Edition, December 1996 (i.e., API Base Oil Interchangeability Guidelines for Passenger Car Motor Oils and Diesel Engine Oils), which is incorporated herein by reference. The API guideline defines a base stock as a lubricant component that may be manufactured using a variety of different processes. Groups I, II and III base stocks are mineral oils, each with specific ranges of the amount of saturates, sulfur content and viscosity index. Group IV base stocks are polyalphaolefins (PAO). Group V base stocks include all other base stocks not included in Group I, II, III, or IV. In particular embodiments, the base oil comprises a combination of the base stocks in Groups I-V.

[00255] In other embodiments, the base oil comprises a natural oil, a synthetic oil or a combination thereof. Non-limiting examples of suitable natural oils include animal oils (e.g., lard oil), vegetable oils, (e.g., corn oil, castor oil, and peanut oil), oils derived from coal or shale, mineral oils (e.g., liquid petroleum oils and solvent treated or acid-treated mineral oils of the paraffinic, naphthenic or mixed paraffinic-naphthenic types) and combinations thereof. Non-limiting examples of suitable synthetic lubricating oils include poly-alpha-olefins, alkylated aromatics, polybutenes, aliphatic diesters, polyol esters, polyalkylene glycols, phosphate esters and combinations thereof.

[00256] In further embodiments, the base oil comprises hydrocarbon oils such as polyolefins

(e.g., polybutylenes, polypropylenes, propylene isobutylene copolymers, polyhexene, polyoctene, polydecene, and the like); alkylbenzenes (e.g., dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di-(2-ethylhexyl)benzenes, and the like); polyphenyls (e.g., biphenyls, terphenyls, alkylated polyphenyls, and the like); alkylated diphenyl ethers; alkylated diphenyl sulfides; and the derivatives, isomers, analogs, homologs and combinations thereof.

[00257] In further embodiments, the base oil comprises a poly-alpha-olefin (PAO). In general, the poly-alpha-olefins may be derived from an alpha-olefin having from about 2 to about 30, or from about 4 to about 20, or from about 6 to about 16 carbon atoms. Non-limiting examples of suitable poly- alpha-olefins include those derived from octene, decene, mixtures thereof, and the like. These poly- alpha-olefins may have a viscosity from about 2 to about 15, or from about 3 to about 12, or from about 4 to about 8 centistokes at 100°C. In some instances, the poly-alpha-olefins may be used together with other base oils such as mineral oils.

[00258] In further embodiments, the base oil comprises a polyalkylene glycol or a polyalkylene glycol derivative, where the terminal hydroxyl groups of the polyalkylene glycol may be modified by esterification, etherification, acetylation and the like. Non-limiting examples of suitable polyalkylene glycols include polyethylene glycol, polypropylene glycol, polyisopropylene glycol, and combinations thereof. Non-limiting examples of suitable polyalkylene glycol derivatives include ethers of

polyalkylene glycols (e.g., methyl ether of polyisopropylene glycol, diphenyl ether of polyethylene glycol, diethyl ether of polypropylene glycol, etc.), mono- and polycarboxylic esters of polyalkylene glycols, and combinations thereof. In some instances, the polyalkylene glycol or polyalkylene glycol derivative may be used together with other base oils such as poly-alpha-olefins and mineral oils.

[00259] In further embodiments, the base oil comprises any of the esters of dicarboxylic acids

(e.g., phthalic acid, succinic acid, alkyl succinic acids, alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acids, alkenyl malonic acids, and the like) with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol, and the like). Non-limiting examples of these esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, and the like.

[00260] In further embodiments, the base oil comprises a hydrocarbon prepared by the Fischer-

Tropsch process. Fischer-Tropsch process prepares hydrocarbons from gases containing hydrogen and carbon monoxide using a Fischer-Tropsch catalyst. These hydrocarbons may require further processing in order to be useful as base oils. For example, the hydrocarbons may be dewaxed, hydroisomerized, and/or hydrocracked using processes known to a person of ordinary skill in the art.

[00261] In further embodiments, the base oil comprises a refined, unrefined, or rere fined oil.

Unrefined oils are those obtained directly from a natural or synthetic source without further purification treatment. Non-limiting examples of unrefined oils include shale oils obtained directly from retorting operations, petroleum oils obtained directly from primary distillation, and ester oils obtained directly from an esterification process and used without further treatment. Refined oils are similar to the unrefined oils except the former have been further treated by one or more purification processes to improve one or more properties. Many such purification processes are known to those skilled in the art such as solvent extraction, secondary distillation, acid or base extraction, filtration, percolation, and the like. Rerefined oils are obtained by applying to refined oils processes similar to those used to obtain refined oils. Such rerefined oils are also known as reclaimed or reprocessed oils and often are additionally treated by processes directed to removal of spent additives and oil breakdown products.

[00262] Optionally, the lubricant composition may further comprise at least an additive or a modifier (hereinafter designated as "additive") that can impart or improve any desirable property of the lubricant composition. Any additive known to a person of ordinary skill in the art may be used in the lubricant compositions disclosed herein. Some suitable additives have been described in Mortier et al., "Chemistry and Technology of Lubricants 2nd Edition, London, Springer, (1996); and Leslie R.

Rudnick, "Lubricant Additives: Chemistry and Applications ," New York, Marcel Dekker (2003), each of which are incorporated herein by reference. In some embodiments, the additive can be selected from the group consisting of detergents, dispersants, friction modifiers, pour point depressants, demulsifiers, anti- foams, corrosion inhibitors, anti-wear agents, antioxidants, rust inhibitors, and combinations thereof. In general, the concentration of each of the additives in the lubricant composition, when used, can range from about 0.001 to about 20 wt%, from about 0.01 to about 10 wt% or from about 0.1 to about 5 wt%, based on the total weight of the lubricant composition.

[00263] The lubricant composition disclosed herein may comprise a detergent that can control varnish, ring zone deposits, and rust by keeping insoluble particles in colloidal suspension and in some cases, by neutralizing acids. Any detergent known by a person of ordinary skill in the art may be used in the lubricant composition. Non-limiting examples of suitable detergents include metal sulfonates, phenates, salicylates, phosphonates, thiophosphonates and combinations thereof. The metal can be any metal suitable for making sulfonate, phenate, salicylate or phosphonate detergents. Non-limiting examples of suitable metals include alkali metals, alkaline metals and transition metals. In some embodiments, the metal is Ca, Mg, Ba, K, Na, Li or the like. The amount of the detergent may vary from about 0.01 to about 10 wt%, from about 0.05 to about 5 wt%, or from about 0.1 to about 3 wt%, based on the total weight of the lubricant composition. Some suitable detergents have been described in Mortier et al., "Chemistry and Technology of Lubricants " 2nd Edition, London, Springer, Chapter 3, pages 75-85 (1996); and Leslie R. Rudnick, "Lubricant Additives: Chemistry and Applications ," New York, Marcel Dekker, Chapter 4, pages 113-136 (2003), both of which are incorporated herein by reference.

[00264] The lubricant composition disclosed herein may comprise a dispersant that can prevent sludge, varnish, and other deposits by keeping particles suspended in a colloidal state. Any dispersant known by a person of ordinary skill in the art may be used in the lubricant composition. Non-limiting examples of suitable dispersants include succinimides, succiamides, benzylamines, succinate esters, succinate ester-amides, Mannich type dispersants, phosphorus-containing dispersants, boron-containing dispersants and combinations thereof. The amount of the dispersant may vary from about 0.01 to about 10 wt%, from about 0.05 to about 7 wt%, or from about 0.1 to about 4 wt%, based on the total weight of the lubricant composition. Some suitable dispersants have been described in Mortier et al., "Chemistry and Technology of Lubricants " 2nd Edition, London, Springer, Chapter 3, pages 86-90 (1996); and Leslie R. Rudnick, "Lubricant Additives: Chemistry and Applications " New York, Marcel Dekker, Chapter 5, pages 137-170 (2003), both of which are incorporated herein by reference.

[00265] The lubricant composition disclosed herein may comprise a friction modifier that can lower the friction between moving parts. Any friction modifier known by a person of ordinary skill in the art may be used in the lubricant composition. Non-limiting examples of suitable friction modifiers include fatty carboxylic acids; derivatives {e.g., esters, amides, metal salts and the like) of fatty carboxylic acid; mono-, di- or tri-alkyl substituted phosphoric acids or phosphonic acids; derivatives {e.g., esters, amides, metal salts and the like) of mono-, di- or tri-alkyl substituted phosphoric acids or phosphonic acids; mono-, di- or tri-alkyl substituted amines; mono- or di-alkyl substituted amides and combinations thereof. In some embodiments, the friction modifier is selected from the group consisting of aliphatic amines, ethoxylated aliphatic amines, aliphatic carboxylic acid amides, ethoxylated aliphatic ether amines, aliphatic carboxylic acids, glycerol esters, aliphatic carboxylic ester-amides, fatty imidazolines, fatty tertiary amines, wherein the aliphatic or fatty group contains more than about eight carbon atoms so as to render the compound suitably oil soluble. In other embodiments, the friction modifier comprises an aliphatic substituted succinimide formed by reacting an aliphatic succinic acid or anhydride with ammonia or a primary amine. The amount of the friction modifier may vary from about 0.01 to about 10 wt%, from about 0.05 to about 5 wt%, or from about 0.1 to about 3 wt%, based on the total weight of the lubricant composition. Some suitable friction modifiers have been described in Mortier et al., "Chemistry and Technology of Lubricants " 2nd Edition, London, Springer, Chapter 6, pages 183-187 (1996); and Leslie R. Rudnick, "Lubricant Additives: Chemistry and Applications " New York, Marcel Dekker, Chapters 6 and 7, pages 171-222 (2003), both of which are incorporated herein by reference.

[00266] The lubricant composition disclosed herein may comprise a pour point depressant that can lower the pour point of the lubricant composition. Any pour point depressant known by a person of ordinary skill in the art may be used in the lubricant composition. Non-limiting examples of suitable pour point depressants include polymethacrylates, polyacrylates, di(tetra-paraffin phenol)phthalate, condensates of tetra-paraffin phenol, condensates of a chlorinated paraffin with naphthalene and combinations thereof. In some embodiments, the pour point depressant comprises an ethylene -vinyl acetate copolymer, a condensate of chlorinated paraffin and phenol, polyalkyl styrene or the like. The amount of the pour point depressant may vary from about 0.01 to about 10 wt%, from about 0.05 to about 5 wt%, or from about 0.1 to about 3 wt%, based on the total weight of the lubricant composition. Some suitable pour point depressants have been described in Mortier et al., "Chemistry and Technology of Lubricants," 2nd Edition, London, Springer, Chapter 6, pages 187-189 (1996); and Leslie R. Rudnick, "Lubricant Additives: Chemistry and Applications," New York, Marcel Dekker, Chapter 11, pages 329- 354 (2003), both of which are incorporated herein by reference.

[00267] The lubricant composition disclosed herein may comprise a demulsifier that can promote oil-water separation in lubricant compositions that are exposed to water or steam. Any demulsifier known by a person of ordinary skill in the art may be used in the lubricant composition. Non-limiting examples of suitable demulsifiers include anionic surfactants (e.g., alkyl-naphthalene sulfonates, alkyl benzene sulfonates and the like), nonionic alkoxylated alkylphenol resins, polymers of alkylene oxides (e.g., polyethylene oxide, polypropylene oxide, block copolymers of ethylene oxide, propylene oxide and the like), esters of oil soluble acids and combinations thereof. The amount of the demulsifier may vary from about 0.01 to about 10 wt%, from about 0.05 to about 5 wt%, or from about 0.1 to about 3 wt%, based on the total weight of the lubricant composition. Some suitable demulsifiers have been described in Mortier et al., "Chemistry and Technology of Lubricants," 2nd Edition, London, Springer, Chapter 6, pages 190-193 (1996), which is incorporated herein by reference. [00268] The lubricant composition disclosed herein may comprise an anti-foam that can break up foams in oils. Any anti-foam known by a person of ordinary skill in the art may be used in the lubricant composition. Non-limiting examples of suitable anti-foams include silicone oils or

polydimethylsiloxanes, fluorosilicones, alkoxylated aliphatic acids, polyethers (e.g., polyethylene glycols), branched polyvinyl ethers, polyacrylates, polyalkoxyamines and combinations thereof. In some embodiments, the anti-foam comprises glycerol monostearate, polyglycol palmitate, a trialkyl monothiophosphate, an ester of sulfonated ricinoleic acid, benzoylacetone, methyl salicylate, glycerol monooleate, or glycerol dioleate. The amount of the anti-foam may vary from about 0.01 to about 5 wt%, from about 0.05 to about 3 wt%, or from about 0.1 to about 1 wt%, based on the total weight of the lubricant composition. Some suitable anti-foams have been described in Mortier et al., "Chemistry and Technology of Lubricants " 2nd Edition, London, Springer, Chapter 6, pages 190-193 (1996), which is incorporated herein by reference.

[00269] The lubricant composition disclosed herein may comprise a corrosion inhibitor that can reduce corrosion. Any corrosion inhibitor known by a person of ordinary skill in the art may be used in the lubricant composition. Non-limiting examples of suitable corrosion inhibitor include half esters or amides of dodecylsuccinic acid, phosphate esters, thiophosphates, alkyl imidazolines, sarcosines and combinations thereof. The amount of the corrosion inhibitor may vary from about 0.01 to about 5 wt%, from about 0.05 to about 3 wt%, or from about 0.1 to about 1 wt%, based on the total weight of the lubricant composition. Some suitable corrosion inhibitors have been described in Mortier et al., "Chemistry and Technology of Lubricants 2nd Edition, London, Springer, Chapter 6, pages 193-196 (1996), which is incorporated herein by reference.

[00270] The lubricant composition disclosed herein may comprise an anti-wear agent that can reduce friction and excessive wear. Any anti-wear agent known by a person of ordinary skill in the art may be used in the lubricant composition. Non-limiting examples of suitable anti-wear agents include zinc dithiophosphate, metal (e.g., Pb, Sb, Mo and the like) salts of dithiophosphate, metal (e.g., Zn, Pb, Sb, Mo and the like) salts of dithiocarbamate, metal (e.g., Zn, Pb, Sb and the like) salts of fatty acids, boron compounds, phosphate esters, phosphite esters, amine salts of phosphoric acid esters or thiophosphoric acid esters, reaction products of dicyclopentadiene and thiophosphoric acids and combinations thereof. The amount of the anti-wear agent may vary from about 0.01 to about 5 wt%, from about 0.05 to about 3 wt%, or from about 0.1 to about 1 wt%, based on the total weight of the lubricant composition. Some suitable anti-wear agents have been described in Leslie R. Rudnick, "Lubricant Additives: Chemistry and Applications " New York, Marcel Dekker, Chapter 8, pages 223- 258 (2003), which is incorporated herein by reference.

[00271] The lubricant composition disclosed herein may comprise an extreme pressure (EP) agent that can prevent sliding metal surfaces from seizing under conditions of extreme pressure. Any extreme pressure agent known by a person of ordinary skill in the art may be used in the lubricant composition. Generally, the extreme pressure agent is a compound that can combine chemically with a metal to form a surface film that prevents the welding of asperities in opposing metal surfaces under high loads. Non-limiting examples of suitable extreme pressure agents include sulfurized animal or vegetable fats or oils, sulfurized animal or vegetable fatty acid esters, fully or partially esterified esters of trivalent or pentavalent acids of phosphorus, sulfurized olefins, dihydrocarbyl polysulfides, sulfurized Diels-Alder adducts, sulfurized dicyclopentadiene, sulfurized or co-sulfurized mixtures of fatty acid esters and monounsaturated olefins, co-sulfurized blends of fatty acid, fatty acid ester and alpha-olefin,

functionally-substituted dihydrocarbyl polysulfides, thia-aldehydes, thia-ketones, epithio compounds, sulfur-containing acetal derivatives, co-sulfurized blends of terpene and acyclic olefins, and polysulfide olefin products, amine salts of phosphoric acid esters or thiophosphoric acid esters and combinations thereof. The amount of the extreme pressure agent may vary from about 0.01 to about 5 wt%, from about 0.05 to about 3 wt%, or from about 0.1 to about 1 wt%, based on the total weight of the lubricant composition. Some suitable extreme pressure agents have been described in Leslie R. Rudnick,

"Lubricant Additives: Chemistry and Applications " New York, Marcel Dekker, Chapter 8, pages 223- 258 (2003), which is incorporated herein by reference.

[00272] The lubricant composition disclosed herein may comprise an antioxidant that can reduce or prevent the oxidation of the base oil. Any antioxidant known by a person of ordinary skill in the art may be used in the lubricant composition. Non-limiting examples of suitable antioxidants include amine- based antioxidants {e.g., alkyl diphenylamines, phenyl-a- naphthylamine, alkyl or aralkyl substituted phenyl-a-naphthylamine, alkylated p-phenylene diamines, tetramethyl-diaminodiphenylamine and the like), phenolic antioxidants {e.g., 2-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 2,4,6-tri-tert- butylphenol, 2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butylphenol, 4,4'-methylenebis-(2,6-di-fert- butylphenol), 4,4'-thiobis(6-di-tert-butyl-o-cresol) and the like), sulfur-based antioxidants {e.g., dilauryl- 3,3'-thiodipropionate, sulfurized phenolic antioxidants and the like), phosphorous-based antioxidants {e.g. , phosphites and the like), zinc dithiophosphate, oil-soluble copper compounds and combinations thereof. The amount of the antioxidant may vary from about 0.01 to about 10 wt %, from about 0.05 to about 5%, or from about 0.1 to about 3%, based on the total weight of the lubricant composition. Some suitable antioxidants have been described in Leslie R. Rudnick, "Lubricant Additives: Chemistry and Applications," New York, Marcel Dekker, Chapter 1, pages 1-28 (2003), which is incorporated herein by reference.

[00273] The lubricant composition disclosed herein may comprise a rust inhibitor that can inhibit the corrosion of ferrous metal surfaces. Any rust inhibitor known by a person of ordinary skill in the art may be used in the lubricant composition. Non-limiting examples of suitable rust inhibitors include oil- soluble monocarboxylic acids {e.g., 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, behenic acid, cerotic acid and the like), oil-soluble polycarboxylic acids (e.g., those produced from tall oil fatty acids, oleic acid, linoleic acid and the like), alkenylsuccinic acids in which the alkenyl group contains 10 or more carbon atoms (e.g., tetrapropenylsuccinic acid, tetradecenylsuccinic acid, hexadecenylsuccinic acid, and the like); long-chain alpha,omega-dicarboxylic acids having a molecular weight in the range of 600 to 3000 daltons and combinations thereof. The amount of the rust inhibitor may vary from about 0.01 to about 10 wt %, from about 0.05 to about 5%, or from about 0.1 to about 3%, based on the total weight of the lubricant composition.

[00274] The additives may be in the form of an additive concentrate having more than one additive. The additive concentrate may comprise a suitable diluent, most preferably a hydrocarbon oil of suitable viscosity. Such diluent can be selected from the group consisting of natural oils (e.g., mineral oils), synthetic oils and combinations thereof. Non-limiting examples of the mineral oils include paraffin-based oils, naphthenic-based oils, asphaltic-based oils and combinations thereof. Non-limiting examples of the synthetic base oils include polyolefin oils (especially hydrogenated alpha-olefin oligomers), alkylated aromatic, polyalkylene oxides, aromatic ethers, and carboxylate esters (especially diester oils) and combinations thereof. In some embodiments, the diluent is a light hydrocarbon oil, both natural or synthetic. Generally, the diluent oil can have a viscosity in the range of 13 to 35 centistokes at 40°C.

[00275] The lubricant composition disclosed herein may be suitable for use as motor oils (or engine oils or crankcase oils), transmission fluids, gear oils, power steering fluids, shock absorber fluids, brake fluids, hydraulic fluids and/or greases.

[00276] In some embodiments, the lubricant composition disclosed herein is a motor oil. Such a motor oil composition may be used to lubricate all major moving parts in any reciprocating internal combustion engine, reciprocating compressors and in steam engines of crankcase design. In automotive applications, the motor oil composition may also be used to cool hot engine parts, keep the engine free of rust and deposits, and seal the rings and valves against leakage of combustion gases. The motor oil composition may comprise a base oil and the Diels-Alder adduct disclosed herein. The motor oil composition may further comprise at least an additive. In some embodiments, the motor oil composition further comprises a pour point depressant, a detergent, a dispersant, an anti-wear, an antioxidant, a friction modifier, a rust inhibitor, or a combination thereof.

[00277] In other embodiments, the lubricant composition disclosed herein is a gear oil for either automotive or industrial applications. The gear oil composition may be used to lubricate gears, rear axles, automotive transmissions, final drive axles, accessories in agricultural and construction equipment, gear housings and enclosed chain drives. The gear oil composition may comprise a base oil and the Diels-Alder adduct disclosed herein. The gear oil composition may further comprise at least an additive. In some embodiments, the gear oil composition further comprises an anti-wear, an extreme pressure agent, a rust inhibitor, or a combination thereof. [00278] In further embodiments, the lubricant composition disclosed herein is a transmission fluid. The transmission fluid composition may be used in either automatic transmission or manual transmission to reduce transmission losses. The transmission fluid composition may comprise a base oil and the Diels-Alder adduct disclosed herein. The transmission fluid composition may further comprise at least an additive. In some embodiments, the transmission fluid composition further comprises a friction modifier, a detergent, a dispersant, an antioxidant, an anti-wear agent, an extreme pressure agent, a pour point depressant, an anti-foam, a corrosion inhibitor or a combination thereof.

[00279] In further embodiments, the lubricant composition disclosed herein is a grease used in various applications where extended lubrication is required and where oil would not be retained, e.g., on a vertical shaft. The grease composition may comprise a base oil, the Diels-Alder adduct disclosed herein and a thickener. In some embodiments, the grease composition further comprise a complexing agent, an antioxidant, an anti-wear agent, an extreme pressure agent, an anti-foam, a corrosion inhibitor or a mixture thereof. In some embodiments, the thickener is a soap formed by reacting a metal hydroxide (e.g., lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, zinc hydroxide and the like) with a fat, a fatty acid, or an ester. In general, the type of soap used depends on the grease properties desired. In other embodiments, the thickener may be a non-soap thickener selected from the group consisting of clays, silica gels, carbon black, various synthetic organic materials and combinations thereof. In further embodiments, the thickener comprises a combination of soaps and non-soap thickeners.

[00280] The lubricant compositions disclosed herein can be prepared by any method known to a person of ordinary skill in the art for making lubricating oils. In some embodiments, the base oil can be blended or mixed with the Diels-Alder adduct disclosed herein and optionally at least an additive. The Diels-Alder adduct disclosed herein and the optional additives may be added to the base oil individually or simultaneously. In some embodiments, the Diels-Alder adduct disclosed herein and the optional additives are added to the base oil individually in one or more additions and the additions may be in any order. In other embodiments, the Diels-Alder adduct disclosed herein and the additives are added to the base oil simultaneously, optionally in the form of an additive concentrate. In some embodiments, the solubilizing of the Diels-Alder adduct disclosed herein or any solid additives in the base oil may be assisted by heating the mixture to a temperature between about 25 and about 200°C, from about 50 and about 150°C or from about 75 and about 125°C.

[00281] Any mixing or dispersing equipment known to a person of ordinary skill in the art may be used for blending, mixing or solubilizing the ingredients. The blending, mixing or solubilizing may be carried out with a blender, an agitator, a disperser, a mixer (e.g., Ross double planetary mixers and Collette planetary mixers), a homogenizer (e.g., Gaulin homogeneizers and Rannie homogenizers), a mill (e.g., colloid mill, ball mill and sand mill) or any other mixing or dispersing equipment known in the art. [00282] "Viscosity index" as used herein refers to viscosity index as measured according to

ASTM D2270-10el "Standard Practice for Calculating Viscosity Index From Kinematic Viscosity at 40 and 100°C," published by ASTM International, which is incorporated herein by reference in its entirety.

[00283] Kinematic viscosities at 40°C and at 100°C are measured according to ASTM D445-12

"Standard Test Method for Kinematic Viscosity of Transparent and Opaque Liquids (and Calculation of Dynamic Viscosity)," published by ASTM International, which is incorporated herein by reference in its entirety.

[00284] "Pour point" is measured according to ASTM D97- 11 "Standard Test Method for Pour

Point of Petroleum Products," published by ASTM International, which is incorporated herein by reference in its entirety.

[00285] In some embodiments, the Diels-Alder adducts can be formulated for use in the following lubricant applications described below.

[00286] Engine oils. Diels-Alder adducts comprising ester functionality and having low volatility, high viscosity index, clean burning, and high lubricity may be used in automotive applications. In some cases, a PAO is blended with a Diels-Alder adduct comprising ester functionality (e.g., a diester), with the ester present at about 5%-50%, 5%-40%, 5%-30%, 5%-20%, or 5%-10% to make a lubricant useful in automotive applications.

[00287] Organic friction modifiers. A Diels-Alder adduct comprising a nonpolar hydrocarbon chain and a polar group as described herein may be used as a friction modifier. For example, a Diels- Alder adduct comprising one or two ester groups and/or one or two amide groups may be used as a friction modifier. In some variations, a Diels-Alder adduct comprising one or two ester groups and/or one or two amide groups may be used in combination with one or more organometallic compounds as a friction modifier. Non-limiting examples of suitable organometallic compounds include oil-soluble titanium compounds, oil-soluble organo-molybdenum compounds (e.g., molybdenum dithiocarbamate) and oil-soluble organo-tungsten compounds.

[00288] Two stroke oils. A Diels-Alder adduct as described herein (e.g., a Diels-Alder adduct comprising one or two ester groups) may be used in a two stroke oil, e.g., to replace mineral oil as lubricant component of a conventional two stroke oil. Use of Diels-Alder adducts comprising one or more ester groups may provide increased lubricity because of polar groups interaction with metal. In some variations, use of Diels-Alder adducts containing one or more ester groups in a lubricant formulation may remove or reduce a need to use brightstock. In some variations, a two stroke oil may be formulated with a Diels-Alder described herein without use of a solvent.

[00289] Metal working fluids. The Diels-Alder adducts (e.g., those comprising one or more ester groups or one or more carboxyl groups) may be used as metal working fluids in a variety of applications, such as steel rolling, aluminum drawing and cutting oils. A metal working fluid may perform a variety of functions, including emulsification, metal complexing agent, solubilizing sludge and the like, and adding lubricity between the metal and a working tool. An ester-containing Diels-Alder adduct may be used as a metal working fluid in some variations. A carboxyl group containing Diels-Alder adduct may be used as a metal working fluid in some variations. In some variations, a Diels-Alder adduct between a conjugated terpene (e.g., farnesene) and itaconic acid derived from renewable sources is used as a metal working fluid. In other variations, an ester-containing Diels-Alder adduct may be used as an additive in a metal working fluid, e.g., where the Diels-Alder adduct is present at about 5%-50%, about 5%-40%, about 5%- 30%, about 5%-20%, or about 5%-10%. The ester-containing Diels-Alder adducts may be selected to function as boundary lubricants, as friction modifiers, and to demonstrate sufficient wetting ability to penetrate between tool and work piece. In some variations, ester-containing Diels-Alder adducts may be used as quench fluids. Other suitable applications for the Diels-Alder adducts (e.g., ester-containing Diels-Alder adducts) include in air compressors and refrigerants, to lubricate and reduce friction between moving parts, function at oil seal at rings, screws, and the like, and to cool bearings and points of friction. In some variations, a Diels-Alder adduct (e.g., an ester-containing Diels-Alder adduct) may be used as a high temperature chain oil, e.g., in factories, roller chains, sliding chains, and the like.

[00290] Base oil for grease. In some variations, an ester-containing Diels-Alder adduct is used as an ester as a base oil for grease.

[00291] Drilling fluid. In some variations, a Diels-Alder adduct (e.g., an ester-containing Diels-

Alder adduct) is used as a base fluid added to drilling mud, where the Diels-Alder adduct functions to cool and lubricate the drill bit and to bring cuttings to the surface. Diels-Alder adducts that do not contain aromatic groups may be used to lower accumulation of undesired aromatic species during drilling.

[00292] Dielectric fluid. In some variations, a Diels-Alder adduct (e.g., an ester-containing

Diels-Alder adduct) may be used to replace some or all mineral oil in a dielectric fluid in transformers, capacitors, and the like. Select Diels-Alder adducts may demonstrate resistance to discharge and high permittivity, and low moisture content.

[00293] Non-limiting examples of ester-containing lubricants are provided in Examples 41-47.

One non-limiting example of a Diels-Alder adduct between b-farnesene and 1 ,4-benzoquinone is provided in Example 48.

[00294] It should be understood that lubricants and lubricant additives may be made from conjugated hydrocarbon terpenes that are not farnesene. In some variations, the conjugated terpene used to make a Diels-Alder adduct useful as a lubricant or lubricant additive is myrcene. In some variations, the conjugated terpene used to make a Diels-Alder adduct useful as a lubricant or lubricant additive is not myrcene or farnesene, and may for example be any of the Cio-C₃₀ conjugated hydrocarbon terpenes described herein, or any other conjugated hydrocarbon terpene otherwise known in the art.

(J-II) Polymers

[00295] The Diels-Alder adducts disclosed herein comprising one or more functional groups, such as one or more anhydride groups or two or more epoxy groups, may be used as comonomers for making addition polymers (e.g., epoxy resins) or a condensation polymer (e.g., polyesters or polyamides).

[00296] In some embodiments, the Diels-Alder adduct having formula (J-XVA) or (J-XVB):

where n is 1 , 2, 3 or 4,

can be used to react with a diol to form a polyester or with a diamine to form a polyamide or with a dithiol to form a polythioester. Non-limiting examples of suitable diols include 2,2'-bi-7-naphtol, 1,4- dihydroxybenzene, 1,3 dihydroxybenzene, 10,10 bis(4 hydroxyphenyl)anthrone, 4,4'-sulfonyldiphenol, bisphenol, 4,4' (9 fluorenylidene)diphenol, 1,10-decanediol, 1,5-pentanediol, diethylene glycol, 4,4' -(9- fluorenylidene)-bis(2-phenoxyethanol), bis(2 hydroxyethyl) terephthalate, bis[4 (2- hydroxyethoxy)phenyl] sulfone, hydroquinone-bis (2-hydroxyethyl)ether, and bis(2 -hydroxyethyl) piperazine. Non- limiting examples of suitable diamine include diaminoarenes such as 1 ,4- phenylenediamine, 4,4-diaminobenzophenone and 4,4-diaminodiphenyl sulfone, and diaminoalkanes such as 1 ,2-ethanediamine and 1 ,4-butanediamine, dibenzo[b,d]furan-2,7-diamine, and 3,7-diamino- 2(4),8-dimethyldibenzothiophene 5,5-dioxide. Non-limiting examples of suitable dithiol include 3,6- dioxa-l,8-octanedithiol, erythro-l,4-dimercapto-2,3-butanediol, (±)-threo-l,4-dimercapto-2,3-butanediol, 4,4'-thiobisbenzenethiol, 1,4 benzenedithiol, 1,3-benzenedithiol, sulfonyl-bis(benzenethiol), 2,5 dimecapto 1,3,4 thiadiazole, 1 ,2-ethanedithiol, 1,3-propanedithiol, 1 ,4-butanedithiol, 2,3-butanedithiol, 1,5-pentanedithiol, and 1,6-hexanedithiol.

[00297] In certain embodiments, the Diels-Alder adduct having formula (J-XVIA) or (J-XVIB):

where n is 1, 2, 3 or 4; and R¹¹, R¹², R¹³ and R¹⁴ are as defined herein, can be used to react with a diamine to form an epoxy resin. Non-limiting examples of suitable diamine include diaminoarenes such as 1 ,4- phenylenediamine, 4,4-diaminobenzophenone and 4,4-diaminodiphenyl sulfone, and diaminoalkanes such as 1 ,2-ethanediamine and 1 ,4-butanediamine, dibenzo[b,d]furan-2,7-diamine, and 3,7-diamino- 2(4),8-dimethyldibenzothiophene 5,5-dioxide.

[00298] In some embodiments, the Diels-Alder adduct as described herein comprises one or more functional groups suitable for making an addition polymer or a condensation polymer such as a polyester or a polyamide. For example, X_CHT and/or Y_DP may be functionalized with one or more hydroxy groups and/or ester groups that are used to make a polyester. In some embodiments, a Diels-Alder adduct as described herein is used to make an alkyd polymer, without the need for adding in an additional oil because X_CHT may provide sufficient oily properties. In some embodiments, X_CHT and/or Y_DP may be functionalized with one or more hydroxyl groups and/or amide groups to make a polyamide.

[00299] In some embodiments, a Diels-Alder adduct between β-farnesene and a dienophile is a monomer that undergoes co-polymerization with one or more co-monomers to make a polymer. The nature of the polymerization reaction and type and relative amounts of one or more co-monomers may be selected to tune one or more physical properties of the resulting polymer. For example, polymerization conditions favorable to the formation of block copolymers may be selected in one instance, and polymerization conditions favorable to the formation of random copolymers may be selected in another instance. In one embodiments, a conjugated terpene Diels-Alder adduct replaces an acid anhydride, a carboxylic acid, an amine, and/or a polyol in a polymerization reaction, e.g., in a condensation polymerization reaction. For example, a β-farnesene Diels-Alder adduct can replace an acid anhydride, a carboxylic acid and/or a polyol to make a polyester, or a β-farnesene Diels-Alder adduct can replace an acid anhydride, a carboxylic acid, or an amine to make a polyamide.

[00300] In one example, a Diels-Alder adduct that includes an anhydride moieity is used as a monomer that undergoes a condensation reaction with a polyol to make an unsaturated polyester resin, or an alkyd resin. In some variations, unsaturated polyester resins or alkyd resins are useful as coatings. Optionally, one or more fatty acids may be co-reacted with the polyol and the anhydride-containing adduct to make an alkyd resin. In some circumstances, the aliphatic tail originating from the hydrocarbon terpene may provide sufficient long chain hydrocarbon functionality to the resulting resin so a fatty acid is not used. In some embodiments, the polyol used to make an alkyd resin is glycerine.

[00301] In one example, a Diels-Alder adduct that includes an anhydride moiety is useful as a paper sizing agent, e.g., for cellulose-containing papers. The hydrophilic head of the Diels-Alder adduct may interact with cellulose fibers to provide cohesion, and the hydrophobic tail originating from the conjugated terpene may provide printability and water resistance. The hydrocarbon terpene used in such applications may in some paper sizing applications be β-farnesene or a-farnesene. However, other conjugated hydrocarbon terpenes described herein or otherwise known may be used. Any of the anhydride -containing adducts described herein may be used for paper sizing applications, e.g., maleic anhydride and substituted maleic anhydrides, citraconic anhydride and substituted citraconic anhydrides, itaconic acid and substituted itaconic acids, itaconic anhydride and substituted itaconic anhydrides.

[00302] In some embodiments, Diels-Alder adducts described herein have utility as cross-linking agents, curing agents, or as reactive diluents for resins. In some embodiments, the cross-linking agents, curing agents comprise epoxidized farnesene, epoxidized dimers of farnesene, epoxidized oligomers of farnesene, epoxidized Diels-Alder adducts of farnesene, and epoxidized Diels-Alder adducts of conjugated terpenes other than farnesene. In some embodiments, epoxidized farnesene or epoxidized Diels-Alder adducts of farnesene have utility as UV-cured cross-linking agents or curing agents. In some embodiments, epoxidized farnesene or epoxidized derivatives of farnesene have utility as multifunctional cross linking agents, e.g., comprising reactive sites that can undergo addition reactions, and reactive sites that can undergo hydrogen abstraction and subsequent cross-linking.

[00303] The polymers derived from the Diels-Alder adducts disclosed herein can be used to prepare useful polymer compositions for various applications. In some embodiments, the polymer compositions comprise the polymer derived from the Diels-Alder adducts and optionally one or more additives.

[00304] Optionally, the compositions disclosed herein comprise at least one additive for the purposes of improving and/or controlling the processibility, appearance, physical, chemical, and/or mechanical properties of the polymer compositions. In some embodiments, the compositions do not comprise an additive. Any plastics additive known to a person of ordinary skill in the art may be used in the compositions disclosed herein. Non-limiting examples of suitable additives include plasticizers, oils, waxes, antioxidants, UV stabilizers, colorants or pigments, fillers, tackifier, flow aids, coupling agents, crosslinking agents, surfactants, solvents, and combinations thereof. In certain embodiments, the additive is plasticizer, such as a mineral oil, liquid polybutene or a combination thereof.

[00305] The total amount of the additives can range from about greater than 0 to about 80%, from about 0.001 % to about 70%, from about 0.01 % to about 60%, from about 0.1 % to about 50%, from about 1 % to about 40%>, or from about 10 % to about 50%> of the total weight of the polymer composition. The amount of each of the additives can range from about greater than 0 to about 25%, from about 0.001 % to about 20%, from about 0.01 % to about 15%, from about 0.1 % to about 10%, from about 0.1 % to about 5%>, or from about 0.1 % to about 2.5%> of the total weight of the polymer composition. Some polymer additives have been described in Zweifel Hans et al., "Plastics Additives Handbook Hanser Gardner Publications, Cincinnati, Ohio, 5th edition (2001), which is incorporated herein by reference in its entirety.

[00306] Optionally, the compositions disclosed herein can comprise a wax, such as a petroleum wax, a low molecular weight polyethylene or polypropylene, a synthetic wax, a polyolefin wax, a beeswax, a vegetable wax, a soy wax, a palm wax, a candle wax or an ethylene/a-olefin interpolymer having a melting point of greater than 25 °C. In certain embodiments, the wax is a low molecular weight polyethylene or polypropylene having a number average molecular weight of about 400 to about 6,000 g/mole. The wax can be present in the range from about 10% to about 50%> or 20%> to about 40%> by weight of the total composition.

[00307] Optionally, the compositions disclosed herein can comprise a plasticizer. In general, a plasticizer is a chemical that can increase the flexibility and lower the glass transition temperature of polymers. Any plasticizer known to a person of ordinary skill in the art may be added to the polymer compositions disclosed herein. Non-limiting examples of plasticizers include mineral oils, abietates, adipates, alkyl sulfonates, azelates, benzoates, chlorinated paraffins, citrates, epoxides, glycol ethers and their esters, glutarates, hydrocarbon oils, isobutyrates, oleates, pentaerythritol derivatives, phosphates, phthalates, esters, polybutenes, ricinoleates, sebacates, sulfonamides, tri- and pyromellitates, biphenyl derivatives, stearates, difuran diesters, fluorine -containing plasticizers, hydroxybenzoic acid esters, isocyanate adducts, multi-ring aromatic compounds, natural product derivatives, nitriles, siloxane-based plasticizers, tar-based products, thioesters and combinations thereof. Where used, the amount of the plasticizer in the polymer composition can be from greater than 0 to about 15 wt.%, from about 0.5 wt.% to about 10 wt.%), or from about 1 wt.% to about 5 wt.% of the total weight of the polymer composition. Some plasticizers have been described in George Wypych, "Handbook of Plasticizers " ChemTec Publishing, Toronto-Scarborough, Ontario (2004), which is incorporated herein by reference.

[00308] In some embodiments, the compositions disclosed herein optionally comprise an antioxidant that can prevent the oxidation of polymer components and organic additives in the polymer compositions. Any antioxidant known to a person of ordinary skill in the art may be added to the polymer compositions disclosed herein. Non-limiting examples of suitable antioxidants include aromatic or hindered amines such as alkyl diphenylamines, phenyl-a- naphthylamine, alkyl or aralkyl substituted phenyl-a-naphthylamine, alkylated p-phenylene diamines, tetramethyl-diaminodiphenylamine and the like; phenols such as 2,6-di-t-butyl-4-methylphenol; l,3,5-trimethyl-2,4,6-tris(3',5'-di-t-butyl-4'- hydroxybenzyl)benzene; tetrakis[(methylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)]methane {e.g., IRGANOX™ 1010, from Ciba Geigy, New York); acryloyl modified phenols; octadecyl-3,5-di-t-butyl- 4-hydroxycinnamate {e.g., IRGANOX™ 1076, commercially available from Ciba Geigy); phosphites and phosphonites; hydroxylamines; benzofuranone derivatives; and combinations thereof. Where used, the amount of the antioxidant in the polymer composition can be from about greater than 0 to about 5 wt.%, from about 0.0001 to about 2.5 wt.%, from about 0.001 wt.% to about 1 wt.%, or from about 0.001 wt.% to about 0.5 wt.%) of the total weight of the polymer composition. Some antioxidants have been described in Zweifel Hans et al., "Plastics Additives Handbook " Hanser Gardner Publications,

Cincinnati, Ohio, 5th edition, Chapter 1, pages 1-140 (2001), which is incorporated herein by reference. [00309] In other embodiments, the compositions disclosed herein optionally comprise an UV stabilizer that may prevent or reduce the degradation of the polymer compositions by UV radiations. Any UV stabilizer known to a person of ordinary skill in the art may be added to the polymer compositions disclosed herein. Non-limiting examples of suitable UV stabilizers include

benzophenones, benzotriazoles, aryl esters, oxanilides, acrylic esters, formamidines, carbon black, hindered amines, nickel quenchers, hindered amines, phenolic antioxidants, metallic salts, zinc compounds and combinations thereof. Where used, the amount of the UV stabilizer in the polymer composition can be from about greater than 0 to about 5 wt.%, from about 0.01 wt.% to about 3 wt.%, from about 0.1 wt.% to about 2 wt.%, or from about 0.1 wt.% to about 1 wt.% of the total weight of the polymer composition. Some UV stabilizers have been described in Zweifel Hans et al., "Plastics Additives Handbook " Hanser Gardner Publications, Cincinnati, Ohio, 5th edition, Chapter 2, pages 141- 426 (2001), which is incorporated herein by reference.

[00310] In further embodiments, the compositions disclosed herein optionally comprise a colorant or pigment that can change the look of the polymer compositions to human eyes. Any colorant or pigment known to a person of ordinary skill in the art may be added to the polymer compositions disclosed herein. Non-limiting examples of suitable colorants or pigments include inorganic pigments such as metal oxides such as iron oxide, zinc oxide, and titanium dioxide, mixed metal oxides, carbon black, organic pigments such as anthraquinones, anthanthrones, azo and monoazo compounds, arylamides, benzimidazolones, BONA lakes, diketopyrrolo-pyrroles, dioxazines, disazo compounds, diarylide compounds, flavanthrones, indanthrones, isoindolinones, isoindolines, metal complexes, monoazo salts, naphthols, β-naphthols, naphthol AS, naphthol lakes, perylenes, perinones,

phthalocyanines, pyranthrones, quinacridones, and quinophthalones, and combinations thereof. Where used, the amount of the colorant or pigment in the polymer composition can be from about greater than 0 to about 10 wt.%), from about 0.1 wt.% to about 5 wt.%, or from about 0.25 wt.% to about 2 wt.% of the total weight of the polymer composition. Some colorants have been described in Zweifel Hans et al., "Plastics Additives Handbook," Hanser Gardner Publications, Cincinnati, Ohio, 5th edition, Chapter 15, pages 813-882 (2001), which is incorporated herein by reference.

[00311] Optionally, the compositions disclosed herein can comprise a filler which can be used to adjust, inter alia, volume, weight, costs, and/or technical performance. Any filler known to a person of ordinary skill in the art may be added to the polymer compositions disclosed herein. Non-limiting examples of suitable fillers include talc, calcium carbonate, chalk, calcium sulfate, clay, kaolin, silica, glass, fumed silica, mica, wollastonite, feldspar, aluminum silicate, calcium silicate, alumina, hydrated alumina such as alumina trihydrate, glass microsphere, ceramic microsphere, thermoplastic microsphere, barite, wood flour, glass fibers, carbon fibers, marble dust, cement dust, magnesium oxide, magnesium hydroxide, antimony oxide, zinc oxide, barium sulfate, titanium dioxide, titanates and combinations thereof. In some embodiments, the filler is barium sulfate, talc, calcium carbonate, silica, glass, glass fiber, alumina, titanium dioxide, or a mixture thereof. In other embodiments, the filler is talc, calcium carbonate, barium sulfate, glass fiber or a mixture thereof. Where used, the amount of the filler in the polymer composition can be from about greater than 0 to about 80 wt.%, from about 0.1 wt.% to about 60 wt.%), from about 0.5 wt.% to about 40 wt.%, from about 1 wt.% to about 30 wt.%, or from about 10 wt.%) to about 40 wt.% of the total weight of the polymer composition. Some fillers have been disclosed in U.S. Patent No. 6,103,803 and Zweifel Hans et al., "Plastics Additives Handbook " Hanser Gardner Publications, Cincinnati, Ohio, 5th edition, Chapter 17, pages 901-948 (2001), both of which are incorporated herein by reference.

[00312] Optionally, the polymer compositions disclosed herein may be crosslinked, partially or completely. When crosslinking is desired, the polymer compositions disclosed herein comprise a cross- linking agent that can be used to effect the cross-linking of the polymer compositions, thereby increasing their modulus and stiffness, among other things. An advantage of a polymer composition is that crosslinking can occur in its side chains instead of the polymer backbone like other polymers such as polyisoprene and polybutadiene. Any cross-linking agent known to a person of ordinary skill in the art may be added to the polymer compositions disclosed herein. Non-limiting examples of suitable crosslinking agents include organic peroxides {e.g., alkyl peroxides, aryl peroxides, peroxyesters, peroxycarbonates, diacylperoxides, peroxyketals, and cyclic peroxides) and silanes {e.g.,

vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, vinyltriacetoxysilane, vinylmethyldimethoxysilane, and 3-methacryloyloxypropyltrimethoxysilane). Where used, the amount of the cross-linking agent in the polymer composition can be from about greater than 0 to about 20 wt.%, from about 0.1 wt.% to about 15 wt.%, or from about 1 wt.% to about 10 wt.% of the total weight of the polymer composition. Some suitable cross-linking agents have been disclosed in Zweifel Hans et al., "Plastics Additives Handbook,'' Hanser Gardner Publications, Cincinnati, Ohio, 5th edition, Chapter 14, pages 725-812 (2001), both of which are incorporated herein by reference.

[00313] The cross-linking of the polymer compositions can also be initiated by any radiation means known in the art, including, but not limited to, electron-beam irradiation, beta irradiation, gamma irradiation, corona irradiation, and UV radiation with or without cross-linking catalyst. U.S. Patent Application No. 10/086,057 (published as US2002/0132923 Al) and U.S. Patent No. 6,803,014 disclose electron-beam irradiation methods that can be used in embodiments of the invention.

[00314] In some variations, Diels-Alder adducts described herein function as cross-linking agents or as curing agents in polymer systems. For example, any of the Diels-Alder adducts containing one or more epoxy groups, hydroxyl groups, acid groups, and/or unsaturated double bonds may function as cross-linking agents, e.g., in epoxy and/or polyester coatings, or in structural materials requiring crosslinking for increased mechanical strength or solvent resistance. Any of the Diels-Alder adducts described herein containing one or more epoxy groups may function as an epoxy curing agent, or as a UV curing agent. A Diels-Alder adduct used as a UV curing agent may be used with or without a photosensitizer. As described herein, it is possible to tune UV absorption of Diels-Alder adducts by increasing conjugation, which may allow the Diels-Alder adducts to be used as a UV curing agent without a photosensitizer in some applications. In some variations, an unsaturated Diels-Alder adduct containing epoxy groups may have utility as a multi-functional cross-linker in UV cured cationic epoxy systems in which the unsaturated ethylenic bonds are reactive and the epoxy groups are reactive and able to crosslink with acids, amines, and the like.

[00315] In some variations, a polyol formed from a Diels-Alder adduct as described herein may be used as a cross-linker and/or monomer in a polymer resin (e.g., a polyurethane or polyester). A polyol formed from a Diels-Alder adduct may be used in polymer formulations to enhance hardness, mechanical performance, and/or increase solvent resistance.

[00316] In some variations, an unsaturated Diels-Alder adduct formed between a conjugated hydrocarbon terpene (e.g., famesene) and an acrylate ester may be used as a renewable starch bioplastic modifier. The ester function on the Diels-Alder adduct may react with hydroxyl groups in starch, and unsaturated ethylenic bonds on the adduct may react with other unsaturated monomers.

[00317] It should be understood that monomers, cross-linking agents, curing agents, and reactive diluents may be made from conjugated hydrocarbon terpenes that are not famesene. In some variations, the conjugated terpene used to make a Diels-Alder adduct useful as a monomer, cross-linking agent, or reactive diluent is myrcene. In some variations, the conjugated terpene used to make a Diels-Alder adduct useful as a monomer, cross-linking agent, or reactive diluent is not myrcene or famesene, and may for example be any of the Cio-C₃₀ conjugated hydrocarbon terpenes described herein, or any other conjugated hydrocarbon terpene otherwise known in the art.

J-III) Plasticizers

[00318] In some embodiments, a Diels-Alder adduct (which includes any Diels-Alder adduct that has undergo post-Diels-Alder reaction modification) between a conjugated terpene and a dienophile is incorporated into a polymer to plasticize the polymer. In some embodiments, the conjugated terpene is β -famesene. In some embodiments, the conjugated terpene is a-famesene. In certain embodiments, the dienophile is selected from maleic anhydride and substituted maleic anhydrides, citraconic anhydride and substituted citraconic anhydrides, itaconic acid and substituted itaconic acids, itaconic anhydride and substituted itaconic anhydrides, acrolein and substituted acroleins, crotonaldehyde and substituted crotonaldehydes, monoalkyl and dialkyl maleates, monoalkyl and dialkyl fumarates, monoalkyl and dialkyl itaconates, acrylic acid esters, methacrylic acid esters, cinnamic acid esters, mesityl oxide and substituted mesityl oxides, hydroxyalkyl acrylates, carboxyalkyl acrylates, (dialkylamino)alkyl acrylates, dialkyl acetylene dicarboxylates, vinyl ketones, maleimide and substituted maleimides, fumaramide and substituted fumaramides, dialkyl azidocarboxylates, acetylene dicarboxylic acid, dialkyl acetylene dicarboxylates, 1 ,4-benzoquinone and substituted 1 ,4-benzoquinones, 1 ,2-benzoquinone and substituted 1 ,2-benzoquinones, sulfur dioxide, naphthoquinones, phosphorus trihalide and combinations thereof.

[00319] A plasticizer as used herein refers to a compound that can be added to a host polymer

(thermoplastics, thermosets, or elastomers), polymer blends, polymer composites, synthetic rubbers, natural rubbers, or other resins (individually and collectively referred to "resin" or "resins" herein) to lower glass transition temperature or melt temperature, increase flexibility, increase toughness, increase elasticity, decrease rigidity, improve low temperature brittleness, and/or improve processibility of the host polymer. For example, a plasticizer may act to modify any one of or any combination of glass transition temperature, melt temperature, tensile properties (e.g., toughness, % elongation at break, load at break, displacement at break, Young's modulus), flexural properties, impact resistance, extrudability, flexibility, processability, workability, stretchability, and improve a low temperature brittleness or low temperature strength. In some variations, a plasticizer acts to lower glass transition temperature of the host resin. In some variations, a plasticizer increases toughness, increases impact resistance, increases % elongation at break, decreases Young's modulus, increases displacement at break, increases load at break, increases processability, increases flexibility, improves low temperature brittleness, or any combination of two or more of the foregoing.

[00320] Polymer compositions are disclosed herein that comprise one or more plasticizers described herein in a host resin, wherein the plasticizer is present in an effective amount to modify one or more of the glass transition temperature, elasticity, toughness, elongation at break, displacement at break, load at break, energy to yield, impact resistance, flexibility, processability, or low temperature brittleness. In some variations, the host resin is PVC, a polycarbonate, a polyurethane, a nitrile polymer (such as acrylonitrile butadiene styrene (ABS)), an acrylate polymer, a polystyrene, a polyester, a polyamide, a polyimide, a polyvinyl acetal, a cellulose polymer, a polyolefin, a natural rubber, a synthetic rubber, a copolymers of any of the foregoing, a polymer blend of any of the foregoing, or a polymer composite of any of the foregoing. In some variations, polymer compositions comprise one or more additives in addition to one or more plasticizers described herein, e.g., an antioxidant, a flame retardant, a processing aid, an inorganic filler, or a colorant.

[00321] The polymer to be plasticized can be a vinyl polymer or copolymer, a non- vinyl polymer or copolymer, or a combination thereof. Some non-limiting examples of vinyl polymers and copolymers are disclosed in Malcolm P. Stevens, "Polymer Chemistry, an Introduction " Third Edition, Oxford University Press, pp. 17-21 and 167-279 (1999), which is incorporated herein by reference. Some non- limiting examples of polymer include polyolefms, polyurethanes, polyesters, polyamides, styrenic polymers, phenolic resins, polyacrylates, polymethacrylates and combinations thereof. If PVC is used as the host polymer resin, any suitable grade of PVC can be used, to be selected by intended application. For example, a rigid grade or a flexible grade of PVC may be used. In some cases, a flexible grade of PVC is used. In some cases, a grade of PVC suitable for making bottles is used. In some cases, a grade of PVC suitable for making thin films is used. In some cases, a grade of PVC suitable for making blown films is used. In some cases, a grade of PVC suitable for extrusion is used. In some cases, a grade of PVC suitable for coating wire is used. In some variations, a host resin comprises a chlorinated PVC (CPVC). In some cases, one or more solubility parameters (e.g., Hansen solubility parameters) may be useful in determining a suitable plasticizer for a given PVC host resin. PVC may be plasticized using one or more plasticizers described herein to decrease rigidity, increase flexibility, improve processibility, increase toughness, improve low temperature brittleness, and the like.

[00322] In some embodiments, the polymer comprises a polyolefin (e.g., polyethylene, polypropylene, an ethylene/a-olefm interpolymer, a copolymer of ethylene and propylene, and a copolymer of ethylene and vinyl acetate (EVA)), polyurethane, polyester, polyamide, styrenic polymer (e.g., polystyrene, poly(acrylonitrile-butadiene-styrene), poly(styrene-butadiene-styrene) and the like), phenolic resin, polyacrylate, polymethacrylate or a combination thereof. In some embodiments, the polymer is polyethylene, polypropylene, polystyrene, a copolymer of ethylene and vinyl acetate, poly(acrylonitrile-butadiene-styrene), poly(styrene-butadiene-styrene) or a combination thereof.

[00323] In some embodiments, the host resin comprises a polyolefin. Nonlimiting examples of polyolefins that may be plasticized with plasticizers described herein include polyethylene,

polypropylene, an ethylene/a-olefm interpolymer, a copolymer of ethylene and propylene, a copolymer of ethylene and vinyl acetate (EVA), a polyfarnesene, a polyfarnesane, an interpolymer of farnesene such as a copolymer of farnesene and a styrene), or hydrogenated versions farnesene interpolymers.

Nonlimiting examples of farnesene interpolymers are disclosed in U.S. Pat. Publ. 2010/0056714, which is incorporated by reference herein in its entirety. In some cases, one or more solubility parameters (e.g., Hansen solubility parameters) may be useful in determining a suitable plasticizer for a given polyolefin host resin.

[00324] In some embodiments, the host resin comprises a styrenic polymer. Non-limiting examples of styrenic polymers that may be plasticized with plasticizers described herein include polystyrene, poly(acrylonitrile-butadiene-styrene), poly(styrene-butadiene-styrene), poly(styrene- isoprene-styrene, poly(styrene-butadiene-isoprene-styrene and the like. In some cases, one or more solubility parameters (e.g., Hansen solubility parameters) may be useful in determining a suitable plasticizer for a given styrenic host resin.

[00325] In some variations, the host resin comprises a polyester or a copolymer comprising a polyester. A polyester that may be plasticized with one or more plasticizers described herein may be aromatic, aliphatic, or aliphatic-aromatic interpolymers. In some instances, a linear saturated aromatic polyester such as polyethylene terephthalate (PET) or polybutylene terephthalate (PBT) is plasticized with one or more plasticizers described herein. In some instances, an aliphatic-aromatic terpolyester (e.g., poly(butylene terephthalate -co-succinate-co-adipate) is plasticized with one or more plasticizers described herein. In some instances, an aliphatic polyester or copolyester such as a lactic-acid based polyester, a polycaprolactone, a polyesteramide, or a polyhydroxyalkanoate (e.g., poly(hydroxybutyrate- co-hydroxyvalerate) may be plasticized with one or more plasticizers described herein.

[00326] In some variations, the polymer is a biodegradable polyester such as poly(lactic acid) or an interpolymer of lactic acid, a polycaprolactone, a polyesteramide, a polyhydroxyalkanoate, or an aliphatic-aromoatic terpolyester. Non-limiting examples of aliphatic lactic acid-based polyesters that may be plasticized with plasticizers described herein include poly(lactic acid) (PLA); interpolymers between lactic acid and an aliphatic hydroxycarboxylic acid; aliphatic polyesters comprising

polyfunctional polysaccharides and a lactic acid repeat unit; aliphatic polyesters comprising an aliphatic polyvalent carboxylic acid unit, an aliphatic polyvalent alcohol unit, and a lactic acid unit; and mixtures or blends of the foregoing. Further non-limiting examples of polyesters that may be plasticized with certain plasticizers described herein are described in U.S. Patent No. 6,544,607, which is incorporated herein by reference. Lactic acid used in poly(lactic acid) and interpolymers of lactic acid can be produced in any manner known in the art, e.g., by chemical synthesis, or by fermentation of a sugar source from lactobacillus, and the term lactic acid encompasses both D-lactic acid and L-lactic acid. Poly(lactic acid) or interpolymers of lactic acid can be made using enantiomeric monomers D-lactic acid and/or L-lactic acid by known methods. Poly(lactic acid) may be poly(L-lactic acid) (solely composed of L-lactic acid), poly(D-lactic acid) (solely composed of D-lactic acid), poly(DL-lactic acid), composed of both D-lactic acid and L-lactic acid in varying proportions, e.g., a molar ratio of D-Lactic acid:L-Lactic acid of about 100:1, 50:1, 10:1, 5:1, 2:1, 1:1, 1 :2, 1:5, 1 :10, 1 :50, or 1 :100. Properties of PLA and interpolymers of lactic acid are affected by relative amounts of the D- and L- forms. For example, poly(L-lactic acid) may exhibit a higher degree of crystallinity than copolymers of L-lactic acid and D- lactic acid, or copolymers of L-lactic acid with other non-lactic acid monomers.

[00327] In some variations, one or more plasticizers described herein is used to plasticize an interpolymer between lactic acid and another aliphatic hydroxycarboyxlic acid, such as glycolic acid, 3- hydroxybutyric acid, 4-hydroxybutyric acid, 4-hydroxyvaleric acid, 5-hydroxyvaleric acid, 6- hydroxycaproic acid, and the like. Any relative proportions of lactic acid and another aliphatic hydroxycarboxylic acid may be used in the plasticized interpolymers, e.g., lactic acid: aliphatic hydroxycarboxylic acid molar ratio of about 1 :10, 1 :5, 1 :2, 1:1, 2:1, 5:1 or 10:1.

[00328] In some variations, one or more plasticizers described herein is used to plasticize an interpolymer between lactic acid and a saccharide, such as cellulose, cellulose acetate, cellulose nitrate, methyl cellulose, ethyl cellulose, celluloid, viscose rayon, regenerated cellulose, cellophane, cupra, cupro-ammonoium rayon, cuprofan, bemberg, hemicellulose, starch, acropectin, dextrin, dextran, glycogen, pectin, chitin, chitonsan, gum Arabic, cyamoposis gum , locust bean gum, acacia gum, and mixtures or blends thereof, or derivatives thereof. Any relative proportions of lactic acid and a saccharide may be used in the plasticized interpolymers, e.g., lactic acid: saccharide molar ratio of about 1 : 10, 1 :5, 1 :2, 1 : 1, 2: 1, 5: 1 or 10: 1.

[00329] In some variations, one or more plasticizers described herein is used to plasticize an interpolymer between lactic acid, an aliphatic polyvalent carboxylic acid (e.g., oxalic acid, succinic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, undecanedioic acid, dodecanedioic acid, and anhydrides thereof), and an aliphatic polyvalent alcohol (e.g., ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3 -butanediol, 1,4- butanediol, 3-methyl-l,5-pentanediol, 1 ,6-hexandediol, 1 ,0-nonanediol, neopentyl glycol, tetramethylene glycol, 1 ,4-cyclohexandimethanol, and the like. Any relative proportions of lactic acid, aliphatic polyvalent carboxylic acid, and aliphatic polyvalent alcohol may be used, e.g., molar ratio of lactic acid: acid: alcohol of about 1 : 1 : 1, 2: 1 : 1, 3: 1 : 1, 4: 1 : 1, 5:1 :1, 10: 1 :1, 1 :2:2, 1 :3:3, 1 :4:4, 1 :5:5, 1 : 10: 10:, 10:2: 1, 5:2: 1, 2:2: 1, 10: 1 :2, 5: 1 :2, 2: 1 :2.

[00330] Any suitable plasticizer may be selected to plasticize a polyester such as a lactic-acid based polyester as described above. For example, alcohols (e.g., monoalcohols, diols or other polyols) may be useful as plasticizers for polyesters. In some variations, esters (e.g., monoesters or diesters) described herein may be useful as plasticizers for polyesters. In some cases, one or more solubility parameters (e.g., Hansen solubility parameters) may be useful in determining a suitable plasticizer for a given polyester host resin. PLA or interpolymers of lactic acid may be plasticized using one or more plasticizers described herein to decrease rigidity and increase flexibility. In some instances, plasticized PLA or interpolymers of lactic acid may be sufficiently plasticized to attain a flexibility making it suitable for use in applications traditionally using polyethylene, polypropylene, soft polyvinyl chlorides, and the like.

[00331] A variety of useful articles may be formed from plasticized polyesters (e.g., lactic acid based polyesters such as PLA) as described herein, e.g., trays, cups, plates, bottles, films, cutlery, toys, storage containers, tools, and the like.

[00332] The adduct may be incorporated into the polymer using any suitable method. For example, in some embodiments, the adduct may be mechanically mixed with the polymer (e.g., melt blended). In some embodiments, the adduct may be co-dissolved with the polymer in a solution, and solvent cast. In some embodiments, the adduct may be chemically reacted with the host polymer to incorporate into the matrix, e.g., by cross-linking, transesterification, or the like.

[00333] The ingredients (i.e., the adduct, the polymer and optional additives) can be mixed or blended using methods known to a person of ordinary skill in the art. Non-limiting examples of suitable blending methods include melt blending, solvent blending, extruding, and the like.

[00334] In some embodiments, the ingredients are melt blended by a method as described by

Guerin et al. in U. S. Patent No. 4, 152, 189. First, all solvents, if there are any, are removed from the ingredients by heating to an appropriate elevated temperature of about 100 °C to about 200 °C or about 150 °C to about 175 °C at a pressure of about 5 torr (667 Pa) to about 10 torr (1333 Pa). Next, the ingredients are weighed into a vessel in the desired proportions and the foam is formed by heating the contents of the vessel to a molten state while stirring.

[00335] In other embodiments, the ingredients are processed using solvent blending. First, the ingredients are dissolved in a suitable solvent and the mixture is then mixed or blended. Next, the solvent is removed.

[00336] In further embodiments, physical blending devices that can provide dispersive mixing, distributive mixing, or a combination of dispersive and distributive mixing can be used in preparing homogenous blends. Both batch and continuous methods of physical blending can be used. Non- limiting examples of batch methods include those methods using BRABENDER^® mixing equipments (e.g., BRABENDER PREP CENTER^®, available from C. W. Brabender Instruments, Inc., South Hackensack, N.J.) or BANBURY^® internal mixing and roll milling (available from Farrel Company, Ansonia, Conn.) equipment. Non-limiting examples of continuous methods include single screw extruding, twin screw extruding, disk extruding, reciprocating single screw extruding, and pin barrel single screw extruding. In some embodiments, the additives can be added into an extruder through a feed hopper or feed throat during the extrusion of the farnesene interpolymer, the optional polymer or the foam. The mixing or blending of polymers by extrusion has been described in C. Rauwendaal, "Polymer Extrusion", Hanser Publishers, New York, NY, pages 322-334 (1986), which is incorporated herein by reference.

[00337] It is known that plasticized thermoplastics have greater strain at break than unplasticized thermoplastics do when subjected to sufficient stress. Therefore, plasticizers serve various functional roles when compounded with thermoplastics including making them more flexible, durable, tough, extrudable and moldable. When plasticizers are selected for such functional roles they are incorporated with the thermoplastic at levels anywhere from about 5 phr to about 60 phr either depending upon the mechanical or geometric properties needed of the finished article or composition or depending upon the properties needed for their fabrication. A plasticizer's ability to modify the stress-strain properties of a thermoplastic is generally related to the mutual solubility of the plasticizer and thermoplastic where, in general, the greater the mutual solubility then the more effective the modification. Solubility parameter methodologies, in particular the Hansen methodology (see, e.g., http://hansen- solubility.com/index.php?id=l 1), are often employed to predict or explain the solubility interaction between plasticizers and thermoplastics and in general when they have similar solubility parameters then the more effective the modification. There are a variety of energetic methods known in the art for compounding plasticizers and thermoplastics. In most embodiments some combination of mechanical and thermal energy is employed in the compounding process. In general, the greater the molar volume of the plasticizer then the greater energy employed for plasticizers having similar solubility parameters. In many applications, plasticizer-thermoplastic compositions are formulated with additional ingredients for various purposes including facilitating compounding, facilitating later stage processing or fabrication, and providing additional functional features in the final plasticized article or composition. Examples of these additional ingredients include acid scavengers, radical scavengers, flow viscosity improvers, UV absorbers, fire retardants, and colorants. Also, as is well known, plasticizers, when incorporated in high levels, typically in the 50-100 phr range, can modify thermoplastics to give fluid compositions known as plastisols which are compositions of sufficiently low viscosity that may be applied to the surfaces of solid or porous articles, such as metals, plastics, and textiles for example, by various coating means including spray, dip, knife over drum and gravure. Such coated articles may sometimes be finished in a subsequent step in order to cure the composition or to remove some or all of the plasticizer.

[00338] Non-limiting examples of plasticizer candidates based on farnesene, farnesene oligomers, and their derivitives and examples of these molecules are disclosed in Table 5. One reason why these plasticizers are especially advantageous over existing plasticizers is because between about 50- 100% of their carbon atoms can be derived from renewable resources. While some of the molecules of Table 5 possess one or more ester chemical groupings, which is the typical chemical grouping possessed by the majority of today's commercial plasticizers, certain farnesene based plasticizers may additionally or alternatively possess chemical groupings considered novel for many plasticizers including, in combination or independently, amide, imide, halogen, carbonate, epoxy, alkenyl, anhydride, lactam, lactone, nitrile, indole, sulfone, and diiminoisoindoline chemical groupings. Also disclosed are articles and compositions made from these plasticizers and thermoplastics.

[00339] Using ordinary methodologies, the plasticizers described herein (e.g., plasticizers derived from farnesene) may be compounded with the thermoplastic, along with any additional additives, to give useful compositions including compositions suitable for shaping or forming, by extrusion or compression molding for example, into useful articles and useful plastisol compositions.

[00340] The amount of plasticizer used in a polymer composition to impart the desired physical or mechanical properties to the plasticized resin may be affected by a number of factors, including the compatibility between the resin and the plasticizer, the effectiveness of the plasticizer, migration of the plasticizer within and/or out of the host resin, the intended use for the plasticized resin, processing conditions, and any applicable industry standards. A plasticizer disclosed herein is added to a resin in an amount sufficient to impart desired physical or mechanical properties to the plasticized resin. In some variations, about 5 wt%, 10wt%, 20wt%, 30wt%, 40wt%, 50wt%, 60wt%, 70wt%, 80wt%, or 90wt% plasticizer is used to impart desired physical or mechanical properties to the plasticized resin, where wt% is based on the total weight of the plasticized resin. In certain variations, the amount of plasticizer in a plasticized resin is about 30wt% or less, e.g. about 30wt%, 20wt%, 10wt% or 5wt%, based on total weight of the plasticized resin.

[00341] A plasticizer may be either a liquid or a solid at ambient temperature. The plasticizer exhibits sufficient thermal stability at temperatures at which the resin will be processed, including temperatures used for melt-mixing, extrusion, injection molding, compression molding calendaring, laminating, blown film processing, and the like. The plasticizer exhibits sufficiently low volatility at typical resin processing temperatures so as to allow melt mixing, extrusion, injection molding, compression molding, calendaring, laminating, blown film processing, and the like. For example, a plasticizer used to plasticize PVC may exhibit sufficient thermal stability and sufficiently low volatility to allow polymer processing at temperatures in a range from 170°C-210°C. If a plasticizer is solid at ambient temperature, in some variations, the plasticizer has a softening temperature that allows melt mixing with the polymer to be plasticized, e.g., if used to plasticize PVC, a solid plasticizer may have a softening temperature appropriate for melt mixing at temperatures in a range from 170°C-210°C.

[00342] A plasticizer may be incorporated into the resin and interact with the resin in any suitable manner to impart the desired physical or mechanical properties to the plasticized resin. In some variations, there is a chemical interaction between the plasticizer and the resin. In some variations, the plasticizer is at least partially miscible in the host resin. In some variations, a portion of the plasticizer is compatible with the resin. In some variations, the plasticized resin is not completely homogeneous in composition, such that domains rich in resin or domains rich in plasticizer are formed. In some variations, the plasticized resin shows evidence of phase separation between the resin and the plasticizer.

[00343] In some variations, a plasticizer for a target resin is selected based on one or more measured or calculated solubility parameters of plasticizer and of the target resin. For example, a measured or calculated Hansen solubility parameter may be used to select a plasticizer for use in a target resin, e.g., a PVC, as illustrated in Table 5. For example, a plasticizer for use in PVC may be selected to have a solubility parameter close to that of PVC.

[00344] In those variations in which there is no or weak chemical interaction between the plasticizer and the resin, migration or diffusion of the plasticizer within the resin may occur, and in some cases diffusion out of the resin may occur. The rate of diffusion depends on the characteristics of each of the plasticizer and resin, the thickness of the resin, absorption of the plasticizer into surfaces adjacent the resin, the interaction between the resin and the plasticizer, and the environment (temperature, pressure, atmosphere). In some variations, a plasticizer is selected to exhibit a reduced rate of diffusion in its intended resin and intended use conditions. Plasticizer characteristics that can affect diffusion include polarity of the plasticizer, polarity of the resin, plasticizer interaction with or compatibility with the resin, plasticizer molecular weight, and viscosity of the resin and/or plasticizer under use conditions.

[00345] In some variations, a plasticizer may comprise a Diels Alder adduct between a conjugated terpene (e.g., farnesene) and a dienophile as described herein; or a derivative of such a Diels- Alder adduct as described herein, in which one or more carbon-carbon double bonds has been oxidized (e.g., epoxidized). Such oxidized (e.g., epoxidized) farnesene derivatives may be useful as plasticizers in relatively polar host resins such as PVC. Any suitable oxidation technique known to oxidize carbon- carbon double bonds may be used. For example, any suitable oxidant such as peroxides, peracetic acid, meta chloroperoxybenzoic acid, enzymes, or peroxide complexes such as urea-peroxide complexes (e.g., Novozyme-435™ urea-peroxide complex) may be used. In some variations, the oxidation (e.g., epoxidation) conditions are adjusted to oxidize only one carbon-carbon double bond, e.g., one carbon- carbon double bond that originated in the β -farnesene starting material. In some variations, the oxidation (e.g., epoxidation) conditions are adjusted to oxidize two carbon-carbon double bonds, e.g., two carbon- carbon double bonds that originated in the β -farnesene starting material. In some variations, oxidation (e.g., epoxidation) conditions are adjusted to oxidize three or more carbon-carbon double bonds, e.g., three or more carbon-carbon double bonds that originated in the β -farnesene starting material. In some variations, oxidation (e.g., epoxidation) conditions are adjusted to oxidize substantially all carbon-carbon double bonds originating in the β -farnesene starting material. A molar ratio of oxidant: farnesene may be lowered (e.g., lower than about 5: 1, such as about 4: 1, 3: 1, 2: 1, 1 : 1 or 0.5: 1 to produce compositions in which fewer carbon-carbon double bonds are oxidized (e.g., epoxidized).

[00346] In some variations, a plasticizer may comprise a Diels Alder adduct between a conjugated terpene (e.g., farnesene) and a dienophile as described herein; or a derivative of such a Diels- Alder adduct as described herein, in which one or more carbon-carbon double bonds is halogenated, e.g., where one chlorine atom is added to each double bond using a reagent such as HC1, or where two chlorine atoms are added to each double bond using a reagent such as chlorine gas. Such chloride containing farnesene derivatives may be useful as plasticizers in relatively polar host resins such as PVC. In some variations, the reaction conditions are adjusted such only one carbon-carbon double bond is halogenated, e.g., one carbon-carbon double bond that originated in the conjugated terpene starting material. In some variations, the reaction conditions are adjusted so two carbon-carbon double bonds are halogenated, e.g., two carbon-carbon double bonds that originated in the conjugated terpene starting material. In some variations, reaction conditions are adjusted such that three or more carbon-carbon double bonds are halogenated, e.g., three or more carbon-carbon double bonds that originated in the conjugated terpene (e.g., farnesene) starting material. In some variations, substantially all carbon-carbon double bonds originating from the conjugated hydrocarbon terpene are halogenated. In certain variations, such halogenated derivatives of a Diels-Alder adduct of a conjugated terpene may have use as a plasticizers for PVC.

[00347] Hydroxy versions of epoxidized Diels-Alder adducts may be prepared using any known technique that allows for reaction of epoxy groups to form hydroxyl groups. For example, an epoxy group can be reduced to form a single hydroxy group, or an epoxy group can be hydrolyzed to form two hydroxy groups. The hydroxyl groups may be subsequently acetylated to form a compound that may have use as a plasticizer, e.g., for PVC.

[00348] A Diels-Alder adduct to be used as a plasticizer may be tuned to increase compatibility with a host resin. For example, in one variation, a plasticizer disclosed herein comprises a Diels Alder adduct of β-farnesene and a dienophile in which the aliphatic portion of the Diels Alder adduct originating from the β-farnesene and/or one or more substituents of the Diels Alder adduct originating from the dienophile have been selected or modified to increase compatibility with the host resin. For example, the aliphatic portion of the adduct may be oxidized (e.g., epoxidized) or chlorinated across one or more carbon-carbon double bonds and/or one or more substituents of the adduct originating from the dienophile may be selected or modified to include one or more polar moieties (e.g., one or more hydroxyl, ester, ether, epoxy, carboxy, amino, and/or chloro groups) to increase compatibility with polar host resins. In other cases, it may be desirable to have a relatively nonpolar plasticizer or a plasticizer comprising nonpolar substituents (e.g., for plasticizing nonpolar polymers such as polyolefms). Such nonpolar substituents may include one or more relatively long (e.g., C6-C₂₀, or C6-C30) aliphatic substituents, which may be introduced into the Diels Alder adduct via the dienophile, or by subsequent modification of the Diels Alder adduct.

[00349] In certain variations, a plasticizer disclosed herein comprises a Diels Alder adduct that has been hydrogenated so as to saturate the aliphatic portion of the Diels Alder adduct originating from the conjugated terpene (e.g., farnesene). Such hydrogenated Diels Alder adducts (and derivatives thereof) may in certain circumstances exhibit improved thermo-oxidative stability in use. In certain variations, a hydrogenated Diels Alder adduct undergoes post-hydrogenation reaction, e.g., to modify one or more substituents originating in the dienophile. For example, one or more a carboxylic acid ester moieties remaining in the hydrogenated Diels Alder adduct may undergo transesterification, reduction, hydrolysis, and the like.

[00350] Any one of, or any combination of two or more of the compounds shown herein may have utility as a plasticizer. Any one of, or any combination of two or more of the examples illustrated in Table 5 herein may have utility as a plasticizer, e.g., for PVC.

[00351] In some variations, a compound having utility as a plasticizer (e.g., for PVC or any polymer composition disclosed herein) is, comprises, or is derived from a Diels-Alder adduct between a conjugated terpene and acrylic acid or an acrylate ester. Non- limiting examples of Diels-Alder adducts formed when the hydrocarbon terpene is farnesene are given by formulae (H-IA), (H-IB), (H-IC), (H-ID), (H-IE), (H-IF), (H-IG) and (H-IH) as shown in Section H above. In some variations, plasticizers have formulae (H-IC) and/or (H-ID). In some variations, plasticizers have formulae (H-IG) and/or (H-IH). In those variations in which the Diels-Alder adduct produces more than one isomer, any one of the isomers may be present without significant amounts of other isomers may be used as a plasticizer, or any mixture of the isomers may be used, with the isomers present in any relative amounts. For example, any mixture comprising a ratio of 1,3- isomer: 1 ,4-isomer of about 0.1 :99.9, 5:95, 1 :99, 10:90, 20:80:, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90:10, 95:5, 99:1, or 99.9:0.1 may be used as a plasticizer.

[00352] In some variations, a compound having utility as a plasticizer (e.g., for PVC or any polymer composition disclosed herein) is, comprises, or is derived from a Diels-Alder adduct between a conjugated terpene and a dialkyl maleate or a dialkyl fumarate. Non-limiting examples of Diels-Alder adducts produced when the hydrocarbon terpene is farnesene are given by formula (H-IIA), (H-IIB), (H- IIC) and (H-IID) as shown in Section H above. In some variations, plasticizers have formula (H-IIB). In some variations, plasticizers have formula (H-IID).

[00353] In some embodiments, a plasticizer is, comprises, or is derived from a compound having formula (H-XIIA), (Η-ΧΙΙΑ'), (H-XIIB), (Η-ΧΙΙΒ'), (H-XIIC), (H-XIIC), (H-XIID), (H-XIID'), (H- XIIE), (Η-ΧΙΙΕ'), or (H-XIIF). In some embodiments, a plasticizer is, comprises, or is derived from a compound having formula (Η-ΧΙΙΑ'), (Η-ΧΙΙΒ'), (H-XIIC), (H-XIID'), (Η-ΧΙΙΕ'), or (H-XIIF).

[00354] In one embodiment, a plasticizer is or comprises one of or a mixture of Compounds (J-

3a) and (J-3b), where a ratio of (J-3a):(J-3b) is about 0.1 :99.9, 5:95, 1 :99, 10:90, 20:80:, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90:10, 95:5, 99:1, or 99.9:0.1 :

In certain instances, compound (J-3a) and/or (J-3b) may be useful as plasticizers in relatively low polarity host resins, e.g., in polyolefins, polystyrenes, synthetic rubbers, natural rubbers, or in copolymers thereof, or in polymer blends thereof, or in polymer composites thereof.

[00355] In one embodiment, a plasticizer is or comprises compound (J-5):

[00356]

[00357] In one embodiment, a plasticizer is or comprises compound (J-9):

[00358] In one embodiment, a plasticizer is or comprises compound (J-11):

[00359] In one embodiment, a plasticizer is or comprises one of or a mixture of compounds (J-

13a) and (J-13b), where a ratio of 13a:13b is about 0.1:99.9, 5:95, 1 :99, 10:90, 20:80:, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90:10, 95:5, 99:1, or 99.9:0.1 ::

J-13b

[00360] In some embodiments, a plasticizer is, comprises, or is derived from a Diels-Alder adduct between a conjugated terpene and maleic anhydride. In some embodiments, a plasticizer is, comprises, or is derived from a compound having formula (H-IIIA), (H-IIIB), (H-IIIC), or (H-IIID) as shown in Section H above. In some embodiments, a plasticizer is, comprises, or is derived from a compound having formula (H-IIIB) or (H-IIID) as shown in Section H above.

[00361] In one variation, a Diels-Alder adduct comprising one or more alcohol substituents is reacted with a fatty acid, succinic acid, or the like to make a plasticizer. In one variation, a Diels-Alder adduct comprising one or more carboxylic acid substituents is reacted with an isosorbide or a fatty alcohol to make a plasticizer. One non-limiting example of a plasticizer derived from β-farnesene and isosorbide is shown as Example 47.

[00362] In one embodiment, a plasticizer is or comprises one or more of compounds (J- 15a), (J-

15b) (J-16), (J-17), and (J-18):

[00363] In one embodiment, a plasticizer is or comprises compound (J- 19):

[00364] In one embodiment, a plasticizer comprises a dimer of β-farnesene (e.g., a cyclic or linear dimer as described in U.S. Pat. No. 7,691,792, which is incorporated by reference herein in its entirety) that has had one or more, or essentially all, of the carbon-carbon double bonds oxidized (e.g., epoxidized). In some variations, a β-farnesene derived plasticizer comprises one of or a mixture of two or more of compounds (J-21), (J-22), (J-23), and (J-24):

[00365] embodiment, a plasticizer is or comprises compound (J-25):

[00366] Also, disclosed are molecules, herein referred to as multifunctional plasticizer molecules or multifunctional plasticizers, having at least two functions when they are combined with thermoplastics where one of these functions relates to modifying the mechanical, geometric, or fluid flow properties of thermoplastics or articles made therefrom and where the other one or more functions may fulfill any beneficial purposes including charge dissipation, antithrombosis, heat stabilization, fire retardation, corrosion inhibition, flow viscosity improvement at relatively low plasticizer levels, radical scavenging, acid scavenging, oxygen scavenging, dye site creating, adhesion promoting, particularly of paints and coatings, blowing (to give foams and popcorns), and mold releasing. One key advantage of the multifunctional plasticizers of the present invention is a cost savings relating to the use of fewer molecules in plasticizer-thermoplastic formulations.

[00367] It should be recognized that in addition to the plasticization function of a multifunctional plasticizer, its other one or more functions may provide a feature benefiting the fabrication of the composition or article or may provide a feature benefiting the final composition or article. In fact, the other one or more functions may provide a benefit both to fabrication and to the final composition or article. For example, a multifunctional plasticizer that provides an HC1 acid scavenging benefit is useful during the processing of PVC at elevated temperatures because it prevents degradation and the formation of color bodies during processing. Also, for example, a multifunctional plasticizer that provides dye sites for anionic dyes for example, is useful to the final article or composition because it improves its ability to be colored with dyes without containing pigment additives which often damage the mechanical properties of plasticized thermoplastics. Further, for example, a multifunctional plasticizer that provides an anticorrosion benefit is useful both during and after processing because it keeps the processing equipment corrosion free and provides for corrsion protection to plasticized articles when they contact or contain metal parts such as nails and screws for example.

[00368] Also disclosed are useful articles and compositions made from multifunctional plasticizers and thermoplastics. In most embodiments, using ordinary methodologies, the multifunctional plasticizers may be compounded with the thermoplastic, along with any additional additives, to give useful compositions including compositions suitable for shaping or forming, by extrusion or compression molding for example, into useful articles and useful plastisol compositions. While it is the purpose of the plasticization function of a multifunctional plasticizer that it be directed toward affecting the bulk property of the thermoplastic article or composition, it should be recognized that in some application areas it is desirable that the other one or more functions of a multifunctional plasticizer be directed to the surface of the article or composition. For example, it is desirable that a multifunctional plasticizer that also functions as a antithrombolytic is present both in the bulk and entangled with the thermoplastic at the surface of the article or composition. At least three methods for effecting migration of some of the multifunctional plasticizer towards the surface whilst maintaining a level of plasticizer in the bulk that is satisfactory for good plasticization. One of these methods employs a thermal treatment step. Another method employs contact of the surface of said article with a liquid which promotes migration either by swelling, chemical potential, or diffusion gradient mechanisms. A third method employs the use of small amount of a separate surfactant molecule that when added to the multifunctional plasticizer-thermoplastic composition effects surface migration.

[00369] In certain embodiments, a conjugated terpene (e.g., β-farnesene) and its oligomers to be advantageous precursors to multifunctional plasticizer molecules due to the ease of derivatization of its double bonds (in the case of farnesene, up to four of its double bonds) can be derivatized, and in some embodiments selectively derivatized, with groupings which give the derivative multiple functions. For example, the diene moiety of farnesene and certain oligomers can be easily made to enter into Diels- Alder reactions and the trisubstituted double bonds of farnesene can be easily made to enter into electrophilic and nucleophilic reactions. Independently or together, these groupings give the derivative both plasticizing function and one or more aditional functions. Also, for example, the farnesene molecule and its derivatives can be readily cyclized, bicylized, and tricylized to give useful

multifunctional plasticizers. Many examples of multifunctional plasticizers, especially multifunctional plasticizers for PVC, made from farnesene and its derivatives are disclosed in the examples of Table 5.

[00370] In one variation, a plasticizer described herein (e.g., plasticizers in Table 5) is used to plasticize PVC to make a bottle cap. For example, a plasticizer provided herein may be mixed together in a 1 :4 weight ratio respectively in a blender for a suitable length of time (e.g., about 10 minutes) to give a divided composition. Next, an acid scavenger in a suitable amount (e.g., about 1 phr) may be added and the divided composition may be blended for an additional time period (e.g., about 5 minutes). Next, the resulting composition may be kneaded for a suitable length of time in a suitable mixing apparatus (e.g., about 20 minutes under moderate energy using a Banbury batch mixer at about 200 degree blade temperature) to give a doughy composition. Next, a portion of the composition may be compression molded, e.g., into a 9x9x0.03" rectangular sheet using a Carver Press at a guage pressure of 10 tons and a mold temperature of about 230 degrees. Upon cooling, dog bone specimens may be cut from the molded sheet and its tensile properties measured using methods prescribed in ASTM D638. The specimens may give an average elongation at break of about 20%, 30%, 40%, 50%, 100%, 150%, 200%), 250%) or 300%. Next, round coupons may be cut from the sheet with a punch and then pressed into HDPE bottle caps. The resulting lined caps may exhibit good barrier and excellent sealing properties when fitted to bottles. Bottle caps may be prepared with an additional step of incorporating a commercial oxygen scavenger during the mixing step. The resulting lined caps may exhibit excellent barrier and sealing properties. In some variations, a low-color molded article comprising PVC and a multifunctional plasticizer possessing acid scavenging function may be made by incorporating a plasticizer described herein with alkenyl chemical groupings into PVC by any method known in the art, but withought adding any separate acid scavenger ingredient giving a plasticized sheet or article with very low color. In some variations, a low-color molded article comprising PVC and a multifunctional plasticizer possessing acid scavenging function may be made by incorporating a plasticizer described herein with epoxy chemical groupings into PVC by any method known in the art, but without adding any separate acid scavenger ingredient giving a plasticized sheet or article with very low color. In some variations, a plasticizer described herein may be used to make a flexible safety hose having a charge dissipating fluid-contact surface. For example, a plasticizer described herein with an anhydride chemical grouping may be extruded in a continuous process into a hose geometry using any suitable method known in the art. For example, a screw extruder equipped with a tube die head may be used.

[00371] In certain embodiments, a conjugated terpene (e.g., β-farnesene) and its oligomers may be advantageous precursors to multifunctional plasticizer molecules due to the ease of derivatization of its double bonds (in the case of famesene, up to four of its double bonds) can be derivatized, and in some embodiments selectively derivatized, with groupings which give the derivative multiple functions. For example, as described herein, the diene moiety of famesene and certain oligomers can undergo Diels- Alder reactions and the trisubstituted double bonds of famesene can undergo electrophilic and nucleophilic reactions. Independently or together, these groupings may give the derivative (e.g., Diels- Alder adducts) both plasticizing function and one or more additional functions. Also, for example, the famesene molecule and its derivatives (e.g., Diels-Alder adducts) can be readily cyclized, bicylized, and tricylized to give useful multifunctional plasticizers. Many non-limiting examples of multifunctional plasticizers, especially multifunctional plasticizers for PVC, made from famesene and its derivatives are disclosed in the plasticizer candidates of Table 5.

[00372] In certain embodiments, a plasticizer may be altered in a processing step to give multifunctional properties. For example, anhydride groupings at the surface can be solvolyzed after extrusion in an alkaline water-alcohol quench bath to give a charge dissipating plasticized material. In one variation, such a charge dissipating plasticized material may safely eliminate charge buildup resulting from the streaming of fluids.

[00373]

[00374] Table 5 and 6 and certain Examples provide non- limiting examples of Diels-Alder adducts that may be used as plasticizers in suitable polymer hosts. Examples 24-26 provide non-limiting examples of epoxidized famesenes that may have utility as plasticizers, monomers in making oligomers or polymers, as cross-linking agents, curing agents, as reactive solvents or diluents, and the like.

[00375] It should be understood that plasticizers may be made from conjugated hydrocarbon terpenes that are not famesene. In some variations, the conjugated terpene used to make a Diels-Alder adduct useful as a plasticizer is myrcene. In some variations, the conjugated terpene used to make a Diels-Alder adduct useful as a plasticizer is not myrcene or famesene, and may for example be any of the C10-C30 conjugated hydrocarbon terpenes described herein, or any other conjugated hydrocarbon terpene otherwise known in the art.

(J-IV) Surfactants [00376] In some variations, a Diels-Alder adduct as described herein may be used as a nonionic surfactant. The surfactants described herein include a hydrophilic portion that is soluble in water, including cold water in some variations, and a hydrophobic portion that can solubilize and efficiently remove oily soils (oil, fatty substance, grease, clay, and the like). Some of the surfactants described herein may demonstrate rapid water-oil interface kinetics so as to be able to effectively remove soil within a short wash time. In some cases, a Diels-Alder adduct may be modified so as to form an anionic or cationic compound that has utility as a surfactant. For example a Diels-Alder adduct incorporating one or more carboxylic acid salts may be made, a sulfate may be formed (e.g., using standard sulfation techniques such as SC oleum sulfation), a phosphate or phosphite may be formed, or an ammonium ion may be made. Cationic Diels-Alder adducts (e.g., ammonium ions such as quaternary ammonium ions) and anionic Diels-Alder adducts (e.g., sulfates or phosphates) may be useful as surfactants in applications such as soaps, detergents, wetting agents, dispersants, emulsifiers, foaming agents, antistatic agents, corrosion inhibitors, and antimicrobials.

[00377] Certain anionic surfactants derived from Diels-Alder adducts may be useful in detergents, soaps, builders and other cleaning agents, emulsifiers and the like. Certain cationic surfactants derived from the Diels-Alder adducts described herein may have use in personal care products. For example, ammonium ions (e.g., quaternary ammonium ions) may have use in hair products such as shampoos, conditioners and the like. Ammonium ions (e.g., quaternary ammonium ions) may be useful as dye sites, antimicrobials, and herbicides. N-oxides formed from the Diels-Alder adducts described herein may have use as surfactants, e.g., for use in personal care products (e.g., shampoos, conditioners, and the like).

[00378] In some variations, anionic surfactants may be used at levels as high as about 30 to 40% of a detergent formulation. Other important surfactants used in consumer products include amine oxides, cationic surfactants, zwitterionic surfactants, alkyl polyglycoside surfactants, soaps, and fabric softening cationic surfactants. These additional types of surfactants provide additional cleaning benefits over those provided by anionic surfactants, as well as enhanced foaming, enhanced skin mildness, and fabric softening. The conjugated terpene and/or post-Diels-Alder reaction chemical modification may be selected to design surfactants that provide enhanced cold water cleaning performance, enhanced cleaning performance in general, and process and/or rheological advantages. In some variations, it is desired that materials be readily biodegradable and substantially derived from biomaterials to make consumer products.

[00379] In addition to nonionic surfactants as described above, the Diels-Alder adducts described herein may be used to form cationic surfactants, zwitterionic surfactants, amine oxide surfactants, soaps and fatty acids, alkypolyglycoside surfactants, di-long-chain alkyl cationic surfactants and detergent products comprising them. [00380] As described herein, aldehydes or polyaldehydes are converted to alcohols or polyalcohols, respectively. In some variations, alcohols or polyalcohols are converted to functionalized or polyfunctionalized surfactants. For example, it is desired to create surfactants (e.g., polyfunctionalized such as di-anionic) that have soil suspending capacity while reducing or minimizing tendency to crystallize or exhibit poor solubility. In some variations, a process is used which is tuned to create a polyalcohol (e.g., a di, a tri, or a tetraalcohol) in addition to or instead of a monoalcohol.

[00381] Surfactants may be formed from aldehyde-containing or alcohol-containing Diels-Alder adducts by way of any alcohol-to-surfactant or aldehyde-to-surfactant derivatization process known in the industry. Fatty alcohols and aldehydes may be converted into additional surfactants such as cationic surfactants, zwitterionic surfactants, amine oxide surfactants, alkylpolyglycoside surfactants, soaps, fatty acids, and/or long-chain alkyl (e.g., di-long-chain alkyl) cationic surfactants. Non-limiting examples of synthetic procedures for obtaining these materials from the parent alcohols or aldehydes may be found in the Kirk Othmer Encyclopedia of Chemical Technology or other suitable references.

[00382] Cationic surfactant, zwitterionic surfactants, amine oxide surfactants, alkylpolyglycoside surfactants, soaps, fatty acids, may in some variations be combined with nonionic and/or anionic surfactants derived from alcohols. For example, an alcohol may be treated with an alkylene oxide such as ethylene oxide and/or propylene oxide to create an alkoxylated alcohol which may be used in or as a nonionic surfactant, or which optionally may undergo sulfation to create an anionic surfactant.

[00383] In some variations, cationic surfactants may be derived from aldehydes or alcohols described herein. For example, an alcohol or aldehyde may be converted to a tertiary amine vi direct amination via reaction with secondary amines such as monoethanol amine to provide a methyl, hydroxyethyl tertiary amine or via reaction with dimethyl amine to provide a dimethyl tertiary amine. Direct amination may occur in the presence of the reactant amine at about 230°C and 0.1-0.5 MPa using copper chromite (from an alcohol) or a noble metal, copper chelate, or copper carboxylate catalyst from an aldehyde. Tertiary amines may be converted to a hydroxyalkyl quat or trimethyl quat via reaction with methyl chloride or dimethyl sulfate. Ester quats may be prepared by oxidation of alcohols or aldehydes using any suitable oxidizing agent (e.g., potassium permanganate, Jones reagent, etc.) to form a carboxylic acid, followed by esterification (or diesterification) of N-methyldiethanolamine with the carboxylic acid, followed by quatermization with methyl chloride or dimethyl sulfate. Alternatively, an amine oxide is prepared from a tertiary amine by oxidizing the peroxide in water with a bicarbonate buffer. Amine oxides may be used in formulations in which grease cleaning and/or foaming ability is desired. In some variations, a fabric softener component comprises a quat-containing Diel-Alder adduct. Ester quats (e.g., diester quats) and dialkyl quats may be used in fabric softeners. [00384] To prepare zwitterionic betaine surfactants, tertiary amines may be reacted with a substituted or unsubstituted 1,3-sultone, e.g., in acetone. Zwitterionic surfactants may be useful in enhancing cold water performance and/or formulability.

[00385] Soaps and fatty acids are sometimes useful in laundry detergents as surfactants and/or as additives to provide mildness or other tactile or sensorial benefits. In some variations, a soap or fatty acid Diels-Alder adduct described herein provides a surfactant with increased solubility. Fatty acids and soaps may be prepared via oxidation of aldehydes or alcohols using any suitable oxidizing agent, e.g., potassium permanganate, Jones regent, or any other technique known in the art.

[00386] Alkylpolyglycosides derived from the Diels-Alder adducts described herein may be useful for their mildness, foaming ability and/or cold temperature solubility. In some variations, an alkylpolyglycoside (e.g., with 0, 1, 2, 3, or 4 repeat units) is prepared from a Diels-Alder adduct containing an alcohol via acid-catalyzed reaction with a monosaccharide. Non-limiting examples are provided in U.S. Pat. No. 4,950,743, which is incorporated herein by reference in its entirety.

[00387] In some variations, detergent alcohols may be used in shampoos, laundry detergents, dishwashing detergents, and/or hard surface cleaners after being formulated into appropriate surfactant compositions. In some variations, detergents and hard surface cleaners may comprise additional polymers as washing substances, cleaning polymers (modified or unmodified polycarboxylates, ethoxylated amines and derivatives of each of the foregoing), builders, co-builders, complexing agents, bleaches, standardizers, graying inhibitors, dye transfer inhibitors, enzymes and/or fragrances.

[00388] Surfactants derived from the Diels-Alder adducts may be used in any suitable amount in a cleaning, fabric softening, or personal care product formulation. In some variations, a surfactant derived from a Diels-Alder adduct is present in an amount from about 0.05wt% to about 70wt%, or from about 0.1 wt% to about 40wt%, or from about 0.25wt% to about 10 wt% of a cleaning, fabric softening, or personal care product formulation.

[00389] In some variations, the nonionic surfactants described herein comprise alkoxylated Diels-

Alder adducts as described herein. In those instances in which the conjugated terpene is β-farnesene, the nonionic surfactants described herein comprise 4,8-dimethylnonyl-substituted

hydroxymethylcyclohexanes or alkoxylated 4,8-dimethylnonyl-substituted hydroxymethylcyclohexanes.

[00390] To meet environmental standards, the surfactants described herein are nonaromatic and are biodegradable. Some of the surfactants described here may exhibit low levels of foaming or may not foam detectably. In some embodiments, a nonionic surfactant described herein may function as a defoaming agent.

[00391] The nonionic surfactants described herein comprise a hydrophobic end and a hydrophilic end, each connected to the cyclic structure residue from the Diels-Alder reaction. The hydrophobic end originates from the conjugated hydrocarbon terpene, and the hydrophilic end originates from the dienophile. As described above, the hydrophobicity and hydrophilicity of the Diels-Alder adducts can be tuned by selection of the conjugated hydrocarbon terpene, the dienophile, and by post-Diels-Alder reaction chemical modifications of the aliphatic tail originating from the terpene and/or chemical modifications of the portion of the molecule originating from the dienophile. In some variations in which β-farnesene is used as the conjugated terpene, the hydrophobic end comprises at least one 4,8- dimethylnonyl substituent. In some variations, the hydrophilic end comprises an alkyl alcohol, or any hydrophilic group that can be derived from an alkyl alcohol. In some variations, the hydrophilic end comprises an alkoxyl chain comprising one or more types of alkoxyl repeat units. For example, the hydrophilic end can be represented as R³-0-R_a]_k-H, wherein R³ represents a linear or branched alkyl group (e.g., -CH2- or -CH(CH₃)-) and R_ai_k includes an alkoxyl chain that comprises one or more types of alkoxyl repeat units R¹ O _s wherein R¹ is a CpCio or C₁-C4 linear or branched alkyl group. An average number j of a given type of alkoxyl repeat unit in R_ai_k of the hydrophilic end may be represented as:

wherein j is in a range from 1 to 30, from 5 to 25, from 6 to 20, or from 6 to 12, e.g. j=l, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30. In some variations, R¹⁼-CH₂-, in other variations, ethoxyl repeat units are present in the hydrophilic end such that R¹⁼-CH₂CH₂-, and in still other variations, propoxyl repeat units are present in the hydrophilic end such that R¹⁼-CH(CH₃)CH₂-. In certain embodiments, the alkoxyl chain in the hydrophilic end comprises more than one type of alkoxyl repeat unit such that R_a[k can be represented by the formula:

wherein R¹ and R² are each independently C₁-C₁₀ or Q-C4 linear or branched alkyl groups, p represents

2 an average number of repeating R alkoxy units, and q represents an average number of repeating R alkoxy units. The average numbers p and q independently range from 1 to 30, from 5 to 25, from 6 to 20, or from 6 to 12, e.g. p and q are independently 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30. In some variations the sum p+q is in the range 1 to 30, from 5 to 25, from 6 to 20, or from 6 to 12, e.g. p+q=l, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30. In some variations, both ethoxy and propoxy repeat units are present such that R¹⁼-CH₂CH₂- and R²=-CH(CH₃)CH₂-. In those variations in which more than one type of alkoxy repeat unit is present, the differing alkoxyl units can be distributed in any pattern, e.g., as a continuous series or block of a first type of alkoxyl repeat unit separated by a continuous series or block of a second type of alkoxyl repeat unit, or repeat units of the first type of alkoxyl repeat unit may be randomly interspersed with repeat units of the second type.

[00392] In some variations, a Diels Alder adduct that has utility as a nonionic surfactant can be obtained by reacting a conjugated hydrocarbon terpene (e.g., β-farnesene or a-farnesene) with any suitable dienophile that can be converted to an alcohol or diol. For example, any substituted or unsubstituted α,β-unsaturated aldehyde such as:

where each of R¹, R², and R³ is independently, H, Ci-Cio alkyl, C₃-C₆ cycloalkyl, aryl, substituted aryl, and the like; or the dienophile may be an acrylate or substituted acrylate such as:

wherein R¹ is H or C_rC₈ alkyl, and R², R³, and R⁴ are, each independently, H, C_rCi₀ alkyl, C₃-C₆ cycloalkyl, aryl, substituted aryl, and the like. In some variations, allylic alcohols may be used as a dienophile in a Diels-Alder reaction with a conjugated terpene such as β-farnesene or a-farnesene. In some variations, methyl vinyl ketones may be used in a Diels-Alder reaction with a conjugated terpene such as β-farnesene or a-farnesene.

[00393] In some variations, the surfactants described herein comprise or are derived from alcohol

(J-4-1):

Alcohol (J-4-1) represents any one of, or any combination of the two isomers J-4-IA and J-4-IB shown below:

In some variations, alcohol J-4-I includes both isomers, J-4-IA and J-4-IB. In some variations, alcohol J- 4-1 includes isomer J-4-IA, with only trace amounts or no detectable amount of isomer J-4-IB. In some variations, alcohol J-4-I includes isomer J-4-IB, with only trace amounts or no detectable amount of isomer J-4-IA. In some variations, alcohol J-4-I includes about 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 99 wt.% of isomer J-4-IA. Alcohol J-4-I may include any ratio of isomer J-4-IA to isomer J-4-IB. In some variations, alcohol J-4-I includes a ratio of isomer J-4-IA to isomer J-4-IB of about 0.001:1, 0.005:1, 0.01 :1, 0.05:1, 0.1 :1, 0.5:1, 1 :1, 3:1, 3.2:1, 3.4:1, 3.6:1, 3.8:1, 4:1, 4.2:1, 4.4:1, 4.6:, 4.8:1, 5:1, 10:1, 50:1, 100:1, 500:1, or 1000:1 .

[00394] In some variations, compound J-4-11 as shown below functions as a nonionic surfactant:

wherein n represents an average number of ethoxyl repeat units and n is in a range from 1 to 30, from 5 to 25, from 6 to 20, or from 6 to 12, e.g., n=l, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30. Compound J-4-11 represents any one of or any combination of the two isomers J-4-IIA and J-4-IIB as shown below:

[00395] In some variations, compound J-4-11 includes both isomers, J-4-IIA and J-4-IIB. In some variations, compound J-4-11 includes isomer J-4-IIA, with only trace amounts or no detectable amount of isomer J-4-IIB. In some variations, compound J-4-11 includes isomer J-4-IIB, with only trace amounts or no detectable amount of isomer J-4-IIA. In some variations, compound J -4-II includes 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 99 wt.% of isomer J -4-IIA. Compound J -4-II may include any ratio of isomer J -4-IIA to isomer J -4-IIB. In some variations, compound J -4-II includes a ratio of isomer J -4-IIA to isomer J -4-IIB of about 0.001 :1, 0.005:1, 0.01 :1, 0.05:1, 0.1 :1, 0.5:1, 1 :1, 3:1, 3.2:1, 3.4:1, 3.6:1, 3.8:1, 4:1, 4.2:1, 4.4:1, 4.6:, 4.8:1, 5:1, 10:1, 50:1, 100:1, 500:1, or 1000:1. [00396] As described above, some variations of surfactants contain alkoxy repeat units that are different than ethoxyl repeat units. For example, some surfactants include propoxyl repeat units in the hydrophilic end, rather than ethoxyl repeat units. Some surfactants include both ethyoxyl and propoxyl repeat units.

[00397] Thus, some surfactants are derived from alcohols described herein (e.g., J -4-1 J -4-V, J -

4-VIIA, J -4-VIIB, J -4-IX and have structures analogous to compounds J -4-II, J -4-VI, J -4-VIIIA, J -4- VIIIB and J -4-X, except with propoxy repeat units:

substituted for ethoxy repeat units:

CH_? CH

/n

The average number m of propoxyl repeat units on these analogs of compound J -4-II, J -4-VI, J -4- VIIIA, J -4-VIIIB and J -4-X can be varied depending on reaction conditions as is known in the art. In some variations of the surfactants, m is in the range 1 to 30. In some variations, m is in the range 5 to 25. In some variations of the surfactants, m is in the range 6 to 20. In some variations, m is in the range 6 to 12. In some variations, m is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30. In some variations, m is 9.

[00398] Some variations of surfactants contain both ethoxy and propoxy repeat units, and have structures analogous to compound J -4-II, J -4-VI, J -4-VIIIA, J -4-VIIIB and J -4-X, with the following structure substituted for the ethoxy repeat units:

in which the ethoxy and propoxy repeat units can be distributed in any way along the chain, e.g., as blocks of ethoxyl units grouped together and blocks of propoxyl units grouped together, or with ethoxyl units randomly interspersed among propoxyl units. As is known in the art, the average number p of propoxyl repeat units and the average number q of ethoxyl repeat units can be varied depending on reaction conditions. In some variations of the surfactants, p and q are independently in the range 1 to 30. In some variations of the surfactants, p and q are independently in the range 6 to 20. In some variations, p and q are independently in the range 5 to 25. In some variations p and q are independently in the range 6 to 12. In some variations, p and q are independently 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30. In some variations, the sum (p+q) is in the range 1 to 30, or 6 to 20, or 5 to 25, or 6 to 12. In some variations, the sum (p+q) is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30.

[00399] In some variations, compound J-4-III as shown below functions as a nonionic surfactant:

where the 1,3- and 1,4- isomers of compound J -4-III may be present in any relative amount, and where m represents an average number of propoxyl repeat units and m is in a range from 1 to 30, from 5 to 25, from 6 to 20, or from 6 to 12, e.g., m=l, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 1,5 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30. In some variations, compound J-4-III includes the 1,3- isomer with only trace amounts or no detectable amount of the 1,4- isomer. In some variations, compound J -4-III includes the 1,4- isomer with only trace amounts or no detectable amount of the 1,3- isomer. In some variations, compound J -4-III includes a ratio of the 1,3- isomer to the 1,4- isomer of about 0.001 :1, 0.005:1, 0.01 :1, 0.05:1, 0.1 :1, 0.5:1, 1 :1, 3:1, 3.2:1, 3.4:1, 3.6:1, 3.8:1, 4:1, 4.2:1, 4.4:1, 4.6:, 4.8:1, 5:1, 10:1, 50:1, 100:1, 500:1, or 1000:1.

[00400] In some variations, compound J -4-IV as shown below functions as a nonionic surfactant:

where the 1,3- and 1,4- isomers of compound J-4-IV may be present in any relative amount, and where p represents an average number of propoxyl repeat units and q represents an average number of ethoxyl repeat units, and p and q are each independently in a range from 1 to 30, from 5 to 25, from 6 to 20, or from 6 to 12, e.g. p=l, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30 and q=l, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30. The ethoxy and propoxy repeat units can be distributed in any way along the chain, e.g., as blocks of ethoxyl units grouped together and blocks of propoxyl units grouped together, or with ethoxyl units randomly interspersed among propoxyl units. As is known in the art, the average number p of propoxyl repeat units and the average number q of ethoxyl repeat units can be varied depending on reaction conditions. In some variations, compound J-4-IV includes the 1,3- isomer with only trace amounts or no detectable amount of the 1,4- isomer. In some variations, compound J -4-IV includes the 1,4- isomer with only trace amounts or no detectable amount of the 1,3- isomer. In some variations, compound J -4-IV includes a ratio of the 1,3- isomer to the 1 ,4- isomer of about 0.001:1, 0.005:1, 0.01:1, 0.05:1, 0.1:1, 0.5:1, 1:1, 3:1, 3.2:1, 3.4:1, 3.6:1, 3.8:1, 4:1, 4.2:1, 4.4:1, 4.6:, 4.8:1, 5:1, 10:1,50:1, 100:1, 500:1, or 1000:1.

[00401] As described above, it is possible to derive a variety of 4,8-dimethylnonyl-substituted alkyl alcohols using β-farnesene as a starting material. For example, if methyl vinyl ketone is used as the dienophile in a Diels-Alder type reaction with β-farnesene, after reduction and hydrogenation an alcohol J -4-V can be formed:

which comprises any one of or any combination of the isomers J -4-VA and J -4-VB:

Isomers J-4-VA and J-4-VB can be present in any relative amount, e.g., alcohol J-4-V may consist of isomer J -4-VA with no detectable amount of isomer J-4-VB, or may consist of isomer J-4-VB with no detectable amount of isomer J-4-VA, or a ratio of isomer J -4-VA: J-4-VB may be about 0.001:1, 0.005:1, 0.01:1, 0.05:1, 0.1:1, 0.5:1, 1:1, 3:1, 3.2:1, 3.4:1, 3.6:1, 3.8:1, 4:1, 4.2:1, 4.4:1, 4.6:, 4.8:1, 5:1, 10:1, 50:1, 100:1, 500:1, or 1000:1. Alternatively, alcohol J -4-V can be formed by carrying out a Diels- Alder reaction of β-farnesene with acrolein in the presence of a methyl magnesium halide (e.g. methyl magnesium bromide) or the like. The alcohol J-4-V may be used as is in a formulation in some embodiments, or in other embodiments, the alcohol may be subsequently alkoxylated to form a surfactant. For example, alcohol J-4-V can be ethoxylated to form surfactant J-4-VI:

which comprises any one of or any combination of the isomers J-4- VIA and J-4-VIB:

Isomers J-4-VIA and J-4-VIB can be present in any relative amount, e.g. surfactant J-4-VI may consist of isomer J-4-VIA with no detectable amount of isomer J-4-VIB, or may consist of isomer J-4-VIB with no detectable amount of isomer J-4-VIA, or a ratio of isomer J-4-VIA:J-4-VIB may be about 0.001 :1, 0.005:1, 0.01 :1, 0.05:1, 0.1 :1, 0.5:1, 1 :1, 3:1, 3.2:1, 3.4:1, 3.6:1, 3.8:1, 4:1, 4.2:1, 4.4:1, 4.6:, 4.8:1, 5:1, 10:1, 50:1, 100:1, 500:1, or 1000:1. For surfactant J-4-VI, an average number z of ethoxyl repeat units can be in a range from 1 to 30, from 5 to 25, or from 6 to 20, e.g. z=l, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 25, 25, 26, 27, 28, 29, or 30.

[00402] If crotonaldehyde is used as the dienophile in a Diels Alder type reaction with β- farnesene, a mixture of alcohols J-4-VIIA and J-4-VIIB is produced after reduction and hydrogenation of the Diels Alder

below:

SCHEME J-4-VII

[00403] The resulting alcohol has structure J-4-VIIA and/or J-4-VIIB:

The alcohols J-4-VIIA and J-4-VIIB may be used in a formulation as is in some embodiments, or in other embodiments, may be subsequently treated with an alkylene oxide (e.g., ethylene oxide and/or propylene oxide) to form a mixture of surfactants J-4-VIIIA and J-4-VIIIB (where ethoxylation is shown as a model alkoxylation):

(J-4-VIIIA)

(J-4-VIIIB).

The average number of ethoxyl repeat units y and y' for surfactants J-4-VIIIA and J-4-VIIIB, respectively, is independently in the range of 1 to 30, or 5 to 25, 6 to 20, or 6 to 12. That is, y and y' can each independently be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30.

[00404] In some variations, nonionic surfactants comprise or are derived from diol J-4-IX:

[00405] In some variations, the diol J-4-IX is used as is in a formulation, and in other embodiments, the diol may be treated with an alkylene oxide (e.g., ethylene oxide and/or propylene oxide) to form a nonionic surfactant having formula J-4-X (where ethoxylation is shown as a model alkoxylation):

[00406] The average number n of alkoxy (e.g., ethoxy) repeat units in compound J-4-X can be varied depending on reaction conditions as described below. In some variations of the surfactants, n is in the range 1 to 30. In some variations, n is in the range 5 to 25. In some variations of the surfactants, n is in the range 6 to 20. In some variations n is in the range 6 to 12. In some variations, n is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30. In some variations, n is about 9. [00407] It should be understood that analogs of surfactants J-4-VI, J-4-VIIIA, J-4-VIIIB, and J-4-

X are contemplated, in which a different alkoxyl repeat unit is substituted in place of some of or all of the ethoxyl repeat units. For example, the alcohols J-4-V, J-4-VIIA, J-4-VIIB, and J-4-IX can be propoxylated instead of ethoxylated, or propoxylated and ethoxylated instead of ethoxylated.

[00408] The alcohols and surfactants described herein can be made by any suitable method now known or later developed by one skilled in the art. In some variations, the compounds and surfactants can be made by Diels Alder addition of a dienophile to the diene functionality of the conjugated terpene (e.g., β-farnesene). Non- limiting examples of suitable dienophiles that can be used to produce substituted aldehydes (e.g., 4,8-dimethyl-3,7-nonadienyl-substituted) include: substituted

α,β-unsaturated aldehydes such as:

wherein R¹, R², and R³ are, each independently, H, CpCio alkyl, C₃-C₆ cycloalkyl, aryl, substituted aryl, and the like; and acrylates or substituted acrylates such as:

wherein R¹ is H or CpCg alkyl, and R², R³, and R⁴ are, each independently, H, Ci-Cio alkyl, C3-C6 cycloalkyl, aryl, substituted aryl, and the like. In some variations, an allylic alcohol may be used as the dienophile in a Diels-Alder reaction with a conjugated terpene such as β-farnesene or a-farnesene.

[00409] Substituted aldehydes resulting from a Diels-Alder reaction can be reduced to form a substituted alcohol as described above. Any suitable reducing methods and conditions may be used. In some variations, the unsaturated aldehyde (e.g., 4,8-dimethyl-3,7-nonadienyl-substituted aldehyde) is reduced to an unsaturated alcohol (e.g., 4,8-dimethyl-3,7-nonadienyl-substituted alcohol), which is hydrogenated to form the saturated alcohol (e.g., 4,8-dimethylnonyl-substituted alcohol). One non- limiting example of such a method is shown in Example 28, in which the 4,8-dimethyl-3-7-nonadiene substituted aldehyde (28-2) is first reduced using sodium borohydride to form a 4,8-dimethyl-3,7- nonadienyl-substituted alcohol (28-3). The 4,8-dimethyl-3,7-nonadienyl-substituted alcohol is then hydrogenated, e.g., using a palladium catalyst such as Pd/C, a platinum catalyst, or a commercial nickel- based catalyst in a fixed-bed reactor, to saturate double bonds to form a 4,8-dimethylnonyl-substituted alcohol (28-4), which corresponds to Compound J-4-I above).

[00410] In some variations, the unsaturated aldehyde resulting from the Diels-Alder reaction is reduced to a saturated alcohol (e.g., 4,8-dimethylnonyl-substituted alcohol) in a single step, without forming an unsaturated alcohol intermediate. One non-limiting example of such a process in shown in Example 29. As shown, a catalyst such as a ruthenium catalyst over carbon or a palladium catalyst over carbon can be used to reduce the 4,8-dimethyl-3,7-nonadienyl-substituted aldehyde (28-2) directly to a 4,8-dimethylnonyl-substituted alcohol (28-4). Such a reaction is described on page 1198 in "March's Advanced Organic Chemistry," by Michael B. Smith and Jerry March, 5^th edition (John Wiley and Sons, Inc., 2001), which is incorporated herein by reference in its entirety as if put forth fully below.

[00411] An alcohol made by any of the methods described above can be further alkoxylated by any method now known or later side chain. Any of the mono-alcohols or diols described herein may be reacted with an alkylene oxide (e.g., ethylene oxide as shown in Examples 28 and 35-37, or propylene oxide, or both ethylene oxide and propylene oxide) under standard industrial alkoxylation conditions (e.g. sodium hydride, potassium tert-butoxide, or any base having pK>about 16 or 17). The reaction conditions (e.g. time, temperature, pK, concentrations of reagents, solvents) can be varied by any method known in the art to vary the length and/or composition of the alkyloxyl chain. For example, if an alkoxyl chain includes both ethoxyl and propoxyl repeat units, the ratio of ethoxyl to propoxyl repeat units can be controlled by adjusting the ratio of ethylene oxide to propylene oxide during the alkoxylation reaction.

[00412] It should be understood that surfactants may be made from conjugated hydrocarbon terpenes that are not farnesene. In some variations, the conjugated terpene used to make a Diels-Alder adduct useful as a surfactant is myrcene. In some variations, the conjugated terpene used to make a Diels-Alder adduct useful as a surfactant is not myrcene or farnesene, and may for example be any of the Cio-C₃₀ conjugated hydrocarbon terpenes described herein, or any other conjugated hydrocarbon terpene otherwise known in the art.

[00413] The surfactants described herein are nonaromatic and are readily biodegradable. The hydrocarbon terpene (e.g., β-farnesene or a-farnesene) feed used to make the surfactants described herein can be derived from renewable carbon sources. The surfactants described herein can be used as nonionic surfactants. However, it should be recognized that anionic sulfate surfactants can be derived from the surfactants described herein using standard sulfation techniques (e.g. SOs/oleum sulfation) as is used for conventional alkyl ethoxylated sulfates.

[00414] The surfactants described herein can be formulated into a variety of compositions adapted to specific purposes. For example, formulations comprising the surfactants described herein can be designed as emulsifiers, solubilizers, wetting agents, dispersants, anti-foam agents, detergents (e.g., laundry detergents, dishwasher soaps and the like), industrial and household cleaning products (e.g., floor and other surface cleansers, bathroom cleansers, furniture cleansers, degreasers, and the like), fabric care products, oil recovery surfactants, and personal care products (e.g., cleansing bars and liquids, hair care products, moisturizers, dental care products, emollients, humectants and the like). [00415] Within each of these broad purposes, formulations comprising the surfactants described herein can be adapted for certain applications. For example, laundry detergents comprising the surfactants described herein can be developed to remove soil under a variety of laundry conditions, such as varied cycle time (e.g., cycle times as short as 15-20 minutes to cycle times as long as multiple hours), varied water conditions (e.g., hot or cold water, hard or soft water), water level (e.g., high volume water wash as in conventional washing machines to low volume water wash as used in high efficiency washing machines), washing machine design (e.g., degree of agitation) and hand washing.

[00416] The formulations comprising the surfactants describe herein can optionally comprise additional components. For example, detergents comprising one or more surfactants described herein can additionally comprise any one of or any combination of builders, enzymes, polymer additives, and bleach. In some variations, detergents comprise one or more surfactants described herein and one or more builders, one or more enzymes, and one or polymer additives. A builder, enzyme, polymer additive, or bleach, or any combination thereof that can be used in combination with the surfactants described herein can be selected from those builders, enzymes, polymer additives, bleaches, and combinations thereof that are known in the detergent industry. In some variations of detergents made using one or more surfactants described here, the surfactant comprises at least about 5 wt.%, lOwt.%, 15%, 20wt.%, 25wt.%, 30 wt.%, 35 wt.%, 40 wt.%, 45 wt.% or 50 wt.% of the total detergent. In some formulations, more than one surfactant is present, e.g. a nonionic surfactant as described herein, and one or more additional surfactants (e.g. one or more anionic surfactants). In certain embodiments, formulations comprising the surfactants described herein comprise any one of or any combination of the following non-limiting examples of additives: corrosion inhibitors, thickeners, colorants, fragrances, stabilizers, antioxidants, odorants, additional surfactants, stabilizers, emollients or humectants.

[00417] A surfactant described herein can be present in a formulation in any suitable amount.

Depending on the application, a surfactant described herein may be present in an amount in a range from about 0.01 wt.% to about 99.99 wt.%, about 0.1 wt.% to about 99.9 wt.%, about 1 wt.% to about 99 wt.%, about 5 wt.% to about 95 wt.%, about 10 wt.% to about 90 wt.%, about 20 wt.% to about 80 wt.%, from about 30 wt.% to about 70 wt.%, from about 40 wt.% to about 60 wt.% in a formulation, from about 1% wt.% to about 50%wt.%, from about 1% wt.% to about 40wt.%, from about 1 wt.% to about 30wt.%, from about 1 wt.% to about 20wt.%, from about 1 wt.% to about 10 wt.%, where wt.% refers to the weight of the surfactant as a percent of the total weight of the formulation. In some formulations, a surfactant described herein is present in an amount as small as about 1 wt.%, 0.5 wt.%, 0.1 wt.%, or even smaller, e.g. about 0.01 wt.% or 0.05 wt.%. In some formulations, a surfactant described here is present in an amount of about 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 99, 99.9, or 99.99 wt.%) of the total formulation. [00418] A compound, composition, or surfactant described herein is used as a substitute for a nonylphenol or alkoxylated nonylphenol in some formulations. For example, alcohol J-4-I, J-4-V, J-4- VIIA, J-4-VIIB, or J-4-IX as described above may be used as a substitute for a nonylphenol in some formulations. In other formulations, compound J-4-II, J-4-VI, J-4-VIIIA, J-4-VIIIB, or J-4-X as described above (e.g., with n being about 9) can be used as a substitute for an ethoxylated nonylphenol. When using a composition or surfactant described herein as a substitute for a nonylphenol, e.g. an ethoxylated nonylphenol, the composition or surfactant described herein can in some circumstances be used as a direct replacement for the nonylphenol, while in other circumstances, the amount of surfactant substituted for the nonylphenol may be different, or one or more additives (e.g. , an additional surfactant such as an anionic surfactant) may be used in combination with the surfactant described herein to substitute for the nonylphenol.

[00419] In some variations, certain ones of the Diels-Alder adducts described herein have utility as a surfactant for rubber emulsion (e.g., styrene-butadiene rubber) polymerization. For example, a Diels-Alder adduct that comprises one or more carboxyl groups may be used as an aid in rubber emulsion polymerization.

[00420] "HLB" refers to hydrophobic-lipophilic balance. HLB is calculated as follows:

(molecular weight due to ethoxylate units/molecular weight of molecule) x 100%/5. In operation, HLB values range from about 0.5 to 19.5. A low HLB indicates a nonionic surfactant that has high solubility in oil; a high HLB value indicates a nonionic surfactant that has high solubility in water or other polar solvents. For mixing unlike oils together, a surfactant having a HLB in a range from about 1 to about 3 may be used. For making an emulsion by mixing water into oil, a surfactant having a HLB in a range from about 4 to about 6 may be used. For wetting powders into oils, or for making self-emulsifying oils, a surfactant having a HLB in a range from about 7 to about 10 may be used. For making an emulsion by mixing oil into water, a surfactant or blend of surfacts having HLBs in a range from about 8 to about 16 may be used. For making detergent solutions, surfactants having HLBs in a range from about 13 to about 15 may be used. For solubilizing oils into water, surfactants or surfactant blends having HLBs of about 13 to about 18 may be used. HLB value may be selected to lower or minimize the interfacial tension between an oil phase and a water phase.

[001] One measure for quantifying the hydrophilic and hydrophobic content of a nonionic surfactant is the Hydrophile-Lipophile Balance (HLB). A low HLB indicates a nonionic surfactant that has high solubility in oil; a high HLB value indicates a nonionic surfactant that has high solubility in water or other polar solvents. HLB value may be selected to lower or minimize the interfacial tension between an oil phase and a water phase.

[002] HLB values can be calculated for simple alcohol ethoxylates, or measured empirically for other types of nonionic surfactants. HLB is calculated as follows: (molecular weight due to ethoxylate units/molecular weight of molecule) x 100%/ 5. In operation, HLB values range from about 0.5 to 19.5. HLB values for a mixture of surfactants can be determined as a weighted average of the HLB value for each separate surfactant weighted by the amount of that surfactant in the mixture. In some circumstances, an oil supplier supplies an HLB value for a surfactant (or mixture of surfactants) to be used in applications with that oil (e.g., emulsification).

[003] In some cases, a Diels-Alder adduct surfactant as described herein having an HLB value in a range from 0-3 is insoluble in water or has limited solubility in water, and may have application as a defoaming agent. For mixing unlike oils together, a surfactant having a HLB in a range from about 1 to about 3 may be used. In some cases, a Diels-Alder adduct surfactant having an HLB value in a range from 3-6 is insoluble in water or has limited solubility in water, but is dispersible in water, and may have application in forming water-in-oil emulsions. In some cases, a Diels-Alder adduct surfactant having an HLB value in a range from 6-9 is dispersible in water, and may have application as a wetting agent, in forming water-in-oil emulsions, or in forming self-emulsifying oils. In some cases, a Diels-Alder adduct surfactant having an HLB value in a range from 8-10 is somewhat soluble in water, and may have application as a wetting agent. For making an emulsion by mixing oil into water, a surfactant or blend of surfactants having HLBs in a range from about 8 to about 16 may be used. In some cases, a Diels-Alder adduct surfactant having an HLB value in a range from 10-13 is soluble in water, and may have application in forming oil-in-water emulsions, detergents, or cleaning products. In some cases, a Diels- Alder adduct surfactant having an HLB value in a range from 13-15 is soluble in water, and may have utility in forming oil-in-water emulsions, detergents, or cleaning products. For solubilizing oils into water, surfactants or surfactant blends having HLBs of about 13 to about 18 may be used. In some cases, a Diels-Alder adduct surfactant having an HLB value that is greater than equal to about 15 is soluble in water, and may have application as a solubilizer, detergent, or cleaning product.

[00421] The Diels-Alder adducts disclosed herein may be used as surfactants if they comprises one or more ionic groups or polar group. In some embodiments, the Diels-Alder adduct having formula (J-XVIIA) or (J-XVIIB):

(J-XVIIB), where n is 1, 2, 3 or 4; and each of Mi and M₂ is independently a monovalent cation such as Fr+, Cs+, Rb+, K+, Na+, Li+, Ag+, Au+, Cu+, NH4+, primary ammonium, secondary ammonium, tertiary ammonium, or quaternary ammonium, where Mi⁺ and M₂ ⁺may the same or different.

[00422] The Diels-Alder adducts of formulae (J-XVIIA) and (J-XVIIB may be used as surfactants since each of them comprises both a hydrophobic group and a hydrophilic group. [00423] In some variations, the surfactant compounds described herein are useful as solvents.

They may be useful as solvents in a variety of formulations for a variety of applications (e.g., personal care products, industrial solvents, cleaning products, lubricants, agricultural products, coatings, and the like). To evaluate suitability as solvents in particular applications, Hansen solubility parameters may be used. Hansen solubility parameters were calculated for a number of theoretical and synthesized solvents derived from myrcene or farnesene using HSPiP software program, available at www.hansen- solubility.com. The Y-MB algorithm was used to calculate estimated HSP parameters 3D, δΡ and δΗ for Diels-Alder adducts that may be derived from β -farnesene or myrcene as described herein, and are shown in Table S.4. Hansen solubility parameters were also calculated for a number of commercial solvents (Table S.5). As used below, glu indicates a glucose unit.

[00424] In some variations, a Diels-Alder adduct or derivative thereof as described herein has utility as an emollient and as a UV absorber (e.g., for a light stabilizing compound or sunscreen applications). One illustrative and nonlimiting example of a compound that may exhibit properties as an emollient and be capable of absorbing UV light in a useful wavelength range is a Diels-Alder adduct between β-farnesene and a quinone (preparation provided in theExamples). In some variations, a Diels- Alder adduct between β -farnesene and a quinone may be oxidized to increase the degree of conjugation, thereby tuning the UV absorption to the red.

Table S.4. 5D, δΡ and δΗ for Myrcene and β-Farnesene Derived Solvents

ı64 15.6 7.2 13.6 propylene glycol methyl ether

15.5 4.0 11.5 dipropylene glycol methyl ether

15.1 3.5 11.5 tripropylene glycol methyl ether

15.1 5.7 11.7 propylene glycol n propyl ether

15.0 3.0 9.6 dipropylene glycol n propyl ether

14.9 4.9 10.7 propylene glycol n butyl ether

14.8 2.5 8.7 dipropylene glycol n butyl ether

19.6 5.0 7.8 tetrahydrofurfuryl alcohol

18.0 12.3 7.2 n-pyrol

15.5 10.4 7.0 acetone

15.8 4.8 5.8 soy methyl ester

15.8 8.8 19.4 ethanol

16.0 7.6 12.3 butyl cellosolve

18.4 3.0 5.0 hexyl cellosolve

15.6 7.4 12.2 ethyl lactate

[00425] The solvents described herein can be compared with existing solvents and used to replace existing solvents in formulations, or in combination with existing solvents in formulations. One method that can be used to identify potential applications for the solvents described herein (e.g., those identified in Table S.4) is to plot δΗ vs. δΡ for hydrocarbon terpene derived solvent described herein as well as existing solvents, and identify existing solvents with having similar (δΗ, δΡ).

[00426] Described herein are compounds comprising a Diels-Alder adduct of a hydrocarbon terpene (e.g., β-farnesene, such as trans-P-farnesene) comprising a conjugated diene and a dienophile, wherein the Diels-Alder adduct is adapted for use as an additive for a polymer to modify at least one physical property of the polymer. The dienophile may be any suitable dienophile, with non-limiting examples including maleic anhydride and substituted maleic anhydrides, fumaric acid, citraconic anhydride and substituted citraconic anhydrides, itaconic acid and substituted itaconic acids, itaconic anhydride and substituted itaconic anhydrides, acrolein and substituted acroleins, crotonaldehyde and substituted crotonaldehydes, monoalkyl and dialkyl maleates, monoalkyl and dialkyl fumarates, monoalkyl and dialkyl itaconates, acrylic acid esters, methacrylic acid esters, cinnamic acid esters, mesityl oxide and substituted mesityl oxides, hydroxyalkyl acrylates, carboxyalkyl acrylates,

(dialkylamino)alkyl acrylates, dialkyl acetylene dicarboxylates, vinyl ketones, maleimide and substituted maleimides, fumaramide and substituted fumaramides, dialkyl azidocarboxylates, acetylene dicarboxylic acid, dialkyl acetylene dicarboxylates, monoalkyl acetylene carboxylates, 1 ,4-benzoquinone and substituted 1 ,4-benzoquinones, 1 ,2-benzoquinone and substituted 1 ,2-benzoquinones, vinyl sulfinates, vinyl sulfonates, vinyl sulfoxides, sulfur dioxide, naphthoquinones, phosphorus trihalide, and combinations thereof. In some cases, the Diels-Alder adduct is chemically modified prior to being used as an additive for the polymer. [00427] The Diels-Alder adducts may be incorporated into the polymer in any suitable manner to modify at least one physical property of the polymer. For example, the adduct may be physically blended with the polymer or chemically reacted with the polymer. The polymer to be modified may be a thermoplastic, a thermoset or an elastomer. In some cases, the polymer to be modified is a condensation polymer. In some cases, a hydrogenated Diels-Alder adduct is used to modify at least one physical property of the polymer.

[00428] In some cases, the Diels-Alder adduct of a hydrocarbon terpene comprising a conjugated diene and a dienophile may be used as a monomer and polymerized to make a homopolymer, or reacted with one or more comonomers to make an interpolymer. The dienophile may be any suitable dienophile, with non-limiting examples including maleic anhydride and substituted maleic anhydrides, fumaric acid, citraconic anhydride and substituted citraconic anhydrides, itaconic acid and substituted itaconic acids, itaconic anhydride and substituted itaconic anhydrides, acrolein and substituted acroleins, crotonaldehyde and substituted crotonaldehydes, monoalkyl and dialkyl maleates, monoalkyl and dialkyl fumarates, monoalkyl and dialkyl itaconates, acrylic acid esters, methacrylic acid esters, cinnamic acid esters, mesityl oxide and substituted mesityl oxides, hydroxyalkyl acrylates, carboxyalkyl acrylates,

(dialkylamino)alkyl acrylates, dialkyl acetylene dicarboxylates, vinyl ketones, maleimide and substituted maleimides, fumaramide and substituted fumaramides, dialkyl azidocarboxylates, acetylene dicarboxylic acid, dialkyl acetylene dicarboxylates, monoalkyl acetylene carboxylates, 1 ,4-benzoquinone and substituted 1 ,4-benzoquinones, 1 ,2-benzoquinone and substituted 1 ,2-benzoquinones, vinyl sulfinates, vinyl sulfonates, vinyl sulfoxides, sulfur dioxide, naphthoquinones, phosphorus trihalide, and combinations thereof. In some cases, the Diels-Alder adduct is chemically modified prior to being used as a monomer to make a polymer. In some cases, the Diels-Alder adducts may be used as monomer and reacted with one or more co-monomers to make an alkyd resin, a polyester, or a polyamide. In some cases, a Diels-Alder adduct is hydrogenated prior to being used as a monomer for making a polymer.

[00429] In some cases, a Diels-Alder adduct of a hydrocarbon terpene (e.g., β-farnesene such as trans-P-farnesene) comprising a conjugated diene and a dienophile as described herein, is suitable for use as an additive or as a base oil in a lubricant composition. For example, a Diels-Alder adduct containing one or more carboxylate ester groups may be used as a lubricant (e.g., a base oil), or as an additive for a lubricant composition. Any suitable dienophile may be used in the Diels-Alder reaction, with non-limiting examples including monoalkyl and dialkyl maleates, monoalkyl and dialkyl fumarates, monoalkyl and dialkyl itaconates, acrylic acid esters, methacrylic acid esters, cinnamic acid esters, hydroxyalkyl acrylates, (dialkylamino)alkyl acrylates, dialkyl acetylene dicarboxylates, maleimide and substituted maleimides, 1 ,4-benzoquinone and substituted 1 ,4-benzoquinones, 1 ,2-benzoquinone, substituted 1 ,2-benzoquinones, and combinations thereof. In some variations, the Diels-Alder adduct may be hydrogenated prior to use as a lubricant or as an additive in a lubricant composition. In some cases, a Diels-Alder adduct (e.g., a carboxylate ester containing Diels-Alder adduct) may be used as a viscosity index improver in a lubricant composition. In some cases, a Diels-Alder adduct (e.g., a carboxylate ester containing Diels-Alder adduct) may be used as a pour point modifier in a lubricant composition. In some cases, a Diels-Alder adduct (e.g., a carboxylate ester containing Diels-Alder adduct) may be used as a friction modifier in a lubricant composition. In some cases, a Diels-Alder adduct (e.g., a carboxylate ester containing Diels-Alder adduct) may be used as a cutting oil, or as an additive in a cutting oil formulation.

[00430] Also described herein are compounds comprising epoxidized β -farnesene, e.g., mono- epoxidized β -farnesene and Diels-Alder adducts between a hydrocarbon terpene (e.g., β-farnesene) and a dienophile in which at least one carbon-carbon double bond originating from the hydrocarbon terpene has been epoxidized, e.g., mono-epoxidized β -farnesene, mono-epoxidized Diels-Alder adducts, di- epoxidized β-farnesene, di-epoxidized Diels-Alder adducts, β-farnesene functionalized with more than two epoxy groups, and Diels-Alder adducts functionalized with more than two epoxy groups. The epoxidized β -farnesene or epoxidized Diels-Alder adducts may be used as monomers or as cross-linking agents to make polymers. For the epoxidized b-farnesene or Diels-Alder adducts, at least one of the epoxy functional groups may be hydrolyzed (and in some cases, such hydrolyzed derivative may beused as a monomer or as a cross-linking agent to make a polymer).

[00431] Described herein are solvents comprising a Diels-Alder adduct between a hydrocarbon terpene (e.g., b-farnesene) comprising a conjugated diene and a dienophile. In some variations, the solvent is a reactive solvent that reacts with one or more co-solvents or one or more solutes.

[00432] For any of the compounds comprising a Diels-Alder adduct between a hydrocarbon terpene (e.g., β-farnesene such as trans-β -farnesene) comprising a conjugated diene moiety and a dienophile described herein, the hydrocarbon terpene may be derived from a simple sugar by a microorganism.

[00433] Any of the compounds according to any of formulas VIIA, VIIB, VIIA', VIIB', VIIIA,

VIIIB, VIIIA', VIIIB', VIIIA", VIIIB", IXA, IXB, IXA', IXB', Bl, B2, B3, B4, B5, H-1A, H-IB, H-IC, Hl-D, Hl-E, H-IF, H-IG, H-IH, H-IIA, H-IIB, H-IIC, H-IID, H-IIIA, H-IIIB, H-IIIC, H-IIID, H-IVA, H- rVB, H-rVC, H-IVD, H-VA, H-VB, H-VC, H-VD, H-VIA, H-VIB, H-VIIA, H-VIIB, H-VIIC, H-VIID, H-VIIE, H-VIIF, H-VIIG, H-VIIH, H-VIIIA, H-VIIIB, H-VIIIC, H-VIIID, H-VIIIE, H-VIIIF, H-VIIIG, H-VIIIH, H-VIIIJ, H-VIIIK, H-VIIIL, H-VIIIM, H-IXA, H-IXB, H-IXC, H-IXD, H-IXE, H-IXF, H- IXG, H-IXH, H-XA, H-XB, H-XC, H-XD, H-XE, H-XF, H-XG, H-XH, H-XIA, H-XIB, H-XIC, H-XID, H-XIE, H-XIF, H-XIG, H-XIH, H-XIJ, H-XIK, H-XIL, H-XIM, Η-ΧΓΝ, H-XIO, H-XIP, H-XIQ, H-XIR, H-XIS, J-XVA, J-XVB, J-XVIA, J-XVIB, Table 2, Table 3, Table 5, Table S.4, Examples 1-82 may be adapted for use as an additive for a polymer to modify at least one physical property of the polymer, for use as a monomer to make a polymer, for use as an additive or as a base oil in a lubricant composition, for use as a monomer or cross-linking agent to make a polymer, for use in a surfactant, or for use in a solvent. The compounds described herein may be used as additives to modify mechanical properties of any type of polymer, including thermoplastics, thermosets, and elastomers. In some cases, the compounds are used as additives to modify mechanical properties of alkyd resins, condensation polymers (e.g., polyesters or polyamides), or addition polymers. In some cases, the compounds described herein may be used as monomers to make homopolymers or as monomers to be reacted with one or more comonomers to make interpolymers. The compounds may be used to make thermoplastics, thermosets or elastomers. In some cases, the compounds described herein are used as monomers to make a condensation polymer (e.g., a polyester or a polyamide). In some cases, the compounds described herein are used to make alkyd resins. The compounds described herein may be adapted for use as lubricants (e.g., base oils), or as additives to lubricant compositions (e.g., as a viscosity index improver, a friction modifier, or a pour point modifier). In some cases, the compounds described herein are used as cutting oils or as components in a cutting oil formulation.

[00434] While the compounds, compositions and methods have been described with respect to a limited number of embodiments, the specific features of certain embodiments should not be attributed to other embodiments described herein. No single embodiment is representative of all aspects of the compositions or methods. In some embodiments, the compositions or methods may include numerous compounds or steps not mentioned herein. In other embodiments, the compositions or methods do not include, or are substantially free of, any compounds or steps not enumerated herein. Variations and modifications from the described embodiments exist.

EXAMPLES

[00435] For the following Examples β-farnesene refers to trans-P-farnesene. Unless otherwise specified, b-farnesene is manufactured using genetically modified organisms by Amyris, Inc., and has been distilled prior to use to result in a purity of >97%, and includes lOOppm 4-tert-butylcatechol (TBC) as a stabilizer. As used herein, Me refers to a methyl group, nBu refers to an n-butyl group.

Example 1. Preparation of 5-(4,8-Dimethylnona-3,7-dienyl)cyclohex-4-enecarboxylic acid methyl

la lb

[00436] A 3 L round-bottomed flask equipped with a magnetic stirrer, heating mantle and reflux condenser was charged with 704 g (3.44 mol) of β-farnesene (>97% pure, Amyris, Inc.), 342 mL (326 g, 3.79 mol) of methyl acrylate and 1.0 g (3.1 mmol) of Znl. Toluene (200 mL) was added and the stirring mixture was heated to 80-95 °C. After 14 hours the reaction was allowed to cool to ambient temperature and filtered through a 9.5 cm X 5.5 cm column of neutral alumina using 300 mL of hexane as a rinsing solvent. The bulk of the two solvents were removed under reduced pressure to afford 1025 g of crude isomeric ester mixture la, lb as a pale yellow oil. The product was characterized by the following NMR data: ^lH NMR (CDC1₃): δ 5.39 (s, br, 1H), 5.10 (m, 2H), 3.69 and 3.60 (s, 3H total), 2.45 (m, 1H), 2.27- 1.92 (m, 13H), 1.68 (s, 3H), 1.67 (m, 1H), 1.60 (s, 3H) and 1.59 (s, 3H).

Example 2. Preparation of 4-(4,8-Dimethylnona-3,7-dienyl)cyclohex-3-enecarboxylic acid dodecyl ester (2a) and 5-(4,8-Dimethylnona-3,7-dienyl)cyclohex-4-enecarboxylic acid dodecyl esters (2b).

2b

[00437] A 5 L three-necked round-bottomed flask equipped with a magnetic stirrer, heating mantle and dean stark trap carrying a reflux condenser was charged with 486 g (1.76 mol) of la, lb, 332 g (1.78 mol) of 1-dodecanol, 0.10 g of / toluenesulfonic acid and 200 mL of toluene. The mixture was stirred and heated to refluxing. When the required amount of water had been collected the toluene was removed by distillation and the crude product allowed to cool to ambient temperature and vacuum filtered through a 25 mm X 80 mm plug of silica gel to afford 763 g (97.6%) of isomeric ester mixture comprising esters 2a and 2b as a pale yellow oil. The product was characterized by the following NMR data: ¾ NMR (400MHZ, CDC1₃): δ 5.38 (s, br, 1H), 5.09 (m, 2H), 4.07 (m, 2H), 2.47 (m, 1H), 2.3-1.9 (m, 13H), 1.68 (s, 3H), 1.63 (m, 1H), 1.59 (s, 6H), 1.27 (s, br, 20H) and 0.88 (t, J = 6.4 Hz, 3H); ¹³C NMR (100.5 MHz, CDC1₃): δ 175.94, 175.90, 137.3, 136.0, 135.0, 131.1, 124.5, 124.2, 120.3, 119.1, 64.42, 64.38, 40.0, 39.8, 39.6, 37.8, 37.6, 32.0, 29.7, 29.63, 29.60, 29.5, 29.4, 28.8, 27.8, 26.8, 26.4, 26.0, 25.7, 25.6, 22.8, 17.7, 16.0 and 14.2.

Example 3. Preparation of 4-(4,8-Dimethylnonyl)cyclohexane carboxylic acid dodecyl ester (3a) and 3-(4,8-Dimethylnonyl)cyclohexane carboxylic acid dodecyl ester (3b) [FW-00448-024]).

3b

[00438] A solution of 1484 g of 2a, 2b in 7 L of hexane was hydrogenated over 587.5 g of

N1/AI₂O₃ using a flow-through reactor at 500 psig H₂ and 150 °C with a linear space velocity of 2.0. At the conclusion of the reaction the reactor was washed with 0.75 L of EtOAc (ethyl acetate) which was combined with the product solution. The solvents were removed under reduced pressure and the residual oil distilled at 185 °C (1 torr) to afford 1142 g of a mixture comprising esters 3a and 3b as a colorless oil. The product was characterized by the following NMR data: ^lH NMR (400 MHz, CDC1₃): δ 4.05 (m, 2H), 2.60 (p, J = 3.0Hz, 0.05H), 2.50 (p, J = 3.0Hz, 0.20H), 2.28 (tt, J = 10.8 and 3.2 Hz, 0.12H), 2.21 (tt, J = 12.0 and 3.2 Hz, 0.13H), 1.94 (m, 2H), 1.80 (m, 0.5H), 1.65-1.42 (m, 2.5H), 1.44-1.00 (m, 20.5H), 1.26 (s, br, 20H) 0.88 (t, J = 6.8Hz, 3H), 0.86 (d, J = 5.6Hz, 3H), 0.850 and 0.848 (d, J = 6.4Hz, 3H together); ¹³C NMR (100.5 MHz, CDC1₃): δ 176.35, 176.29, 175.7, 175.6, 64.29. 64.26, 64.23, 43.72, 43.67, 40.8, 39.4, 37.7, 37.6, 37.5, 37.1, 37.0, 35.73, 35.68, 35.5, 32.8, 32.6, 32.53, 32.46, 32.4, 29.7,

29.6, 29.6, 29.4, 29.3, 29.2, 29.1, 28.7, 28.6, 28.0, 26.3, 26.0, 25.9, 25.6, 24.8, 24.54, 25.47, 24.3, 24.2,

22.7, 22.6, 19.7 and 14.1.

Example 4. Preparation of 5-(4,8-dimethylnona-3,7-dienyl)cyclohex-4-ene-l,2-dicarboxylic acid din-butyl ester (4).

[00439] β-Farnesene (537 g, 2.63 mol), di(2-«-butyl)maleate, Znl (1.0 g, 3.1 mmol) and 200 mL of toluene were combined in a 3 L round-bottomed flask equipped with a magnetic stirrer, heating mantle and reflux condenser attached to a nitrogen bubbler. The mixture was stirred and heated to refluxing. After 18 hours the reaction was allowed to cool to ambient temperature and the bulk of the toluene removed under reduced pressure. The residue was transferred to a separatory funnel with 400 mL of EtOAc and washed with water (3 X 250 mL), 10% citric acid solution (1 X 250 mL, water (2 X 250 mL), brine (2 X 250 mL), dried (MgS0₄) and the solvent removed under reduced pressure to afford 1160 g of crude ester 4 as a pale yellow oil that was carried on to the next step without further purification. The product was characterized by the following NMR data: ^lH NMR (400 MHz, CDC1₃): δ 5.38 (s, br, 1H), 5.09 (t, br, J = 6.7 Hz, 2H), 4.08 (dt, J = 1.6 and 6.4 Hz, 4H), 3.01 (m, 2H), 2.53 (m, 2H), 2.30 (m, 2H), 2.07 (h, J = 7.2 Hz, 4H), 1.97 (m, 4H), 1.68 (s, 3H), 1.60 (s, 6H), 1.58 (m, 2H), 1.38 (m, 4H) and 0.92 (t, J = 7.6 Hz, 6H); ¹³C NMR (100.5 MHz, CDC1₃): δ 173.40, 173.38, 136.18, 135.15, 131.24, 129.8, 124.4, 124.0, 118.9, 64.44, 64.40, 40.4, 39.8, 39.7, 37.5, 30.7, 29.0, 26.8, 26.2, 26.0, 25.7, 19.18, 17.7, 16.0 and 13.7.

Example 5. Preparation of 4-(4,8-Dimethylnonyl)cyclohexane-l,2-dicarboxylic acid dibutyl ester (5, [FW-00448-025]).

5 (FW-00448-025)

[00440] A solution of 1207 g of crude 4 in 5 L of hexane was hydrogenated as described for 3 above and the product distilled at 185 °C at 5 torr to provide 1160 g of 5 as a colorless oil. The product was characterized by the following NMR data: ^lH NMR (400 MHz, CDC1₃): δ 4.07 (m, 4H), 3.22 (s, br, 1H), 2.42 (dt, J = 3.5 and 12.8 Hz, 1H), 2.27 (s, br, 1H), 2.06 (d, br, J = 14.0 Hz, 4H), 1.00-1.65 (m, 22H), 0.93 (t, J = 7.2 Hz, 6H), 0.87 (d, J = 6.4 Hz, 6H) and 0.84 (d, J = 6.4 Hz, 3H); ¹³C NMR (100.5 MHz, CDC1₃): δ 173.9, 173.5, 64.2, 43.7, 41.6, 39.4, 37.4, 37.3, 37.1, 32.8, 30.68, 30.67, 30.60, 28.9, 28.8, 28.3, 28.0, 24.8, 24.2, 22.7, 22.6, 19.7, 19.20, 19.16, 13.73 and 13.69. Subsequent GPC analysis showed 12.7% polymer (by area).

Example 6. Preparation of 5-(4,8-Dimethylnona-3,7-dienyl)cyclohex-4-ene-l,2-dicarboxylic acid bis-(2-ethylhe

6

[00441] Using the procedure for the preparation of mixture 4 , with the exception of the Znl catalyst, 375 g (1.84 mol) of β-farnesene and 662 g (1.83 mol) of di(2-ethylhexyl)maleate were heated at 90-95 °C for 18 hours to afford 1028 g of crude 6 that was carried on to the next step without purification. The product was characterized by the following NMR data: ^lH NMR (400 MHz, CDC1₃): δ 5.38 (s, Br, 1H), 5.09 (t, br, J = 6.40 Hz, 2H), 4.01 (m, 4H), 2.53 (m, 2H), 2.31 (m, 1H), 2.07 (m, 4H) and 1.98 (m, 4H).

Example 7. Preparation of 4-(4,8-Dimethylnonyl)cyclohexane-l,2-dicarboxylic acid bis-(2- ethylhexyl) ester (7

[00442] A solution of 1477 g of crude 6 in 5 L of hexane was hydrogenated as described for 3 above and the product distilled at 150 °C (5 torr) to provide 1143 g of 7 as a colorless oil. The product was characterized by the following NMR data: ^lH NMR (400 MHz, CDC1₃): 3.99 (m, 4H), 3.25 (s, br, 0.81H), 2.43 (m, 0.85H), 2.25 (m, 0.81H), 2.05 (m, 2.11H), 1.69-1.45 (m, 6H), 1.42-1.00 (m, 30H) and 0.93-.80 (m, 21H). ¹³C NMR (100.5 MHz, CDC1₃): δ 173.9, 173.6, 66.78, 66.77, 66.64, 66.62, 43.7, 41.7, 39.4, 38.83, 38.77, 37.4, 37.3, 37.1, 32.8, 30.6, 30.54, 30.50, 30.4, 29.0, 28.9, 28.5, 28.0, 24.8, 24.2, 23.89, 23.88, 23.85, 23.81, 23.0, 22.8, 22.6, 19.7, 14.1, 11.06, 11.01, 10.99 and 10.96. Subsequent GPC analysis showed 14.1% polymer (by area).

Example 8. Preparation of 5-(4,8-Dimethylnona-3,7-dienyl)cyclohex-4-ene-l,2-dicarboxylic acid dimethyl ester (8).

[00443] Using the procedure for 5 above 587 g (2.87 mol) of β-farnesene and 414 g (2.87 mol) of dimethyl maleate were heated at 90-95 °C for 18 hours to afford 1047 g of crude 8 as a nearly colorless oil. The product was characterized by the following NMR data: ^lH NMR (400 MHz, CDC1₃): δ 5.38 (s, br, 1H), 5.08 (t, br, J = 6.4 Hz, 2H), 3.68 (s, 3H), 3.02 (m, 2H), 2.51 (m, 2H), 2.30 (m, 2H), 2.07 (m, 4H), 1.98 (m, 4H), 1.68 (s, 3H), 1.60 (s, 3H)and 1.59 (s, 3H); ¹³C NMR (100.5 MHz, CDC1₃): δ 173.8, 136.1, 135.2, 131.2, 124.4, 123.9, 118.8, 51.77, 51.75, 40.3, 39.7, 37.4, 28.8, 26.7, 26.1, 25.9, 25.7, 17.7 and 16.0.

Example 9. Preparation of 4-(4,8-Dimethylnonyl)cyclohexane-l,2-dicarboxylic acid dimethyl ester (9) [FW-00448-027]).

[00444] A solution of 913 g of crude 8 in 5 L of hexane was hydrogenated as described for 3 above and the product distilled at 150 °C (5 torr) to provide 817 g of 9 as a colorless oil. The product was characterized by the following NMR data: ^lH NMR (400 MHz, CDC1₃): δ 3.68 (s, 3H), 3.66 (s, 3H), 3.23 (m, 1H), 2.44 (dt, J = 4.0 and 12.3 Hz, 1H), 2.22 (m, 1H), 2.06 (d, br, J = 13.6 Hz), 1.63- 0.97 (m, 22H), 0.87 (s, 3H), 0.86 (s, 3H) and 0.83 (d, J = 6.8 Hz); ¹³C NMR (100.5 MHz, CDC1₃): δ 174.4, 173.9, 51.67, 51.56, 43.7, 41.5, 39.4, 37.3, 37.1, 32.7, 30.63, 30.56, 28.9, 28.8, 28.1, 28.0, 24.8, 24.2, 22.7, 22.6 and 19.7. Subsequent GPC analysis showed no detectable amount of polymer.

Example 10. 5-(4,8-Dimethylnona-3,7-dienyl)cyclohex-4-ene-l,2-dicarboxylic acid diheptyl ester (10).

[00445] Using the procedure for 5 above 444 g (2.17 mol) of β-farnesene and 678 g (2.17 mo 1) of diheptyl maleate were heated at 90-95 °C for 18 hours to afford 1060 g of crude 10 as a nearly colorless oil. ^lH NMR (400 MHz, CDC1₃): δ 5.38 (s, br, 1H), 5.09 (t, br, J = 7.2 Hz, 2H), 4.06 (dt, J = 1.6 and 6.8Hz, 4H), 3.01 (m, 2H), 2.50 (t, br, J = 5.6 Hz, 2H), 2.30 (t, br, J = 5.6 Hz, 2H), 2.09 (m, 4H), 1.98 (m, 4H), 1.68 (s, 3H), 1.68 (s, 3H), 1.67 (m, 4H), 1.59 (s, 3H), 1.29 (m, 16H) and 0.88 (t, J = 6.8 Hz, 6H); ¹³C NMR (100.5 MHz, CDC1₃): δ 173.42, 173.39, 136.1, 135.2, 131.3, 124.4, 124.0, 118.9, 64.8, 64.7, 40.3, 39.8, 39.7, 37.5, 31.8, 28.9, 28.6, 26.7, 26.2, 25.9, 25,7, 22.6, 17.7, 16.0 and 14.1.

Example 11. 4-(4,8-Dimethylnonyl)cyclohexane-l,2-dicarboxylic acid diheptyl ester (compound 11 below) [FW-004 -031]).

[00446] A solution of 1254 g of crude 10 in 5 L of hexane was hydrogenated as described for 3 above and the product distilled at 175 °C (25 torr) to remove a small amount of low boiling material and then redistilled at 215 °C (5 torr) afford 1101 g of 11 as a colorless oil. The product was characterized by the following NMR data: ^lH NMR (400 MHz, CDC1₃): δ 4.06 (m, 4H), 3.23 (s, br, 1H), 2.42 (dt, J = 4.0 and 12.0 hZ, 1H), 2.27 (m, 1H), 2.06 (d, br, J = 13.0Hz, 1H), 2.00 (m, 1H), 1.67-1.43 (m, 9H), 1.40 1.00 (m, 29H), 0.88 (t, J = 6.8 Hz, 6H), 0.87 (s, 3H), 0.86 (s, 3H) and 0.84 (d, J = 6.4 Hz, 3H); ¹³C NMR: (100.5 MHz, CDC1₃): δ 173.9, 173.5, 64.6, 64.5, 43.7, 41.6, 39.4, 37.39, 37.35, 37.21, 37.16, 32.8, 31.8, 30.7, 30.6, 29.0, 28.9, 28.8, 28.7, 28.6, 28.3, 28.0, 26.0, 25.93, 25.87, 24.8, 24.2, 22.7, 22.6, 19.7 and 14.1. Subsequent GPC analysis showed the presence of about 12.5% polymer (by area).

Example 12. 4-(4,8-Dimethylnona-3,7-dienyl)cyclohex-3-enecarboxylic acid 2-ethylhexyl ester (12a) and 5-(4,8

[00447] A 1000 mL three-necked round-bottomed flask equipped with a magnetic stir bar, thermometer, and condenser was charged with 2-ethylhexyl acrylate (283.7 g, 1.540 mol) and trans- - farnesene (314.6 g, 1.539 mol). The mixture was stirred until homogenous and heated to 100 °C. After 6 hours the reaction was analyzed by GCMS, which showed that 11.6 % (area percent) 2-ethylhexyl acrylate and 16.6 % farnesene still had not reacted. The reaction was continued overnight at 84 °C while stirring. The reaction was analyzed by GCMS after 25 hours, indicating the presence of the following compounds: 5.4 % ethylhexyl acrylate, 6.0 % farnesene, and two peaks corresponding to the 1,3- and 1,4- isomers of (12b and 12a, respectively) representing 29.2 and 58.0 % of the final product mixture. Heating was discontinued and the mixture was subjected to hydrogenation. The product was characterized by the following NMR data: ^lH NMR (400 MHz, CDC1₃): δ 5.393 (1H, broad singlet), 5.098 (2H, broad singlet), 3.999(2H, m), 2.5(1H, multiplet), 1.93-2.27 (13H, broad multiplet), 1.65-1.73 (1H, multiplet), 1.68 (3H, broad singlet), 1.53-1.63 (1H, multiplet), 1.597 (6H, broad singlet), 1.26-1.4 (8H, multiplet) and 0.895 (6H, overlapping triplets) Example 13. Preparation of 4-(4,8-Dimethylnonyl)cyclohexane carboxylic 2-ethylhexyl ester (13a) and 3-(4,8 56-01]

[00448] Two different lots of a mixture of compounds (12a, 12b) were hydrogenated in a continuous flow reactor. The hydrogenation system was a 0.5 inch outer diameter stainless steel tube reactor equipped with a 1/8 inch thermocouple rod. The latter runs through the length of the reactor and monitors the temperature at six different points. The flow reactor was packed with 40 mL of 20% N1/AI2O3 (whole extradate). The catalyst bed was activated over H₂ flow at 230 °C for 1 hour. A mixture of compounds (13a, 13b) was hydrogenated under the following conditions: 1.0 LHSV, H₂ mass flow controller set to 300 seem, 500 psi H₂, and 100 °C. The product was collected and analyzed by GCMS to determine complete saturation. All the lots were combined for purification on a wiped- film evaporator. Analysis by GPC showed no detectable polymer.

[00449] The hydrogenated final product which was a complex mixture of isomers (1,3 and 1,4- disubstituted cis- and iroro-isomers on the ring). The stereocenter on the side chain of the product exhibited characteristic peaks in the ^lH NMR spectrum (400 MHz, CDC1₃) at δ 3.994 (d, 2H, from some of the isomers), 3.973 (d, 2H, from the other isomers), 2.622 (dt, minor isomer(s)), 2.515 (dt, major isomer(s)), 2.276 (tt, minor isomer(s)), 2.218 (tt, major isomer(s)), 1.96 (bd) and 1.799 (bd).

[00450] Reaction scheme for Examples 12 and 13 is as follows, with only the 1,4 isomer shown for simplicity:

Example 14. Incorporation of plasticizers into PVC at 5wt% using a twin screw extruder

[00451] A Berstorff Model #ZE40A x 32D twin screw extruder was used to compound the samples by addition of 5% plasticizer to Geon 06935 White Rigid PVC pellets supplied by PolyOne Corporation. The feed zone temperatures for the extruder are as follows (temperatures in °F):

[00452] The melt temperatures ran between 345°F and 355°F, with the higher temperatures required for the neat resin and the lower for the plasticized batches. Batches were prepared in poly buckets at 5% loadings and 5g of plasticizer added back in to compensate for the loss of plasticizer on the bucket and hopper/screws. Each plasticizer run was flushed with 2 to 3 lb of neat resin before the start of the next run and plasticizer samples were taken at mid run. This temperature profile followed PolyOne 's general recommendation for rigid PVC extrusion. Each of samples FW-00448-024 (Example 3), FW- 00448-025 (Example 5 above), FW-00448-026 (Example 7 above), FW-00448-027 (Example 9 above), FW-00448-031 (Example 11 above), and KJF-437-56-01 (Example 13 above) compounded with the twin screw extruder were homogeneous and light in color. For this rigid PVC, no significant differences in physical properties were observed with the addition of 5% of the plasticizer candidates and neat PVC samples.

Examples 15-20 and Comparative Examples CE 1-CE 3. Incorporation of plasticizers into PVC at 25wt% using a Brabender Melt-mixer Compounder

[00453] The Brabender melt-mixer compounder was pre -heated to 400°F. Neat Geon® 06935

PVC, available from PolyOne Corp., was added to the Brabender then mixed until melted (approx. 5 minutes). One to two gram quantities of each of the plasticizers listed in Table 1 below were added to the well of the compounder and mixed until incorporated. The addition is repeated until the target % of plasticizer was added (10 minutes) or until the sample showed visual incompatibility after 20 to 30 minutes of mixing. If the sample was mixing well such that compatibility was observed, it was mixed for an additional 5 minutes after the last of the plasticizer was added. Example 15 shows incorporation of the plasticizer described in Example 13 into PVC; Example 16 shows incorporation of the plasticizer described in Example 3 into PVC; Example 17 shows incorporation of the plasticizer described in Example 11 into PVC; Example 18 shows incorporation of the plasticizer described in Example 7 into PVC; Example 19 shows incorporation of the plasticizer described in Example 5 into PVC; Example 20 shows incorporation of the plasticizer described in Example 9 into PVC; Comparative Example CE 1 shows incorporation of the commercially available DOP (dioctyl phthalate) into PVC; Comparative Example CE 2 shows incorporation of Hexamoll® DINCH (1,2-Cyclohexanedicarboxylic acid, diisononyl ester), available from BASF into PVC; and Comparative Example CE 3 shows incorporation of CITROFLEX® A-4 (Acetyltri-n-butyl Citrate), available from Vertellus Specialities, Inc., into PVC.

Table E.l . Sample identifications and processing results for Examples 15-20 and Comparative Examples CE 1-CE 3

[00454] For each of Examples 15 and 19, the plasticizers, KJF-437-56-01 and FW-00448-025, discolored early into the compounding operation and did not incorporate well into the PVC, so that compounding was discontinued prior to reaching 25wt%> loading. For each of Example 16 (plasticizer of Example 3), Example 17 (plasticizer of Example 11), and Example 18 (plasticizer of Example 7), incorporation was not observered or discoloration indicated degradation during the compounding procedure described here, so that physical testing was not continued.

Examples 21-22 and Comparative Examples CE 4-CE 9. Physical testing of compounded PVC samples

[00455] Compounded PVC from Example 20 and Comparative Examples CE 1 -CE 3 were pressed into plaques for measuring tensile properties and Izod impact strength. One hundred and ten grams of each plasticized PVC sample were placed into a 5 inch x 6 inch x 0.08 inch mold lined with Kapton® polyimide sheets. A pressure between 10 to 12 tons was applied to the press, which was preheated to 390°F (199°C).

[00456] The plaques were die cut into test specimens for tensile property testing according to

ASTM D638 "Standard Test Method for Tensile Properties of Plastics," which is incorporated by reference herein in its entirety and for Izod impact strength testing according to ASTM D256 "Standard Test Methods for Determining the Izod Pendulum Impact Resistance of Plastics," which is incorporated by reference herein in its entirety. A second set of test specimens cut in the same manner as the first set and heat aged in an oven for 120 hours at 70°C. Heat aged samples were weighed prior to and after heat aging for 120 hours at 70°C. The heat aged samples were conditioned for at least 40 hours in a constant temperature humidity (70°F / 50% Relative Humidity) room prior to testing.

[00457] FIGURE 1 shows percentage change in weight before and after heat aging for 5 test specimens each for Example 22 and Comparative Examples CE 7-CE 9. Also, percentage changes in weight for several test specimens of neat PVC are shown. PVC samples including 25wt% plasticizer FW-0448-027 show about 0.8-1% weight loss after heat aging at 70°C for 120h, whereas PVC samples including 25wt% DOP show about 0.2% weight loss, PVC samples including 25wt% DINCH show about 0.2-0.4% weight loss, and PVC samples including 25wt% CITROFLEX® A-4 show about 1-1.6% weight loss under the same conditions.

[00458] Tensile properties for Examples 21 and 22 and Comparative Examples CE 4-CE 9 were measured according to ASTM D638, using a pull rate of 50mm/min. Engineering stress (MPa) vs. strain (%) curves are measured for using 5 test specimens each of Examples 21 and 22 and Comparative Examples CE 4-CE 9. Tensile properties are shown in FIGURES 2-8, where each bar represents a mean value for 5 test specimens, and the error bars indicate maxima and minima of the 5 individual test results.

[00459] Toughness is calculated as the area under the stress-strain curves, up to point of fracture.

FIGURE 2 shows calculated toughness in MPa for Examples 21 and 22, Comparative Examples CE 4- CE 9, and for neat PVC specimens. Plasticizer FW-0448-027 increases toughness of the PVC from about 10-20 MPa to about 40 MPa in both heat aged and non heat aged samples, which is comparable to the increase in toughness observed for DOP, DINCH, and CITROFLEX® A-4.

[00460] Young's modulus (or modulus of elasticity) is calculated as the slope of the early (low strain) portion of the measured stress-strain curves. FIGURE 3 shows Young's modulus in MPa for Examples 21 and 22 and Comparative Examples CE 4-CE 9. Elasticity represents the property of complete and immediate recovery of displacement of a sample caused by loading of that sample, upon release of the load.

[00461] FIGURE 4 shows engineering strain (% elongation) at break measured according to

ASTM D638 for Examples 21 and 22, Comparative Examples 4-9, and neat PVC specimens. As shown, the percent elongation for heat aged and non heat treated specimens of PVC including 25wt% FW-0448- 027 plasticizer is about 265%, comparable to that for Comparative Examples 4-9. Heat aged samples with 25wt% FW-0448-027 show a slight decrease in percent elongation at failure relative to non-heat aged samples, where the loss in percent elongation at failure is intermediate between that observed for heat aged samples with 25wt% CITROFLEX A-4 and 25wt% DOP.

[00462] Other tensile properties measured according to ASTM D638 are shown in FIGURES 5-8.

FIGURE 5 shows displacement at break, FIGURE 6 shows load at break, FIGURE 7 shows stress at break, and FIGURE 8 shows energy to yield point. [00463] Izod impact strength measurements according to ASTM D256 for Examples 21 and 22 resulted in a non-break failure, and no useful data. The samples did not show notch propagation or other visual change, and energy to bend the samples could not be measured.

Example 23. Preparation o -Farnesene-Maleic Anhydride Diels Alder Adduct (14)

[00464] Distilled β-farnesene (Amyris, about 1.5 L) was stirred with anhydrous magnesium sulfate (Fisher Scientific, 150 g) for about 15 minutes, and then filtered (5 micron, nylon). The filtrate was stirred for about 30 minutes with basic super I alumina (Sorbent Technologies, Inc., 75 g) and filtered (5 micron, nylon) to give a colorless, highly transparent filtrate which was identified as β- farnesene. A portion of the filtrate (502.7 g, 2.460 mol) was combined with ethyl acetate (obtained from J.T. Baker 9282-03, 2201.8 g) and the resulting solution stirred for 30 minutes at room temperature under nitrogen. To the solution was added maleic anhydride (obtained from Aldrich Chemical, Ml 88, 99.8%, 240.3 g) and the suspension thus obtained was stirred at room temperature under nitrogen for 12 hours to give a solution. The solution was rotary evaporated (31 °C, 50 torr) and a portion (118.06 g) was distilled (0.17 mm Hg, 220 °C) to give a colorless liquid (73.07g). GC-MS: 13.969 min (99.3 area%), 302 (M+, m/z), Karl Fischer titration determination of water (according to ASTM D6304, which is incorporated herein by reference in its entirety): 18 ppm.

Example 24. Preparation of -(2,8-Dimethyl-3,4,7,8-diepoxynonyl)-2-vinyloxirane (15)

[00465] A 2 L round-bottomed flask equipped with a magnetic stirrer and a pressure equalizing addition funnel was charged with β-farnesene (>97% pure, Amyris, Inc., 20.4 g, 0.100 mol) and 300 mL of CH₂CI₂. The flask was immersed in a water bath and solution of 3-chloroperoxybenzoic acid (obtained from Sigma Aldrich, 77%, 58.1 g, 0.259 mol) in 500 mL of CH₂CI₂ added dropwise over one hour. Periodically small portions of ice were added to the water bath to prevent the reaction mixture from refluxing. When the addition was complete the stirring was continued at ambient temperature for 16 hours. The precipitated 3-chlorobenzoic acid was removed by vacuum filtration and the CH₂C1₂ removed from the crude product by rotary evaporation. The residue was taken up in 200 mL of ethyl acetate and washed with saturated NaHC0₃ solution (5 X 75 mL), H₂0 (2 X 50 mL), brine (2 X 50 mL), dried (MgS0₄) and the solvent removed under reduced pressure. The residue was dissolved in a minimum volume of 20% EtOAc/hexane solution and passed through a 2.5 X 15 cm column of silica gel to remove the last traces of 3-chlorobenzoic acid. Evaporation of the solvents afforded 21.0 g (89.0%>) of triepoxide 15 as a colorless oil. The product was characterized by the following NMR data: ^lH NMR (CDC1₃): δ 5.76 (m, 1H), 5.35 (m, 1H), 5,23 (m, 1H), 2.83 (m, 1H), 2.73 (m, 1H), 2.70 (m, 2H), 1.67 (8H), 1.31 (s, 3H), 1.28 (s, 3H) and 1.27 (s, 3H).

Example 25. Preparation of 2-( utadiene (16)

16

[00466] A 25 mL round-bottomed flask equipped with a magnetic stirrer and glass stopper was charged with β-farnesene (1.00 g, 4.89 mmol), Novozyme-435™ (0.147 g, Sigma Aldrich) urea-peroxide complex (0.920 g, 9.78 mmol) and 10 mL of ethyl acetate. The mixture was stirred at 20 °C for 16 hours. An additional 0.150 g of urea-peroxide complex was added in two equal portions 24 hours apart to consume the starting material and form a mixture of 82%> of diepoxide 16 and 9%> of triepoxide 15.

Example 26. Preparation farnesene

17 18

[00467] β-Farnesene (>97%> pure, Amyris, Inc., 6.81 g, 33.4 mmol) was diluted in 140 mL methylene chloride and the clear solution was cooled in an ice water bath. Solid MCPBA (meta chloroperoxybenzoic acid) (77%> pure maximum, 8.2 g, 36.6 mmol theoretical) was added to the solution in two portions. After 80 minutes, GCMS shows a mixture of 29%> unreacted farnesene and 71 > of the two monoepoxides 17 and 18. After stirring for 18 hours, conversion had increased to 76%>. The mixture was filtered through paper and then washed twice with a mixture of 40 mL water and 40 mL saturated sodium bicarbonate. After drying over potassium carbonate, filtering, and solvent removal, 7.59 g crude monoepoxide mixture was obtained.

Example 27. Epoxidation of n-butyl 4,8-dimethyl-nona-3,7-dienyl cyclohexene carboxylates (mixture of 1 ,3 and 1 ,4 disubstituted isomers)

[00468] A solution of 4-(4,8-dimethylnona-3,7-dienyl)cyclohex-3-enecarboxylic acid n-butyl ester and 5-(4,8-dimethylnona-3,7-dienyl)cyclohex-4-enecarboxylic acid n-butyl ester (19a, 19b), which can be prepared according to the procedure for Example 12, except substituting n-butyl acetate for 2- ethylhexyl acetate (5.3 g, 16.0 mmol), in 150 mL ethyl acetate is cooled in an ice water bath and solid MCPBA (17.62 g, 77% max., 78.6 mmol theoretical) is added in 4 portions over 60 minutes. After the addition, the mixture is stirred at ice bath temperature for 1 hour and then at room temperature for 4 hours. The crude reaction mixture is washed twice with 100 ml 5% sodium bicarbonate solution and dried over solid potassium carbonate. The solution is filtered and concentrated to give about 4.8 g light yellow oil as a mixture of isomers, with a yield of about 76%.

[00469] Partially epoxidized dicarboxylic acid esters derived from β-farnesene can be obtained in a similar manner using a higher ratio of starting ester to oxidant, e.g., so that the ratio of starting ester to oxidant is greater than about 1 :5, such as about 1 :4, 1 :3, 1 :2, 1 :1 or 0.5: 1.

Example 28: Preparation of Ethoxylated Alcohol from Diels- Alder Adduct

[00470] An ethoxylated alcohol is prepared from a Diels-Alder adduct between β-farnesene and acrolein according to Scheme 28 below.

28-1 28-2

28-3 28-4

SCHEME 28

Preparation of Aldehyde (28-2).

[00471] A 3 L round-bottomed flask equipped with a magnetic stirrer, heating mantle and reflux condenser connected to a nitrogen bubbler was flushed with nitrogen and charged with β-farnesene (785 g, 3.84 mol), Znl₂ (available from Sigma-Aldrich) ( 1.0 g, 3.1 mmol) and toluene (200 mL). The stirring was started and 80 mL of acrolein (available from Sigma-Aldrich) added. The mixture was then heated to a very low reflux and after two hours an additional 177 mL of acrolein were added at such a rate that the refluxing was controlled. After 24 hours the reaction was allowed to cool to ambient temperature and filtered sequentially through a 9.5 X 5.5 cm column of silica gel and a 3cm x 4cm pad of Celite filter (available from Sigma-Aldrich). The filtrations were washed with 1 L of hexane. The combined filtrates and washings were evaporated under reduced pressure to afford 1014 g of crude product as a very pale yellow oil. The pale yellow oil was characterized as follows: GC/MS, m/z 260 (M⁺); ^lH NMR (CDC1₃), δ (9.69, J=1.2 Hz, 1H and 9.68, J=1.2 Hz, 1H, ratio 1 :3.8), 5.42 (brs, 1H), 5.10 (dt, J=3.4 and 1.2 Hz, 2H), 2.45 (m 1H), 2.22 (m, 2H), 2.05 (m, 8H), 1.99 (m, 4H), 1.68 (s, 3H), 1.60 (s, 3H), 1.59 (s, 3H).

Preparation of Alcohol (28-3).

[00472] To a 1L round-bottomed flask equipped with a magnetic stirrer were added 58 1 g (0.223 mol) of aldehydes (28-2) and 250 mL of absolute ethanol. The mixture was stirred and 3.09 g (0.0812 mol) of NaBH₄ were added in portions at such a rate that the rate of gas evolution was controlled. One hour after addition of the last portion the reaction was complete. A solution of 0.3% aqueous HC1 was carefully added dropwise to destroy the excess NaBH₄ and the bulk of the ethanol removed under reduced pressure. The oily aqueous residue was partitioned between 100 mL of ethyl acetate and 250 mL of H₂0. The layers were separated and the aqueous phase extracted with ethyl acetate (2 times 50 mL). The organic phases were combined washed with saturated NaCl solution (2 times 50 mL), dried (MgS0₄) and the solvent removed under reduced pressure. The residual oil was distilled using a Kugelrohr distillation apparatus to provide 43.4 g (74.2%) of a 1 :3.8 isomer mixture of alcohol (28-3) as a colorless oil: Bp 190°C @ 1.0 mm: GC/MS, m/z 262 (M⁺); ¾ NMR (CDC1₃), δ 5.37 (brs, 1H), 5.10 (dt, J=3.4 and 1.2 Hz, 2H), 3.50 (m, 2H), 2.07 (m, 6H), 1.98 (m, 5H),1.82 (m, 1H), 1.73 (m, 1H), 1.68 (s, 3H), 1.60 (s, 6H), 1.26 (m, 1H); ¹³C NMR (CDC1₃), δ 137.7, 136.5, 135.0, 131.2, 124.4, 124.3, 120.7, 119.5, 67.8, 67.7, 39.7, 37.9, 37.7, 36.8, 36.3, 31.4, 28.3, 27.8, 26.8, 26.4, 25.7, 25.3, 24.8, 17.7, 16.0.

Preparation of Alcohol (28-4).

[00473] Alcohol (28-3) (43.0 g, 0.164 mol), 10% Pd/C and ethyl acetate (350 mL) were placed in a IL Parr autoclave and placed under 950 psig of hydrogen. The mixture was rapidly stirred (500 rpm) and heated to 75°C. As the reaction progressed the hydrogen pressure was readjusted to 950 psig. After 36 hr the heating was discontinued and the catalyst removed by vacuum filtration. The ethyl acetate was removed under reduced pressure to afford 43.0 g (91.1%) of alcohol (28-4) as a colorless oil with isomer ratio as above for alcohol (3): GC/MS, m/z 268 (M⁺); ^lH NMR (CDC1₃), δ 3.51 (d, J=6.4 Hz, 2H), 3.42 (d, J=6.4 Hz, 2H), 1.78 (d, J=8.4 Hz), 1.7-1.0 (m, 21H), 0.90 (m, 2H), 0.87, 0.86, 0.85, 0.83 (s, CH₃, total 9H); ¹³C NMR (CDC1₃), δ 68.7, 68.7, 40.7, 40.6, 39.4, 38.4, 38.0, 37.9, 37.8, 37.4, 37.4, 37.3, 37.3, 32.8, 32.7, 29.6, 29.5, 28.9, 28.8, 28.0, 25.8, 25.4, 24.8, 24.4, 24.3.

Preparation of Ethoxylated Alcohol (28-5) (prophetic).

[00474] Alcohol 28-4 will be ethoxylated under standard industrial conditions to produce the ethoxylated alcohol 28-5 as a colorless oil. To achieve ethoxylated alcohol 28-5 having an average value of n=9, nine molar equivalents of ethylene oxide can be used per mole of alcohol 28-4.

Example 29. Preparation of an Ethoxylated Alcohol from a Diels-Alder Adduct (prophetic)

[00475] An ethoxylated alcohol may be prepared from a Diels-Alder adduct between β-farnesene and acrolein according to Scheme 29 below.

n= ca. 9

28-5

SCHEME 29

[00476] Referring to Scheme 29, the aldehyde (28-2) will be prepared as described in Example

28 above. The aldehyde (28-2) will be reduced with a Ruthenium on carbon catalyst using a hydrocarbon co-solvent in an autoclave at elevated temperature (75 to 100°C) with hydrogen gas at pressures between about 500 to 1000 psig. The catalyst will be removed by vacuum filtration and the co-solvent evaporated under reduced pressure to produce the alcohol (28-4). The ethoxylated alcohol (28-5) will be produced from alcohol (28-4) as described in Example 28 above.

Example 30. Preparation of (E)-dimethyl 4-(4,8-dimethylnona-3,7-dienyl)cyclohex-4-ene-l,2-

Organics (New Jersey)

Silica (SiliaFlash® 4.5 kg

F60, available from

Silicycle, Inc., Quebec

City, Quebec, CA

CH₂C1₂, Fisher 1.5 L

Scientific, Inc.,

certified ACS

Ethyl acetate, 10 L

Pharmco-Aaper,

reagent ACS, USP/NF

grade

Hexanes, Fisher 34 L

Scientific, Inc.,

certified ACS

[00477] A 5 L, 3 neck flask was equipped with a magnetic stir bar, a N₂ inlet, a type-J teflon covered thermocouple, and a reflux condenser. β-Farnesene (900 g, 4.40 mol) and dimethyl maleate (604 mL, 4.63 mol) were added. The mixture was heated to 110°C and stirred overnight. After it was determined by GC/MS and NMR that the reaction had not gone to completion, the mixture was heated to 130°C and stirred overnight, after which time it was complete. The material was pre-adsorbed onto 1.5 kg flash-grade silica by dissolving in CH₂CI₂ (1.5 L) followed by concentration under reduced pressure. The material was then loaded onto a column of flash-grade silica (3 kg) and eluted with: hexanes (4 L), 10% ethyl acetate / hexanes (10 L), 20%> ethyl acetate / hexanes (10 L), 30%> ethyl acetate / hexanes, 40%> ethyl acetate / hexanes. The fractions (2 L) were collected. Those fractions containing the desired compound were collected (10 L - 22 L) and concentrated to provide (E)-dimethyl 4-(4,8-dimethylnona- 3,7-dienyl)cyclohex-4-ene-l,2-dicarboxylate (1414 g, 92% yield). FIG. 9 shows a proton NMR spectrum of (E)-dimethyl 4-(4,8-dimethylnona-3,7-dienyl)cyclohex-4-ene-l ,2-dicarboxylate.

Aldrich

Heptanes, Reagent Plus 3.4 L

99%, Sigma Aldrich

[00478] To a N₂ flushed carboy (8 L) was added nickel catalyst ~65 wt% on silica/alumina (101 g), heptanes (2 L), (E)-dimethyl 4-(4,8-dimethylnona-3,7-dienyl)cyclohex-4-ene-l,2-dicarboxylate (501 g, 1.44 mol) and further heptanes (1.4 L). This slurry was transferred to the autoclave with additional heptanes (700 mL) then purged twice with N₂ (500 psi). H₂ (500 psi) was added and solution was heated to 80-90°C. Upon reaching temperature, further H₂ was added (1100 psi). Samples were pulled by venting H₂ followed by a N₂ purge. By NMR, the reaction was determined to be complete at 48h. The slurry was discharged from the autoclave. The autoclave was rinsed with heptanes (3 L). The slurry was filtered through ¼" celite in a 2L fritted funnel (M) then chased with further heptanes (4 L). The solution was concentrated under reduced pressure to provide dimethyl 4-(4,8- dimethylnonyl)cyclohexane-l,2-dicarboxylate (498 g, 98% yield). FIG. 10 shows a proton NMR spectrum of dimethyl 4-(4,8-dimethylnonyl)cyclohexane-l,2-dicarboxylate.

[00479] A 22 L, 4 neck flask was equipped with an overhead mechanical stirrer, a N₂ inlet, a type-J TEFLON® covered thermocouple, a reflux condenser, an addition funnel and a water bath. A THF solution of Lithium aluminum hydride (4.0 L, 4.0 mol) was cannulated into the flask. Dimethyl 4- (4,8-dimethylnonyl)cyclohexane-l,2-dicarboxylate (941 g, 2.65 mol) was added to the addition funnel, diluted with heptane (2.8 L) and added to the flask over 50 min. while maintaining a reaction temperature of < 40°C. Following the addition, the water bath was dropped and the reaction was stirred for lh. By TLC, the reaction was determined to be complete (R_f (Dimethyl 4-(4,8-dimethylnonyl)cyclohexane-l,2- dicarboxylate) = 0.70 (30% ethyl acetate/hexanes) vs. R_f(4-(4,8-dimethylnonyl)cyclohexane-l,2- diyl)dimethanol) = 0.10 (30% ethyl acetate/hexanes). The solution was cooled to 5°C. Water (150 mL) was added over 30 min. 15%> NaOH (150 mL) was added followed by a further portion of water (450 mL). The solution was stirred for 25 min. Na₂S0₄ (400 g) was added. The slurry was stirred overnight, filtered through celite and concentrated to provide (4-(4,8-dimethylnonyl)cyclohexane-l,2- diyl)dimethanol (784 g, 99% yield). FIG. 11 and FIGS. 12A and 12B shows proton and ¹³C NMR spectra, respectively, of (4-(4,8-dimethylnonyl)cyclohexane-l,2-diyl)dimethanol.

Example 33. Preparation of a mixture of (E)-3-(4,8-dimethylnona-3,7-dienyl)cyclohex-3-

[00480] A 3 L, 4 neck flask was equipped with an overhead mechanical stirrer, a N₂ inlet, a type-

J TEFLON® covered thermocouple, a reflux condenser, and an addition funnel. Toluene (200 mL), zinc iodide (7.81 g, 2.45 mmol) and acrolein (50 mL, 711 mmol) were added. The solution was heated to 70°C to initiate the reaction. Acrolein (250 mL 3.55 mol) and zinc iodide (2.84 g, 8.9 mmol) were added to maintain a reaction temperature of 70-80°C. (N.B. When the reaction failed to display an exotherm upon addition of acrolein, the solution was cooled to rt and a further charge of zinc iodide was added. The solution was then warmed to 70°C and addition of acrolein continued). Following the addition, the solution was stirred at reflux overnight. The solution was concentrated to provide the crude material (1078 g) which was pre-adsorbed onto 1.3 kg flash-grade silica by dissolving in CH₂CI₂ (2.0 L) followed by concentration under reduced pressure. The material was then loaded onto a column of flash-grade silica (3.8 kg) and eluted with: hexanes (6 L), 10% EtOAc / hexanes (10 L), 20% EtOAc / hexanes (20 L). The fractions (2 L) were collected. Those fractions containing the desired compound were collected (12 L - 24 L) and concentrated to provide a mixture of (E)-3-(4,8-dimethylnona-3,7-dienyl)cyclohex-3- enecarbaldehyde and (E)-4-(4,8-dimethylnona-3,7-dienyl)cyclohex-3-enecarbaldehyde (859 g, 89% yield) as shown by ^lB NMR in FIG. 13 and by GC/MS in FIGS. 14A-14B.

Example 34. Preparation of a mixture of (3-(4,8-dimethylnonyl)cyclohexyl)methanol and (4-(4,8-

[00481] To a N₂ flushed 600 mL Parr autoclave was added the mixture of (E)-3-(4,8- dimethylnona-3,7-dienyl)cyclohex-3-enecarbaldehyde and (E)-4-(4,8-dimethylnona-3,7-dienyl)cyclohex- 3-enecarbaldehyde (50 g, 192 mmol), ruthenium on carbon (6.2 g) and 2-propanol (200 mL). The vessel was pressure -tested with N₂ (900 psi) and purged twice with N₂ (600 psi). H₂ (600 psi) was added and the slurry was heated to 75°C. H₂ (700 psi) was added and maintained for 48h. By NMR, it was determined that the reaction had gone to completion. The slurry was filtered through ¼" celite in a 200 mL fritted funnel (M) then chased with further 2-propanol (100 mL). The solution was concentrated under reduced pressure to provide a mixture of (3-(4,8-dimethylnonyl)cyclohexyl)methanol and (4-(4,8- dimethylnonyl)cyclohexyl)methanol (52 g, 100% yield) as shown by proton NMR in FIG. 15.

Examples 35-37: P

SCHEME 35

[00482] A mixture of (3-(4,8-dimethylnonyl)cyclohexyl)methanol and (4-(4,8- dimethylnonyl)cyclohexyl)methanol as prepared in Example 34 was ethoxylated according to Scheme 35 using standard industrial ethoxylation methods, where n molar equivalents ethylene oxide) was used per mol mixture (3-(4,8-dimethylnonyl)cyclohexyl)methanol and (4-(4,8- dimethylnonyl)cyclohexyl)methanol, where n represents the average number of glycol units in the resulting ethoxylated alcohol. Thus, 5 molar equivalents of ethylene oxide per mol of the mixture of (3- (4,8-dimethylnonyl)cyclohexyl)methanol and (4-(4,8-dimethylnonyl)cyclohexyl)methanol as prepared in Example 34 was used for n=5, 10 molar equivalents of ethylene oxide per mol of the mixture as prepared in Example 34 was used for n=10, and 15 molar equivalents of ethylene oxide per mol of the mixture as prepared in Example 34 was used for n=15. Table 35 shows the resulting ethoxylated alcohols and a calculated HLB value for each ethoxylated alcohol.

[00483] Example 35 was an off-white semi-solid. ^lH NMR are shown in FIGS. 16A-16C, and are consistent with the structures shown in Table 35, with n approximately equal to 5 (average number of glycol units). The NMR showed trace amounts of solvents were present (0.7% dichloromethane and 1.0%) toluene). FIGS. 16D- 16F show ¹³C NMR spectra that are consistent with the structures shown in Table 35.

[00484] Example 36 was an off-white semi-solid. NMR spectra are shown in FIGS. 17A-

17C, and are consistent with the structures shown in Table 35, with n approximately equal to 10 (average number of glycol units). The NMR showed the presence of trace amounts of solvent (toluene, 0.3%>). FIGS. 17D-17F show ¹³C NMR spectra that are consistent with the structures shown in Table 35.

[00485] Example 37 was an off-white semi-solid. NMR spectra are shown in FIGS. 18A-

18C, and are consistent with the structures shown in Table 35, with n approximately equal to 15 (average number of glycol units). The NMR showed the presence of trace amounts of solvent (toluene, 0.3%). FIGS. 18D-18F show ¹³C NMR spectra that are consistent with the structures shown in Table 35.

TABLE 35

Examples 38-40: Preparation of ethoxylated diols

n=5, 10 and 15

SCHEME 38

[00486] (4-(4,8-dimethylnonyl)cyclohexane-l,2-diyl)dimethanol as prepared in Example 32 was ethoxylated according to Scheme 38 using standard industrial ethoxylation methods, where 2n molar equivalents ethylene oxide) were used per mol (4-(4,8-dimethylnonyl)cyclohexane-l,2-diyl)dimethanol), where n represents the average number of glycol units in the resulting ethoxylated alcohol. Thus, 10 molar equivalents of ethylene oxide per mol of (4-(4,8-dimethylnonyl)cyclohexane-l,2-diyl)dimethanol as prepared in Example 32 was used for n=5, 20 molar equivalents of ethylene oxide per mol of the compound as prepared in Example 32 was used for n=10, and 30 molar equivalents of ethylene oxide per mol of the compound as prepared in Example 32 was used for n=15. Table 38 shows the resulting ethoxylated alcohols and a calculated HLB value for each ethoxylated alcohol.

[00487] Ethoxylation for Example 38 was carried out as follows. A 20L Parr reactor was rinsed with toluene (2L), and purged with nitrogen by pressurizing to 200 psi and venting 2-3 times. This purge was also used to check that all of the fittings on the apparatus were sealed and that no drop in pressure was observed after 1 hour. The vessel was then charged with potassium hydroxide (7.04g, 0.126 mol, 0.075 eq), diol SM2 (500g, 1.675 mol) and toluene (2L), then sealed and stirred. The vessel was purged one last time with nitrogen (up to -100 psi) and vented before proceeding. A 5L round bottom flask— equipped with a dry-ice condenser (passive N₂ flow to top of condenser)— was charged with toluene (2L) and cooled to -78°C with dry-ice/heptanes. The ethylene oxide cylinder was connected to a pressurizing N₂ line on the gas take-off side, and pressurized to 50°C. The liquid take-off side was connected to the metering valve (needle valve), then placed on a balance and tared. All likely places for gas to escape were checked with a handheld monitor for ethylene oxide and secured if necessary. Ethylene oxide (738 g, 16.75 mol) was then bubbled into the cold toluene at a feed rate of ~2g/sec. The ethylene oxide solution temperature rose to slightly above -60°C. While the ethylene oxide was being metered into the cold solvent, the Parr reactor was heated to 120°C. Once the ethylene oxide transfer into the cold solvent was complete, the heads of a prep HPLC pump (Hitachi Prep36) were covered with a bag of dry ice to cool the heads and prevent cavitation. The pump was primed with pure toluene, and then used to meter the cold ethylene oxide solution into the Parr reactor (already at 8psi from heating the toluene solution to 120°C). The feed rate was nominally -27 mL/min (according to the pump display) but the solution required 2.5 hours to complete which equates to ~8 mL/min (most likely due to partial cavitation in the pump heads). The pressure during this time rose as high as 60 psi. The reaction mixture was stirred at 120°C for 2 hours, then cooled to room temperature and stirred overnight. The reaction mixture was drained out of the reactor, and the reactor was rinsed with 2L toluene. The light brown solution was concentrated on a rotary evaporator to give 1,233 g amber oil (yield=99%). Ethoxylation of Examples 35-37, 39 and 40 were carried out in a similar manner. For Examples 35-37, 39 and 40, the product froze (at least partially) on standing to give an off-white semi-solid (melting points <50°C). For Example 38, no solid was observed at room temperature.

[00488] Example 38 was an amber oil. ^lH NMR are shown in FIGS. 19A- 19C, and are consistent with the structure shown in Table 38, with n approximately equal to 5 (average number of glycol units). The NMR showed trace amounts of solvent was present (<0.1% toluene). FIGS. 19D- 19F show ¹³C NMR spectra that are consistent with the structure shown in Table 38.

[00489] Example 39 was a hazy amber oil. ^lH NMR spectra are shown in FIGS. 20A-20C, and are consistent with the structure shown in Table 38, with n approximately equal to 9.2 (average number of glycol units). The ^lH NMR showed the presence of trace amounts of solvent (toluene, 0.4%). FIGS. 20D-20F show ¹³C NMR spectra that are consistent with the structure shown in Table 38.

[00490] Example 40 was an off-white semi-solid. NMR spectra are shown in FIGS. 21A-

21C, and are consistent with the structure shown in Table 38, with n approximately equal to 15 (average number of glycol units). The NMR showed the presence of trace amounts of solvent (toluene, <0.1%). FIGS. 21D-21F show ¹³C NMR spectra that are consistent with the structures shown in Table

38.

TABLE 38

Examples 41-46: Preparation of Ester-Containing Lubricants

[00491] Six examples of ester-containing Diels-Alder adducts that have utility as lubricants were made. Kinematic viscosity (KV) at 40°C and at 100°C were measured according to ASTM D445, which is incorporated herein by reference in its entirety. Viscosity index (VI) was determined according to ASTM D2270, which is incorporated herein by reference in its entirety. Volatility was evaluated by measuring average % wt. loss using TGA-Noack analysis. Results are summarized in Table 41.

[00492] For Example 41, first a mixture of (E)-2-(2-(2-Ethoxyethoxy)ethoxy)ethyl 3-(4,8- dimethylnona-3,7-dien-l -yl)cyclohex-3-enecarboxylate and (E)-2-(2-(2-ethoxyethoxy)ethoxy)ethyl 4- (4,8-dimethylnona-3,7-dien-l -yl)cyclohex-3-enecarboxylate (compound 41-1 below) was prepared according to the following procedure.

41-1

Mixture of isomers

[00493] β-Farnesene (12.3 g, 60.1 mmol), 2-(2-(2-ethoxyethoxy)ethoxy)ethyl acrylate (14.1 g,

60.1 mmol) and toluene (20 mL) were combined in a 250 mL round-bottomed flask equipped with a heating mantle, magnetic stirrer and reflux condenser. The mixture was stirred and heated to refluxing. After 30 hours the mixture was allowed to cool and the toluene removed under reduced pressure. The residual oil was subjected to kugelrohr distillation to provide 16.4 g (64.0 %) of the isomeric products as a pale yellow oil; bp 235 °C @ 0.08 torr.

[00494] A mixture of 2-(2-(2-Ethoxyethoxy)ethoxy)ethyl 3-(4,8- dimethylnonyl)cyclohexanecarboxylate and 2-(2-(2-ethoxyethoxy)ethoxy)ethyl 4-(4,8- dimethylnonyl)cyclohexane-carboxylate (compound 41-2 below) was prepared according to the following procedure.

41-2

Mixture of isomers

[00495] Compound 41-1 was placed in a 100 mL autoclave with 0.28 g of 5% Pd/C and 20 mL of ethyl acetate. After three evacuate/N₂ flush cycles the reactor was charged with hydrogen 400 psig) and the mixture stirred and heated to 75 °C. As the reaction proceeded the hydrogen pressure was periodically adjusted back to 400 psig. When hydrogen uptake had ceased the reactor was allowed to cool, the mixture filtered through Celite and the solvent removed under reduced pressure to afford 19.6 g (97.1%) of isomeric products as a colorless oil. 'HNMR; (CDC1₃) δ 4.22 (m, 2H), 3.71-3.50 (m, 10H), 3.58 (t, J = 7.2 Hz, 2H), 2.54 (m, 0.3H), 2.25 (m, 0.7H), 1.96 (m, 2H), 1.80 (m, 1.4H), 1.58-1.00 (m, 16.6H), 1.21 (t, J = 7.2 Hz, 3H), 0.86 (d, J = 6.8 Hz, 6H), 0.84 (d, J = 6.8 Hz, 3H). ¹³CNMR; δ 196.2, 176.2, 70.7, 70.638, 70.609, 69.8, 69.3, 69.2, 66.6, 63.3, 63.2, 43.5, 43.4, 39.4, 37.5, 37.3, 37.033, 36.966, 32.8, 32.4, 32.3, 29.5, 29.4, 29.099, 29.042, 28.0, 26.1, 24.8, 24.5, 24.2, 22.7, 22.6, 19.7, 15.2.

[00496] Example 42 [4-(4,8-Dimethylnonyl)cyclohexane-l,2-dicarboxylic acid diheptyl ester] was prepared as in Example 11.

[00497] For Example 43, first (E)-2-(2-Ethoxyethoxy)ethyl 3-(4,8-dimethylnona-3,7-dien-l- yl)cyclohex-3-enecarboxylate and (E)-2-(2-ethoxyethoxy)ethyl 3-(4,8-dimethylnona-3,7-dien-l- yl)cyclohex-3-enecarboxylate (compound 43-3 below) was prepared according to the following procedure.

43-3

Mixture of 1,3- and 1,4-isomers

[00498] Using the procedure for Example 41 , excluding the toluene solvent that was used for making compound 41-1, 105 g (0.513 mol) of β-farnesene and 100 g (0.489 mol) of 2-(2- ethoxyethoxy) ethyl acrylate were combined in a 500 mL round-bottomed flask, stirred and heated to 1 10 °C for 40 hours. The reaction mixture was allowed to cool and the excess β-farnesene removed by kugelrohr distillation to provide 190 g (99%) of 43-3 as a colorless oil. 'HNMR; (CDC1₃) δ 5.4 (s, br, 1H), 5.10 (s, br, 2H), 4.24 (m, 2H), 3.71 , (m, 2H), 3.64 (m, 2H), 3.58, (m, 2H), 3.52 (t, J = 6.8 Hz, 2H), 2.57 (m, 1H), 2.34-1.84 (m, 14H), 1.67 (s, 3H), 1.60 (s, 6H), 1.21 (t, J = 6.8 Hz). ¹³CNMR; δ 175.9, 175.8, 137.3, 136.0, 135.0, 131.1 , 124.4, 124.1 , 120.3, 1 19.0, 70.7, 70.5, 69.9, 69.2, 69.2, 66.7, 63.4, 39.8, 39.7, 39.4, 37.7, 37.5, 30.6, 27.7, 26.8, 26.3, 25.7, 25.6, 25.2, 24.6, 17.7, 16.0, 15.2.

[00499] A mixture of 2-(2-Ethoxyethoxy)ethyl 3-(4,8-dimethylnonyl)cyclohexanecarboxylate and 2-(2-ethoxyethoxy)ethyl 4-(4,8-dimethylnonyl)cyclohexanecarboxylate (compound 43-4 below) was made according to the following procedure.

43-4

Mixture of isomers [00500] Using the procedure for compound 41-2 above 30.0 g of 43-3, 0.35 g of 5% Pd/C and 20 mL of hexane were combined in a 100 mL autoclave and heated to 90 °C under 800 psig of hydrogen for 18 hours to afford 24.6 g of 43-4 as a colorless oil. 'HNMR; (CDC1₃) δ 4.24 (m, 2H), 3.70 (m, 2H), 3.65 (m, 2H), 3.59 (m, 2H), 3.53 (2H, J = 6.8 Hz, 2H), 2.65-2.51 (m, 0.5H), 2.35-2.22 (m, 0.5H), 1.98 (m, 2H), 1.83-1.68 (m, 1H), 1.52 (m, 2H), 1.45-1.00 (m, 18H), 1.21 (t, J = 6.8Hz, 3H), 0.87 (t, J = 6.8 Hz, 3H), 0.84 (t, J = 6.4 Hz, 3H). ¹³CNMR; δ 176.2, 176.1, 175.7, 175.5, 70.6, 69.9, 69.284, 69.254, 66.7, 63.246, 63.166, 43.5, 43.4, 40.6, 39.4, 37.7, 37.5, 37.3, 37.031, 36.961, 35.6, 35.5, 35.462, 32.8, 32.6, 32.5, 32.4, 32.3, 29.5, 29.4, 29.1, 29.0, 28.0, 26.2, 25.5, 24.8, 24.5, 24.247, 24.163, 22.7, 22.6, 19.7, 15.2.

[00501] Example 44 [a mixture of 4-(4,8-Dimethylnonyl)cyclohexane carboxylic acid dodecyl ester and 3-(4,8-Dimethylnonyl)cyclohexane carboxylic acid dodecyl ester] was prepared as in Example 3.

[00502] Example 45 [4-(4,8-Dimethylnonyl)cyclohexane-l,2-dicarboxylic acid dimethyl ester] was prepared as in Example 9.

[00503] Example 46 [4-(4,8-Dimethylnonyl)cyclohexane-l,2-dicarboxylic acid bis-(2- ethylhexyl) ester] was prepared as in Example 7.

TABLE 41

Example 47: Preparation of Isosorbide diesters

[00504] Acrylic Acid/Farnesene Adduct Reaction with Isosorbide: Carboxylic acid 47-1 (49.2 g, 0.178 mol) (mixture of 1,3- and 1,4- isomers), isosorbide (47-2, 12.4 g, 0.850 mol), / toluene sulfonic acid (100 mg) and 150 mL of toluene were placed in a 500 mL round-bottomed flask equipped with a magnetic stirrer, heating mantle and dean stark trap carrying a reflux condenser. The mixture was stirred and heated to refluxing. After three days the theoretical amount of water had collected in the trap and the mixture was allowed to cool to ambient temperature. The toluene was removed under reduced pressure and the residual oil chromatographed on a 24 cm X 6.5 cm column of silica gel with 20% ethyl acetate/hexane to remove a small amount of unreacted starting materials and monoester. Removal of the solvent afforded 32.8 g (58.6%>) of 47-3 (mixture of 1,3- and 1,4- isomers) as colorless oil.

[00505] Hydrogenation of Diester 47-3: Isosorbide diester 47-3 (32.8 g, 49.5 mmol), 10% Pd/C

(Alfa Aesar, 0.25 g) and 20 mL of 1 : 1 ethyl acetate/hexane were combined in an autoclave. After three evacuate N₂ flush cycles the reactor was charged with 800 psig of hydrogen, stirred at 400 rpm and the mixture heated to 90 °C. As the reaction progressed the pressure was periodically brought back to 800 psig until hydrogen uptake ceased. The catalyst was removed by filtration and the solvents under reduced pressure to afford 32.5 g (97.3%>) of product 47-4 (mixture of 1,3- and 1,4- isomers) as thick colorless oil. The product was characterized by 'HNMR.

Example 48: Preparation s-Alder adduct between β-farnesene and 1,4-benzoquinone

MW=20₄.36 MW=108.10 MW=516.81

MF=C_1¾H , MF=C_RH,0,

Sch erne 48 MW mass volume

Reagent/ Solvent Supplier Lot # (g/mL) \ (g/mol) ; mmol ; (g) \ (mL) : equiv. :

; beta-fa rnesene :Amyri s 10025-125-20L \ 204.36 : 580 118.50 1.0

[00506] Procedure: In each of 3 separate pressure vessels, 1 ,4-benzoquinone (10.46 g, 96.8 mmol) was suspended in β-farnesene (39.5 g, 193 mmol). A magnetic stirring bar was place in each of the vessels and the three vessels were placed in a sandbath which was heated to 73 °C (thermocouple monitored near the vessels). Due to the nature of the setup, it is unlikely that the magnetic stir bar was sufficiently coupled with the magnetic stirrer to insure efficient stirring throughout the time of the reaction. The reaction mixture was heated in this manner for two days. On the third day, two of the three reaction mixtures were pulled from the sand bath. One of the mixtures was dark brown and

heterogeneous with dark solids in the bottom of the vessel. The other mixture was dark brown and homogeneous. The third mixture was also dark brown and homogeneous. Since there was a difference noted, a small amount from each of the two differing mixture was taken and combined for GC/MS analysis of the crude reaction mixture. GC/MS showed good conversion to the desired product (retention time -24 min; m/z = 516). Later that third day, on standing, the homogeneous reaction mixture which had been removed from the sand bath for sampling became rather thick with solids. The parallel reaction mixture which was heterogeneous on removing from the sand bath showed no noticeable change. 10 g of the "homogeneous" reaction mixture was placed on 300 mL of silica gel. The material was eluted using 1200 mL of petroleum ether wherein the top spot by TLC eluted (likely unreacted farnesene). Eluting was continued with 2% ethyl acetate in petroleum ether (500 mL), 4% ethyl acetate in petroleum ether (500 mL), and 6% ethyl acetate in petroleum ether (1000 mL) until the second fastest spot on TLC eluted completely. After evaporation of the volatiles from this second eluting compound, 5.34 g of product was obtained as a slightly yellow waxy solid. (A yellow band elutes at the leading edge of the product which may be a colored impurity). The remainder of this "third" of the reaction mixture was purified on 500 mL of silica gel by eluting first with petroleum ether (2L) followed by 6% Ethyl acetate to elute the product. Each of the remaining parallel reactions was also purified using this procedure. In total, 67.86 g (45% of theoretical) of product was obtained as a slightly yellow low melting waxy semi-solid after evaporation of the eluent.

Example 49: Preparation of rac-3a,7a-syn-((E)-5-(4,8-dimethylnona-3,7-dien-l-yl)-3a,4,7,7a- tetrahydroisobenzofuran-l,3-dione) (49)

49

[00507] A 50 gallon GLS reactor which was purged with argon was charged first with ethyl acetate (80 L) followed by butylhydroxytoluene (BHT) (9.8 g) and trans-beta-farnesene (26.3 kg, 129 mol). Maleic anhydride (12.0 kg, 122 mol) was added in portions over 1.5 hours while the temperature was maintained through water cooling <25 °C. The reaction was then allowed to proceed at ambient temperature under an atmosphere of Ar for 21.5 hours once the addition of maleic anhydride was complete. Ethyl acetate was removed at 35 torr where the reactor jacket temperature was raised to 65 °C. An analysis of this product mixture by GC indicated 3.0 wt% EtOAc. Excluding EtOAc, the product was shown to be 96.9 wt% pure with 1.55 wt % unreacted beta-farnesene. The product was a clear and colorless viscous liquid. Analyses were performed on a product purified by distillation: GC-MS (m/z = 302); 'H NMR (400MHZ, CDC1₃): δ 5.63-5.65 (m, br, 1H), 5.03-5.10 (m, 2H), 3.32-3.42 (m, 2H), 2.51 - 2.64 (m, 2H), 2.24-2.29 (m, 2H), 1.94-2.10 (m, 8H), 1.68 (s, 3H), 1.60 (s, 3H), 1.58 (s, 3H).

[00508] A 50 gallon GLS reactor which was purged with argon was charged first with ethyl acetate (80 L) followed by butylhydroxytoluene (BHT) (9.8 g) and trans-beta-farnesene (17.8 kg, 87.3 mol). Maleic anhydride (12.0 kg, 83.3 mol) was added in portions over 1.5 hours while the temperature was maintained through water cooling <25 °C. The reaction was then allowed to proceed at ambient temperature under an atmosphere of Ar for 21.5 hours once the addition of maleic anhydride was complete. Ethyl acetate was removed at 35 torr where the reactor jacket temperature was raised to 65 °C. An analysis of this product mixture by GC indicated 3.0 wt% ethyl acetate (EtOAc). Excluding EtOAc, the product was shown to be 96.9 wt% pure with 1.55 wt % unreacted beta-farnesene. The product was a clear and colorless viscous liquid. Analyses were performed on a product purified by distillation: GC- MS (m/z = 302); ¾ NMR (400MHz, CDC1₃): δ 5.63-5.65 (m, br, 1H), 5.03-5.10 (m, 2H), 3.32-3.42 (m, 2H), 2.51-2.64 (m, 2H), 2.24-2.29 (m, 2H), 1.94-2.10 (m, 8H), 1.68 (s, 3H), 1.60 (s, 3H), 1.58 (s, 3H).

Example 50: Preparation of rac-5-(4,8-dimethylnonyl)hexahydroisobenzofuran-l,3-dione (50)

[00509] A 5L Parr reactor was charged with the triolefm intermediate (49) produced in the manner described above (2520 g, 8.33 mol). The hydrogenation catalyst, 5% Pd/C (20 g) was then added. The reactor was sealed and was then pressurized with hydrogen (550 psi). The mixture was heated (140 °C) with stirring. The reactor was repressurized in a repetitive manner until a constant pressure of H₂ was maintained. The reactor was then cooled and cautiously vented. The material was then diluted with heptane (1.5L), and the resulting solution was filtered through a pad of celite 545 (200 g). The volatile materials were removed under vacuum yielding the crude product as a slightly yellow oil. This material was fractionally distilled at 0.8 torr pressure. The fraction boiling between 230 °C and 245 °C was collected as the product. The product was obtained in this manner as a slightly yellow oil (1399 g, 54% yield). GC-MS (m/z = 308); ^lH NMR (400MHz, CDC1₃): δ 4.65-4.70 (m, 0.23H - unreacted olefin), 3.17-3.29 (m, 1H), 2.97-3.08 (m, 1H), 2.50-2.65 (m, 0.33H), 2.15-2.46 (m, 2.5H), 1.88-2.05 (m, 0.58H), 0.9-1.82 (m, 22.6H), 0.82-0.88 (m, 11.2H).

Example 51: Preparation of rac-l,2-syn-(dimethyl 4-((E)-4,8-dimethylnona-3,7-dien-l-yl)cyclohex- 4-ene-l,2-dicarboxylate) (51)

51

[00510] In a 15 gallon stainless steel batch reactor which was purged with nitrogen, xylenes

(10.85 kg, 12.62 L) were charged followed by dimethyl maleate (8.53 kg, 7.42 L, 59.2 mol). The resulting mixture was stirred and was heated to 140 °C at a rate of l°C/min. Trans-beta-farnesene (11.00 kg, 13.75 L, 53.8 mol) was then added by feed pump to the reactor at a rate of 19.3 g/min (total feed time 10.8 hours). The reaction mixture was then cooled to 25 °C and held at that temperature for 13 hours. The reaction mixture was then brought back to 140 °C for 8 hours. The reaction mixture was then cooled to 25 °C and was held at that temperature for 73 hours. The reaction mixture was then brought back to 140 °C for 6.5 hours at which point analysis of the reaction mixture by GC-MS showed a satisfactory conversion to the desired product. The reaction mixture was cooled. The product was obtained in this manner as a slightly yellow mixture. (16.30 kg uncorrected yield based on GC analysis of the mixture , 87% yield). Analyses were performed on a product purified by distillation: GC-MS (m/z = 348);

NMR (400MHz, CDC1₃): δ 5.37 (s, br, 1H), 5.06-5.10 (m, 2H), 3.69 (s, 3H), 3.68 (s, 3H), 2.98-3.06 (m, 2H), 2.23-2.58 (m, 4H), 2.01-2.12 (m, 4H), 1.94-2.01 (m, 4H), 1.68 (s, 3H), 1.60 (s, 3H), 1.59 (s, 3H). Optionally, the quantity of farnesene in the reaction mixture may be kept to about 14%> or less to reduce formation of thermal dimers from farnesene.

[00511] An alternative preparation for compound 51 is as follows. A reactor is purged with nitrogen, and a nitrogen blanket is maintained throughout reaction. Dimethyl maleate (0.71 kg, 12.17 L) is charged into the reactor vessel. BHT is charged into the reactor vessel. Stirring at 250-300 rpm is initiated. The reactor contents are heated to 140 +/- 5 oC (heating rate 1.0 oC/min). Trans- β -farnesene (distilled and containing 300ppmw butylated hydroxytoluene (BHT)) stabilizer, 1.00 kg, 1.25 L) is charged to the reactor using a feed pump. The feed rate is 17.6-25.4 g/min. Reaction is monitored hourly and feed rate of farnesene is adjusted as necessary. The feed rate of farnesene is controlled to minimize pooling of farnesene in vessel and to control the exothermic reaction. Limiting the amount of farnesene in the reaction mixture by controlled additioni rate favors the Diels-Alder reaction over the formation of thermal dimers. If the temperature begins to increase by greater than or equal to 5 °C/2 min, the feed rate is reduced or feed is stopped until the temperature is stabilized at 140 +/- 5 °C. Reactor contents are sampled hourly to determine area% (by GC-FID) for dimethyl maleate, farnesene and product. Reactor contents are maintained at 140 +/- 5 °C until GC-FID indicates reaction completion (approximately 20 hours). When the amount of dimethyl maleate remaining is about 2 area% or less by GC-FID, temperature can be increased to 160°C. Reaction is complete when the area % by GC-FID of dimethyl maleate is about 1.0% or less. For non-continuous operation, the reactor contents may be held for up to 62 hours at ambient temperature (20 +/- 5 °C) while stirring under nitrogen. Optionally, additional BHT may be added to the reaction to control formation of high boiling side products. Compound 51 is sensitive to air and is stored under nitrogen or other inert atmosphere. Optionally, the reaction products may be distilled to isolate the desired compound 51 from any residual reactants and higher boiling byproducts that may have been formed. Distillation conditions take into account sensitivity of compound 51 to air. A wiped film evaporator operating at 260°C (top and bottom heating zones), pressure of 2 torr, feed flow rate of 15 mL/min, wiper blade rotation at 60%> may be used to distill compound 51 to about 94-95wt% purity.

[00512] In a scaled up procedure for preparing Example 51, a reactor is purged with nitrogen, and a nitrogen blanket is maintained throughout reaction. Dimethyl maleate (DMM) (651 kg, 4523 mol) is charged into the reactor vessel. The DMM is sparged with nitrogen for 30 minutes. Trans- β -farnesene (distilled and containing 300 ppmw butylated hydroxytoluene (BHT)) stabilizer) (924 kg, 4523 mol) is staged to be charged to the reactor using a feed pump. The reactor is heated to 160°C +/- 5°C and stirred at 85 rpm. Farnesene is delivered into the reactor over a period of approximately 28 hours using a metered pump at a feed rate of 33 kg/hr. The reaction mixture and farnesene delivery is monitored during the reaction by in process control GC-FID. The flow rate is adjusted so that the farnesene area % as measured by GC-FID is below 4%> during addition. Once product area%> by GC-FID is greater than 90%, farnesene area % and DMM area % are monitored. Reaction is complete when DMM area%> is less than 1 % and farnesene area % is less than 1.5 % (approximately 36 hours). The reactor is cooled to 30°C. The product is filtered through a 1 micron filter and stored under nitrogen blanket in a container that has been purged with nitrogen. Theoretical yield: 1575 kg Example 51.

[00513] The reaction of trans-β -farnesene with dimethyl maleate produces a racemic mixture of two enantimoers of the syn- Diels-Alder product:

(IS, 2R)-dimethyl-4-((£^')- -dimethylnona-3,7-dien-l-yl)cyclohex-4-ene-l,2-dicarboxylate; and

(1R, 2S)-dimethyl-4-((£^')-4,8-dimethylnona-3,7-dien-l-yl)cyclohex-4-ene-l,2-dicarboxylate.

The formation of the syn- Diels-Alder product was confirmed by NMR analysis. The syn- enantiomers were resolved by a two step process. First, by silica gel chromatography to remove impurities in Example 51 , and second, by chiral HPLC chromatography to provide the ratio of each enantiomer. First, a 20" long by 1" diameter column of silica was equilibrated with hexanes and Example 51 (2.3 g as prepared above) was added and eluted with 9: 1 hexanes/ethyl acetate to yield the pure syn racemic Example 51 (1.7 g). Next in order to establish the ratio of enantiomers, a sample of the syn racemic Example 51 was analyzed by chiral HPLC using a CHIRALPAK AY-3 (150 x 4.6 mm i.d., 3 micron) column, a mobile phase of hexane/ethanol 95:5 (about 3.0 mg sample/mL in 20% ethanol in hexane), injection volume of 5 microL, a flow rate of 0.70 mL/min, and a UV detector, 220 nm, reference 450 nm. The chromatograph showed two peaks (3.881 min and 4.256 minutes) representing the two enantiomers. The respective area counts of 1981 and 1991 support the conclusion that Example 51 is comprised of about 1 : 1 mixture of the syn enantiomers, (IS, 2R)-dimethyl-4-((is)-4,8-dimethylnona-3,7- dien-l-yl)cyclohex-4-ene-l ,2-dicarboxylate, and (1R, 2S)-dimethyl-4-((£^')-4,8-dimethylnona-3,7-dien-l - yl)cyclohex-4-ene-l,2-dicarboxylate.

[00514] Typical constituents include: 48 wt% (1 S,2R) -dimethyl 4-((E)-4,8-dimethylnona-3,7- dien-l-yl)cyclohex-4-ene-l ,2-dicarboxylate, 48 wt% (lR,2S)-dimethyl 4-((E)-4,8-dimethylnona-3,7- dien-l-yl)cyclohex-4-ene-l ,2-dicarboxylate, about 1.4 wt% DMM, about 1 wt% (2E,6E)-3,7,11- trimethyldodeca-2,6,10-trien-l-ol (farnesol), about 0.1 wt% (6E)-7,1 l-dimethyl-3-methylenedodeca- 1 ,6, 10-triene (trans-P-farnesene), about 0.1 wt% of a first diastereomer of Example 51, and about 0.8 wt% of a second diastereoisomer of Example 51.

Example 52: Preparation of rac-l,2-syn-(dimethyl 4-(4,8-dimethylnonyl)cyclohexane-l,2- dicarboxylate) (52)

52 [00515] The triolefin intermediate (51) produced in the manner described above (13.918 kg, 40.0 mol) was fed into a fixed bed hydrogenation reactor which contained a nickel catalyst bed (Johnson Matthey, HTC Ni 500, RP 1.2 mm). The first pass conditions were: feed rate 12 mL/min under 500 psig H₂ 5 slpm at 138-157 °C. The second pass conditions were: feed rate 11.5-12.2 mL/min under 500 psig H₂ 5 slpm at 150-156 °C. After the 2^rd pass, GC analysis showed complete hydrogenation. The product was obtained in this manner as a colorless oil (13.976 kg, 99% yield). GC-MS (m/z = 354); ^lH NMR (400MHz, CDC1₃): δ 3.69 (s, 3H), 3.66 (s, 3H),3.20-3.25 (m, br, 1H), 2.42-2.47 (m, 1H), 2.19-2.25 (m, 1H), 2.03-2.08 (m, br, 1H), 0.90-1.65 (m, 20.5H), 0.83-0.87 (m, 10H).

Example 53: Preparation of rac-l,2-anti-(dimethyl 4-(4,8-dimethylnonyl)cyclohexane-l,2- dicarboxylate) (53)

53

[00516] In a 5L Parr reactor, beta-farnesene (1768 g, 8.65 mol) was heated to 95 °C with stirring.

Solid dimethylfumarate (1215 g, 8.43 mol, 0.97 equivalents) was added portionwise. The resulting mixture was allowed to stir at 95 °C overnight. The reaction mixture was then cooled and subjected to wiped film evaporation to remove the volatile components providing the triolefin intermediate as a slightly yellow liquid (2837 g, 97% yield). HPLC Purity (>95%); LCMS (ESI: 349.0 = M⁺ +1); ^lH NMR (300MHz, CDCI₃): δ 5.37 (s, br, 1H), 5.06 (m, 2H), 3.67 (s, 3H), 3.66 (s, 3H), 2.72-2.88 (m, 2H), 2.22- 2.44 (m, 2H), 1.90-2.20 (m, 10H), 1.65 (s, 3H), 1.57 (s, 6H).

Example 54: Preparation of rac-l,2-anti-dimethyl 4-(4,8-dimethylnonyl)cyclohexane-l,2- dicarboxylate (54)

54

[00517] A 5L Parr reactor was charged with the triolefin intermediate (53) produced in the manner described above (2000 g, 5.74 mol). The hydrogenation catalyst, 5%> Pd/C (20 g) was then added. The reactor was sealed and was then pressurized with hydrogen (525 psi). The mixture was heated (140 °C) with stirring. The reactor was repressurized in a repetitive manner until a constant pressure of H₂ was maintained. The reactor was then cooled and cautiously vented. The material was then diluted with heptane (1.5L), and the resulting solution was filtered through a pad of celite 545 (200 g). The volatile materials were removed under vacuum yielding the product as a slightly yellow oil (2005 g, 99% yield). GC-MS (m/z = 354); ^ι¥ί NMR (400MHz, CDC1₃): δ 2.68 (s, 6H), 3.671 (s, 6H), 3.667 (s, 6H), 2.89-2.95 (m, 1H), 2.75-2.80 (m, 1H), 2.53-2.68 (m, 4H), 2.05-2.11 (m, 4H), 1.63-1.84 (m, 8H), 0.85-1.60 (m, 54H), 0.83-0.88 (m, 28H). Example 55: Preparation of rac-l,2-anti-dibutyl 4-((E)-4,8-dimethylnona-3,7-dien-l-yl)cyclohex-4- ene-l,2-dicarboxylate (55)

55

[00518] In a 5L Parr reactor, beta-farnesene (1300 g, 6.36 mol) was heated to 90 °C with stirring.

Di-n-butylfumarate (1.45 kg, 1.47 L, 6.38 mol, 1.00 equivalents) was added dropwise over 4 hours. The resulting mixture was allowed to stir at 90 °C overnight. The reaction mixture was then cooled and subjected to wiped film evaporation to remove the volatile components providing the triolefm intermediate as a slightly yellow liquid (2467 g, 90% yield). HPLC Purity (>95%); LCMS (ESI: 433.2 = M⁺ +1); 'H NMR (300MHZ, CDC1₃): δ 5.38 (s, br, 1H), 5.08 (m, 2H), 4.05-4.12 (m, 4H), 2.74-2.88 (m, 2H), 2.24-2.44 (m, 2H), 1.92-2.18 (m, 12H), 1.66 (s, 3H), 1.56-1.64 (m, 8H), 1.30-1.42 (m, 4H), 0.88- 0.96(m, 6H).

Example 56: Preparation of rac-l,2-anti-(dibutyl 4-(4,8-dimethylnonyl)cyclohexane-l,2- dicarboxylate) (56)

56

[00519] The triolefm intermediate (55) produced in the manner described above (2.300 kg, 5.32 mol) was fed into a fixed bed hydrogenation reactor which contained a nickel catalyst bed (Johnson Matthey, HTC Ni 500, RP 1.2 mm). The first pass conditions were: feed rate 10 mL/min under 500 psig H₂ 5 slpm at 70-99 °C. The second pass conditions were: feed rate 10 mL/min under 500 psig H₂ 5 slpm at 156-160 °C. The third pass conditions were: feed rate 10 mL/min 500 psig H₂ 5 slpm at 148-154 °C. The higher temperature conditions of the second pass resulted in some decomposition and the material obtained during this pass was not combined with the final product. After the 3^rd pass, analysis showed complete hydrogenation. The product was obtained after evaporation of the volatiles using wiped film evaporation as a slightly yellow oil (1.371 kg, 60% yield). GC-MS (m/z = 438); ^lH NMR (400MHz, CDC1₃): δ 4.00-4.13 (m, , 8H), 2.88-2.94 (m, 1H), 2.75-2.80 (m, 1H), 2.52-2.66 (m, 2H), 2.05-2.10 (m, 2H), 1.00-1.85 (m, 57H), 0.83-0.95 (m, 31H).

Example 57: Preparation of rac-l,2-anti-diisopropyl 4-((E)-4,8-dimethylnona-3,7-dien-l- yl)cyclohex-4-ene-l,2-dicarboxylate (57)

57 [00520] In a 5L Parr reactor, beta-farnesene (1456 g, 7.13 mol) was heated to 80 °C with stirring.

Di-isopropylfumarate (1.405 kg, 7.02 mol, 0.98 equivalents) was added dropwise over 4 hours. The resulting mixture was allowed to stir at 100 °C overnight. The reaction mixture was then cooled and subjected to wiped film evaporation to remove the volatile components providing the triolefin intermediate as a slightly yellow liquid (2580 g, 91% yield). HPLC Purity (>95%); LCMS (ESI: 405.2 = M⁺ +1); 'H NMR (300MHZ, CDC1₃): δ 5.36 (s, br, 1H), 5.02-5.08 (m, 2H), 4.92-5.01 (m, 2H), 2.66-2.80 (m, 2H), 2.21-2.40 (m, 2H), 1.98-2.13 (m, 6H), 1.90-1.98 (m, 4H), 1.64 (s, 3H), 1.56 (s, 6H), 1.16- 1.22(m, 12H).

Example 58: Preparation of rac-l,2-anti-(diisopropyl 4-(4,8-dimethylnonyl)cyclohexane-l,2- dicarboxylate) (58)

58

[00521] A 5L Parr reactor was charged with the triolefin intermediate (57) produced in the manner described above (2050 g, 5.07 mol). The hydrogenation catalyst, 5% Pd/C (20 g) was then added. The reactor was sealed and was then pressurized with hydrogen (550 psi). The mixture was heated (140 °C) with stirring. The reactor was repressurized in a repetitive manner until a constant pressure of H₂ was maintained. The reactor was then cooled and cautiously vented. The material was then diluted with heptane (1.5L), and the resulting solution was filtered through a pad of celite 545 (200 g). The volatile materials were removed under vacuum yielding the product as a slightly yellow oil (2027 g, 97% yield). GC/MS (m/z = 410); ¾ NMR (400MHz, CDC1₃): δ 4.93-5.04 (m, 3H), 2.84-2.87 (m, 0.5H), 2.70-2.75 (m, 0.5H), 2.46-2.61 (m, 2H), 2.04-2.09 (m, 2H), 0.90-1.85 (m, 47H), 0.80-0.90(m, 14H).

Example 59: Preparation of rac-l,2-syn-dibutyl 4-((E)-4,8-dimethylnona-3,7-dien-l-yl)cyclohex-4- ene-l,2-dicarboxylate (59)

59

[00522] In a 5L Parr reactor, beta-farnesene (1166 g, 5.70 mol) was heated to 90 °C with stirring.

Di-n-butylmaleate (1.245 L, 5.40 mol, 0.95 equivalents) was added dropwise over 4 hours. The resulting mixture was allowed to stir at 95 °C over a weekend followed by 120 °C for an additional 72 hours to drive the reaction to near completion. The reaction mixture was then cooled and subjected to wiped film evaporation to remove the volatile components providing the triolefin intermediate as a slightly yellow liquid (2100 g, 90% yield). HPLC Purity (>95%); LCMS (ESI: 433.2 = M⁺ +1); ^lH NMR (300MHz, CDCI₃): δ 5.36 (s, br, IH), 5.03-5.10 (m, 2H), 4.03-4.10 (m, 4H), 2.93-3.4 (m, 2H), 2.40-2.58 (m, 2H), 2.20-2.37 (m, 2H), 1.90-2.12 (m, 10H), 1.66 (s, 3H), 1.52-1.62 (m, 8H), 1.28-1.41(m, 4H), 0.90 (t, 6H).

Example 60: Preparation of rac-l,2-syn-diisobutyl 4-(4,8-dimethylnonyl)cyclohexane-l,2- dicarboxylate (60)

60

[00523] A 5L Parr reactor was charged with the triolefm intermediate (59) produced in the manner described above (2035 g, 4.71 mol). The hydrogenation catalyst, 5% Pd/C (20 g) was then added. The reactor was sealed and was then pressurized with hydrogen (500 psi). The mixture was heated (140 °C) with stirring. The reactor was repressurized in a repetitive manner until a constant pressure of H₂ was maintained. The reactor was then cooled and cautiously vented. The material was then diluted with heptane (1.5L), and the resulting solution was filtered through a pad of celite 545 (200 g). The volatile materials were removed under vacuum yielding the product as a slightly yellow oil (1911 g, 93% yield). GC/MS (m/z = 438); ¾ NMR (300MHz, CDC1₃): δ 4.04-4.10 (m, 4H), 3.22 (s, br, IH), 2.39-2.44 (m, IH), 2.20-2.25 (m, IH), 1.00-2.10 (m, 28 H), 0.83-0.94 (m, 15H).

Example 61: Preparation of rac-l,2-anti-diisobutyl 4-((E)-4,8-dimethylnona-3,7-dien-l- yl)cyclohex-4-ene-l,2-dicarboxylate (61)

61

[00524] In a 5L Parr reactor, beta-farnesene (1366 g, 6.68 mol) was heated to 80 °C with stirring.

Di-n-butylmaleate (1.526 L, 6.55 mol, 0.98 equivalents) was added dropwise over 4 hours. The resulting mixture was allowed to stir at 95 °C for 48 hours. The reaction mixture was then cooled and subjected to wiped film evaporation to remove the volatile components providing the triolefin intermediate as a slightly yellow liquid (2660 g, 94% yield). HPLC Purity (>97%); LCMS (ESI: 433.2 = M⁺ +1); ^lH NMR (300MHz, CDCI₃): δ 5.38 (s, br, IH), 5.03-5.11 (m, 2H), 3.88-3.96 (m, 4H), 2.76-2.92 (m, 2H), 2.25-2.48 (m, 2H), 1.83-2.22 (m, 12H), 1.66 (s, 3H), 1.58 (s, 6H), 0.88-0.93 (m, 12H).

Example 62: Preparation of rac-l,2-anti-diisobutyl 4-(4,8-dimethylnonyl)cyclohexane-l,2- dicarboxylate (62)

62 [00525] A 5L Parr reactor was charged with the triolefin intermediate (61) produced in the manner described above (2.037 kg, 4.71 mol). The hydrogenation catalyst, 5% Pd/C (20 g) was then added. The reactor was sealed and was then pressurized with hydrogen (550 psi). The mixture was heated (140 °C) with stirring. The reactor was repressurized in a repetitive manner until a constant pressure of H₂ was maintained. The reactor was then cooled and cautiously vented. The material was then diluted with heptane (1.5L), and the resulting solution was filtered through a pad of celite 545 (200 g). The volatile materials were removed under vacuum yielding the product as a slightly yellow oil (2199 g, 106% yield indicating incomplete removal of the heptane diluent). GC/MS (m/z = 438); ^lH NMR (400MHz, CDC1₃): δ 3.79-3.92 (m, 12H), 2.90-3.00 (m, 1H), 2.79-2.86 (m, 1H), 2.55-2.70 (m, 4H), 2.05-2.15 (m, 4H), 0.95-2.00 (m, 64H), 0.83-0.94 (m, 62H).

Example 63: Preparation of (E)-dimethyl 4-(4,8-dimethylnona-3,7-dien-l-yl)cyclohexa-l,4-diene- 1,2-dicarboxylate (63)

63

[00526] In a 1L Parr reactor, beta-farnesene (413.6 g, 2.02 mol) was heated to 90 °C with stirring. Dimethylacetylenedicarboxylate (255 mL, 2.00 mol) was added dropwise at such a rate so as to maintain an internal temperature below 105 °C. The reaction was then allowed to stir at 90 °C overnight. The nearly completed reaction solution was then subjected to a wiped-film evaporation (one pass) to remove the volatile components. The desired product was obtained as a yellow oil (685.8 g, 98% yield). HPLC Purity (>95%); LCMS (ESI: 346.99 = M⁺ +1); ^lH NMR (300MHz, CDC1₃): δ 5.39 (s, br, 1H), 5.02-5.10 (m, 2H), 3.76 (s, 3H), 3.76 (s, 3H), 2.94-3.04 (m, 2H), 2.86-2.94 (m, 2H), 1.90-2.15 (m, 8H), 1.65 (s, 3H), 1.57 (s, 6H).

[00527] In an alternative scheme for making compound 63, a reactor system is purged with nitrogen and charged with dimethylacetylenedicarboxylate (1.1 molar equivalent, relative to farnesene). Vigorous stirring is initiated and 3 vacuum/nitrogen purge cycles are repeated (to greater than or equal to 28 in. Hg vacuum and greater than or equal to 0 psig nitrogen) to strip dissolved oxygen out of the liquid, and then a pressure of 1 -5 psig nitrogen is added to prevent potential ingress of atmospheric oxygen. Farnesene is distilled and stabilized with 300 ppmw BHT. Farnesene is stripped with nitrogen by sparging the material in a feed tank with ten times the volume of the vessel while stirring. The reactor contents are heated to 85 +/- 3 °C. Reactor vessel pressure is monitored. Temperature of the reactor is maintained at 85 +/- 3 °C using the reactor coolant system. Farnesene (1 molar equivalent) is delivered at a rate such that the temperature is maintained at 85 +/- 3 °C. An excess of

dimethylacetylenedicarboxylate may result in reduced formation of farnesene dimers. Reaction completion is monitored based on analytic analysis. Optionally, a final charge of farnesene may be added to consume residual dimethylacetylenedicarboxylate. After cooling, the reactor contents are filtered through a 5 micron PTFE filter. The product is stored in containers that have been sparged with nitrogen and sealed under nitrogen atmosphere.

[00528] An alternate synthesis for Example 63 is as follows. To a 1L 3-necked round bottom flask fitted with two temperature probes (one recording, one readout), water condenser and an addition funnel was charged with 217.5g (1500 mmol) dimethylacetylene dicarboxylate (DMAD) (98% pure, available from TCI Chemicals). The DMAD was sparged with nitrogen gas for 15 minutes. 1500mmol trans-P-farnesene (Amyris, Inc., distilled and filtered through alumina, containing 100 ppm TBC (4-tert butyl catechol) as a stabilizer, having a purity of 99%) was sparged with nitrogen gas. DMAD was heated to 75°C and held for 5 minutes, β-farnesene (306.5g, 372.9ml, 1500mmol) was added dropwise to the flask containing DMAD at a rate of 0.5-2 drops/second to result in an average rate of 83 ml/hour over a period of 4.5 hours, with addition rate controlled to maintain temperature at 75°C (temperature maintained at or below 77°C with addition rate of 0.5 drops/sec, momentary temperature spike to 90.1 °C observed when addition rate was increased to 2 drops/sec). The reaction mixture was allowed to cool to room temperature overnight. The following day, the reaction mixture was reheated to 75 °C to allow remaining (approximately 2%) DMAD to react for approximately 31 hours. The reaction mixture was observed to be a clear yellow liquid containing no crystals. The product was filtered through a 4 micron nylon filter. Yield was estimated to about 93%. The product was analyzed by GC-MS, proton NMR, and ¹³C NMR to be Example 63, and purity analyzed by HPLC to be 91% and by GC-FID to be 90-91%.

[00529] In a scaled up synthesis for Example 63, a reactor system is purged with nitrogen. 8.85 kg trans-β -farnesene (distilled and stabilized with 300 ppmw BHT) (15% total amount) is charged to the reactor. Agitation is started and the reactor is heated to 80-90°C. 6.21 kg

dimethylacetylenedicarboxylate (DMAD) (15% total amout) is delivered to the reactor over a period of 3 hours using at an addition rate of 2.1 kg/hr. DMAD is monitored using in process control HPLC and flow rate is adjusted so that area % DMAD is less than 4%. Agitation is continued for 30 minutes. Temperature is increased to 100-110°C. Over the next 3-5 hours, 35.21 kg DMAD and 50.13 kg farnesene are charged in parallel to the reactor. The DMAD addition rate is 7.04-11.34 kg/hr and the farnesene addition rate is 10.03-16.71 kg/hr. The reaction is agitated for 5-10 hours. The reaction is complete when HPLC area % for DMAD is less than 0.65 %, HPLC area % for farnesene is less than 1.3 %, HPLC area % for Example 63 is greater than 93 %. When the reaction is complete the reactor is cooled to 20-30°C. The product is filtered and stored in containers that have been sparged with nitrogen and sealed under nitrogen atmosphere.

[00530] Typical product yield is 89 wt%, with 5 wt% farnesene, 0.6 wt% trimethyl 5- methoxyfuran-2,3,4-tricarboxylate, 0.5 wt% dimethyl but-2-ynedioate, 0.2 wt% (E)-dimethyl 4-(4,8- dimethylnona-3,7-dien-l -yl)phthalate. Other impurities that have not been conclusively identified but may be present include: about 0.1 wt% (E)-dimethyl 4-(4,8-dimethylnona-3,7-dien-l-yl)-3- hydroxycyclohexa-l,4-diene-l,2-dicarboxylate, about 0.4 wt% farnesol, about 1 wt% (E)-dimethyl 5- (4,8-dimethylnona-3,7-dien-l-yl)-5-(2-methoxy-5-(methoxycarbonyl)furan-3-yl)cyclohexa-l,3-diene- 1,2-dicarboxylate, about 0.2 wt% (E)-trimethyl 5-(l-(4,8-dimethylnona-3,7-dien-l-yl)-4,5- bibs(methoxycarboonyl)cyclohexa-2,4-dien-l-yl)-6-methoxy-4H-pyran-2,3,4-tricarboxylate, about 1 wt% dimethyl 5-((Z)-l,4-dimethoxy-l,4-dioxobut-2-en-2-yl)-5-((E)-4,8-dimethylnona-3,7-dien-l- yl)cyclohexa-l,3-diene-l,2-dicarboxylate, about 0.2 wt% (Z)-tetramethyl 2,2'-(4-((E)-4,8-dimethylnona- 3,7-dien-l-yl)-l,2-bis(methoxycarbonyl)cyclohexa-2,5-diene-l,4-diyl)dimaleate, and about 1.8 wt% trimethyl 5-(4-((Z) ,4-dimethoxy-l,4-dioxobut-2-en-2-yl) -((E)-4,8-dimethylnona-3,7-dien-l-yl)-3,4- bis(methoxycarbonyl)cyclohexa-2,5-dien-l -yl)-6-methoxy-4H-pyran-2,3,4-tricarboxylate. In some cases, up to 2.4 area% polymer is detected by GPC analysis, and up to 7.4% DMAD adducts may be present.

Examples 64-77 and Comparative Examples CE 10-CE 13: Plasticization of suspension grade PVC

[00531] For Examples 64-77, plasticizer candidates of Examples 50, 51, 52, 54, 56, 58, 60, 62,

63, 7 and 11 were evaluated for use with a suspension grade PVC by roll milling at about 305°F. For Comparative Examples CE 10-CE 13, PVC compositions comprising commercially available plasticizers bis(2-ethylhexyl) Phthalate (DOP), cyclohexane-l,2-dicarboxylic acid diisononyl ester (DINCH) (available from BASF Corp.), and CITROFLEX® A-4 (Acetyltri-n-butyl Citrate) were made for comparison. Ease of compounding, tensile measurements, hardness durometer A, low temperature brittleness, and colorimetric measurements were performed for various plasticized compositions.

[00532] For Examples 64-74, each plasticizer candidate was mixed with Shintech SE1300 suspension grade IV 1.035 PVC, calcium stearate, zinc stearate, and stearic acid using 100 parts (by weight) PVC resin, 50 phr plasticizer, 1.7 phr calcium stearate, 0.8 phr zinc stearate and 0.25 phr stearic acid. For Example 75, 25 phr plasticizer was used, with the other components remaining the same as in Examples 64-74. For Example 76, 35 phr plasticizer was used, with the other components remaining the same as in Examples 64-74.

[00533] For Example 77, the plasticizer of Example 51 is used in combination with DOP to act as a heat stabilizer. A composition comprising ESO as a heat stabilizer is provided for comparison.

Example 77 is prepared as in Examples 64-76, except consisting of 100 parts PVC by weight, 50 phr DOP, 0.25 phr stearic acid, 5 phr plasticizer from Example 51, and containing no calcium stearate or zince stearate. Comparative Example CE 13 is prepared as in Examples 64-76, except consisting of 100 parts PVC by weight, 50 phr DOP, 0.25 phr stearic acid, 5 phr ESO and containing no calcium stearate or zinc stearate.

[00534] For Example 81 , the plasticizer of Example 79 is used as in Examples 64-76, consisting of 50 phr Example 79. For Example 82, the plasticizer of Example 80 is used as in Examples 64-76, consisting of 50 phr Example 80. [00535] The compounding procedure for each of Examples 64-77 and Comparative Examples CE

10-CE 13 is as follows. Approximately 600 gram beaker batches were made of each plasticizer candidate. The addition of ingredients was PVC resin, plasticizer, lubricants. There was no preheating of any ingredient. Material was mixed thoroughly with a hand held spatula. Material was poured onto a Swabenthall two roll mill set at 305°F. Material was banded and then a timer started for 5 minutes.

Material was worked on the mill by a cut and pass procedure every 30 seconds. At the end of 5 minutes the sheet was removed from the mill. For each composition, a qualitative ease of processing under the described conditions was noted by the operator, with 3 representing easy to process, 2 representing average ease of processing, 1 representing very difficult to process, and 0 representing not processible.

[00536] While sheet is still warm, templates are cut out to make 7.5 in. X 7.5 in. plaques. The templates are put between two platens with a center platen having an open area of 7.5 inches X 7.5 Inches and a thickness of 75 mils. The assembly is inserted into a Wabash compression molding press. The press temperature is 350°F and the pressure is 16,000 Psi. The heating cycle is 4 minutes with a cooling cycle of 4 minutes. The plaque is removed from the assembly and then using specific dies the test specimens are punched out of the pressed plaques. The test specimens are moved to a constant temperature and humidity room for conditioning. The temperature is 71°F plus or minus 3.1°F and the relative humidity is 50% plus or minus 5%. Test specimens are conditioned for a minimum of 24 hours before testing.

[00537] Tensile measurements based on ASTM D638-10, which is incorporated herein by reference in its entirety, using test specimens having a width of 0.25 inches and thickness 0.075-0.085 inches, a speed of 20 inches/min, and a gauge length of 1 inch. ASTM D638-10 involves inserting a test sample having a specified dog-bone shape into a tensile testing machine that applies a uniaxial load to the sample along the axis of the sample by fixing one end of the sample and pulling on the opposite end along the sample axis, or by pulling on both ends of the sample in opposite directions along the sample axis at the specified rate. Stress as the applied force per unit area is measured as a function of strain (derived from % elongation) to generate a stress-strain curve. Tensile strength in Table 64 refers to the maximum stress the sample can withstand before failing. Tensile measurements indicate averages from 3 separate samples, unless indicated otherwise.

Table 64. Tensile measurements of plasticized PVC samples

Tensile measurements were made according to ASTM D412 "Standard Test Methods for

Rubber and Thermoplastic Elastomers— Tension" using Test Method A at a speed of 2 in/min. ASTM D412 is incorporated herein by reference in its entirety. Two samples were tested instead of three. 2Represents a single measurement for a single sample. No measurement of modulus at 100% elongation was possible for second sample.

3Average for two samples.

4Became much stiffer with time.

[00538] Durometer (Shore) Hardness A of the samples is measured according to ASTM D2240-

05 "Standard Test Method for Rubber Property— Durometer Hardness," which is incorporated herein by reference in its entirety. The durometer of a material indicates a depth that an indentor having a defined tip geometry penetrates into a material by application of a known force for a specified period of time with a calibrated spring, without the application of shock. For Type A Durometer Hardness, a 35° truncated cone having a 1.40 mm outer diameter and a 2.54mm extension is applied with 8.05 N force with a calibrated spring. Displacement of the tip into the material is measured. If no measureable displacement occurs, a durometer value of 100 is obtained. If the tip displaces 2.5mm, a durometer value of 0 is measured. Durometer hardness results are shown in Table 64.

[00539] Low temperature brittleness of the plasticized samples was measured according to

ASTM D746-07 "Standard Test Method for Brittleness Temperature of Plastics and Elastomers by Impact," which is incorporated herein by reference in its entirety. Type A apparatus, Type I specimens having a length x width of 32mm x 6.35mm were used. The Brittleness temperature is the temperature at which 50% of the tested specimens show brittle failure under defined impact conditions. Prior to testing, samples were conditioned at a temperature of 23 +1-2 °C, and a relative humidity of 50 +1-5% RH for 40 hours. The cooling medium used was silicone oil. Samples are mounted into a sample holder such that the thin planar sample extends sideways (parallel to earth) 25.4 mm from the edge of the sample holder and immersed in the cooling medium at a temperature. A striker having an edge radius of 1.6mm impacts the sample at a striking radius of 7.87mm extending from the edge of the sample holder at a specified velocity, and the samples are inspected for cracking or fracture. Results are shown in Table 65. The brittleness temperature is the temperature at which 50%> of the tested specimens show cracking visible to the unaided eye or fracture under defined impact conditions.

Table 65. Low Temperature Brittleness of Plasticized PVC Compositions

Ex. Plasticizer Temp Pass Fail Thickness Brittleness

(°C) (mm) Temp (°C)

10 -30 5 5

-35 0 10

[00540] Color of the mill sheets and the pressed plaques is evaluated by reflectance using

Comparative Example 10 as a reference, and using the CIE (International Commission on Illumination) coordinates L*, a*, and b*. L*=0 represents a specimen that appears black to the human eye, L*=100 represents a specimen that appears diffuse white, a* represents a value between red and green (with negative values indicating green and positive values indicating red), and b* represents a value between yellow and blue (with negative values indicating blue and positive values indicating yellow). See, e.g., Commission Internationale de L'Eclairage at www.cie.co.at. The observer was positioned at 10°, and the illuminant was a CIE standard D65 illuminant to simulant standard daylight illumination. An Color- Eye® 7000A spectrophotometer (available from XRite Corp., Grand Rapids, MI) was used to evaluate color of the samples relative to the standard. The coordinates L*, a*, and b* was measured for each sample. The difference between each of the coordinates L*, a* and b* of a sample and that of the reference was calculated, and a color parameter DE*=sqrt{[(L*(sample)-L*(ref)]²+[a*(sample)- a*(ref)]²+[b*(sample)-b*(ref)]²} was calculated. Results are shown in Table 66.

Table 66. Colorimetric evaluation of plasticized PVC samples

Ex. Plasticizer DE* from mill DE* from pressed sheet plaque

63

68 Ex.58 3.698 6.657

^^^COOi-Pr

58

69 Ex.56 7.696 3.565

^\ , OOn-Bu

56

70 Ex.50 2.818 2.199

O

50 O

75 Ex.52 12.396 9.881

^^ ^COOMe

52

76 Ex.52 6.702 1.291

^^ ^COOMe

52

77 DOP + 3.918 23.990

^^ -COOMe

51

81 27.510 27.348

Ex.79 Ex. Plasticizer DE* from mill DE* from pressed

sheet plaque

82 Ex. 80 9.112 36.345

^\ COOMe statistical mixture of unreacted starting material,

isomeric monoepoxides, isomeric diepoxides and

isomeric triepoxides

Comparative Examples

CE DOP 0 (reference) 0 (reference)

10

CE DINCH 1.962 8.495

11

CE CITROFLEX ® A-4 5.783 5.866

12

CE DOP + ESO 4.128 47.770

13

[00541] Weight losses of tensile bars after thermal aging for the plasticized compositions of

Examples 64, 65, 66 and Comparative Example CE 10 were measured according to ASTM D573. Samples were weighed initially, aged in an oven at 100°C for 7 days, and weighed again. Percentage weight loss is calculated as [1 -(final weight)/(initial weight)] x 100%. Results are shown in Table 67. Tensile measurements of plasticized PVC compositions following thermal aging at 100°C for 7 days showed increased rigidity. For CE 10, % elongation at break after thermal aging was 204%. For the samples of Examples 64-66, % elongation at break after thermal aging ranged from 0% to about 5%.

Table 67. Percentage weight loss for plasticized PVC compositions following thermal aging.

Ex. Plasticizer Weight loss (%)

51

CE DOP 5

10

Example 78. Plasticization of PVC by Plasticizer of Example 7 in Solvent Cast Thin Film

A. Preparation of Casting Solutions:

[00542] PVC Casting Solution. PVC (52.0 g, Shintech SE-1300, three ball bearings (-Γ dia, stainless steel) and tetrahydrofuran (THF) (245.1 g, BHT stabilized) were added to a jar and capped. The mixture was agitated on a paint shaker for four six-minute cycles to give a viscous transparent solution (17.5 % w/w). The solution was diluted with an additional portion of THF (135.6 g, BHT stabilized) and was lightly shaken to give a less viscous transparent solution (12.0 % w/w).

[00543] PVC with Plasticizer Casting Solution. The plasticizer of Example 7 (FW- 00448 -026)

(5.1 g) was added to PVC Casting Solution (41.6 g, 4.99 g contained PVC) and the resultant was shaken to give a slightly hazy solution (represents 102 phr).

B. Preparation of Cast Films:

[00544] PVC Film: A bead of PVC Casting Solution (20 mL, -6-7" length) was poured across a glass plate and the bead was drawn down the plate with a doctor blade (30 mil gap). The wet film was allowed to stand for 24 hours (note: there was no tack sensation after - 10 minutes) to give a thin transparent plastic film that was easily removed from the glass plate.

[00545] PVC with Plasticizer Film: A bead of PVC Casting Solution (20 mL, -6-7" length) was poured across a glass plate and the bead was drawn down the plate with a doctor blade (30 mil gap). The wet film was allowed to stand for 24 hours (note: there was no tack sensation after - 10 minutes) to give a thin slightly hazy plastic film that was easily removed from the glass plate.

C. Film Tension Measurements:

[00546] Instrument Setup: A dynamic mechanical analyzer equipped with a film tensile clamp

(DMA Q800 TA Instruments, Inc.) and operated in controlled force mode was used to evaluate select tensile properties of the films. The key conditions of the experiment were: temperature (25 deg C); preload force (0.0010 N); soak time (5 min); ramp: 3 N/min); max force (18 N). Results for PVC Film (13.5991 mm (1) x 6.95 mm (w) x 0.04 mm (t); film cut in casting direction): The tensile plot is shown in FIG. 24. The stress and strain at break were (34.49 MPa, 4.991%). Results for PVC with Plasticizer Film (13.5674 mm (1) x 7.16 mm (w) x 0.08 mm (t); film cut in casting direction): The tensile plot is shown in FIG. 24. The sample did not break but rather elongated over the entire length of the drive arm. The stress and strain at the drive arm maximum displacement was (9.75 MPa, 65.51%).

Example 79. Imide-containing Plasticizer

[00547] In a 2L round bottom flask equipped with a magnetic stir bar, the anhydride (106.7 g,

0.346 mol) was taken up in benzene (100 mL) and toluene (400 mL). Benzyl amine (37.8 mL, 37.1 g, 0.346 mmol) was added followed by / toluenesulfonic acid (200 mg). A Dean-Stark trap was attached to the flask. The resulting solution was heated to reflux using a heating mantle. After 2h, the

stoichiometric amount of water had collected in the Dean-Stark sidearm. The completion of the reaction was verified by GC/MS analysis of the crude reaction mixture. The reaction mixture was cooled to room temperature and was washed with saturated aqueous K₂CO₃ solution (100 mL). A stable emulsion resulted and this was broken by addition of water and ethyl acetate. The organic phase was separated and dried (MgSO i). The volatile materials were removed on a rotary evaporator. A small amount of residual toluene was removed using a Kugelrohr (230 °C at 1.65 torr). The product was obtained in this manner as a thick yellow oil (131.2 g, 95.4% yield). The identity of the product was verified by ^lH and ¹³C NMR analysis. GPC analysis showed up to about 2.6 % polymer, which may be farnesene dimers.

Example 80. Epoxidized Diels-Alder add net

statistical mixture of unreacted starting material, isomeric monoepoxides, isomeric diepoxides and isomeric triepoxides

[00548] The triene (20.00 g, 57.4 mmol) was taken up in ethyl acetate (140 mL) with stirring.

The resulting solution was cooled to 0 °C using an ice/water bath. NaHC0₃ (25.0 g, 298 mmol) was added to the stirring reaction mixture. A solution of w-chloroperbenzoic acid (25.0 g, 77% assay, 112 mmol) in EtOAc (100 mL) was added dropwise to the cooled stirring slurry over the course of 1 hour. The resulting mixture was stirred overnight while allowing the mixture to slowly come to ambient temperature. The following morning, a solid mass was noted. The material was diluted with water (100 mL). The aqueous layer was discarded. The organic layer was washed with 10% aqueous K₂CO₃ (9 x 100 mL). The organic layer was then dried (MgSO i). The volatiles were removed on a rotary evaporator. The product was obtained in this manner as a colorless oil (20.2 g, 93% yield). The identity of the product was confirmed by ^lH NMR and GC/MS.

Surfactant characterization

[00549] Surfactant properties of Examples 35-40 are compared to a commercially available nonionic surfactant, NP-9 (nonylphenol + 9 EO), as a Comparative Example. Properties measured include Cloud Point (a predictor of temperature for optimum surface activity of surfactants), cmc (critical micelle concentration, ppm), surface tension (measured at 0.01% in aqueous solution, mN/m), interfacial tension (0.1%> in aqueous solution against mineral oil), interfacial tension (0.1%> in aqueous solution against Cg-Cio triglyceride), and Ross Miles foam.

Cloud point

[001] Cloud points of the surfactants of Examples 35-40 at 0.1%> in distilled water were measured. Results are shown in Table 39. Cloud points are measured in a standard manner, e.g., by heating the solution to point of clarity, and allowed to cool slowly, and the temperature at which turbidity is first observed upon cooling is recorded as the cloud point.

Critical Micelle Concentration (cmc)

[002] Critical micelle concentration was measured using a Kruess model Kl 00MK2 tensiometer. Thirteen different solutions of each of the surfactants in distilled water are prepared at concentrations ranging from 10^"3 ppm to 10³ ppm. Using the tensiometer, curves of log (surfactant concentration in ppm) vs. surface tension (mN/m) were generated. Log(surface tension) decreases with increasing surfactant concentration over a transition region, and log( surface tension) reaches a plateau at high surfactant concentration. The cmc was determined as the intersection between a line drawn through data points in the transition region, and a line drawn through data points in the plateau region at high surfactant concentration. Surface tension vs. logl0(surfactant concentration) are shown in FIGURES 25A, 25B, 25C, and 25D for the surfactants of Example 37, Example 38, Example 39, and Example 40, respectively. As illustrated in FIGURE 25 A, the cmc for the surfactant of Example 37 is about 7 ppm. As illustrated in FIGURE 25B, the cmc for the surfactant of Example 38 is about 2 ppm. As illustrated in FIGURE 25C, the cmc for the surfactant of Example 39 is about 8 ppm. As illustrated in FIGURE 25D, the cmc for the surfactant of Example 40 is about 17 ppm. Results are shown in Table 39.

[003] The surface tension was determined from the data obtained from the cmc determination described above using the Kruess tensiometer and the Wilhelmy plate attachment. The surface tension at 0.01%) was interpolated from the curve (which was in the plateau region). Results are shown in Table 39.

[004] Interfacial tension of the surfactants of Examples 35-40 at 0.1%> in water against mineral oil and against Cg-Cio triglycerides (Lipo GC triglycerides, available from Lipo Chemicals, Inc., Paterson, NJ) were measured using the Kruess K100MK2 tensiometer and the du Nouy ring, essentially following ASTM D1331 "Standard Test Methods for Surface and Interfacial Tension of Solutions of Surface-Active Agents," which is incorporated herein by reference in its entirety. Results are shown in Table 39.

[005] Foam at 25°C was evaluated by the Ross Miles Method (ASTM Dl 173, "Standard Test

Method for Foaming Properties of Surface-Active Agents," which is incorporated herein by reference in its entirety). Solutions of the surfactants of Examples 35-40 at 0.1% in distilled water were prepared. Foam heights (mm) were evaluated immediately after foam preparation, and after 5 minutes. Results are shown in Table 39.

Table 39. Characterization of surfactants of Examples 35-40

Note 1. Sample was cloudy in water and sample appearance did not change with temperature

Note 2. Sample was not sufficiently soluble to allow measurement.

Note 3. Lamella broke before meaningful data was obtained.

Note 4. Literature value is 4 mN/m. See, e.g., Rosen, Milton J.; Dahanayake, Manilal (2000). Industrial Utilization of Surfactants - Principles and Practice. AOCS Press. Note 5. Literature value is 105mm (initial) and 90mm (5 min). See, e.g., Technical Datasheet for TERGITOL™ NP-9 Surfactant, available at http://www.dow.com.

Note 6. Literature value is 54°C. See, e.g., Technical Datasheet for TERGITOL™ NP-9 Surfactant, available at http://www.dow.com.

Note 7. Literature value is 60 ppm. See, e.g., See, e.g., Technical Datasheet for TERGITOL™ NP-9 Surfactant, available at http ://www. dow.com.

Note 8. Data for NEODOL™ surfactants are from Shell product literature, available at

http://www.shell.com. Interfacial tension values are from Rosen, Milton J.; Dahanayake, Manilal (2000). Industrial Utilization of Surfactants - Principles and Practice. AOCS Press

Note 9. Ross Miles foam measured at 0.1%, 50°C

Emulsification

[006] Emulsification with various oil substances was evaluated for the surfactants of Examples

35-40 and Comparative Examples (NP-9, PEG 400 Dioleate, PEG 600 Dioleate, Sorbitan Oleate + 5 EO, Sorbitan Oleate + 20 EO, Castor Oil + 25 EO, Castor Oil + 40 EO). The oils were selected to represent certain commercially important products in the agricultural, personal care, and cleaning products applications. Mineral spirits, xylene, and soy methyl ester are used in emulsifiable concentrates in agricultural products; mineral oil, cetyl alcohol, C₈-Ci₀ triglycerides, myristyl myristate, and Ci₂-Ci₅ benzoates are common in personal care products; mineral spirits, pine oil and d-limonene are used in household and industrial cleaning products.

[007] Emulsification was evaluated by first preparing emulsions containing 10%> oil and 10%> surfactants in water. The emulsions were formed by mixing the components with a Tekmar Ultra Turrax mixer, and allowing the resulting mixture to stand for 24 hours, and inspected for separation after 24 hours. If the first emulsion made with 10%> surfactant was stable after 24 hours, a second mixture was made in which the amount of surfactant was 5% and the amount of oil remained at 10%>, and the second mixture was allowed to stand for 24 hours, and inspected for separation after 24 hours. If the second emulsion made with 5% surfactant was stable after 24 hours, a third mixture was made in which the amount of surfactant used was 2.5% and the amount of oil remained at 10%, and the third mixture was allowed to stand for 24 hours, and inspected for separation after 24 hours. Cetyl alcohol emulsions were pastes in water when 10% cetyl alcohol was used, so these mixtures were prepared starting at 5% cetyl alcohol and 5% surfactant. Results are shown in Table 40 and in Table 41. The percentage values in Table 40 and in Table 41 represent the level of surfactant at which the emulsion had separated after 24 hours. That is, a value of 10% in Table 40 or Table 41 indicates the emulsion formed with 10% surfactant and 10% oil was unstable after 24h; 5% indicates the emulsion formed with 10% surfactant and 10% oil was stable after 24h, but an emulsion formed with 5% surfactant and 10% oil in water was unstable after 24h; 2.5% indicates the emulsions formed with 10% surfactant and 10% oil, and 5% surfactant and 10% oil were stable after 24h, but an emulsion formed with 2.5% surfactant and 10% oil was unstable after 24h; and <2.5% indicates that emulsions formed with 10% surfactant and 10% oil, 5% surfactant and 10% oil, and 2.5% surfactant and 10% oil were stable after 24h. [008] Table 40 shows emulsions formed with surfactants of Examples 31-36 herein and oils chosen to represent commercially important products in agricultural, personal care and cleaning products industries, using nonylphenol-9 (NP-9) as a Comparative Example. The oils ranged from nonpolar hydrocarbons to esters to more polar alcohols. Mineral spirits, xylene and soy methyl ester may be used in emulsifiable concentrates in agricultural products; mineral oil, cetyl alcohol and Cg-Cio triglyceride may be used in personal care products; mineral spirits, pine oil and d-limonene may be used in household and industrial cleaning products.

[009] Table 41 shows emulsions formed with Examples 35-40 herein and oils and waxes that are important in personal care products, using PEG 400 dioleate, PEG 600 dioleate, sorbitan oleate + 5 ethylene oxide units, sorbitan oleate + 20 ethylene oxide units, castor oil + 25 ethylene oxide units, and castor oil + 40 ethylene oxide units as Comparative Examples. In some instances combinations of surfactants with differing HLBs may be more effective emulsifiers than individual surfactants used alone.

Table 40. Amount of surfactant that when mixed with 10% oil in water results in separation of emulsion after 24 hours

Comparative Example

Saybolt Universal Seconds

Table 41. Amount of surfactant that when mixed with 10%> oil in water results in separation of emulsion after 24 hours

Comparative Examples

Solubility in electrolytes

[010] The solubility of the surfactants in electrolytes was evaluated as an indicator of builder tolerance of the surfactants. Builders are typically used in household and industrial cleaners to provide alkalinity and soil dispersion. The solubility of surfactants in builders depends on builder concentration and is relatively insensitive to surfactant concentration above the critical micelle concentration.

[011] To measure solubility of surfactants in electrolytes, mixtures of 10%> salts and 5% surfactants were prepared, and water was added until the mixtures were clear at temperatures up to 50°C. The salts used as representative of builders were potassium tripolyphosphate (TKPP), sodium metasilicate, and potassium hydroxide. Table 42 shows results for surfactants of Examples 37-40 and Comparative Examples. Examples 35 and 36 were not sufficiently soluble in water to be included in this evaluation. The values in Table 42 represent the maximum concentration of the builder salt at which the surfactant was soluble. Table 42 also provides the calculated HLB for each of Examples 37-40 and Comparative Examples (NP-9 and NP-12, nonylphenol ethoxylate with an average of 12 ethoxylate units). Examples 38-40 (each with two ethoxylate chains) were highly soluble in the builder solutions, exhibiting greater solubility in electrolytes than NP-9 or NP-12. Example 37 (having a single ethoxylate chain and having a calculated HLB similar to that of NP-12) demonstrated similar solubility in electrolytes to NP-12.

Table 42. Builder Tolerance

Comparative Example

Hard surface cleaning [012] Hard surface cleaning was evaluated according to ASTM D4488 A5 "Standard Guide for

Testing Cleaning Performance of Products Intended for Use on Resilient Flooring and Washable Walls" (now withdrawn by ASTM), which is incorporated herein by reference in its entirety. ASTM D4488 A5 involves soiling white vinyl floor tile with a mixture of oily and particulate soils, and cleaning with detergent-saturated sponges in a Gardner Scrubbability Apparatus. Formulations were prepared using 10% TKPP and 5% surfactant. Cleaning was evaluated at dilutions of 1/64 (2 fluid oz./gal.) and 1/128 (1 fluid oz./gal). Cleaning efficiency is determined by measuring reflectance at 45 degrees on a black-white scale of virgin tiles, soiled tiles and cleaned tiles. Table 43 shows results for Examples 36-40 and Comparative Example (NP-9). The percentage values in Table 43 indicate % soil removed from the tiles as measured by the reflectance (higher numbers indicate more soil has been removed). The least significant difference at 90%> confidence for the measurements was 4.8%.

Table 43. Hard Surface Detergency measured according to ASTM D4488 A5.

*Comparative Example

Laundry Detergency

[013] Laundry detergency was evaluated by formulating detergents at 10% surfactant and 2% soda ash to provide alkaline buffering. The detergent formulations were used at 1 gram/liter in a 100°F wash in tap water (about 60ppm hardness) in a Terg-O-Tometer. The swatches used were dust-sebum soiled fabrics (cotton and durable press fabric) from Scientific Services S/D, Inc., Sparrow Bush, NY. For each wash, triplicate swatches were used. The results are reported as change in reflectance of the swatches before and after washing and are shown in Table 44 for Examples 36-40 and NP-9 as a Comparative Example. Larger numbers indicate more soil removed. The results show that Examples 37 and 38 were highly effective detergents under these conditions. Example 37 included a single ethoxylate chain with an average of 15 repeat units, and Example 38 included two ethoxylate chains each with an average of 5 ethoxylate units. Relative to Examples 37 and 38, detergency effectiveness decreased for Example 36 (single chain ethoxylate with 10 ethoxylate units) and Example 40 (two ethoxylate chains each with 15 ethoxylate repeat units). Example 35 was not evaluated due to limited solubility. The experiment was repeated for Examples 37 and 38 with a different lot of soiled cloths from Scientific Services. The results of the additional laundry detergency tests are shown in Table 45. Also shown in Table 45 are measurements from additional nonyl phenol ethoxylates as Comparative Examples (NEODOL 25-7, 25-9, 45-13, 91-6, 91-8 surfactants, available from Shell Chemicals). In the second test, gel formation was not observed when the surfactants of Examples 37 and 38 were added to water.

Table 44. Laundry Detergency

Comparative Example

Claims

CLAIMS What is claimed is:

1. A lubricant comprising a Diels-Alder adduct of a C₁₀-C30 hydrocarbon terpene comprising a

conjugated diene and a dienophile.

2. The lubricant of claim 1 , wherein the dienophile is selected from the group consisting of maleic anhydride and substituted maleic anhydrides, citraconic anhydride and substituted citraconic anhydrides, itaconic acid, itaconic anhydride, monoalkyl maleates, dialkyl maleates, monoalkyl fumarates, dialkyl fumarates, dialkyl itaconates, acrylic acid esters, methacrylic acid esters, cinnamic acid esters, hydroxyl acrylates, carboxyalkyl acrylates, 1 ,4-benzoquinone and substituted 1,4-benzoquinones, 1 ,2-benzoquinone and substituted 1 ,2-benzoquinones, and combinations thereof.

3. The lubricant of claim 1 or 2, wherein the Diels-Alder adduct is hydrogenated.

4. The lubricant of any one of claims 1 to 3, wherein the Diels-Alder adduct comprises one or more carboxylate ester groups.

5. The lubricant of any one of claims 1 to 4, wherein the Diels-Alder adduct comprises an alkoxylated chain.

6. The lubricant of claim 5, wherein the alkoxylated chain is end-capped with an alkyl group.

7. The lubricant of any one of claims 1-6, wherein the hydrocarbon terpene is β-farnesene.

8. The lubricant of any one of claims 1-8, adapted for use as a base oil.

9. A composition comprising a base oil and a friction modifier comprising the lubricant of any one of claims 1 -8.

10. A composition comprising a base oil and a viscosity index modifier comprising the lubricant of any one of claims 1-8.

11. A composition comprising a base oil and a pour point modifier comprising the lubricant of any one of claims 1-8.

12. A solvent comprising a Diels-Alder adduct of a Ci₀-C₃₀ hydrocarbon terpene comprising a

conjugated diene and a dienophile.

13. The solvent of claim 12, wherein the hydrocarbon terpene is β-farnesene.

14. The solvent of claim 12, wherein the dienophile is selected from the group consisting of maleic anhydride and substituted maleic anhydrides, citraconic anhydride and substituted citraconic anhydrides, itaconic acid, itaconic anhydride, monoalkyl maleates, dialkyl maleates, monoalkyl fumarates, dialkyl fumarates, dialkyl itaconates, acrylic acid esters, methacrylic acid esters, cinnamic acid esters, hydroxyl acrylates, carboxyalkyl acrylates, 1 ,4-benzoquinone and substituted 1,4-benzoquinones, 1 ,2-benzoquinone and substituted 1 ,2-benzoquinones, and combinations thereof.

15. A method for making a polymer, the method comprising polymerizing a Diels-Alder adduct of a C10-C30 hydrocarbon terpene comprising a conjugated diene and a dienophile.

16. The method of claim 15, wherein the hydrocarbon terpene is β-farnesene.

17. The method of claim 15, wherein the the dienophile is selected from the group consisting of maleic anhydride and substituted maleic anhydrides, citraconic anhydride and substituted citraconic anhydrides, itaconic acid, itaconic anhydride, monoalkyl maleates, dialkyl maleates, monoalkyl fumarates, dialkyl fumarates, dialkyl itaconates, acrylic acid esters, methacrylic acid esters, cinnamic acid esters, hydroxyl acrylates, carboxyalkyl acrylates, 1 ,4-benzoquinone and substituted 1,4-benzoquinones, 1 ,2-benzoquinone and substituted 1 ,2-benzoquinones, and combinations thereof.

18. A method for making a polymer, the method comprising copolymerizing a Diels-Alder adduct of a C10-C30 hydrocarbon terpene comprising a conjugated diene and a dienophile with one or more comonomers.

19. The method of claim 18, wherein the hydrocarbon terpene is β-farnesene.

20. The method of claim 18, wherein the dienophile is selected from the group consisting of maleic anhydride and substituted maleic anhydrides, citraconic anhydride and substituted citraconic anhydrides, itaconic acid, itaconic anhydride, monoalkyl maleates, dialkyl maleates, monoalkyl fumarates, dialkyl fumarates, dialkyl itaconates, acrylic acid esters, methacrylic acid esters, cinnamic acid esters, hydroxyl acrylates, carboxyalkyl acrylates, 1 ,4-benzoquinone and substituted 1,4-benzoquinones, 1 ,2-benzoquinone and substituted 1 ,2-benzoquinones, and combinations thereof.