WO2012158250A1

WO2012158250A1 - Plasticizers

Info

Publication number: WO2012158250A1
Application number: PCT/US2012/028956
Authority: WO
Inventors: Frank X. Woolard; Daniel Batzel
Original assignee: Amyris, Inc.
Priority date: 2011-05-13
Filing date: 2012-03-13
Publication date: 2012-11-22

Abstract

This application relates to plasticizers derived from hydrocarbon terpenes (e.g., myrcene or farnesene), methods of making the plasticizers, compositions comprising the plasticizers, and applications for the plasticized compositions.

Description

PLASTICIZERS

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of and priority to U.S. provisional patent application 61/486,156 filed May 13, 2011, 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 plasticizers derived from hydrocarbon terpenes.

BACKGROUND

[0004] Plasticized polymer compositions may be used in a variety of uses, including automotive components (e.g., interiors), footwear, adhesives, sealants, coated fabrics, wire and cable coatings, foams, gaskets, inks, cosmetics, medical devices, medical bags and tubing, toys, electrical devices, films, wall coverings, floor coverings, appliances, furniture, hoses, concrete, and the like.

[0005] Plasticizers are used in a variety of compositions, for instance polymer-based compositions (e.g., polyvinylchloride (PVC)) and in concrete compositions. Commonly used, commercially available phthalate plasticizers include dibutyl phthalate (DBP), dioctyl phthalate (DOP) and diisononyl phthalate (DINP). However, phthalates can cause health concerns, making phthalates unsuitable for use in some applications, such as plastics used in children's toys and in food containers. It is believed that some of the problems are tied to the aromatic nature of the phthalate esters. Therefore, there has been a move toward replacing aromatic phthalates with saturated analogs thereof, for instance 1,2-, 1,3- or 1 ,4-cyclohexane

dicarboxylate esters; see, e.g., Brunner et al. US Pat. No. 7,208,545; Kinkade et al. US Pat. No. 7,973,194; Noe et al. US Pat. No. 7,319,161; Mack et al. US Pat. Publ. 2011/0232825; Hogan et al. US Pat. Publ. 2010/0063178, each of which is incorporated herein by reference. Recently, 1 ,2-cyclohexane dicarboxylic acid diisononyl ester (DINCH) has been used as a replacement for DINP or DOP in PVC, and the resulting plasticized films may be suitable for food-related applications.

[0006] It is desired that plasticizers be prepared from raw materials derived from renewable carbon sources rather than from petroleum or other fossil fuels. Hydrocarbon terpenes such as myrcene and the sesquiterpene β-farnesene can be synthesized via biological routes from renewable carbon sources such as sugars or biomass. For example, myrcene and β- farnesene can be produced from sugars or biomass 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.

[0007] A need exists for new plasticizers for plastics and other resins that are produced from renewable feedstock and that are suitable for use in a variety of applications, including in plastics for food packaging and for baby care products.

SUMMARY

[0008] Disclosed herein are derivatives of hydrocarbon terpenes that can be used as plasticizers, compositions comprising the plasticizers, and methods for making the same. In some variations, a plasticizer comprises a Diels-Alder adduct of a hydrocarbon terpene comprising a conjugated diene and a dienophile, or comprises a derivative of such a Diels-Alder adduct.

[0009] In some variations, the Diels-Alder plasticizer 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.

[0010] The properties of the plasticizers can be tuned depending on the host resin in which they are intended to be used. The plasticizers can be selected to modify any one of or any combination of physical and/or mechanical properties of the host resin, e.g., lower glass transition temperature, lower melt temperature, lower melt viscosity, increase toughness, increase elasticity, increase elongation at break, increase load at break, increase displacement at break, increase strain at break, increase energy to yield point, improve low temperature brittleness properties, and/or modify durometer hardness. [0011] The hydrocarbon terpene can be any hydrocarbon terpene capable of undergoing a Diels- Alder reaction with a dienophile. In some variations, the hydrocarbon terpene is β- farnesene. In some variations, the hydrocarbon terpene is myrcene. 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.

[0012] The dienophile may be 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, α-β-unsaturated aldehydes, dialkyl maleates, dialkyl fumarates, 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, 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, vinyl sulfonates, vinyl sulfmates, vinyl sulfoxides, and combinations thereof. In some variations, the dienophile is maleic anhydride. In some variations, the dienophile is a dialkyl maleate. In some variations, the dienophile is a dialkyl fumarate. In some variations, the dienophile is an α,β-unsaturated aldehyde.

[0013] The plasticizers described herein may be designed for use as plasticizers in a wide variety of host polymers. In some variations, the plasticizers are used in thermoplastics. In some variations, the plasticizers are used in thermosets. In some variations, the plasticizers are used in elastomers or rubbers. Certain examples of the plasticizers are suitable for use in PVC, chlorinated polyvinylchloride, polycarbonates, polyurethanes, nitrile polymers (such as acrylonitrile butadiene styrene (ABS)), acrylate polymers, styrenic polymers, polyesters (e.g., lactic-acid containing polymers), polyamides, polyimides, polyvinyl acetals, cellulose polymers, starches, polyolefms, natural rubbers, synthetic rubbers, co-polymers of any of the foregoing, polymer blends of any of the foregoing, or in polymer composites of any of the foregoing.

[0014] The plasticizers described herein may be selected to have sufficiently low volatility under processing and use conditions such that they do not exhibit undesirable levels of migration within the host polymer or exude from the host polymer. Volatility may be reduced by selecting higher molecular weight plasticizers, selecting plasticizers with a high degree of compatibility with a host resin, and/or by selecting functional groups on the plasticizer that increase interaction with the host polymer.

[0015] In some variations, a plasticizer disclosed herein comprises a Diels-Alder adduct of a hydrocarbon terpene comprising a conjugated diene and a dienophile in which the aliphatic portion of the Diels- Alder adduct originating from the terpene and/or one or more substituents of the adduct originating from the dienophile have been selected or modified to increase compatibility with the host resin. For example, in some variations, unsaturated bonds in the aliphatic portion of the Diels-Alder adduct may be oxidized (e.g., epoxidized) or halogenated (e.g., chlorinated). In some variations, one or more substituents of a Diels-Alder adduct originating from the dienophile may have been selected or chemically modified to include one or more polar groups (e.g., one or more hydroxy, alkoxy, ether, epoxy, carboxy, amino, carbonyl, and/or halogen groups) to increase compatibility with polar host resins.

[0016] In some variations, a plasticizer is or comprises a compound having formula (F-

1) or a derivative thereof:

where R and R' each independently represent H or any C1-C30 linear or branched, cyclic or acyclic, substituted or unsubstituted hydrocarbyl group, where n=l, 2, 3, or 4, and where R and R' may be the same or different. In some variations, R and R' each independently represent 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 variations, R and R' each 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 variations, R and/or R' comprises one or more heteroatoms, e.g., oxygen, nitrogen, sulfur, phosphorus, or halogen atoms (e.g., chlorine, bromine or iodine). In one embodiment, R and R' are each methyl. In some embodiments, a plasticized composition comprises PVC as a host resin and a plasticizer having formula (F-1). In some variations, a plasticized composition comprises PVC as a host resin and a plasticizer having formula (F-1) with n=2 and R and R' are each independently methyl.

[0017] In some variations, a plasticizer is or comprises a compound having formula (F-

2), a derivative thereof, a compound having formula (F-3) a derivative thereof, or a mixture thereof:

where R represents H or any C1-C30 linear or branched, cyclic or acyclic, substituted or unsubstituted hydrocarbyl group, and n=l,2,3, or 4. In some variations, R represents methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, t-butyl, 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.

[0018] In some variations, a plasticizer is or comprises or is derived from a compound having formula (F-4)

where n=l,2,3 or 4.

[0019] In some variations, a plasticizer is or comprises a compound having formula (F-

1 A) or a derivative thereof:

where R and R' each independently represent H or any C₁-C30 linear or branched, cyclic or acyclic, substituted or unsubstituted hydrocarbyl group, where n=l , 2, 3, or 4, and where R and R' may be the same or different. In some variations, R and R' each independently represent 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 variations, R and R' each 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 variations, R and/or R' comprises one or more heteroatoms, e.g., oxygen, nitrogen, sulfur, phosphorus, or halogen atoms (e.g., chlorine, bromine or iodine). In one embodiment, R and R' are each methyl. In some embodiments, a plasticized composition comprises PVC as a host resin and a plasticizer having formula (F-l A). In some variations, a plasticized composition comprises PVC as a host resin and a plasticizer having formula (F-l A) with n=2 and R and R' are each independently methyl.

[0020] In some variations, a plasticizer is or comprises a compound having formula (F-

2A), a derivative thereof, a compound having formula (F-3A) a derivative thereof, or a mixture thereof:

[0021] where R represents H or any C₁-C30 linear or branched, cyclic or acyclic, substituted or unsubstituted hydrocarbyl group, and n=l,2,3, or 4. In some variations, R represents methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, t-butyl, 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, a plasticized composition comprises PVC as a host resin and a plasticizer having formula (F-2A) or (F-3A). In some variations, a plasticized composition comprises PVC as a host resin and a plasticizer having formula (F-2A) or (F-3 A) with n=2 and R and R' are each independently methyl.In some variations, the Diels-Alder adducts derived from the hydrocarbon terpenes that are useful as plasticizers comprise at least one epoxy group. In some variations, the Diels-Alder adducts comprise two epoxy groups. In some variations, the Diels-Alder adducts comprise more than two epoxy groups. In certain variations, the epoxidized Diels-Alder adducts are adapted for use as monomers or as cross- linking agents, or as curing agents to make an oligomer or polymer that has utility as a plasticizer. In certain variations, at least one epoxy group of a Diels-Alder adduct may be hydrolyzed to make a plasticizer or a plasticizer precursor.

[0022] In some variations, a plasticizer is or comprises or is derived from a compound having formula (F-4A)

where n=l,2,3 or 4. In some embodiments, a plasticized composition comprises PVC as a host resin and a plasticizer having formula (F-4A). In some variations, a plasticized composition comprises PVC as a host resin and a plasticizer having formula (F-4A) with n=2.

[0023] In some variations, a plasticizer is, comprises or is derived from a compound having formula (H-XIIA)-(H-XIIF) or (H-XIIA')-(H-XIIE'):

where each of R and R' independently represents H or any C₁-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 some variations, each of R and R' is independently methyl.

[0024] Described herein are polymer compositions comprising a host resin and one or more Diels-Alder plasticizer adducts derived from a hydrocarbon terpene comprising a conjugated diene and a dienophile, wherein the plasticizer has been incorporated into the host resin in an amount effective to reduce the glass transition temperature, increase toughness, increase elasticity, increase elongation at break, and/or improve a low temperature property. In some variations, a plasticized composition comprises two or more plasticizers, e.g., two or more plasticizers as described herein, or one or more plasticizers as described herein and one or more plasticizers known in the art. In some variations, a plasticized composition comprises one or more additives selected from the group consisting of anti-blocking agents, antistatic agents, lubricants, anti-fogging agents, heat stabilizers, antioxidants, discoloration inhibitors, flame retardants, oils, waxes, antioxidants, UV stabilizers, colorants or pigments, tackifiers, waxes, flow aids, coupling agents, crosslinking agents, surfactants, compatibilizers, rheology modifiers, adhesion promoters, catalysts, solvents, corrosion inhibitors, anti-wear agents, antioxidants, rust inhibitors, flame retardants, biocides, algicides, fungicides, acid scavengers, radical scavengers, monomer scavengers, water scavengers, inorganic fillers, conductive particles, fibers, and combinations thereof.

[0025] In some variations, a plasticized composition comprises PVC and one or more

Diels-Alder adducts between a hydrocarbon terpene having a conjugated diene and a dienophile in an amount effective to improve processability, increase toughness, increase flexibility, increase elasticity, reduce rigidity (e.g., increase elongation at break), and/or improve a low temperature property.

[0026] In some variations, a plasticized composition comprises polylactic acid and one or more Diels-Alder adducts between a hydrocarbon terpene having a conjugated diene and a dienophile in an amount effective to improve processability, increase toughness, increase flexibility, increase elasticity, reduce rigidity (e.g., increase elongation at break), and/or improve a low temperature property.

[0027] In some variations, a plasticized composition comprises an adhesive and one or more Diels-Alder adducts between a hydrocarbon terpene having a conjugated diene and a dienophile in an amount effective to improve processability, increase toughness, increase flexibility, increase elasticity, reduce rigidity (e.g., increase elongation at break), and/or improve a low temperature property. Nonlimiting examples of adhesives in which the plasticizers may be utilized include those based on acrylates, methacrylates, silanes, siloxanes, polyethers, polyesters, polyurethanes, polyureas, polysulfides, silylated polyurethanes, silylated polyureas, silylated polyethers, silylated polysulfides and silyl-terminated acrylates and the like. [0028] Described herein are compositions comprising a plasticizer derived from a Diels-

Alder adduct between a hydrocarbon terpene comprising a conjugated diene and a dienophile combined with a host resin, wherein the adduct functions to plasticize the host resin and to provide one or more additional functionalities selected from the group consisting of acid scavenging, radical scavenging, thermal stabilization, color stabilization, charge dissipation, fire retardation, corrosion inhibition, flow viscosity improvement, radical scavenging, dye site creating, adhesion promoting, and mold releasing.

[0029] In some variations, the Diels- Alder plasticizer adduct is physically blended with a polymer. In some variations, the Diels- Alder adduct is chemically reacted with a polymer. In some variations, a Diels-Alder adduct or its derivative is used as a monomer, cross-linking agent, or reactive diluent to make an oligomer or polymer that is used as a plasticizer.

[0030] Advantageously, 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 renewable carbon sources.

[0031] Described herein are methods of making a plasticized composition, comprising reacting a hydrocarbon terpene comprising a conjugated diene with a dienophile to form a Diels- Alder adduct, and combining the adduct with a host polymer to plasticize the host polymer.

[0032] Described herein are methods of making a plasticized composition, comprising reacting a hydrocarbon terpene comprising a conjugated diene with a dienophile to form a Diels- Alder adduct, chemically functionalizing the adduct to form a plasticizer, and combining the plasticizer with the host polymer to plasticize the host polymer, wherein the chemical functionalization of the adduct increases compatibility with the host polymer.

[0033] In any of the plasticizers, compositions, or methods described herein, the hydrocarbon terpene may be derived from a sugar using a genetically modified organism. In some variations, the hydrocarbon terpene is β-farnesene derived from a sugar using a genetically modified organism.

[0034] In some variations, a plasticizer comprises β-farnesene (or a β-farnesene derivative such as a dimer, trimer or tetramer of β-farnesene, or a Diels Alder adduct of β- farnesene and a dieneophile) that has had one, two, three (or four or more, if present) of its double bonds oxidized (e.g., epoxidized) or chlorinated. BRIEF DESCRIPTION OF DRAWINGS

[0035] FIGURE 1 shows weight loss with heat aging for Example 22, Comparative

Examples 7-9, and neat PVC.

[0036] FIGURE 2 shows toughness for Examples 21 and 22, Comparative Examples 4-

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

[0037] FIGURE 3 shows Young's modulus for Examples 21 and 22 and Comparative

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

[0038] FIGURE 4 shows engineering strain (% elongation) at failure for Examples 21 and 22, Comparative Examples 4-9, and neat PVC, measured according to ASTM D638 using a pull rate of 50mm/min.

[0039] FIGURE 5 shows displacement at break for Examples 21 and 22, Comparative

Examples 4-9, and neat PVC, measured according to ASTM D638 using a pull rate of

50mm/min.

[0040] FIGURE 6 shows load at break for Examples 21 and 22, Comparative Examples

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

[0041] FIGURE 7 shows stress at break for Examples 21 and 22, Comparative Examples

[0042] FIGURE 8 shows energy to yield point for Examples 21 and 22, Comparative

50mm/min.

[0043] FIGURE 9 shows 1H NMR spectrum of (E)-dimethyl 4-(4,8-dimethylnona-3,7- dienyl)cyclohex-4-ene-l,2-dicarboxylate of Example 30.

[0044] FIGURE 10 shows 1H NMR spectrum of dimethyl 4-(4,8- dimethylnonyl)cyclohexane-l,2-dicarboxylate of Example 31.

[0045] FIGURE 11 shows 1H NMR spectrum of (4-(4,8-dimethylnonyl)cyclohane- 1 ,2- diyl)dimethanol of Example 32.

[0046] FIGURE 12A and FIGURE 12B show ¹³C NMR spectra of (4-(4,8- dimethylnonyl)cyclohane-l,2-diyl)dimethanol of Example 32. [0047] FIGURE 13 shows 1H 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.

[0048] 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.

[0049] FIGURE 15 shows 1H NMR spectrum of a mixture of (3-(4,8- dimethylnonyl)cyclohexyl)methanol and (4-(4,8-dimethylnonyl)cyclohexyl)methanol of Example 34.

[0050] FIGURES 16A-16C show 1H 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.

[0051] 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.

[0052] FIGURES 17A-17C show 1H 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.

[0053] 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.

[0054] FIGURES 18A-18C show 1H NMR spectra of a mixture of l-(4,8-dimethyl- nonyl)-cyclohexane-3-pentadecaethylene glycol and l-(4,8-dimethyl-nonyl)-cyclohexane-4- pentadecaethylene glycol of Example 37.

[0055] FIGURES 18D-18F show ¹³C NMR spectra of a mixture of l-(4,8-dimethyl- nonyl)-cyclohexane-3-pentadecaethylene glycol and l-(4,8-dimethyl-nonyl)-cyclohexane-4- pentadecaethylene glycol of Example 37.

[0056] FIGURES 19A-19C show 1H NMR spectra of l-(4,8-dimethyl-nonyl)- cyclohexane-3,4-bis(methyl-pentaethylene glycol) of Example 38.

[0057] 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. [0058] FIGURES 20A-20C show 1H NMR spectra of 1 -(4,8-dimethyl-nonyl)- cyclohexane-3,4-bis(methyl-decaethylene glycol) of Example 39.

[0059] 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.

[0060] FIGURES 21 A-21 C show 1H NMR spectra of 1 -(4,8-dimethyl-nonyl)- cyclohexane-3,4-bis(methyl-decapentaethylene glycol) of Example 40.

[0061] 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.

[0062] 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.

[0063] FIGURE 23 shows correlation of durometer hardness A with tensile properties for data shown in Table 64.

[0064] FIGURE 24 shows DMA results for Example 78.

DETAILED DESCRIPTION

[0065] Described herein are plasticizers that comprise or are derived from Diels-Alder adducts between a hydrocarbon terpene comprising a conjugated diene moiety (e.g., myrcene, β- farnesene, or a-farnesene) and a dienophile, methods of making the plasticizers, and to the use of the plasticizers in a variety of applications. For example, certain variations of the plasticizers described herein have utility in construction (e.g., resilient flooring, wall coverings, pool liners, coatings, roofing materials, fillers, insulation backings, adhesives, and the like), electrical products (e.g., wire and cable jackets, electrical tapes, electrical boxes, circuit boards, insulating coatings, and the like), consumer goods (e.g., footwear, toys, clothing, luggage, bookbinding, storage containers, disposable cutlery and plates and cups, garden hose), packaging (e.g., films, bottles, containers, sealants, adhesives and the like), automotive (e.g., upholstery, interior trim, floor mats, hoses, sealants, adhesives, body components, coatings and the like), furnishings (e.g., carpet, furniture, upholstery, lightweight furnitures, curtains such as shower curtains, adhesives, sealants and the like), medical applications (e.g., IV bags, tubing, disposable sheets, disposable garments, and the like). Certain plasticizers derived from Diels-Alder reaction between a hydrocarbon terpene comprising a conjugated diene and a dieneophile are disclosed in U.S. Provisional Patent Application Serial No. 61/486, 156 filed May 13, 201 1 , U.S. Provisional Patent Application Serial No. 61/527,041 filed August 24, 2011, and U.S. Provisional Patent Application Serial No. 61/590,321 filed January 24, 2012, each of which is incorporated herein by reference in its entirety as if put forth fully below.

[0066] Certain variations of the plasticizers comprise a ring structure resulting from a

Diels-Alder reaction between a hydrocarbon terpene comprising a conjugated diene and a dienophile, with one or more aliphatic tails originating from the hydrocarbon terpene attached to the ring structure, and one or more additional substituents originating from the dienophile attached to the ring structure. The hydrocarbon terpene and the dienophile may be selected to impart desired properties to the plasticizer (e.g., to increase compatibility with the host resin, modify molecular weight, modify volatility, and/or modify thermal stability). A Diels-Alder adduct may undergo chemical derivatization following the Diels-Alder reaction to form a plasticizer having desirable properties.

[0067] The plasticizers can be selected to modify any one of or any combination or physical or mechanical properties of the host resin, e.g., lower glass transition temperature, increase toughness, improve low temperature brittleness temperature, increase flexibility, increase processibility, increase elasticity, increase elongation at break, increase load at break, increase displacement at break, increase strain at break, increase energy to yield point, and/or modify a low temperature property. The plasticizers can be designed to be sufficiently compatible with the host resin so that exudation of the plasticizer under use condition is acceptably low.

[0068] The plasticizers described herein may be designed for use as plasticizers in a wide variety of polymers. For example, certain examples of β-farnesene-derived plasticizers are suitable for use in PVC, polycarbonates, polyurethanes, nitrile polymers (such as acrylonitrile butadiene styrene (ABS)), acrylate polymers, polystyrenes, polyesters, polyamides, polyimides, polyvinyl acetals, cellulose polymers, polyolefins, natural rubbers, synthetic rubbers, copolymers of any of the foregoing, polymer blends of any of the foregoing, or in polymer composites of any of the foregoing.

[001] Provided below is Section A), which includes some definitions. Section B) below describes sources of hydrocarbon terpenes comprising a conjugated diene. Section C) includes non- limiting examples of formation of Diels-Alder adducts from which the plasticizers can be derived. Section D) below provides non-limiting examples of dienophiles that can be used in the Diels-Alder reaction to make the plasticizers. Section E) below provides non- limiting examples of hydrocarbon terpenes comprising a conjugated diene that can be used in the Diels- Alder reaction to make the plasticizers. Section F) below provides non-limiting examples of Diels- Alder adducts that can be formed. Section G) below provides non- limiting examples of chemical modifications that can be performed on a Diels-Alder adduct to make a plasticizer having desired properties. Section H) below provides non-limiting examples of farnesene -based Diels-Alder adducts from which plasticizers can be derived. Section J) below provides non-limiting examples of variations of plasticizers that can be derived from the Diels- Alder adducts, selection of plasticizers for certain applications, and non-limiting examples of compositions comprising the plasticizers. Section K) below provides applications for the plasticizers and plasticized compositions described herein. It should be understood that Sections A)-K) are provided for organization purposes only. Any suitable dienophile from Section D) may be reacted with any suitable hydrocarbon terpene from Section E) to form a plasticizer.

A) Definitions

[0069] 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.

[0070] "Terpene" as used herein is 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. 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, but is not part of an aromatic ring. A conjugated hydrocarbon terpene 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 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, cw-phyta- 1,3 -diene, trans-phyta-1,3- diene, isodehydrosqualene, isosqualane precursor I, and isosqualane precursor II.

[0071] 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 sources, they are useful for making eco- friendly and renewable plasticizers. In certain embodiments, the conjugated hydrocarbon terpenes as described herein are derived from microorganisms using a renewable carbon source such as a sugar that can be replenished in a matter of months or a few years unlike fossil fuels.

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

or a stereoisomer thereof.

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

or a stereoisomer thereof.

[0074] Ocimene" refers to a-ocimene, β-ocimene or a mixture thereof.

[0075] a-ocimene" refers to a compound having the following formula: or a stereoisomer (e.g., s-cis isomer) thereof.

[0076] "β-ocimene" refers to a compound having the following formula:

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

[0077] "Farnesene" as used herein refers to a-farnesene, β-farnesene or a mixture thereof.

[0078] "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 α-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 α-farnesene mixture of stereoisomers.

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

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

[0079] "Farnesane" refers to a compound having the following structure:

or a stereoisomer thereof.

[0080] "β-springene" or "springene" refers to a compound having the following structure:

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

[0081] "Geranylfarnesene" refers to a compound having the following structure:

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

[0082] "Neophytadiene" refers to a compound having the following structure:

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

[0083] "7>a/?5-phyta-l,3-diene" refers to a compound having the following structure:

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

[0084] "Cz5-phyta-l,3-diene" refers to a compound having the following structure:

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

[0085] "Isodehydrosqualene" refers to a compound having the following structure:

or a stereoisomer thereof.

[0086] "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.

[0087] "Isosqualane precursor Π" or "2,6,14,18,22-pentamethyl-lO-vinyltricosa-

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

or a stereoisomer thereof.

[0088] "Farnesol" refers to a compound having the following structure:

or a stereoisomer thereof.

[0089] "Nerolidol" refers to a compound having the following structure:

or a stereoisomer thereof.

[0090] 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.

[0091] 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."

[0092] "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). It also encompasses polymers made by polymerizing four or more types of monomers.

[0093] "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 C1-C30 hydrocarbyl group (e.g., C1-C20 alkyl, C1-C20 alkenyl, C1-C20 alkynyl, cycloalkyl, aryl, aralkyl and alkaryl).

[0094] "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 C1-C10 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, 2-ethylhexyl, n-nonyl, isononyl, n-decyl, 2-propylheptyl, 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, 1 1 or 12 carbons. In some embodiments, the alkyl group is branched having 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 or 12 carbons. [0095] "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.

[0096] "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.

[0097] "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.

[0098] "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.

[0099] "Isoprenoid" and "isoprenoid compound" are used interchangeably herein and refer to a compound derivable from isopentenyl diphosphate.

[00100] 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)„-, 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.

[00101] 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 physical properties, 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 physical property. 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 a low

temperature physical property, or any combination of two or more of the foregoing.

B) Source of Conjugated Hydrocarbon Terpenes

[00102] 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)- -farnesene, Aust. J. Chem. 23(10), 2101-2108, which is incorporated herein by reference in its entirety.

[00103] 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.

[00104] 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.

[00105] 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.

[00106] In certain embodiments, a conjugated terpene can be prepared in a facility capable of biological manufacture of isoprenoids. For example, for making a C₁₅ isoprenoid, the facility may comprise any structure useful for preparing C₁₅ isoprenoids (e.g., a-farnesene, β- farnesene, nerolidol or farnesol) using a microorganism capable of making the C₁₅ isoprenoids with a suitable carbon source under conditions suitable for making the C₁₅ isoprenoids. In some embodiments, the biological facility comprises a cell culture comprising a desired isoprenoid (e.g. , a Cio, a C₁₅, a C₂o, 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 C₁₀, a Ci5, a C₂₀, 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 C₁₅, 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.

[00107] The facility may further comprises any structure capable of manufacturing a chemical derivative from the desired isoprenoid (e.g. , a C₁₀, a C₁₅, 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

[00108] 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. 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 catalyst 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 "Z¾e 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. Certain surfactants derived from Diels-Alder reaction between a hydrocarbon terpene comprising a conjugated diene and a dienophile are disclosed in U.S. Provisional Patent Application Serial No. 61/436,165 filed January 25, 2011, U.S. Provisional Patent Application Serial No. US 61/527,041 filed August 24, 2011, U.S. Provisional Patent Application Serial No. 61/543,747 filed October 5, 2011, U.S. Provisional Patent Application Serial No. 61/544,257 filed October 6, 2011, and PCT Application No. PCT/US2012/02245 filed January 24, 2012, each of which is incorporated herein by reference in its entirety as if put forth fully below.

[00109] A variety of electron deficient dienophiles may effectively undergo the Diels-

Alder reaction with conjugated terpenes to produce cyclic compounds that have utility as plasticizers. 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 "Z¾e Diels-Alder Reaction: Selected Practical Methods " 1st 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 a plasticizer. Some non-limiting examples of conjugated hydrocarbon 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, geranylfarnesene, isodehydrosqualene, isosqualane precursor I, and isosqualane precursor II. Some non- limiting examples of Diels-Alder adducts are provided in Section F below. Non- limiting examples of chemical modifications for Diels-Alder adducts are provided in Section G below.

D) Dienophiles

[00110] 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):

R16 _R17__N__N__R18

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., Ci- 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), -CO2R¹⁹, -(CH₂)„C0₂R²⁰, -COO Mi⁺, -(CH₂)_mCOO M₂ ⁺, -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 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; each of R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷ and R²⁸ is independently H, hydrocarbyl, hydroxyalkyl, aminoalkyl, carboxylalkyl, thioalkyl, epoxyalkyl, hydroxyaryl, aminoaryl, carboxylaryl,

25 26 27 28 thioaryl, hydroxyl, amino, halo, cyano, nitro or acyl, or R and R together or R and R together form a benzo ring or a substituted or unsubstituted -CH₂(CH₂)_kCH₂- group; and each of m, n and k is independently an interger 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.

In some embodiments, a dienophile has formula (Al), (A2), (A3), (A4), (A5),

(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

20 21 22 5

substituent (e.g., chloro or bromo), NRA RA or ORA ; QA 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, sulfonate, sulfmate, sulfoxide, carboxyl, epoxy or glycidyl.

[001] 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 C₁-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 sulfmate, or vinyl sulfoxide.

[00112] In certain embodiments, the dienophile comprises sulfur dioxide, or a sulfone

SO₂RR', where R and R' may independently be any C₁-C30 hydrocarbyl group.

[00113] Some non-limiting examples of suitable dienophiles that can form Diels-Alder adducts with conjugated terpenes (e.g., farnesene or myrcene) include acrolein, acrylic acid, acrylate esters, vinyl ketones, dialkyl maleates, dialkyl fumarates, maleic anhydride, itaconic acid, maleimides, fumaronitrile, malononitrile, acetylene dicarboxylic acids, and acetylene dicarboxylic acid esters.

[00114] 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) dialkyl maleates or dialkyl fumarates (e.g., linear or branched, cyclic or acyclic, Ci- 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, di- isopropyl fumarate, di-n-butyl maleate, di-n-butyl fumarate, di(isobutyl) maleate, di(isobutyl) fumarate, di-tert-butyl maleate, di-tert butyl fumate, di-n-pentyl maleate, di-n-pentyl fumarate, di(isopentyl) maleate, di(isopentyl) fumarate, di-n-hexyl maleate, di-n-hexyl fumarate, di(2- ethylhexyl) maleate, di(2-ethylhexyl) fumarate, di(isohexyl) maleate, di(isohexyl) fumarate, di- n-heptyl maleate, di-n-heptyl fumarate, di(isoheptyl) maleate, di(isoheptyl) fumarate, ,di-n-octyl maleate, di-n-octyl fumarate, di(isooctyl) maleate, di(isooctyl) fumarate, di-n-nonyl maleate, di- n-nonyl fumarate, di(isononyl) maleate, di(isononyl) fumarate, di-n-decyl maleate, di-n-decyl fumarate, di(isodecyl) maleate), di(2-propylheptyl) maleate, di(2-propylheptyl) fumarate, and di(isodecyl) fumarate;

(H) dialkyl itaconates (e.g., linear or branched, cyclic or acyclic, C₁-C30 dialkyl itaconates such as dimethyl itaconate, diethyl itaconate, di-n-propyl itaconate, di-isopropyl itaconate, di-n- butyl itaconate, di(isobutyl) itaconate, di-tert-butyl itaconate, di-n-pentyl itaconate, di(isopentyl) itaconate, di-n-hexyl itaconate, di(2-ethylhexyl) itaconate, di(isohexyl) itaconate, di-n-heptyl itaconate, di(isoheptyl) itaconate, di-n-octyl itaconate, di(isooctyl) itaconate, di-n-nonyl itaconate, di(isononyl) itaconate, di-n-decyl itaconate and di(isodecyl) 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, Ci-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, C₁-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-hydroxyethyl acrylate);

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

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

(P) 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, di(isopropyl) acetylene dicarboxylate, di-n- butyl acetylene dicarboxylate, di(isobutyl) acetylene dicarboxylate, di(tert-butyl) acetylene dicarboxylate, di-n-pentyl acetylene dicarboxylate, di(isopentyl) acetylene dicarboxylate, di-n- hexyl acetylene dicarboxylate, di(2-ethylhexyl) acetylene dicarboxylate, di(isohexyl) acetylene dicarboxylate, di-n-heptyl acetylene dicarboxylate, di(isoheptyl) acetylene dicarboxylate, di-n- octyl acetylene dicarboxylate, di(isooctyl) acetylene dicarboxylate, di-n-decyl acetylene dicarboxylate, di(2-propylheptyl) acetylene dicarboxylate, and di(isodecyl) acetylene dicarboxylate); or an alkyl propiolate, an alkyl 2-butynoate, an alkyl 2-pentynoate, an alkyl 2- hexynoate, 2-butynoic acid, 2-pentynoic acid, 2-hexynoic acid;

(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) maleimide and substituted maleimides (e.g., linear or branched, cyclic or acyclic, Ci- C30 alkyl 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, C₁-C30 dialkyl azidocarboxylates, such as dimethyl azidocarboxylate, and diethyl azidocarboxylate;

(T) azidocarboxylic acid and azidodicarboxyhc 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

, andjuglone

(X) phosphorus trihalide (e.g., phosphorus tribromide); and (Y)vinyl sulfonates, vinyl sulfmates, or vinyl sulfoxides. E) Conjugated Hydrocarbon Terpenes

[00115] 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, RB³ and RB⁴ is not hydrogen.

[00116] 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. In some cases, 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, RB¹ and RB² are H, but RB³ and RB⁴ are not H.

[00117] 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 some embodiments, the conjugated hydrocarbon terpene has formula (AI):

wherein n is 1, 2, 3 or 4.

[00118] 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.

[00119] 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):

[00120] 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.

[00121] 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.

[00122] 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

[00123] Diels-Alder adducts can be prepared by reacting a dienophile disclosed herein with one or more conjugated hydrocarbon terpene under Diels-Alder reaction condition 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 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.

[00124] 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.

[00125] 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:

[00126] 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. [00127] 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:

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

[00128] 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 R¹⁶ are as defined herein.

[00129] 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.

[00130] In some embodiments, the Diels-Alder adduct of formula (IXA) and (IXB) 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.

[00131] In some embodiments, each of RB¹, RB³ and RB⁴ of the adduct of formula

(VIIA), (VIIA'), (VIIB), (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.

[00132] In some embodiments, RB² 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):

[00133] 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):

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. [00134] In certain embodiments, each of RB³ and RB⁴ of the adduct of formula (VIIA),

(VIIA'), (VIIB), (VIIB'), (VIIIA), (VIIIA'), (VIIIA"), (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.

[00135] 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 (XIV):

[00136] 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 C₁-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, QB¹ 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 QB¹ 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 QB¹ 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 cyclohex-dienyl ring. In other embodiments, a cyclohexenyl or a cyclohex-dienyl ring may be oxidized so that the ring is aromatic.

[00137] In some embodiments, the Diels-Alder adduct is formed between a conjugated hydrocarbon terpene having formula (AI) and a dienophile disclosed 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:

[00138] 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.

[00139] 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

[00140] 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.

[00141] Table 1 shows RB¹, RB², RB³ and RB⁴ for exemplary conjugated terpenes, where dashed lines indicate unsaturated olefmic 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 RB^1', RB^2', 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

TABLE 2. SOME NON-LIMITING EXAMPLES OF DIENOPHILES AND DIELS-

ALDER ADDUCTS.

C1-C10 alkyl)

and/or

the

[00142] In some variations, a plasticizer is or comprises a compound having formula (F-

1) or (F-IA), or a derivative thereof:

where R and R' each independently represent H or any Ci-C₃o linear or branched, cyclic or acyclic, substituted or unsubstituted hydrocarbyl group, where n=l, 2, 3, or 4, and where R and R' may be the same or different. In some variations, R and R' each independently represent 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 variations, R and R' each 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 variations, R and/or R' comprises one or more heteroatoms, e.g., oxygen, nitrogen, sulfur, phosphorus, or halogen atoms (e.g., chlorine, bromine or iodine). In one embodiment, R and R' are each methyl. In some embodiments, a plasticized composition comprises PVC as a host resin and a plasticizer having formula (F-l) or (F-IA). In some variations, a plasticized composition comprises PVC as a host resin and a plasticizer having formula (F-l) or (F-IA) with n=2 and R and R' each being methyl or ethyl.

[00143] In some variations, a \,2-syn orientation of the carboxylate substituents relative to each other on a plasticizer having formula (F-l) or (F-IA) is preferred. In some variations, a 1 ,2-anti orientation of the carboxylate substituents relative to each other on a plasticizer having formula (F-l) or (F-l A) is preferred. [00144] In some variations, a plasticizer is or comprises a compound having formula (F-

2), a derivative thereof, a compound having formula (F-2A), a derivative thereof, a compound having formula (F-3), a derivative thereof, a compound having formula (F-3A), a derivative thereof, or a mixture thereof:

where R represents H or any C1-C30 linear or branched, cyclic or acyclic, substituted or unsubstituted hydrocarbyl group. In some variations, R represents methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, t-butyl, 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 variations, a plasticized composition comprises PVC as a host resin and a plasticizer having formula (F-2), (F-2A), (F-3) or (F-3 A) with n=2 and R being methyl or ethyl.

[00145] In some variations, a plasticizer is or comprises or is derived from a compound having formula (F-4) or formula (F-4A):

where n=l ,2,3 or 4. In some variations, a plasticized composition comprises PVC as a host resin and a plasticizer having formula (F-4) or (F-4 A) with n=2.

[00146] 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 1 1 , 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 α-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, a- 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).

[00147] 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. 13/1 12,991 (U.S. Patent Publ. 201 1/0287988) filed May 20, 201 1 , 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, each 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

[00148] 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 plasticizers.

[00149] 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) 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 Cg or longer primary alcohol); vi) a formyl group may be reduced to a methyloyl group; vii) a hydroxyl substituent may be alkoxylated to form an alkoxylated substituent (e.g., ethoxylated or propoxylated); viii) one or more double bonds originating from the conjugated terpene can be oxidized (e.g., epoxidized); ix) one or more double bonds originating from the conjugated terpene may be halogenated; x) a hydroxyl or ester group may undergo a

condensation reaction; xi) a hydroxyl group or amide group may undergo a condensation reaction; xii) a hydroxyl group or ester group may be sulfated; xiii) an amine group may be converted to an ammonium ion or an N-oxide; and xiv) a reverse Diels-Alder reaction may occur to yield desired products.

[00150] 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.

[00151] In certain embodiments, the 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.

[00152] 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 oligomerization or polymerization, and/or may provide a site for cross- linking into a matrix.

[00153] Table 3 illustrates some non-limiting examples of chemical modifications of

Diels-Alder adducts between conjugated terpenes and dienophiles.

Table 3. Some exem lary chemical modifications of Diels-Alder adducts.

RB O (reduction, typical reagent

(typical reagent N1BH₄)

[00154] 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 oxidantxonjugated terpene 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).

[00155] Hydroxy versions of epoxidized hydrocarbon terpene 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 hydro lyzed to form two hydroxy groups. The hydroxyl groups may be subsequently acetylated to form a compound that may have use as described herein.

[00156] In some variations, a plasticizer comprises β-farnesene (or a β-farnesene derivative such as a dimer, trimer or tetramer of β-farnesene, or a Diels Alder adduct of β- farnesene and a dieneophile) that has had one, two, three (or four or more, if present) of its double bonds oxidized (e.g., epoxidized) or chlorinated. Hydroxy versions of epoxidized b- farnesene, or dimers, trimers or tetramers of β-farnesene 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 described herein. [00157] In some variations, the alcohols and polyols (e.g., diols) disclosed herein have utility as plasticizers.

[00158] 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 HCl, 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

[00159] Described below in Sections (H-I) - (H-XII) are some non-limiting 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

[00160] In some embodiments, a Diels-Alder adduct is formed between β-farnesene and acrylic acid,

_{s 0}r an acrylate ester, _s where R is as described below. A plasticizer, or a monomer, cross-linking agent or reactive diluent for use in making oligomers or polymers that have utility as plasticizers 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., C1-C30 hydrocarbyl. In some embodiments, R¹ is an aliphatic C1-C30 substituent. In some embodiments, R¹ is a linear saturated or unsaturated Ci- C30 hydrocarbyl group (e.g., Ci, C₂, C₃, C₄, C₅, C₆, C₇, C₈, C₉, C₁₀, Cn, C₁₂, C₁₃, C₁₄, C₁₅, C₁₆, Cn, Ci8, Ci9, C₂o or C21-C30 hydrocarbyl), or a branched saturated or unsaturated C1-C30 hydrocarbyl group (e.g., d, C₂, C₃, C₄, C₅, C₆, C₇, C₈, C₉, C₁₀, Cn, C₁₂, C₁₃, C₁₄, C₁₅, C₁₆, C₁₇, Ci8, Ci9, C₂o or C21-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. 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 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.

[00161] In some embodiments, R¹ is selected to increase the compatibility of the Diels-

Alder adduct with a selected host polymer. For example, if the host polymer is relatively polar (e.g., PVC), R¹ may be selected to be a relatively short linear or branched aliphatic hydrocarbon chain (e.g., a linear or branched C1-C4 hydrocarbyl), and/or R¹ may be substituted with or include one or more polar moieties (e.g., R¹ may be a C1-C30 aliphatic hydrocarbon that includes one or more hydroxy, carboxy, amino, epoxy, or chloro substituents, or R¹ may include a carbonyl group or an ether group). In some variations, R¹ comprises one or more hydroxyl groups 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.

[00162] 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.

[00163] 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 isomer 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. , Ci-C₃₀. In some embodiments, R² is an aliphatic Ci-C₃o substituent. In some embodiments, R² is a linear saturated or unsaturated Ci-C₃o hydrocarbyl group (e.g., d, C₂, C₃, C₄, C₅, C₆, C₇, C₈, C₉, C₁₀, Cn, C₁₂, C₁₃, C₁₄, C₁₅, C₁₆, C₁₇, Ci8, Ci9, C₂o or C₂i-C₃o hydrocarbyl), or a branched saturated or unsaturated Ci-C₃o hydrocarbyl group (e.g., Ci, C₂, C₃, C₄, C₅, C₆, C₇, C₈, C9, C10, Cn, Ci₂, Ci₃, Ci₄, C15, Ci₆, C₁₇, C₁₈, C19, C₂o or C₂i-C₃o 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, 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, R² is an aromatic 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 a hydroxyl 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.

[00164] In some embodiments, R² is selected to increase the compatibility of the Diels-

Alder adduct with a host polymer. For example, 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, or a glucoside.

[00165] 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.

[00166] 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, by mole, 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 or by volume. [00167] 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).

[00168] 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, by mole, 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.

[00169] 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 R² is as described in relation to formulae (H-IC) and (H-ID).

[00170] 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 a plasticizer, and/or as monomers, cross-linking agents, curing agents or reactive diluents for use in making oligomers or polymers that have utility as plasticizers.

(H-II) Dialkyl Maleate or Dialkyl Fumarate Dienophiles

[00171] embodiments, a Diels-Alder adduct between β-farnesene and a dialkyl

maleate,

or maleic acid, in which the carboxylate groups are oriented as a cis-

isomer, or a dialkyl

or fumaric acid, in which the carboxylate groups are oriented as a trans-isomer, has utility in making plasticizers as 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 C1-C30 hydrocarbyl group (e.g., Ci, C₂, C₃, C₄, C₅, C₆, C₇, C₈, C₉, C₁₀, Cn, C₁₂, C₁₃, Ci₄, Ci5, Ci6, C₁₇, Ci8, Ci9, C20 or C₂i-C₃o hydrocarbyl ), or a branched saturated or unsaturated Ci-C₃₀ hydrocarbyl group (e.g., d, C₂, C₃, C₄, C₅, C₆, C₇, C₈, C₉, C₁₀, Cn, C₁₂, C₁₃, C₁₄, C₁₅, Ci₆, C₁₇, Ci₈, Ci₉, C₂o or C₂i-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. 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, a 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 Ci-C₃o 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 the carboxylate substituents on the adduct (H-IIA) have a 1 ,2- syn- orientation relative to each other originating from 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 a dienophile instead of a dialkyl maleate.

[00172] In some embodiments, each of R³ and R³ is independently selected to increase compatibility a host polymer to be modified. 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 C1-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-C₃o aliphatic hydrocarbyl that includes one or more hydroxy, carboxy, 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). In some variations, one or both of R³ and R³ may be selected so that 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, an ethanolamide, or a glucoside.

[00173] 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. [00174] 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 unsubsubstituted substituents, e.g. Ci-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., d, C₂, C₃, C₄, C₅, C₆, C₇, C₈, C₉, C₁₀, Cn, C₁₂, C₁₃, C₁₄, C₁₅, C₁₆, C₁₇, Cig, Cig, C₂o or C₂i-C₃o hydrocarbyl), or a branched saturated or unsaturated Ci-C₃o hydrocarbyl group {e.g., Ci, C₂, C₃, C₄, C₅, C₆, C₇, C₈, C₉, C₁₀, Cn, C₁₂, C₁₃, C₁₄, C₁₅, C₁₆, C₁₇, C₁₈, C₁₉, C₂o or C₂i-C₃o 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, 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, one or both 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 R^4' may independently comprise one or more heteroatoms, e.g., oxygen, phosphorus, sulfur, nitrogen or chloride. In some embodiments, each of R⁴ and R⁴ may independently comprise a carboxylic acid, an ester, a carbonyl, an ether, a polyalkoxylate, a hydroxyl group, an amide group, an amine group, or one or more glucose groups. In some embodiments, each of R⁴ and R^4' may independently include a polyol substituent, e.g., each of R⁴ and R⁴ may

independently include 2, 3 or 4 hydroxyl groups. In some embodiments, each of R⁴ and/or R⁴ is independently a saturated or unsaturated C₈-C₃₀ fatty acid or a saturated or unsaturated C₈-C₃₀ 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 Ci-C₃o aliphatic hydrocarbyl group that contains at least one double bond, e.g., one or more internal double bonds and/or a terminal double bond.

[00175] 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 R^3'. 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 cis- orientation 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.

[00176] In some embodiments, each of R⁴ and R⁴ is independently selected to increase compatibility with a host polymer to be modified. 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 R^4' may independently be substituted with or include one or more polar moieties (e.g., each of R⁴ and R⁴ may independently be a C₁-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 R⁴ may independently include an ether group). In some variations, one or both of R⁴ and R⁴ may be selected so that the adduct comprises a primary alcohol, an amine, an alkoxylated alcohol, an alkyl-capped alkoxylate, a carboxylic acid, an amide, an ethanolamide, a glucoside, or a glucamide. [00177] 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 in 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 the carboxylate substituents on the adduct (H-IIC) have a 1 ,2-syn- orientation relative to each other originating from 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 on the adduct is desired, a dialkyl fumarate may be used as a dienophile instead of a dialkyl maleate.

[00178] 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 cis- orientation 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.

[00179] Compounds of formulae (H-IIA), (H-IIB), (H-IIC) and (H-IID) or derivatives thereof may be useful as plasticizers and/or as monomers, cross-linking agents, curing agents or reactive diluents for use in making oligomers or polymers that have utility as plasticizers.

(H-III) Maleic anhydride Dienophiles [00180] 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):

[00181] Compound (H-IIIA) can be hydrogenated to form Compound (H-IIIB).

[00182] A proposed Diels- Alder reaction product between a-farnesene and maleic anhydride is shown as Compound (H-IIIC):

[00183] Compound (H-IIIC) can be hydrogenated to form Compound (H-IIID).

[00184] The anhydride compounds (H-IIIA), (H-IIIB), (H-IIIC) and (H-IIID) may be used as plasticizers. In some embodiments, the anhydride compounds disclosed herein may be used as monomers, cross-linking agents, curing agents or reactive diluents for use in making oligomers or polymers that have utility as plasticizers. In some cases, the anhydride compounds are treated with one or more polyols such as diols and triols as comonomers to make polyesters that may have utility as plasticizers.

(H-IV) Diols

[00185] Additional compounds disclosed herein are compounds (H-IV A), (H-IVB), (H-

IVC) and (H-IVD):

[00186] 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 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-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.

[00187] 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. In some embodiments, the diols disclosed herein may be use as monomers or comonomers, cross- linking agents, or reactive diluents for making oligomers or polymers that may have utility as plasticizers. Nonlimiting examples of polymers that may employ diols disclosed herein include polyesters, co-polyesters, polyurethanes, and polycarbonates. In some embodiments, the diols disclosed herein may be alkoxylated to make a plasticizer.

(H-V) Maleimide Dienophiles

[00188] Additional compounds disclosed herein are represented by formulae (H-V A), (H-

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

where R⁵ and R⁵ may independently be H, a C1-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 C1-C30 hydrocarbyl group (e.g., Ci, C₂, C₃, C₄, C₅, C₆, C₇, C₈, C9, C₁₀, C11, C12, Ci3, CM, Ci5, Ci6, Ci7, C₁₈, Ci9, C₂o or C21-C30 hydrocarbyl), or a branched saturated or unsaturated C1-C30 hydrocarbyl group (e.g., C C₂, C₃, C₄, C₅, C₆, C₇, C₈, C₉, C₁₀, C_u, C₁₂, C₁₃, CM, Ci5, Ci6, C₁₇, Ci8, Ci9, C₂o 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 is independently aromatic, or alkylaromatic. In some embodiments, each of R⁵ and R⁵' is benzyl. 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 hydro xyl 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.

[00189] 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.

[00190] The maleimide compounds of formulae (H-VA), (H-VB), (H-VC) and (H-VD) may be used in any application utilizing a maleimide. In some embodiments, the maleimide compounds disclosed herein may be used as plasticizers, or as monomers or comonomers, cross- linking agents, or reactive diluents for making oligomers or polymers that may have utility as plasticizers.

(H-VI) Fumaronitrile Dienophiles

[00191] 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 a-farnesene and fumaronitrile is Compound (H-VIB):

The cyano groups in the Diels-Alder adducts have a trans- orientation relative to each other originating from the trans orientation of the fumaronitrile.

[00192] In certain embodiments, compounds having formula (H-VIA) and (H-VIB) or derivatives thereof may be used as plasticizers, and/or as monomers, cross-linking agents, curing agents or reactive diluents for use in making oligomers or polymers that have utility as plasticizers. 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 dicarboxamide 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) Unsaturated Aldehyde Dienophiles

[00193] 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 embodim C1-C30 alkyl . Non- limiting examples of unsaturated aldehydes include acrolein,

, and crotonaldehyde, O . 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, by mole, 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.

[00194] 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, by mole, 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.

[00195] 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, by mole, 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.

[00196] 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, by mole, 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.

[00197] 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 as plasticizers and/or as monomers, cross-linking agents, curing agents or reactive diluents for use in making oligomers or polymers that have utility as plasticizers. For example, compounds 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, e.g., as shown in Examples 3, 4, and 11 herein. As described herein and as illustrated in the Examples, the alcohols may be ethoxylated. The ethoxylated alcohols may have utility as platicizers in certain applications.

(H-VIII) Itaconate Dienophiles

[00198] In some embodiments, itaconic anhydride

, itaconic acid,

or a dialkyl itaconate,

, 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 C₁-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.

[00199] 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).

[00200] The compounds of formulae (H-VIIIA) and (H-VIIIB) can be hydrogenated to form compounds of formulae (H-VIIIC) and (H-VIIID) respectively:

(H-VIIID).

[00201] 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.

[00202] 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-VIIIE): 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.

[00204] 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, by mole, 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.

(H-VIIIJ), (H-VIIIK),

(H-VIIIL), (H-VIIIM). [00205] 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 plasticizers. In some embodiments, the anhydride compounds disclosed herein can be used as monomers or co- monomers, cross-linking agents, or reactive diluents to make oligomers or polymers that have utility as plasticizers. The anhydride compositions may be used in any oligomerization or polymerization reaction that utilizes anhydride monomers to make plasticizers. R or R may be selected to increase compatibility of the plasticizer with a host polymer to be modified. For example, the anhydride functionality may be opened up using known techniques to form a diacid, which may be used as is as a plasticizer, or further reacted to form a plasticizer as described herein.

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

[00206] In some embodiments, acetylene dicarboxylic acid,

, or acetylene

dicarboxamide,

where R can be any suitable hydrocarbyl group (e.g., Ci-C₃₀ hydrocarbyl), is used as a dienophile in a Diels-Alder reaction with farnesene.

[00207] 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.

[00208] 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, by mole, 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, by mole, or by volume.

[00209] 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, by mole, 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, by mole, or by volume.

where each of R⁶ and R⁶ is independently H, a C₁-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 C1-C30 hydrocarbyl group (e.g., Ci, C₂, C₃, C₄, C₅, C₆, C₇, C₈, C9, C₁₀, C11, C12, Ci3, CM, Ci5, Ci6, Ci7, C₁₈, Ci9, C₂o or C21-C30 hydrocarbyl), or a branched saturated or unsaturated C1-C30 hydrocarbyl group (e.g., Ci, C₂, C₃, C₄, C₅, C₆, C₇, C₈, C₉, C₁₀, Cn, C₁₂, C₁₃, C_M, Ci₅, Ci₆, C₁₇, Ci₈, Ci₉, C₂o 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, 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 R⁶ and R⁶ is independently aromatic (e.g., one or both of R⁶ and R⁶ may be phenyl or benzyl groups). 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 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.

[00210] 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).

[00211] 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 plasticizers and/or as monomers, cross-linking agents, curing agents or reactive diluents for use in making oligomers or polymers that have utility as plasticizers.

[00212] In some variations, compound (H-IXB) or (H-IXD) or compounds having formulae (H-IXF) or (H-IXH) may be used in applications utilizing benzoate plasticizers.

(H-X) Acetylene diamide or Dicyanoacetylene Dienophiles

[00213] 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, by mole, 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.

[00214] 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.

[00215] 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, 99.999:0.001 by 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.

[00216] 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.

[00217] 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 P2O5 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.

[00218] 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 plasticizers and/or as monomers, cross-linking agents, curing agents or reactive diluents for use in making oligomers or polymers that have utility as plasticizers.

(H-XI) Quinone Dienophiles [00219] 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.

[00220] 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.

[00221] In some embodiments, Compound (H-XIA) may be oxidized to form a benzoquinone having structure (Η-ΧΙΑ'):

[00222] 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:

[00223] 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:

[00224] 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:

[00225] When 1 ,4-naphthoquinone is used as a dienophile, Compound (H-XIJ) may result from a Diels-Alder reaction with β-farnesene:

(H-XIJ). [00226] α-Farnesene may also react 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):

[00227] Possible reaction products between a-farnesene and 1 ,2-benzoquinone are

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

[00228] A possible reaction product between a-farnesene and 1 ,4-naphthoquinone is

Compound (H-XIS):

[00229] 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 plasticizers, and/or as monomers, cross-linking agents, curing agents or reactive diluents for use in making oligomers or polymers that have utility as plasticizers.

(H-XII) Oxidation of Diels- Alder Adducts

[00230] 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:

[00231] 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 C1-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.

[00232] It should be understood that any suitable Diels-Alder adduct described herein may be oxidized in a similar fashion. Epoxidized Diels-Alder adducts or derivatives thereof may have utility as plasticizers, or as monomers, cross-linking agents, curing agents and/or reactive diluents for making oligomers or polymers that have utility as plasticizers. In some embodiments, the epoxidized Diels-Alder adducts disclosed herein can be used to prepare epoxy containing plasticizers or various epoxidized or epoxy-modified plasticizers.

[00233] 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 plasticizers, or monomers, cross-linking agents, curing agents and/or reactive diluents for making oligomers or polymers that have utility as plasticizers.

[00234] In some variations, a 1 ,2-syn orientation of the carboxylate substituents relative to each other on a plasticizer having formula (F-l) or (F-1A) is preferred. In some variations, a 1 ,2-anti orientation of the carboxylate substituents relative to each other on a plasticizer having formula (F-l) or (F-l A) is preferred.

J) Variations of Plasticizers and Plasticized Compositions [00235] The plasticizers described herein can be used to make a variety of plasticized compositions. Plasticized compositions comprise one or more plasticizers described herein and a host resin (which may comprise a homopolymer, an interpolymer, or a polymer blend, and may be a thermoplastic, thermoset, elastomer or rubber). Optionally, plasticized compositions may comprise one or more secondary plasticizers and/or one or more additives.

[00236] A plasticizer as described herein can be combined with a host polymer

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

[00237] In some variations, a plasticizer as described herein is incorporated into a host polymer at a level as to antiplasticize the polymer, thereby increasing glass transition temperature, increasing rigidity, and/or decreasing flexibility of the host polymer.

[00238] 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, melt viscosity, hardness, impact resistance, low temperature brittleness, elasticity, toughness, elongation at break, displacement at break, load at break, energy to yield, impact resistance, flexibility, flexural strength, processability, or stretchability.

[00239] The plasticizers described herein may be selected to have sufficiently low volatility under processing and use conditions such that they do not exhibit undesirable levels of migration within the host polymer or exude from the host polymer. Volatility may be reduced by selecting higher molecular weight plasticizers, selecting plasticizers with a high degree of compatibility with a host resin, and/or by selecting functional groups on the plasticizer that increase interaction with the host polymer.

[00240] 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 150°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 150°C-210°C.

[00241] Diels-Alder plasticizer adducts and farnesene derivative plasticizers as described herein may be designed using known principles to increase thermal stability while maintaining a desired degree of compatibility with the host polymer. For example, Diels-Alder derivatives having functionality known to exhibit improved thermal stability may be selected, such as imides. Such thermally stable molecules may be functionalized or derivatized using known methods to improve compatibility with host resins. Non- limiting examples of Diels-Alder adducts that are imides have formula (H-VA)-(H-VD). In certain variations, Diels-Alder imide adducts having formula (H-VA), (H-VB), (H-VC), or (H-VD) with R5 or R5' as benzyl are used as plasticizers, e.g., plasticizers exhibiting enhanced thermal stability in some applications. In some variations, Diels-Alder imide adducts having formula (H-VA) or (H-VC) with unsaturated bonds may be chlorinated or oxidized (e.g., to form epoxides) as described herein to improve compatibility with a host polymer.

[00242] 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.

[00243] 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 the host resin, bleeding or leaching of the plasticizer 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 50wt% or less, about 45wt%, or less, about 40 wt% or less, about 30wt% or less, about 35wt% or less, about 30wt% or less, about 25wt% or less, about 20wt% or less, about 15wt% or less, about 10wt% or less, or about 5 wt% or less, based on total weight of the plasticized resin. In some variations, an effective amount of plasticizer is from greater than 0 to about 60 wt%, from greater than 0 to about 50 wt%, from greater than 0 to about 40 wt%, from greater than 0 to about 30 wt%, from greater than 0 to about 20 wt%, from greater than 0 to about 15 wt%, from greater than 0 to about 10 wt%, from greater than 0 to about 5 wt%, from about 1 to about 40 wt%, from about 1 to about 30 wt%, from about 1 to about 20 wt%, from about 5 to about 40 wt%, from about 5 to about 30 wt%, from about 5 to about 20 wt%, about 1 wt%, about 5 wt%, about 10 wt%, about 15 wt%, about 20 wt%, about 25 wt%, about 30 wt%, about 35 wt%, about 40 wt%, about 45 wt%, about 50 wt%, about 55 wt%, or about 60wt%.

Host polymer resin

[00244] The host polymer resin can be any type of polymer in which plasticization is desired to improve one or more physical or mechanical parameters (e.g., decrease glass transition temperature, decrease rigidity, increase flexibility, decrease melt viscosity, toughen, improve low temperature properties, and the like). In some variations, the host resin is a polyvinylchloride, a chlorinated polyvinylchloride, a polycarbonate, a polyurethane, a nitrile polymer (such as acrylonitrile butadiene styrene (ABS)), an acrylate polymer (e.g., a polymethacrylate), a polystyrene, a polyester, a polyamide, a polyimide, a polyvinyl acetal, a cellulose polymer, a polyolefm, a phenolic resin, a starch, a natural rubber, a synthetic rubber, an interpolymer of any of the foregoing, a polymer blend of any of the foregoing, or a polymer composite of any of the foregoing. As described in more detail below, 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.

[00245] 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. 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.

[00246] In some embodiments, the host resin comprises a polyolefm. Nonlimiting examples of polyolefms 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 polyolefm host resin. [00247] 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.

[00248] 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.

[00249] 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 lactobaciUus, 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.

[00250] 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.

[00251] 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.

[00252] 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. [00253] 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.

[00254] 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.

Methods to measure plasticization

[00255] Any suitable test method may be used to evaluate plasticization effects of a plasticizer in a host resin. In a first instance, a plasticizer' s effect on ease of processibility of the host resin in a melt compounder or extruder may be evaluated. In some cases, change in glass transition temperature or melt temperature may be used to evaluate plasticization. In some cases, change in melt viscosity may be used to evaluate plasticization. In some cases, DMA (dynamic mechanical analysis) testing may be used to measure plasticization. In some cases, tensile properties of plasticized samples may be measured. Any suitable tensile measurements may be made. In some cases, tensile measurements may be carried out according to ASTM D638 "Standard Test Method for Tensile Properties of Plastics" or ASTM D412 "Standard Test Methods for Vulcanized Rubber and Thermoplastic Elastomers— Tension," each published by ASTM International, and each of which is incorporated herein by reference in its entirety.

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 (% elongation) to generate a stress-strain curve. Many parameters can be derived from stress-strain curves. For example, elastic or Young's modulus, % elongation at break or strain at break, displacement at break, ultimate tensile strength (stress at break), and toughness can be derived from stress-strain curves. Toughness is calculated as the area under the stress-strain curves, up to point of fracture. Young's modulus (or modulus of elasticity) is calculated as the slope of the early (low strain) portion of the measured stress-strain curves. 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.

[00256] In some cases, a plasticized composition as described herein may provide a % elongation at break that is about 20% or greater, about 50% or greater, about 100% or greater, about 150%) or greater, about 200% or greater, about 250%) or greater, about 300%) or greater, or about 350% or greater. In some variations, a plasticized PVC composition may provide a % elongation at break that is at least about 20-100%, (e.g., at least about 20%, 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%>, at least about 100%), at least about 150%), at least about 200%), at least about 250%), at least about 300%), at least about 350%), or even greater)

[00257] In some cases, a plasticized composition as described herein (e.g., a plasticized

PVC composition) may provide a toughness of about 25 MPa or greater, or about 30 MPa or greater.

[00258] Thermal stability and volatility as to weight loss may be measured by heating aging the samples in an oven using any defined protocol and weighing samples before and after exposure to applicable thermal aging protocols. In some variations, a plasticized sample loses no more than about 15 wt%, no more than about 12 wt%, no more than about 10 wt%, no more than about 8 wt%, or no more than about 5 wt% after thermal aging at 100°C for a week. In some variations, a plasticized sample loses no more than about 2 wt%, or no more than about 1.5 wt%, or no more than about 1 wt% after thermal aging at 70°C for 170 hours.

[00259] Thermal stability as to color of a plasticized sample may be evaluated by reflectance using any suitable reference standard, 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 may be positioned at 10°, and the illuminant may be a CIE standard D65 illuminant to simulant standard daylight illumination. An Color-Eye® 7000A spectrophotometer (available from XRite Corp., Grand Rapids, MI) or similar apparatus may be used to evaluate color of the samples relative to the standard. The coordinates L*, a*, and b* can be measured for each sample. The difference between each of the coordinates L*, a* and b* of a sample and that of the reference can be calculated, and a color parameter

DE*=sqrt{[(L*(sample)-L*(ref)]²+[a^!i:(sample)-a^!i:(ref)]²+[b^!i:(sample)-b^!i:(ref)]²} can be calculated. It is desired that discoloration of the plasticized composition upon exposure to heat during processing (e.g., during molding, extrusion, thermosetting, and the like) and during normal use conditions (e.g., in an automobile or other environment that exposes a sample to long periods at elevated temperatures) be limited.

[00260] Impact strength is a measure of a polymer's ability to absorb impact without cracking or breaking. Toughness contributes to increased impact strength. Impact strength can be measured as a function of temperature, as certain polymers decrease in impact strength at low temperatures. There are a variety of methods known in the art to measure impact strength. Generally, an arm held at a defined height and having a defined potential energy is released to impact the sample. The amount of energy that is absorbed by the sample without failing determines impact strength. Samples may be notched or unnotched. In some variations, Izod impact strength is measured, in which a cantilevered, notched sample is mounted, and a pendulum arm is raised to a variable height and dropped to impact the sample. One test method for measuring Izod impact strength is ASTM D256 "Standard Test Methods for Determining the Izod Pendulum Impact Resistance of Plastics," published by ASTM International, which is incorporated herein by reference in its entirety. Other impact strength measurements that may be used include Charpy impact strength test. Plasticizers as described herein may increase impact strength of the host polymer resin.

[00261] Brittle polymers cannot deform much without cracking or breaking. In some cases, brittle polymers exhibit high tensile strength but low toughness. In some variations, a plasticizer as described herein decreases brittleness, i.e., increases amount of deformation that the polymer can withstand without cracking or breaking.

[00262] Low temperature brittleness testing may be used to evaluate the effect of a plasticizer on low temperature mechanical properties of a composition. One example of a low temperature brittleness test that may be used to evaluate plasticizers is ASTM D746-07

"Standard Test Method for Brittleness Temperature of Plastics and Elastomers by Impact," published by ASTM International, which is incorporated herein by reference in its entirety. [00263] A plasticizer' s effect on hardness may be evaluated using any suitable test method. For example, durometer hardness may be measured. One nonlimiting example of a hardness measurement that can be made to evaluate a plasticizer's effect on a host resin's hardness is ASTM D2240-05 "Standard Test Method for Rubber Property— Durometer

Hardness," published by ASTM International, which is incorporated herein by reference in its entirety. A plasticizer and an amount of plasticizer may be selected to tune the durometer hardness of a plasticized composition. For example, a plasticizer and an amount of plasticizer may be selected to achieve a durometer hardness A of about 80, about 85, or about 90. In some cases, a 5D Hansen solubility parameter of a plasticizer candidate may be correlated with durometer hardness A, as shown in FIGURE 22.

Design of Diels-Alder Plasticizer adduct for effective plasticization

[00264] The properties of a Diels-Alder plasticizer adduct between a conjugated terpene and a dienophile may be tuned, adjusted or modified to accomplish effective compatibility with a host resin and compatibility with processing of the host resin so as to result in effective plasticization with the host resin, while limiting undesired effects such as migration, bleeding out of the host resin, or thermal degradation.

[00265] In certain embodiments, the plasticizers described herein have a structure X_HC_T-

A_DA-Y_DP, in which X_HC_T represents one or more tails originating from one or more conjugated hydrocarbon terpenes reacted with a dienophile, Y_DP represents one or more heads (which may be originating from one or more dienophiles, and A_DA comprises one or more cyclic groups (e.g., a 6-membered ring) resulting from the Diels-Alder reaction between the dienophile and the one or more conjugated hydrocarbon terpenes.

[00266] A Diels-Alder plasticizer may have a single tail and a single head in certain embodiments. In some embodiments, a plasticizer may have a single tail and two heads so as to have structure . In some embodiments, a plasticizer has two tails and a single head. For example, two conjugated hydrocarbon terpenes (which may be the same or different) undergo a Diels-Alder reaction with one dienophile so that the plasticizers may have a structure

₉ where X_HC_TI refers to a first conjugated terpene and A_DA_I refers to a cyclic group resulting from the Diels- Alder reaction between the first conjugated terpene and the dienophile, and X_HCT2 refers to a second conjugated terpene and A_DA2 refers to a cyclic group resulting from the Diels- Alder reaction between the second conjugated terpene and the dienophile. In other

variations, a plasticizer having two tails and a single head has a structure

, which may result from a Diels-Alder reaction with a hydrocarbon terpene having an internal conjugated diene (e.g., isodehydrosqualene, isosqualane precursor I, or isosqualane precursor II) that reacts with a dienophile. In some variations, a Diels-Alder plasticizer has two tails and two

heads. For example, such a plasticizer may have structure ^x or ^x

[00267] X_HCT and/or Y_DP may be selected or chemically modified to make the Diels-Alder adduct suitable for use in certain plasticizer applications. X_HCT (which encompasses X_HCTI, where i=l, 2, or an even higher number) represents one or more tails originating from one or more hydrocarbon terpenes. Y_Dp (which encompasses Y_DPI, where i=l, 2, or an even higher number) represents one or more heads originating or derived from one or more dienophiles. In some variations, XHCT is a C10-C30 (e.g., C10-C15, or C10-C20, C10-C25, or C10-C30) hydrocarbon tail comprising one or more methyl branches having formula (X), (XI), (XIII), or (XIV) as shown herein. In some variations, X_HCT comprises no heteroatoms. In some variations, X_HCT comprises oxygen atoms, e.g., having formula (XII) or an oxidized version thereof. Y_DP may contain heteroatoms such as O, S, P or N. Y_DP may be neutral or charged.

[00268] The hydrophobicity of X_HCT may be tuned or modified in a variety of ways.

X_HCT in general includes methyl substituents originating from the conjugated terpene. In some embodiments, X_HCT is an unsaturated hydrocarbon chain, in other embodiments, X_HCT is a saturated hydrocarbon chain; in some embodiments X_HCT includes one or more nonionic oxygen groups (e.g., epoxy, hydroxy); in some embodiments X_HCT includes one or more halogen atoms. Hydrophobicity of X_HCT may be decreased by using a shorter chain conjugated terpene and/or oxidizing or halogenating one or more of the unsaturated carbon carbon bonds of X_HCT-

[00269] 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 on the Diels- Alder plasticizer adduct. For example, in some situations a dienophile may be selected that results in only one polar substituent to the cyclic group formed by the Diels-Alder reaction. In other situations, a dienophile may be selected that results in more than one (e.g., two) polar substituents to the cyclic group formed by the Diels-Alder reaction, e.g., a dienophile that is an anhydride, a diacid, a diester, or a di-cyano may be selected. 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 hydrophilicity.

[00270] X_HC_T and/or Y_DP may be selected or chemically modified to accomplish any one of or any combination of the following: i) modify hydrophobicity and/or hydophilicity of a portion or the whole of the molecule; ii) improve compatibility with a desired host polymer; iii) provide a reactive site by which the adduct may react with another component of a composition incorporating the adduct; iv) undergo a reverse Diels-Alder reaction to produce desired species; v) inhibit chemical reaction with other components that may be present in a composition; vi) increase thermal stability; vii) increase light stability; viii) modify molecular weight; ix) modify volatility; x) modify viscosity, crystallinity, or volatility at processing temperatures and/or at use temperatures; xi) modify migration or leaching behavior in operation; xii) enable the plasticizer to be suitable for use in food grade applications; xiii) enable the plasticizer to be suitable for use in medical applications; xiv) modify surface tension or interfacial tension; xv) provide a site for making an anion or cation; xvi) modify domain size in a plasticizer host resin; xvii) improve compatibility with other additives that may be present in a composition; xviii) provide antistatic properties; xix) modify color, UV absorption, and/or color stability; xx) provide antimicrobial properties; xxi) provide a desired stereoisomer or modify optical activity. 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.

[00271] In some variations, a plasticizer has structure (Bl), where one of or both of RB² and RB³ represent tails originating from one or more hydrocarbon terpenes, and QB¹ and QB² represent one or two heads originating from one or more dienophiles.

[00272] In some variations, a Diels-Alder plasticizer molecule has structure (Bl) with a single tail originating from a hydrocarbon terpene and a single head originating from the dienophile. For example, in the instances in which carbon-carbon double bonds have been saturated, such a plasticizer molecule may be represented by formula (Jla), (Jib) or a mixture thereof:

where RB¹, RB³ and RB⁴ are as described in connection with formula (Bl) herein, XHCT=RB² which represents the tail originating from the hydrocarbon terpene^J¹ is H or a C1-C30 hydrocarbyl group, and Y_Dp represents the residual of any suitable dienophile as described herein or otherwise known following the Diels- Alder reaction. Non-limiting examples of combinations of RB¹, RB², RB³ and RB⁴ are provided in Table 1 herein, and non-limiting examples of Diels- Alder adducts are provided in Table 2 herein. In some cases, X_Hcr has formula (XI) with n=l,2,3, or 4 or formula (XIII) with m=l,2,3, or 4. In some variations, each of RB¹, RB³, RB⁴ and RJ¹ are H.

[00273] In some variations, a Diels-Alder plasticizer molecule has structure (Bl) with a single tail and two heads. For example, in the instances in which carbon-carbon double bonds have been saturated, such a plasticizer molecule may be represented by formula (J2). Structure (J2) corresponds to structure (Bl) with RB²=XHCT which represents the tail originating from the hydrocarbon terpene.

where RB¹, RB³ and RB⁴ are as described in connection with formula (Bl) herein, X_HCT=RB² which represents the tail originating from the hydrocarbon terpene, and YDPI and YDP2 represent the residual of any suitable dienophile as described herein or otherwise known following the Diels-Alder reaction. Non-limiting examples of combinations of RB¹, RB², RB³ and RB⁴ are provided in Table 1 herein, and non- limiting examples of Diels-Alder adducts are provided in Table 2 herein. In some cases, Xncx has formula (XI) with n= 1,2,3, or 4 or formula (XIII) with m=l,2,3, or 4. In some variations, each of RB¹, RB³, RB⁴ are H. [00274] In some variations, a plasticizer molecule has structure (Bl) and comprises two tails and a single head. For example, in those instances in which unsaturated carbon-carbon bonds have been saturated, such a plasticizer has structure (J3a), (J3b), or comprises a mixture of structures (J3a) and (J3b), or has structure (J4):

where RB¹ and RB³ are as described in connection with formula (Bl) herein, X_HC_TI=RB² and X_HC_T2=RB⁴ which represents the tails originating from one or more hydrocarbon terpenes. RJ² is H or a C 1 -C30 hydrocarbyl group, and Y_DP represents the residual of any suitable dienophile as described herein or otherwise known following the Diels-Alder reaction. Non-limiting examples of combinations of RB¹, RB², RB³ and RB⁴ are provided in Table 1 herein, and non- limiting examples of Diels-Alder adducts are provided in Table 2 herein. In some cases, X_HC_TI and X_HC_T2 have formula (XI) with n=l,2,3, or 4 or formula (XIII) with m=l,2,3, or 4. In some variations, each of RB¹, RB³ and RJ¹ are H.

[00275] In some variations, a Diels-Alder plasticizer molecule has structure (Bl) with two tails and two heads. For example, in the instances in which carbon-carbon double bonds have been saturated, such a plasticizer molecule may be represented by formula (J5):

where RB¹, RB³ and RB⁴ are as described in connection with formula (Bl) herein, X_HC_T=RB² which represents the tail originating from the hydrocarbon terpene, and Y_DPI and Y_DP2 represent the residual of any suitable dienophile as described herein or otherwise known following the Diels-Alder reaction. Non-limiting examples of combinations of RB¹, RB², RB³ and RB⁴ are provided in Table 1 herein, and non- limiting examples of Diels-Alder adducts are provided in Table 2 herein. In some cases, Xncx has formula (XI) with n= 1,2,3, or 4 or formula (XIV) with m=l,2,3, or 4. In some variations, each of RB¹, RB³, and RB⁴ are H.

[00276] In some variations, a plasticizer molecule has formula (Bl) with two tails and two heads has formula (J6):

Non-limiting examples of combinations of RB¹, RB², RB³ and RB⁴ are provided in Table 1 herein, and non- limiting examples of Diels-Alder adducts are provided in Table 2 herein. In some cases, X_HC_TI and X_HC_T2 have formula (XI) with n= 1,2,3, or 4 or formula (XIV) with m=l,2,3, or 4. In some variations, each of RB¹ and RB³ are H.

[00277] It is known that plasticized thermoplastics have greater strain at break than unplasticized thermoplastics do when subjected to sufficient stress. In some variations, plasticizers serve various functional roles when compounded with thermoplastics, thermosets, elastomers or rubbers including making them more flexible, durable, tough, extrudable and/or moldable. In certain variations, when plasticizers are selected for such functional roles they are incorporated with the host polymer at levels anywhere from about 5 phr (parts per hundred parts resin) to about 120 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 more effective modification of the thermoplastic results. 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 some variations, plasticized films may be solvent cast. In general, the greater the molar volume of the plasticizer, the greater energy employed for plasticizers having similar solubility parameters.

[00278] 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.

[00279] 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 plasticizer for use in PVC may be selected to have solubility parameters close to that of PVC. A solubility parameter is empirical, calculated or semi-empirical numerical value that indicates relative solvency of a host resin for a plasticizer. Any suitable solubility parameter or combination of parameters can be used to evaluate and quantify intermolecular interactions between the plasticizer and the host resin to estimate or predict efficacy as a plasticizer.

Nonlimiting 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 plasticizer candidate molecule in a host resin 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 a plasticizer/host resin combination. 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 account for hydrogen bonding, and are more useful for nonpolar systems than for polar systems.

[00280] Hansen solubility parameters include three different parameters: 5D (dispersion), δΡ (dipole moment), and δΗ (hydrogen bonding) and are useful for polar systems as well as nonpolar systems. The parameters 5D, δΡ and δΗ are related to 5Tot, the cohesive energy per molar volume for the solvent as follows: δΤοί²=δϋ²+δΡ²+δΗ². For Hansen solubility parameters, compatibility between a plasticizer candidate and a host resin is represented numerically as a distance R_a, calculated as follows: R_a ⁼{4[6D_pi_as-6D_host]²+[6P_pi_as- 6Phost]²+[6Hpi_as-5H ost]²} ^1/2, where 5D _0St is the dispersion parameter for the host resin,

is the dispersion parameter for the plasticizer, 5P_h0St is the dipole parameter for the host resin, 5P_pi_as is the dipole parameter for the plasticizer, 5H _0St is the hydrogen bonding parameter for the host resin, and 5H_pi_as is the hydrogen bonding parameter for the plasticizer. A smaller value for R_a indicates a greater "likeness" or compatibility between a plasticizer candidate and a host resin. The solubility of a host resin in a variety of candidate plasticizers 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 (5D_host, 6Phost, 6H ost). If R₀ represents a maximum distance for an acceptably compatible interaction between a plasticizer 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 plasticizer/host resin combination indicates that combination is compatible, which will result in effective plasticization. In some cases, a RED value greater than 1 for a particular

plasticizer/host resin combination indicates an incompatible combination, such that the plasticizer is unlikely to be sufficiently compatible with the host resin to provide effective plasticization.

[00281] The parameters 5D, 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, 5D, 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).

[00282] Calculated solubility parameters for various non-limiting examples of farnesene derivatives and Diels- Alder adducts that can be used as plasticizers described herein are shown in Table 5 below. The Hansen solubility parameters are calculated relative to a model PVC having 5D=18.5, δΡ=7.9, δΗ=3.4, and R₀=8. The method illustrated in Table 5 for estimating compatibility of a plasticizer with a host polymer may be extended to any host polymer system to be plasticized for a particular application.

Table 5. Calculated Hansen Solubility parameters for plasticizer candidates in model PVC system

107

108

111

112

113

114

115

117

118

119

121

ı22





130

ı32

ı33



[001] In some variations, the RED for a plasticizer/host resin combination calculated using Hansen solubility parameters is about 1 or less, about 0.95 or less, about 0.9 or less, about 0.85 or less, about 0.8 or less, about 0.75 or less, about 0.7 or less, about 0.65 or less, about 0.6 or less, about 0.55 or less, or about 0.5 or less.

Non- limiting Examples of Plasticizers

[00283] Any combination of conjugated terpene and dienophile may be used to make plasticizers suitable for certain applications. In some embodiments, the conjugated terpene used to make the Diels- Alder plasticizers described herein is β-farnesene. In some embodiments, the conjugated terpene is a-farnesene. 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, dialkyl maleates, dialkyl fumarates, 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, 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, vinyl sulfonates, vinyl sulfmates, vinyl sulfoxides and combinations thereof.

[00284] In some embodiments, monoester or diester Diels-Alder adducts as described herein have utility as plasticizers. 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 plasticizer applications. The polarity of the ester-containing Diels-Alder adduct may increase their compatibility with other polar molecules.

[00285] Monoester, diester-containing Diels-Alder adducts may 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 the presence of moisture is deleterious. [00286] 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 exhibits increased polarity, increased molecular volume, increased molecular weight, and decreased tendency to leach out, migrate out, be extracted out, and the like from a polymer host matrix.

[00287] 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, benzoate, dimerate, or trimellitate plasticizer.

[00288] 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 solubility and molar volume of a plasticizer candidate in a desired host polymeric matrix. For example, longer aliphatic chains may be selected to increase molar volume while exhibiting compatibility with nonpolar host resins (e.g., hydrocarbon polymers such as polyolefms), and shorter chains may be selected to decrease molar volume and increase compatibility with more polar host resins. Increased branching in chains may be selected to increase solubility, decrease waxiness, or modify molecular volume.

[00289] 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 polyalphaolefm (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 stock where biodegradability is desired or high temperature low sludge formation is critical (e.g., lubricants for textile machines or ovens).

[00290] Non-limiting examples of ester-containing plasticizer candidates are provided in the Examples. One non-limiting example of a preparation of Diels-Alder adduct between β- farnesene and 1 ,4-benzoquinone is provided in the Examples.

[00291] 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.

[00292] 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.

[00293] 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).

[00294] 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'), (H-XIIE '), or (H-XIIF). [00295] 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.

[00296] In one embodiment, a plasticizer is or comprises compound (J-5):

[00299] In one embodiment, a plasticizer is or comprises compound (J- 11):

[00300] 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

[00301] 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.

[00302] In some variations, a Diels-Alder adduct that has utility as a plasticizer can be obtained by reacting a conjugated hydrocarbon terpene (e.g., β-farnesene , a-farnesene, or myrcene) 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-Ci₀ 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 Ci-Cg 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, 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.

[00303] In some variations, the compounds and plasticizers 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, Ci-Cio alkyl, C₃-C₆ cycloalkyl, aryl, substituted aryl, and the like; and acrylates or substituted acrylates such as:

wherein R¹ is H or Ci-Cg 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.

[00304] 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 the Examples. [00305] 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 the Examples. 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 directly to a 4,8-dimethylnonyl-substituted alcohol. Such a reaction is described on page 1 198 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.

[00306] 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 the Examples, 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.

[00307] In some variations, the plasticizers described herein comprise or are derived from alcohol (J-4-I):

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

(J-4-IB). In some variations, alcohol J-4-1 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-4-1 includes isomer J-4-IB, with only trace amounts or no detectable amount of isomer J-4-IA. In some variations, alcohol J-4-1 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-4-1 may include any ratio of isomer J-4-IA to isomer J-4-IB. In some variations, alcohol J-4-1 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 .

[00308] In some variations, compound J-4-II as shown below functions as a plasticizer:

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-II represents any one of or any combination of the two isomers J-4-IIA and J-4-IIB as shown below:

[00309] In some variations, compound J-4-II includes both isomers, J-4-IIA and J-4-IIB.

In some variations, compound J-4-II includes isomer J-4-IIA, with only trace amounts or no detectable amount of isomer J-4-IIB. In some variations, compound J-4-II 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.

[00310] Some variations of plasticizers contain alkoxy repeat units that are different than ethoxyl repeat units. For example, some plasticizers include propoxyl repeat units in the hydrophilic end, rather than ethoxyl repeat units. Some plasticizers include both ethyoxyl and propoxyl repeat units.

[00311] Thus, some plasticizers 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:

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 plasticizres, m is in the range 1 to 30. In some variations, m is in the range 5 to 25. In some variations of the plasticizers, 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.

[00312] Some variations of plasticizers 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 plasticizers, p and q are independently in the range 1 to 30. In some variations of the plasticizers, 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.

[00313] In some variations, compound J-4-III as shown below functions as a plasticizer:

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.

[00314] In some variations, compound J -4-IV as shown below functions as a plasticizer:

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.

[00315] 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:

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 plasticizer. For example, alcohol J-4-V can be ethoxylated to form plasticizer J-4-VI:

Isomers J-4-VIA and J-4-VIB can be present in any relative amount, e.g. plasticizer J-4-VI may consist of isomer J-4- VI A 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 maybe 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 plasticizer 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.

[00316] 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 adducts that are illustrated in Scheme J-4-VII

below

SCHEME J-4-VII

[00317] 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 plasticizers J-4-VIIIA and J-4-VIIIB (where ethoxylation is shown as a model alkoxylation):

(J-4-VIIIB).

The average number of ethoxyl repeat units y and y' for plasticizers 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, 1 1 , 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 , 22, 23, 24, 25, 26, 27, 28, 29, or 30. [00318] In some variations, plasticizers comprise or are derived from diol J-4-IX:

[00319] 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 plasticizer having formula J-4-X (where ethoxylation is shown as a model alkoxylation):

[00320] 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 plasticizers, n is in the range 1 to 30. In some variations, n is in the range 5 to 25. In some variations of the plasticizers, 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, 1 1 , 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.

[00321] It should be understood that analogs of plasticizers 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.

[00322] 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 in the Examples.

[00323] In one embodiment, a plasticizer is or comprises one or more of compounds (J-

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

[00324] In one embodiment, a plasticizer is or comprises compound (J- 19):

[00325] 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):

[00326]

[00327] It should be understood that plasticizers 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 plasticizer is myrcene. In some variations, the conjugated terpene used to make a Diels-Alder adduct useful as a plasticizer is not myrcene or farnesene, 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.

Polymeric or Oligomeric Plasticizers

[00328] 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 oligomers or polymers by addition polymerization or for making oligomers or polymers by condensation polymerization (e.g., oligomers of polyesters or polyamides). The oligomers or polymers thus formed may be useful as plasticizers that exhibit limited or no leaching out, migration, or extraction. The oligomers or polymers may be designed to be compatible with a desired host matrix by the use of Hansen solubility parameters as discussed herein.

[00329] 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 an oligomer or polymer having utility as a plasticizer. 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 oligomer or 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.

[00330] In one example, a Diels-Alder adduct that includes an anhydride moiety 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.

[00331] 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- 1 ,8-octanedithiol, erythro- 1 ,4-dimercapto-2,3-butanediol, (±)-threo- 1 ,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.

[00332] 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.

[00333] 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.

Multifunctional Plasticizers

[00334] Disclosed herein are molecules, herein referred to as multifunctional plasticizer molecules or multifunctional plasticizers, having at least two functions when they are combined with thermoplastics, thermosets, elastomers, or rubbers where one of these functions relates to modifying the mechanical, geometric, and/or fluid flow properties of the host resin or articles made therefrom and where the other one or more functions may fulfill any beneficial purposes, with nonlimiting examples 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. Multifunctional plasticizers may be used to eliminate the need for additional additives in some cases, thereby potentially reducing cost and potentially reducing the need for additional blending and/or compatibilization, and potentially simplifying the composition. One advantage of the multifunctional plasticizers is a cost savings relating to the use of fewer molecules in plasticizer- thermoplastic formulations.

[00335] 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 some cases, the other one or more functions may provide a benefit both to fabrication and to the final composition or article. 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. A multifunctional plasticizer that provides dye sites for anionic or cationic 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. 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.

[00336] 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 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, as described herein, the diene moiety of farnesene and certain oligomers can undergo Diels-Alder reactions and the trisubstituted double bonds of farnesene 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 aditional functions. Also, for example, the farnesene 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 farnesene and its derivatives are disclosed in the plasticizer candidates of Table 5.

[00337] In certain embodiments, a plasticizer may be altered in a processing step to give multifunctional properties. For example, anhydride grouings 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.

[00338] In some variations, a plasticizer described herein plasticizes a host polymer and also modifies its gas transport properties towards one or more select gases. For example, if you chlorinate or brominate a plasticizer described herein, the oxygen permeability of the resultant plasticized articles should likely decrease. Certain plasticizers described herein may provide articles having improved permselectivities towards important gas pairs, such as industrial blanketing gas pairs (oxygen/nitrogen), ripening gases (C0₂/0₂/ethylene system), and for industrial hydrocarbon separations (CH₄/H₂, etc.).

[00339] In some variations, a plasticizer candidate as described herein that comprises one or more unsaturated bonds may function both as a plasticizer and as a thermal stabilizers and/or acid scavengers. Examples 72, 73, and 77 provide illustrative, but nonlimiting examples of plasticizers that may function as thermal stabilizers and/or acid scavengers.

Secondary Plasticizers

[00340] Optionally, the compositions disclosed herein may comprise more than one plasticizer. In some cases, one or more secondary plasticizers are used in addition to a primary plasticizer. Secondary plasticizers may be used to allow use of reduced amounts of a primary plasticizer (e.g., to reduce cost) and/or to adjust viscosity of the composition for improved processing. The plasticizers described herein may be employed as primary and/or secondary plasticizers in a composition. Any plasticizer or combination of plasticizers known to a person of ordinary skill in the art may be used in combination with one or more plasticizers described herein in a plasticized composition. Non-limiting examples of plasticizers that may be used in combination with plasticizers described herein include mineral oils, abietates, adipates, alkyl sulfonates, azelates, benzoates, chlorinated paraffins, citrates, epoxides, glycol ethers and their esters, glutarates, hydrocarbon oils, isobutyrates, butyrates, cvoleates, 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 total plasticizer (primary plasticizers plus secondary plasticizers) in the polymer composition can be from greater than 0 to about 90wt%, from greater than 0 to about 80 wt%, from greater than 0 to about 70wt%, from greater than 0 to about 60 wt%, from greater than 0 to about 50 wt%, from greater than 0 to about 40 wt%, from greater than 0 to about 30 wt%, from greater than 0 to about 20 wt%, 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. A ratio of primary:secondary plasticizers may be about 100: 1, 50: 1, 40: 1, 30: 1, 20:1 , 10: 1, 5: 1, 2: 1, 1 : 1, 1 :2, 1 :5, 1 : 10, 1 :20, 1 :30, 1 :40, 1 :50, or 1 : 100.

Additives

[00341] Optionally, the compositions disclosed herein comprise at least one additive or modifier (designated as "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 anti-blocking agents, antistatic agents, lubricants, anti-fogging agents, heat stabilizers, antioxidants, discoloration inhibitors, flame retardants, oils, waxes, antioxidants, UV stabilizers, colorants or pigments, fillers, tackifiers, waxes, flow aids, coupling agents, crosslinking agents, surfactants (e.g., wetting agents, leveling agents, deaerating agents or defoamers, or dispersants), compatibilizers, rheology modifiers, adhesion promoters, catalysts, solvents, corrosion inhibitors, anti-wear agents, antioxidants, rust inhibitors, flame retardants, biocides, algicides, fungicides, acid scavengers, radical scavengers, monomer scavengers, water scavengers, inorganic fillers (e.g., inorganic salts, clays, silica, alumina, magnesia, glass beads, and the like), conductive particles (e.g., carbon black, carbon fibers, C₆o, graphite, graphene, nickel, silver, and the like) and combinations thereof. In some variations, a plasticized composition may comprise or be formed around an insulating mesh (e.g., fiberglass) or a conductive mesh (e.g., carbon fibers or metal- coated insulating fibers). 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.

[00342] 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.

[00343] Nonlimiting examples of anti-blocking agents include silica, calcium carbonate, titania, mica, talc and the like.

[00344] Nonlimiting examples of lubricants include liquid paraffins, polyolefm waxes, fatty acids (e.g., stearic acid or isostearic acid), fatty acid esters, fatty amides, aliphatic alcohols, polyvalent alcohols, polyglycols, metal soaps (e.g., calcium stearate, zinc stearate and the like).

[00345] Nonlimiting examples of antistatic agents include fatty acid salts, alcohol sulfuric acid esters, liquid fatty oil sulfuric acid ester salts, aliphatic amines, aliphatic amides sulfuric acid salts, aliphatic alcohol phosphoric acid ester salts, sulfonic acid salts of dibasic fatty acid esters, aliphatic amide sulfonic acid slats, alkylallylsulfonic acid salts, aliphatic amine salts, quaternary ammonium salts, alkylpyridium slats, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenol ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, polyoxyethylene sorbitan alkyl esters, imidazoline derivatives, alkyl amines, and the like. Nonlimiting examples of antifogging agents include glycerin fatty esters (e.g., glycerin monostearate and the like), sorbitan fatty esters (e.g., sorbitan monolaurate, sorbitan monoleate and the like), polyglycerin fatty esters, propylene glycol fatty esters, and combinations thereof. Nonlimiting examples of UV absorbers include benzotriazoles, benzophenones (e.g., 2-hydroxy-4- methoxybenzophenone), salicylic acid derivates (e.g., p-tert-butylphenyl salicylate).

[00346] Heat stabilizers and light stabilizers may be selected based on the polymer matrix, mechanisms of thermal degradation and light degradation, respectively, and processing and environmental conditions for a particular polymer matrix. For PVC, thermal degradation may occur by a dehydrochlorination reaction, leading to discoloration and degradation of physical and mechanical properties. A thermal stabilizer may replace labile chlorine atoms in the polymer, interrupt or limit formation of hydrogen chloride, and/or interrupt or limit formation of colored unsaturated compounds. Nonlimiting examples of thermal stabilizers for PVC include carboxylic acid metal soaps (e.g., Ba, Ca, Cd, Zn and/or Pb carboxylates), esters or mercaptides of alkyl tin, and epoxy compounds. In some variations, epoxidized sunflower oil is used as a stabilizer for PVC compositions. [00347] Optionally, the plasticized compositions disclosed herein can comprise a wax, such as a petroleum wax, a low molecular weight polyethylene or polypropylene, a synthetic wax, a polyolefm wax, a beeswax, a vegetable wax, a soy wax, a palm wax, a candle wax or an ethylene/a-olefm 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.

[00348] In further embodiments, a plasticized composition comprises one or more plasticizers as described herein and 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.

[00349] In further embodiments, a plasticized composition comprises one or more plasticizers described herein and 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 one or more of 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.

[00350] A plasticized composition disclosed herein may comprise a dispersant that can aid distribution of plasticizer or additives within the host resin during film or article formation (e.g., during melt blending, solvent casting, plastisol formation and the like). Any dispersant known by a person of ordinary skill in the art may be used in the plasticized composition. Non- limiting examples of suitable dispersants include succinimides, succinamides, 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 composition.

[00351] The plasticized composition disclosed herein may comprise an antioxidant that can reduce or prevent the oxidation of the composition. Any antioxidant known by a person of ordinary skill in the art may be used in the plasticized compositions. 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-tert-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. Additional 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. 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 composition.

[00352] The plasticized 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 compositions. Non-limiting examples of suitable rust inhibitors include 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), 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 composition.

[00353] 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.

[00354] 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.

[00355] Optionally, the compositions disclosed herein can comprise an inorganic 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.

[00356] In some variations, a plasticized composition may comprise one or more adhesion promoters. Any adhesion promoter known in the art may be used. For example, one or more silane adhesion promoters may be included in a composition. Nonlimiting examples include epoxysilanes, anhydridosilanes, adducts of silanes with primary aminosilanes, ureidosilanes, aminosilanes, diaminosilanes, and also their analogs in the form of monomer or oligomer and urea-silanes; e.g., Dynasylan AMEO, Dynasylan AMMO, Dynasylan DAMO-T, Dynasylan 1146, Dynasylan 1189, and Silquest A-Link 15.

[00357] In some variations, a plasticized composition may comprise one or more compatibilizers. A compatibilizer, when added to a blend of immiscible substances, modifies the interface between them and stabilizes the blend. Any compatibilizer known in the art may be used, e.g., graft copolymers or block copolymers.

[00358] The additives may be in the form of an additive concentrate having more than one additive. In some embodiments, the solubilizing of the Diels- Alder adduct disclosed herein or any solid additives in the host resin 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.

Carbon Source for Plasticizers

[00359] Certain plasticizers described herein are nonaromatic and are readily

biodegradable. The hydrocarbon terpene (e.g., β-farnesene or a-farnesene) feed used to make the plasticizers described herein can be derived from renewable carbon sources.

[00360] Advantageously, any of the plasticizers comprising or derived from the Diels-

Alder adducts described herein may be made from conjugated terpenes and/or dienophiles that have been derived from renewable carbon sources. 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" "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.

[00361] Renewable carbon content can be measured using any suitable method. For example, renewable carbon content can be measured according to ASTM D6866-1 1 , "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. [00362] 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)]- l }xl 000 %o, where R(sample)=¹³C/¹²C and R(VPDB standard)=¹³C/¹²C for the VPDB standard. Instead

13 12 13 13 12

of a CI C ratio, δ C is the relative change of the CI C ratio for a given sample from that of the VPDB standard. Carbon isotopic ratios are reported on a scale defined by adopting a 5¹³C 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 5¹³C values. In general, for atmospheric C0₂ 5¹³C ranges between -1 1 to -6

0 13 0 13

/oo, for C₃ plants, 5C varies between -22 and -32 l₀o and for C₄ plants δ C varies between -8 to -18 %ο· The ¹⁴C 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.

[00363] 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 As, the sample activity normalized to the reference is ASN and can be expressed as: A_SN=As {[(¹³C/¹²C)reference]/[(¹³C/¹²C)sample]}². [00364] 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 5¹³C=-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 5¹³C=- 17.8 %o (VPDB). Modern carbon, referenced to AD 1950, is 0.95 times ¹⁴C concentration of SRM 4990B, normalized to 5¹³C=-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 (fM) refers to a radiocarbon measured compared to modern carbon, referenced to AD 1950. Modern carbon as defined above has

. 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 fM 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 setting 100% 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%.

[00365] 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 D6866-1 1 "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% ¹⁴C 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.

[00366] 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 Diels-Alder adducts or derivatives have a 5¹³C of from about -11 to about -6 %o, from about -15 to about -10 %₀, from about -22 to about -15 %o, from about -22 to about -32 %o, from -8 to about -18 %o, from about -14 to about -12 %o, or from about -13 to about -11 %₀. In some variations, the Diels- Alder adducts or derivatives have a ΪΜ greater than about 0.3, greater than about 0.4, greater than about 0.5, greater than about 0.6, greater than 0.7, greater than about 0.8, greater than about 0.9, or greater than about 1.0. In some variations, the Diels- Alder derivatives have a fM of about 1.0 to about 1.05, about 1.0 to about 1.1, or about 1.1 to about 1.2. In some variations, the Diels-Alder derivatives have a 5¹³C from about -15 to about -10 %o and a ΪΜ greater than about 0.5, greater than about 0.7, or greater than about 1.0. In some variations, the Diels-Alder derivatives have a 5¹³C from about -8 to about -18 %o and a fM greater than about 0.5, greater than about 0.7, or greater than about 1.0. 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, renewable diols (e.g, 1,4-butane diol), 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 may be measured using any suitable method, e.g., using radiocarbon analysis as described herein.

BLENDING

[00367] The plasticizer may be incorporated into the polymer using any suitable method.

For example, in some embodiments, the plasticizer 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. The ingredients for a plasticized composition (i.e., one or more plasticizers, 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. [00368] In some variations, the incorporation of the one or more plasticizers and any additives into the host matrix may be accomplished by melt-blending, wherein the ingredients are processed at a temperature higher than a temperature at which the host polymer flows to allow mixing of the plasticizers and any additives therein. Any suitable melt-blending equipment known in the art may be used, e.g., melt-blend extruders such as single screw extruders and twin screw extruders, Brabender® melt-blend compounders, two roll mills, and the like). 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.

[00369] 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 to form a plasticized film.

[00370] In some cases incorporation of a plasticizer into a host resin (e.g., PVC) may be sensitive to the method of preparation of the plasticized film. Nonlimiting examples of variables that may affect incorporation of the plasticizer into a host resin to result in sufficient

plasticization include type of PVC resin used (e.g., rigid, semi-rigid or flexible PVC), the type of mixing equipment (two roll mill, extruder, melt compounder and the like), whether melt blending or solvent casting is used, the solvent and solution concentration if solvent casting is used, etc.

[00371] 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.

[00372] Any mixing or dispersing equipment known to a person of ordinary skill in the art may be used for blending, mixing or solubilizing the plasticizers and any additives. 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 homogenizers 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.

[00373] The plasticizers described herein may be incorporated into a melt-blend using a variety of schemes. In certain cases, the plasticizers are pre-blended with one or more components of the composition (e.g., as a masterbatch). In other cases, the plasticizers are added directly into a melt blender (e.g., together with the host resin, or through an addition port or an injection port). One or more Diels-Alder adducts disclosed herein and the optional additives may be added to the host resin individually or simultaneously. In some embodiments, one or more Diels-Alder adducts disclosed herein and the optional additives are added to the host resin individually in one or more additions and the additions may be in any order. In other embodiments, one or more Diels-Alder adduct disclosed herein and the additives are added to the host resin 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 host resin 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.

ARTICLES

[00374] Plasticized polymer compositions can be formed into a suitable structure for the intended use. The plasticized polymer compositions can be extruded into shapes or beads for application on surfaces, spun into fibers, molded into shaped parts, coated on surfaces, and the like. The compositions can be molded using injection molding, blow molding, compression molding, thermoforming and the like.

K) Applications

[00375] The plasticized compositions may be used in a variety of applications.

Nonlimiting examples in which plasticized compositions employing one or more plasticizers described herein include automotive components (e.g., interiors), footwear, adhesives, sealants, coated fabrics, wire and cable coatings, foams, gaskets, inks, cosmetics, medical devices, medical bags and tubing, toys, electrical devices, films, wall coverings, floor coverings, appliances, furniture, hoses, concrete and the like.

[00376] In certain examples, one or more plasticizers described herein is substituted for all or part of an existing vegetable oil or petroleum-derived monoester, diester (e.g., an adipate), phthalate, benzoate, dimerate, or trimellitate plasticizer.

[00377] In some variations, a plasticizer described herein (e.g., an unsaturated Diels-Alder adduct formed between a conjugated hydrocarbon terpene (e.g., farnesene) 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.

[00378] Certain Diels-Alder plasticizers may be adapted for use in food grade

applications, cosmetic applications, or in medical grade applications. Toxicity and

biodegradability of the compositions 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).

[00379] 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, benzoate, dimerate, or trimellitate plasticizer.

Plastisols

[00380] Also, as is well known, plasticizers, when incorporated in high levels, typically in the 50-100 phr range (pounds per hundred pounds resin) 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. Said 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.

[00381] In some cases, the plasticizers described herein are useful as high solvating plasticizers. A desirable procedure involves forming a resin dispersion (e.g., a vinyl chloride resin) that can be cast in a film or thicker article, and heated to form a homogeneous article of plasticized resin. Such dispersions are suspensions of resin particles (e.g., a vinyl chloride resin) in one or more nonaqueous liquids including the plasticizer which do not dissolve the resin at ordinary temperatures but do at elevated temperatures. If the liquid phase consists only of plasticizer, the dispersion is often termed as "plastisol," whereas if the dispersing liquid also contains volatile organic solvents or organic components which evaporate upon heating, the dispersion is often termed as "organosol." Both plastisols and organosols may include other additives, including stabilizers, normally used in vinyl chloride resin compositions. The term "plastisol" as used herein is intended to include both plastisols and organosols. Plastisols can be prepared using any method known in the art. For example, high, low or combination intensity mixers, such as ribbon blenders, conical screw, planetary, Cowles, Morehouse, or any other suitable mixer, may be used. Ingredients used in making plastisols include PVC, acrylic or other polymeric resins; primary or secondary plasticizers; fillers; pigments; heat stabilizers; solvents; and other ingredients known in the industry. According to one embodiment, the plasticizers can be added to the plastisols at a range of from about 1.0 weight % to about 60 weight %, or at a range of from about 5.0 weight % to about 40 weight %, or at a range of from about 10.0 weight % to about 30 weight %, depending on the efficiency of the plasticizer and the desired properties of the final product. Any one of or any combination of the order of ingredients, shaft rpm, mixing times, and temperature may play a role to the producing a plastisol with reproducible quality. In some variations, plastisol temperature during mixing is maintained at less than 95° F. (35° C), or even less than 80° F. (27° C). In some cases where for instance a higher loading is desired, the maximum temperature may be higher. Air is both incorporated in the mixing process and may also be introduced from the surface of the dry ingredients. If necessary, air can be removed by deaeration under reduced pressure either during or after mixing. Some of the air may be released during storage of a plastisol.

[00382] In some cases, the present plasticizers may be incorporated into vinyl chloride resin, with or without other additions, by any suitable process such as, mixing or kneading of the ingredients. The plasticizers described herein may be added at any time and in any convenient manner to the PVC plastisol. If desired, the PVC plastisol and viscosity reducing compounds may be mixed simultaneously, for example, in conventional mixing or blending equipment.

Adhesives

[00383] The plasticizers described herein can be used in a variety of adhesives to increase the flexibility, decrease rigidity (e.g., increase elongation at break), increase toughness, improve low temperature physical properties, and/or improve processability of the adhesives.

Nonlimiting examples of adhesives in which the plasticizers may be utilized include those based on acrylates, methacrylates, silanes, siloxanes, polyethers, polyesters, polyurethanes, polyureas, polysulfides, silylated polyurethanes, silylated polyureas, silylated polyethers, silylated polysulfides and silyl-terminated acrylates and the like. Further nonlimiting examples of adhesives in which the plasticizers may be used are described in U.S. Patent Publ.

2011/0232825, which is incorporated herein by reference in its entirety.

[00384] Besides the polymer and one or more plasticizers, adhesive compositions may comprise additional components. These may include, among others, the following auxiliaries and additives. Adhesion promoters may be included, examples being epoxysilanes,

anhydridosilanes, adducts of silanes with primary aminosilanes, ureidosilanes, aminosilanes, diaminosilanes, and also their analogs in the form of monomer or oligomer and urea-silanes; e.g. Dynasylan AMEO, Dynasylan AMMO, Dynasylan DAMO-T, Dynasylan 1146, Dynasylan 1189, Silquest A-Link 15. Water scavengers may be included, e.g. vinyltriethoxysilane, vinyltrimethoxysilane, a-functional silanes such as N-(silylmethyl)-0-methyl-carbamates, more particularly N-(methyldimethoxysilylmethyl)-0-methyl-carbamate,

(methacryloyloxymethyl)silanes, methoxymethylsilanes, N-phenyl-, N-cyclohexyl- and N- alkylsilanes, ortho formic esters, calcium oxide or molecular sieve. Catalysts may be included, examples being metal catalysts in the form of organotin compounds such as dibutyltin dilaurate and dibutyltin diacetylacetonate, organobismuth compounds or bismuth complexes; compounds containing amino groups, examples being l,4-diazabicyclo[2.2.2]octane and 2,2'- dimorpholinodiethyl ether, and also aminosilanes. Further suitable metal catalysts include titanium, zirconium, bismuth, zinc and lithium catalysts, and also metal carboxylates, it also being possible to use combinations of different metal catalysts and also combinations of aminosilanes and metal catalysts. Light stabilizers and aging inhibitors, which act in particular as stabilizers against heat, light and UV radiation. Flame retardants may be included. Biocides, such as, for example, algicides, fungicides or fungal growth inhibitor substances, may be included. The adhesive compositions may include fillers, e.g., ground or precipitated calcium carbonates, which optionally are coated with fatty acids or fatty acid mixtures, e.g., stearates, more particularly finely divided, coated calcium carbonate, carbon blacks, especially industrially manufactured carbon blacks, kaolins, aluminium oxides, silicas, highly disperse silica from pyrolysis processes, PVC powders or hollow beads, calcium carbonates, such as precipitated or natural chalks such as Omyacarb® from Omya, Ultra P-Flex® from Specialty Minerals Inc, Socal® U1 S2, Socal® 312, Winnofil® 312 from Solvay, Hakuenka® from Shiraishi, highly disperse silicas from pyrolysis processes, and combinations of these fillers. Further examples of suitable additives are minerals such as siliceous earth, talc, calcium sulfate (gypsum) in the form of anhydrite, hemihydrate or dihydrate, finely ground quartz, silica gel, precipitated or natural barium sulfate, titanium dioxide, zeolites, leucite, potash feldspar, biotite, the group of soro-, cyclo-, ino-, phyllo- and hecto silicates, the group of low-solubility sulfates such as gypsum, anhydrite or heavy spar, and also calcium minerals such as calcite. Rheology modifiers may be included, such as thickeners, e.g. urea compounds, polyamide waxes, bentonites, fumed silica and/or acrylates. Surface-active substances may be included such as, for example, wetting agents, leveling agents, deaerating agents or defoamers, and dispersants. Fibers, as for example of polyethylene or polypropylene may be included. Pigments may be included, e.g. titanium dioxide or carbon black. Solvents may be utilized. Any other substances commonly used in moisture-curing compositions may be utilized. In one embodiment the adhesive or sealant comprises 10 to 90% by weight of polymer, 3 to 50%> by weight of plasticizer, 0 to 80%> by weight of fillers, 0 to 20%> by weight of water scavengers and 0.5 to 20%> by weight of rheology modifiers, or an amount of 25 to 40%> by weight of polymer, 5 to 40%> by weight of plasticizers, 30 to 55% by weight of fillers, 1 to 10%> by weight of water scavengers and 1 to 10%> by weight of rheology modifiers.

[00385] Adhesives may be one component (IK) or two-component (2K) systems. IK systems bind through chemical reactions of the binder with the ambient moisture. 2K systems are additionally set by chemical reactions of the mixed components, with continuous solidification. In some variations, an adhesive or sealant is a one-component system. In some variations, it may be advantageous to configure the adhesive or sealant system as a two- component system, e.g., where one component comprises the polymer component, while the second component comprises, for example, a catalyst or water (e.g., micronized water) as a booster to accelerate the curing of the system. It is advantageous to ensure that the components employed in a one-component system do not adversely affect the shelf life of the composition, i.e. that they do not initiate the reaction to a significant extent of the functional groups present in the composition that leads to crosslinking. In some variations, it may be desired to physically or chemically dry certain components before incorporating and mixing them into these

compositions so that such components comprise no water or at most traces of water. In some variations in which drying is not carried out, it may be advantageous or desirable to configure the adhesive or sealant as a two-component system, with the component or components which adversely affect the shelf life being formulated separately from component into the second component.

[00386] The moisture curable adhesives may be stored in the absence of moisture, e.g., kept in a suitable pack or facility, such as a drum, a pouch or a cartridge, for example, over a period of several months to a number of years, without suffering change that significantly affects its properties after curing. The storage stability or shelf-life is typically determined via measurement of the viscosity, the extrusion quantity or the extrusion force.

[00387] Plasticized adhesive or sealant compositions described herein may produce material bonds between parts that are to be joined. On application of the composition to at least one part to be joined, the functional groups of the polymer comes into contact with moisture. A property of the functional groups is that of undergoing hydrolysis on contact with moisture. As the outcome of this reaction, which can be accelerated through the use of catalysts, the composition finally cures or crosslinks. The water required for the curing reaction may come from the air (atmospheric humidity), or else the composition may be contacted with a water- comprising component, by being brushed with a smoothing agent, for example, or by being sprayed, or else a water-comprising component may be added to the composition at application, in the form, for example, of a water-containing paste which is mixed in, for example, via a static mixer. The composition described cures, as already stated, on contact with moisture. Curing takes place at different rates depending on temperature, nature of contact, amount of moisture, and the presence of any catalysts. Curing by means of atmospheric moisture first forms a skin on the surface of the composition. The so-called skin formation time, accordingly, constitutes a measure of the cure rate. Typically it is desirable to aim for a skin formation time of up to 2 hours at 23° C. and 50% relative atmospheric humidity. In the cured state, the plasticized composition possesses a high mechanical strength in conjunction with high extensibility, and also has good adhesion properties. This makes it suitable for a multiplicity of applications, more particularly as an elastic adhesive, as an elastic sealant or as an elastic coating. It is especially suitable for applications which require rapid curing and which impose exacting requirements on extensibility at the same time as exacting requirements on the adhesion properties and the strengths.

[00388] Suitable applications are, for example, the material bonds between parts to be joined made of concrete, mortar, glass, metal, ceramic, plastic and/or wood. In one particular embodiment the parts to be joined are firstly a surface and secondly a covering in the form of carpet, PVC, laminate, rubber, cork, linoleum, wood, e.g. woodblock flooring, floorboards, boat decks or tiles. The plasticized composition can be used in particular for the manufacture or repair of industrial goods or consumer goods, and also for the sealing or bonding of components in construction or civil engineering, and also, in particular, in the sanitary sector. The parts to be joined may especially be parts in auto, trailer, truck, caravan, train, aircraft, watercraft and railway construction.

[00389] An adhesive for elastic bonds in this sector is applied with preference in the form of a bead in a substantially round or triangular cross-sectional area. Elastic bonds in vehicle construction are, for example, the adhesive attachment of parts such as plastic covers, trim strips, flanges, bumpers, driver's cabs or other components for installation, to the painted body of a means of transport, or the bonding of glazing into the bodywork.

[00390] One exemplary area of application in construction and civil engineering is that of construction joints, flooring joints, expansion joints or sealed joints in the sanitary sector. In some embodiments, the composition described is used as an elastic adhesive or sealant. In the form of an elastic adhesive, the composition typically has an elongation at break of at least 50%, and in the form of an elastic sealant it typically has an elongation at break of at least 300%, at room temperature.

[00391] For use of the composition as a sealant for joints, for example, in construction or civil engineering, or for use as an adhesive for elastic bonds in automotive construction, for example, the composition may have a paste-like consistency with properties of structural viscosity. A paste-like sealant or adhesive of this kind is applied by means of a suitable device to the part to be joined. Suitable methods of application are, for example, application from standard commercial cartridges which are operated manually or by means of compressed air, or from a drum or hobbock by means of a conveying pump or an eccentric screw pump, if desired by means of an application robot.

[00392] The parts to be joined may where necessary be pretreated before the adhesive or sealant is applied. Such pretreatments include physical and/or chemical cleaning processes, non- limiting examples being abrading, sandblasting, brushing or the like, or treatment with cleaners or solvents, or the application of an adhesion promoter, an adhesion promoter solution or a primer.

[00393] In the context of its use as an adhesive, the plasticized composition is applied either to one or the other part to be joined, or to both parts to be joined. Thereafter the parts to be bonded are joined, and the adhesive cures through contact with moisture. In each case it is ensured that the joining of the parts takes place within what is referred to as the open time, in order to ensure that the two parts to be joined are reliably bonded to one another.

[00394] Disclosed herein 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, thermosets, elastomers or rubbers, 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 while 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.

[00395] 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.

[00396] Tables 5 and the Examples provide non- limiting examples of Diels- Alder adducts that may be used as plasticizers, and test results for select ones of those plasticizers. The Examples provide non-limiting examples of epoxidized farnesenes 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.

[00397] 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

[00398] For the following examples, β-farnesene refers to trans- β-farnesene. Unless otherwise specified, β-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 stabilizer. Herein, the following abbreviations are used: Me=methyl, i-Pr=isopropyl, n-Bu=n-butyl, i-Bu=isobutyl. CE=comparative example.

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

la lb

[00399] 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: 1H NMR (CDCI3): 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).

[00400] 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: 1H 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 [00401] A solution of 1484 g of 2a, 2b in 7 L of hexane was hydrogenated over 587.5 g of /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: 1H 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, CDCI₃): 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 d -n-butyl ester (4).

[00402] 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: 1H NMR (400 MHz, CDCI3): 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- -025]).

5 (FW-00448-025)

[00403] 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: 1H 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.

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

6

[00404] 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: 1H NMR (400 MHz, CDCI3): 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) es -00448-026]).

[00405] 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: 1H 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.

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

[00406] 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: 1H NMR (400 MHz, CDCI3): 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]).

[00407] 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: 1H 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.

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

[00408] Using the procedure for 5 above 444 g (2.17 mol) of β-farnesene and 678 g (2.17 mol) of diheptyl maleate were heated at 90-95 °C for 18 hours to afford 1060 g of crude 10 as a nearly colorless oil. 1H 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 -00448-031]).

[00409] 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 l lOl g of ll as a colorless oil. The product was characterized by the following NMR data: 1H 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.

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

[00410] 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-P-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: 1H 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-Dimethylnonyl)cyclohexane carboxylic acid 2-ethylhexyl ester (13b) [KJF-437-56-01]

[00411] 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 extrudate). 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.

[00412] The hydrogenated final product which was a complex mixture of isomers (1 ,3 and 1 ,4-disubstituted cis- and trans-isomers on the ring). The stereocenter on the side chain of the product exhibited characteristic peaks in the 1H NMR spectrum (400 MHz, CDCI3) 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).

[00413] Reaction scheme for Examples 12 and 13 is as follows, with only the 1,4 isomer shown for simplicity:

MW 204.36 MW 184.28

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

[00414] 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):

[00415] 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 above), 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

[00416] 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 15 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 1 shows incorporation of the commercially available DOP (dioctyl phthalate) into PVC; Comparative Example 2 shows incorporation of Hexamoll® DF CH (1,2-Cyclohexanedicarboxylic acid, diisononyl ester, available from BASF) into PVC; and Comparative Example 3 shows incorporation of

CITROFLEX® A-4 (Acetyltri-n-butyl Citrate, available from Vertellus Specialities, Inc.), into PVC.

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

Example 19 FW-00448-025 (Example 5) darker color, 3% loading did not incorporate into PVC

Example 20 FW-00448-027 (Example 9) mixed well, light color - similar to DOP - added to 25%

Comparative Example DOP (bis(2-ethylhexyl) phthalate) mixed well, light color added CE 1 to 25%

Comparative Example DINCH (1,2- mixed well, light color added CE 2 Cyclohexanedicarboxylic acid, to 25%

diisononyl ester)

Comparative Example CITROFLEX® A-4 (Acetyltri-n- mixed well, light color added CE 3 butyl Citrate) to 25%

[00417] For each of Examples 15 and 19, the plasticizers of Example 13 (KJF-437-56-01) and Example 5 (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 Examples 16 (plasticizer of Example 3), 17 (plasticizer of Example 11), and 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

[00418] 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 pre -heated to 390°F (199°C).

[00419] 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. Example # or Comparative Example # Description

Example 21 Test specimens die cut from 5 inch x 6 inch x

0.08 inch pressed plaque of Example 20

Example 22 Test specimens die cut from 5 inch x 6 inch x

0.08 inch pressed plaque of Example 20 and heat aged for 120 hours at 70°C.

Comparative Example CE 4 Test specimens die cut from 5 inch x 6 inch x

0.08 inch pressed plaque of Comparative Example CE 1

Comparative Example CE 5 Test specimens die cut from 5 inch x 6 inch x

0.08 inch pressed plaque of Comparative Example CE 2

Comparative Example CE 6 Test specimens die cut from 5 inch x 6 inch x

0.08 inch pressed plaque of Comparative Example CE 3

Comparative Example CE 7 Test specimens die cut from 5 inch x 6 inch x

0.08 inch pressed plaque of Comparative Example CE 1 and heat aged for 120 hours at 70°C.

Comparative Example CE 8 Test specimens die cut from 5 inch x 6 inch x

0.08 inch pressed plaque of Comparative Example CE 2 and heat aged for 120 hours at 70°C.

Comparative Example CE 9 Test specimens die cut from 5 inch x 6 inch x

0.08 inch pressed plaque of Comparative Example CE 3 and heat aged for 120 hours at 70°C.

[00420] FIGURE 1 shows percentage change in sample weight 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 of Example 9 (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.

[00421] 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 (MP a) 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.

[00422] 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. The plasticizer of Example 9 (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.

[00423] 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.

[00424] FIGURE 4 shows engineering strain (% elongation) at break measured according to ASTM D638 for Examples 21 and 22, Comparative Examples CE 4-CE 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 CE 4-CE 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.

[00425] 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.

[00426] 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 of β-Farnesene-Maleic Anhydride Diels-Alder Adduct (14)

[00427] 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 -(2,8-Dimethyl-3,4,7,8-diepoxynonyl)-2-vinyloxirane (15)

[00428] 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 CH₂CI₂ 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: 1H 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-(4,8-Dimethyl-3,4,7,8-diepoxynonyl)butadiene (16)

[00429] 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 of mono-epoxides (17, 18) from β-farnesene

[00430] 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)

[00431] 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) is prepared according to any suitable method. For example, the procedure for Example 1 may be followed, except substituting n-butyl acrylate for methyl acrylate. A solution of the esters (19a,19b) (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%. In some variations, each epoxy group can be hydro lyzed to result in hydroxyl groups on each of the carbon atoms forming the epoxy group using known techniques.

[00432] 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

[00433] 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).

[00434] 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 refiuxing 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⁺); 1H NMR (CDC1₃), δ (9.69, J=1.2 Hz, lH 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).

[00435] 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 NaB¾ 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 HCl 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⁺); 1H 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).

[00436] 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 (97.7%o) of alcohol (28-4) as a colorless oil with isomer ratio as above for alcohol (3): GC/MS, m/z 268 (M⁺); 1H 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).

[00437] 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)

[00438] 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

[00439] 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- -dicarboxylate

Dimethyl maleate, 604 mL 144 4.63

>99% purity, Acros

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

[00440] 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 CH₂C1₂ (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.

Example 31: Preparation of dimethyl 4-(4,8-dimethylnonyl)cyclohexane-l,2-dicarboxylate

Raw Material and Amount molecular weight moles source

Example 30 501 g 348 1.44

Dimethyl maleate, 604 mL 144 4.63

>99% purity, Acros

Organics (New

Jersey)

Nickel, -65 wt% on 108 g

silica / alumina,

Aldrich

Heptanes, Reagent 3.4 L

Plus 99%, Sigma

Aldrich

[00441] 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 1H 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.

Example 32: Preparation of (4-(4,8-dimethylnonyl)cyclohexane-l,2-diyl)dimethanol

Heptane, Reagent 2.8 L

Plus 99%, Sigma

Aldrich

Water 600 mL

15% NaOH, certified 150 mL

ACS, Fisher

Scientific, Inc.

Na₂S0₄, ACS 400 g

reagent, Sigma

Aldrich

Celite, standard

supercell, acid

washed, Sigma

Aldrich

[00442] 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- enecarbaldehyde and (E)-4-(4,8-dimethylnona-3,7-dienyl)cyclohex-3-enecarbaldehyde

Raw Material and Amount molecular weight moles

source

β-farnesene, >97% 754 g 204 3.69 pure, Amyris, Inc.

Zinc Iodide, 99.99%, 10.65 g 318.18 0.0334

Aldrich

Toluene, >99.5% 200 mL

ACS, Sigma Aldrich

Acrolein, 95%, Fluka 300 mL 56.06 4.26

Silica (SiliaFlash® 5.1 kg

F60, available from

Silicycle, Inc.,

Quebec City,

Quebec, CA

CH₂C1₂, certified 2.0 L

ACS, Fisher

Scientific, Inc.

Ethyl acetate, reagent 5 L

ACS, USP/NF grade,

Pharmco-Aaper

Hexanes, certified 31 L

ACS, Fisher

Scientific, Inc.

[00443] 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 room temperature 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 1H 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-dimethylnonyl)cyclohexyl)methanol

[00444] 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 1H 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: Preparation of ethoxylated alcohols

SCHEME 35

[00445] 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. "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.

[00446] Example 35 was an off-white semi- solid. 1H 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 1H 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.

[00447] Example 36 was an off-white semi-solid. 1H 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 1H 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. [00448] Example 37 was an off-white semi-solid. 1H 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 1H 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

[00449] (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.

[00450] 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.

[00451] Example 38 was an amber oil. 1H 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 ¹H 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.

[00452] Example 39 was a hazy amber oil. ^ΧΗ 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 1H 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.

[00453] Example 40 was an off-white semi-solid. 1H 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 ^ΧΗ 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 Plasticizers

[00454] Six examples of ester-containing Diels-Alder adducts that have utility as lubricants and/or plasticizers 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.

[00455] 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 1,3- and 1,4- isomers

[00456] 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.

[00457] 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 1,3- and 1,4-isomers

[00458] 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. ¹HNMR; (CDCls) 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.

[00459] Example 42 [4-(4,8-Dimethylnonyl)cyclohexane-l,2-dicarboxylic acid diheptyl ester] was prepared as in Example 11.

[00460] 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

[00461] 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 110 °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. ¹HNMR; (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, 119.0, 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.

[00462] 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 1,3- and 1,4-isomers

[00463] 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. ¹HNMR; (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. [00464] 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.

[00465] Example 45 [4-(4,8-Dimethylnonyl)cyclohexane-l,2-dicarboxylic acid dimethyl ester] was prepared as in Example 9.

[00466] Example 46 [4-(4,8-Dimethylnonyl)cyclohexane-l,2-dicarboxylic acid bis-(2- ethylhexyl) ester] was prepared as in Example 7.

[00467] Kinematic viscosities (cSt) at 40oC and lOOoC measured according to ASTM

D445, which is incorporated herein by reference, and viscosity index measured according to ASTM 2270, which is incorporated herein by reference are shown in Table 41 below. Also shown in Table 41 is an average percent weight loss measured according to a TGA-Noack method.

TABLE 41

Example 47: Preparation of Isosorbide diesters

[00468] Acrylic Acid/Farnesene Adduct Reaction with Isosorbide: Carboxylic acid 47-1 is prepared using any suitable technique. For example, a mixture of Compounds (la) and (lb) may be prepared according to the method of Example 1, and hydrolyzed with

KOH/Methanol using standard conditions. 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.

[00469] 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 ¹HNMR.

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

MW=20₄.36 MW=108.10 MW=516.81

MF =C,_RH. 0,

Scheme 48

P 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

[00470] 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

[00471] 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); 1H NMR (400MHz, CDCls): 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).

[00472] 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); 1H 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)

[00473] 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 ¾ 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); 1H 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-(dim ethyl 4-((E)-4,8-dimethylnona-3,7-dien-l- yl)cyclohex-4-ene-l,2-dicarboxylate) (51)

51

[00474] 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); 1H 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.

[00475] 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- -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.

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

52

[00476] The triolefm 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); 1H 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

[00477] 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 triolefm intermediate as a slightly yellow liquid (2837 g, 97% yield). HPLC Purity (>95%); LCMS (ESI: 349.0 = M⁺ +1); 1H NMR (300MHz, CDC1₃): 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

[00478] A 5L Parr reactor was charged with the triolefm 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); 1H NMR (400MHz, CDCls): 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

[00479] 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); 1H 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

[00480] The triolefin 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); 1H 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

[00481] 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); 1H 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- 1,2-dicarboxylate) (58)

58 [00482] A 5L Parr reactor was charged with the triolefm 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 ¾ 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); 1H NMR (400MHz, CDCls): 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

[00483] 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 triolefm intermediate as a slightly yellow liquid (2100 g, 90% yield). HPLC Purity (>95%); LCMS (ESI: 433.2 = M⁺ +1); 1H NMR (300MHz, CDC1₃): δ 5.36 (s, br, 1H), 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

[00484] 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 (191 1 g, 93% yield). GC/MS (m/z = 438); 1H NMR (300MHz, CDCls): δ 4.04-4.10 (m, 4H), 3.22 (s, br, 1H), 2.39-2.44 (m, 1H), 2.20-2.25 (m, 1H), 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

[00485] 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 triolefm intermediate as a slightly yellow liquid (2660 g, 94% yield). HPLC Purity (>97%); LCMS (ESI: 433.2 = M⁺ +1); 1H NMR (300MHz, CDC1₃): δ 5.38 (s, br, 1H), 5.03-5.1 1 (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

[00486] A 5L Parr reactor was charged with the triolefm 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); 1H 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-l,2-dicarboxylate (63)

63

[00487] 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); 1H 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).

[00488] 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.

Examples 64-77 and Comparative Examples CE 10-CE 13: Plasticization of suspension grade PVC [00489] 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.

[00490] 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.

[00491] 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.

[00492] 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. [00493] 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.

[00494] 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 Vulcanized 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.

[00495] 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.

[00496] 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

[00497] 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

0

50 ⁰

75 Ex. 52 12.396 9.881

52

76 Ex. 52 6.702 1.291

.^ JDOOMe

52

77 DOP + 3.918 23.990

51

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

[00498] 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 [l-(fmal 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.

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

A. Preparation of Casting Solutions:

[00499] PVC Casting Solution. PVC (52.0 g, Shintech SE-1300, three ball bearings (~1" dia, stainless steel) and tetrahydrofuran (THF) (245.1 g, BHT stabilized) were added to ajar 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).

[00500] PVC with Plasticizer Casting Solution. The plasticizer of Example 7 (F W-

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:

[00501] 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.

[00502] 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:

[00503] 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%).

Claims

CLAIMS What is claimed is:

1. A composition comprising: a Diels- Alder adduct of a hydrocarbon terpene comprising a conjugated diene and a dienophile; and a host polymer, wherein the Diels- Alder adduct plasticizes the host polymer so as to lower a glass transition temperature, lower a melt viscosity, increase a percent elongation at break and/or decrease a rigidity of the host polymer.

2. The composition 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 and substituted itaconic acids, itaconic anhydride and substituted itaconic anhydrides, acrolein and substituted acroleins, crotonaldehyde and substituted crotonaldehydes, dialkyl maleates, dialkyl fumarates, 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, 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, vinyl sulfonates, vinyl sulfmates, vinyl sulfoxides, and combinations thereof.

3. The composition of claim 2, wherein the dienophile is maleic anhydride.

4. The composition of claim 2, wherein the dienophile is a dialkyl maleate.

5. The composition of claim 2, wherein the dienophile is a dialkyl fumarate.

6. The composition of claim 1, wherein the hydrocarbon terpene is β-farnesene.

7. The composition of claim 1, wherein the hydrocarbon terpene is myrcene.

8. The composition of claim 1, wherein the host polymer is selected from the group consisting of: a polyvinylchloride, a chlorinated polyvinylchloride, a polycarbonate, a polyurethane, a nitrile polymer, an acrylate polymer, a polystyrene, a polyester, a polyamide, a polyimide, a polyvinyl acetal, a cellulose polymer, a polyolefm, a phenolic resin, a starch, a natural rubber, a synthetic rubber, an interpolymer of any of the foregoing, a polymer blend of any of the foregoing, and a polymer composite thereof.

9. The composition of claim 1, wherein the host polymer comprises polyvinylchloride.

10. The composition of claim 9, wherein the host polymer comprises a flexible grade of polyvinylchloride.

11. The composition of claim 1 , wherein the host polymer comprises a polylactic acid.

12. The composition of claim 1, wherein the Diels- Alder adduct comprises a monoester or diester functionality.

13. The composition of claim 1, wherein the Diels- Alder adduct plasticizes the host polymer so as to increase a percent elongation at break to at least about 100%.

14. The composition of claim 1, wherein the Diels- Alder adduct comprises or is derived from a compound having formula (F-1):

where R and R' each independently represent H or any C1-C30 linear or branched, cyclic or acyclic, substituted or unsubstituted hydrocarbyl group, where n represents 1, 2, 3, or 4, and where R and R' may be the same or different.

15. The composition of claim 14, wherein R and R' each independently represent a C1-C4 linear or branched alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, or t-butyl; or wherein R and R' each 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.

16. The composition of claim 15, wherein R and R' are each methyl.

17. The composition of claim 1, wherein the Diels- Alder adduct comprises or is derived from a compound having formula (F-2), a compound having formula (F-3), or a mixture thereof:

where each R independently represents H or any C₁-C30 linear or branched, cyclic or acyclic, substituted or unsubstituted hydrocarbyl group, and each n independently represents 1, 2, 3, or 4.

18. The composition of claim 17, wherein each R independently represents methyl, ethyl, n- propyl, isopropyl, n-butyl, 2-butyl, isobutyl, t-butyl, 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.

19. The composition of claim 1, wherein the Diels- Alder adduct comprises or is derived from a compound having formula (F-4):

where n represents 1, 2, 3 or 4.

20. The composition of claim 1, wherein the Diels- Alder adduct 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):

where each of R and R' independently represents H or any C1-C30 linear or branched, cyclic or acyclic, substituted or unsubstituted alkyl group, and R and R' may be the same or different.

21. The composition of claim 20, wherein 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.

22. The composition of claim 20, wherein 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.

23. The composition of claim 20, wherein each of R and R' independently represent methyl.

24. The composition of claim 1, comprising more than one Diels- Alder adduct between a hydrocarbon terpene comprising a conjugated diene and a dienophile.

25. The composition of claim 1, further comprising one or more additional compounds which plasticizes the host polymer so as to lower a glass transition temperature, lower a melt viscosity, increase a percent elongation at break and/or decrease a rigidity of the host polymer.

26. The composition of claim 1, further comprising one or more additives selected from the group consisting of anti-blocking agents, antistatic agents, lubricants, anti-fogging agents, heat stabilizers, antioxidants, discoloration inhibitors, flame retardants, oils, waxes, antioxidants, UV stabilizers, colorants or pigments, tackifiers, waxes, flow aids, coupling agents, crosslinking agents, surfactants, compatibilizers, rheology modifiers, adhesion promoters, catalysts, solvents, corrosion inhibitors, anti-wear agents, antioxidants, rust inhibitors, flame retardants, biocides, algicides, fungicides, acid scavengers, radical scavengers, monomer scavengers, water scavengers, inorganic fillers, conductive particles, fibers, and combinations thereof.

27. The composition of claim 1, wherein 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 adduct are derived from renewable carbon sources.

28. The composition of claim 1, adapted for use as an adhesive.

29. The composition of claim 28, wherein the host polymer is based on an acrylate, methacrylate, silane, siloxane, polyether, polyester, polyurethane, polyurea, polysulfide, silylated polyurethane, silylated polyurea, silylated polyether, silylated polysulfide or a silyl- terminated acrylate.

30. A method of making a plasticized composition, comprising reacting a hydrocarbon terpene comprising a conjugated diene with a dienophile to form a Diels-Alder adduct, and combining the Diels-Alder adduct with a host polymer to plasticize the host polymer.

31. A method of making a plasticized composition, comprising reacting a hydrocarbon terpene comprising a conjugated diene with a dienophile to form a Diels-Alder adduct, chemically functionalizing the Diels-Alder adduct to form a plasticizer, and combining the plasticizer with the host polymer to plasticize the host polymer, wherein the chemical functionalization of the Diels-Alder adduct increases compatibility with the host polymer.

32. The method of any of claims 30 or 31, further comprising obtaining the hydrocarbon terpene from a sugar using a genetically modified organism.

33. The method of any one of claims 30-32, wherein the hydrocarbon terpene is β-farnesene.

34. A composition comprising a plasticizer derived from a Diels-Alder adduct between a hydrocarbon terpene comprising a conjugated diene and a dienophile combined with a host resin, wherein the Diels-Alder adduct functions to plasticize the host resin and to provide one or more additional functionalities selected from the group consisting of acid scavenging, radical scavenging, thermal stabilization, color stabilization, charge dissipation, fire retardation, corrosion inhibition, flow viscosity improvement, radical scavenging, dye site creating, adhesion promoting, and mold releasing.

35. A plasticizer comprising: (i)farnesene; (ii) a dimer of farnesene; (iii) a trimer of farnesene; (iv) a tetramer of farnesene; or (v) a Diels Alder adduct of farnesene and a dieneophile, wherein at least one carbon-carbon double bond has been oxidized or chlorinated.

36. The composition of claim 1, wherein the Diels- Alder adduct comprises or is derived from a compound having formula (F-IA):

37. The composition of claim 36, wherein R and R' each independently represent a C1-C4 linear or branched alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, or t-butyl; or wherein R and R' each 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.

38. The composition of claim 37, wherein R and R' are each methyl.

39. The composition of claim 1, wherein the Diels-Alder adduct comprises or is derived from a compound having formula (F-2A), a compound having formula (F-3A), or a mixture thereof:

where each R independently represents H or any C1-C30 linear or branched, cyclic or acyclic, substituted or unsubstituted hydrocarbyl group, and each n independently represents 1, 2, 3, or 4.

40. The composition of claim 39, wherein each R independently represents methyl, ethyl, n- propyl, isopropyl, n-butyl, 2-butyl, isobutyl, t-butyl, 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.

41. The composition of claim 1, wherein the Diels-Alder adduct comprises or is derived from a compound having formula (F-4A):

where n represents 1, 2, 3 or 4.