CA2111313A1 - Direct synthesis by living cationic polymerization of nitrogen-containing polymers - Google Patents

Abstract

Abstract A method is provided for the direct synthesis by living cationic polymerization of novel polymeric materials functionalized with desirable nitrogen-containing functional groups such as terminal azido, cyano, carbonylamino, cyanato, thiocyanato or_ thiocarbonylamino groups. Polymerization and functionalization occur in a substantially simultaneous manner. All necessary reactants for the functionalization are present when polymerization is initiated. The nitrogen-containing functional group is provided as a part of a molecule having a release moiety which is preferably resonance stabilized or a tertiary alkyl type and which acts to aid the nitrogen-containing species in functioning as a leaving group.

Description

DIRECT SYNTHESIS BY LIVING CATIONIC
POLYMERIZATION OF NITROGEN-CQNTAINING POLYMERS ~PT-930) BACXGROUND OF T~E INVENTION

Field of the Invention This invention relates to a method for direct synthesis, by living cationic polymerization, of nitrogen-containing polymers, and particularly to the production of nitrogen-containing polymeric materials in a single step Friedel-Crafts polymerization of olefinic materials containing substantial amounts of isobutylene. i~

DescriDtion of Related Art A review of carbocationic macromolecular engineering is provided in Kennedy and Ivan, Desianed Polvmers kY
Carbocationic Molecular Enainee~ina: Theorv and Practice, Hanser Publishers, Munich, Vienna, New York and Barcelona, Section II.3.4 which relates to mechanistic considerations: a comprehensive view of living carbocationic polymerization and the spectrum of ionicities of active species. At page 32, living polymerizations are defined as ideal living polymerization in which charge transfer and termination are absent, and quasi-living polymerizations are defined as having rapidly reversible charge transfer and/or termination present wherein the rate of these processes is faster than that of propagation. In either case the living behavior of the polymer results in a po}ymer in which charge, transfer and termination are absent. For the purpose of the present invention, living polymers are therefore defined as polymers which have substantially and preferably no apparent chain transfer and .. ~ . .. ... ... . ..

'~113:~3 termination. Resulting polymers have low polydispersity indices also known as molecular weight distributions of preferably less than 1.5 and in the range of 1.5 to the ideal value of 1, one (1) being where all of the molecular chains are of the same length. Cationic living polymerization systems are disclosed to take place by the polymerization reaction of monomers in the presence of a cationic initiator. A living polymerization system i8 one wherein the molar ratio of the monomer to initiator_ is equal to the degree of polymerization. The calculated molecular weight, therefore, equals the degree of polymerization times the molecular weight of the monomer plus the molecular weight of the initiator. In a living system the measured number average molecular weight should be ideally equal to the calculated molecular weight, again evidencing the absence of true termination of the polymerization system. Further detail i~
described in the Kennedy reference, hereby incorporated by reference.

U.S. Patent Nos. 5,066,730 and 5,122,572 are directed to living catalysts, complexes and polymQrs therefrom. There are disclosed living polymers derived from isobutylene using Lewis acid catalysts and initiating systems based on organic acids or esters. The preferred Lewis acid catalyst is boron trichloride.

An early description of living polymerization using isobutyl vinyl ether was disclosed in M. Miyamoto, M.
Sawamoto, T. Higashimura, Macromolecules, 17, 265 (1984).

It has been disclosed that there is an improvement in a chemical process following a "living behavior", 80 that the polydispersity index of the polymeric products i8 reasonably low, lower than 1.5 in ~any examples, while the terminal function is still a tertiary chloride. This is the case of European Patent No. 341,012 which relates to the production of uniform molecular weight polymers.
This process involves a monomer, a solvent, an initiator component having an acetate, an etherate, a hydroxyl group or a halogen function of a benzylic type initiator, a Lewis acid and an electron donor component having an electron donor number of from 25 to 50.

Chain end functionalization may result from transfer reactions such as those described in U.S. Patent No.
4,568,732 which relates to a continuous procesæ for forming telechelic halogenated polymers wherein a cationically polymerizable monomer and an inifer (initiator-transfer agent) are contacted with a boron chloride solvent solution. Disclosed monomers are olefins of from 4 to 12 carbon atoms, e.g. isobutylene.
Suitable inifers are halogenated aromatic or aliphatic hydrocarbons, vinyl halides, silane-substituted hydrocarbyl halides, dicyclopentadienyl halides, alpha-chlorostyrene homopolymers, and 2-chloro-propene homopolymers and copolymers, wherein the halide is F, Cl or Br. In this patent, the polydispersity index of the polymer was not particularly low, and the terminal function was a tertiary chloride which necessitates subsequent chemical steps in order to obtain the desired nitrogen-containing function.

Polymers, particularly polyolefin substrates, having nitrogen-containing functional groups such as the azide, cyano, carbonylamino or thiocarbonylamino groups are useful since the functional group is polar, and imparts desirable properties to a polyolefinic substrate. Also, these groups may act a~ a reactive site for ~urther modification of the polymer. Nitrogen-containing polyisobutylenes have applications such a~ lube additives, compatibilizers, emulsifiers, and the like.

~ . ~

For example, azide terminal polymers may be further modified ~y pht~alamidation or reduction of the azide group and thus result in polymer products with useful modifications. For instance, reduction of the azide group of polyisobutylenes and addition of a polar moiety to the alpha nitrogen atom may result in improved polymeric compatibilizers, emulsifiers, etc.

Prior art processes for synthesis of polymers having nitrogen-containinq functional groups, such a~ nitrogen~
containing polyisobutylene, involve several reaction steps. Chain end functionalization is known in the field of cationic polymerization.

The art further discloses that it could be possible to achieve direct functionalization by cationic polymerization of polymers end-capped by nitrogen containing functions using, for instance, an initiator having a pseudohalogen function of the benzylic type.
Pseudohalogen or halogenoids include inorganic anions, e.g., CN , CN0 , CNS and N3 which have properties resembling those of halide ions as disclosed in Dlscher, Modern Inoraanic Pharmaceutical Chemistry, John Wiley &
Sons, Inc., N.Y., p. 343 (1964). In a single chemical process a polymer is derived from the monomer, u~ing an initiator having nitrogen-containing function such aB
azide, cyano, carbonylamino or thiocarbonylamino group.
These type of result are referred to in U.S. Patent No.
5,032,653. However, the polymeric products were not disclosed to have a narrow molecular distribution (i.e., monod~spersed type). The molecular weight was controlled by the monomer feed rate and the amount of Lewis acid catalyst as well as the monomer to initiator ratio. ThQ
amount of initiator was based on a Lewis to initiator mole ratio of 3:1 to 1:3 with enhanced results as the ratio approaches 1:1. The molecular weight distribution (MWD) are controlled based on monomer feed rate and product removal rate.

There are three different desirable goals for the synthesis of polymers by cationic polymerization. The first is specific functionalization of the chain ends by a nitrogen-containing function, using direct synthesis from the monomer and the initiator which is incorporated in the resulting polymer. The second is easy control of the molecular weight by adjust~ent of the monomer to initiator ratios and low polydispersity index, (low MWD).
Thirdly, it is a goal to control molecular weight and MWD
in the absence of additive directed to molecular weight control.

The above references do not disclose the possibil~ty of obtaining more than two of the above goals. For instance, U.S. Patent No. 4,568,732 does not offer any of the three above advantages, European Patent No. 341,012 discloses a solution of only the second goal, while U.S.
Patent No. 5,032,653 combine~ only goals Nos. 1 and 3.

Other references of interest include U.S. Patent No.
4,611,037 which relates to a process for preparing polymers having reactive halogen end groups employing cationically polymerizable monomers and a catalyst system consisting of a metal halide and an organic halide, wherein the metal halide is used in from 2 to 500 times molar excess, based on the organic halide.

Chain end functionalization may also be accomplished by termination reactions wherein a functional group i~
imparted to the electrophilic site of a developing polymer. Such systems entail high manufacturing c08t~
and expend considerable process control resources due to the need to keep the electrophilic site available.

X1~1~13 U.S. Patent No. 3,684,713 relates to lubricating oil and fuel compositions containing oil-soluble azo compounds prepared by reacting an oil-soluble, synthetic organic polymer having at least 20 carbon atoms with an azo compound (e.g., azo esters, azo amides such as azodiformates and azodiformamides) at temperatures of from 20C to 200OC. Oil-soluble polymers are disclosed to include polybutenes, and copolymers of isobutylene/styrene and isobutylene/l-decene.

U.S. Patent No. 4,393,199 discloses a cationic polymerization method to produce low molecular weight polymers wherein cyclic ethers (e.g., bis(azidomethyl)oxetane-3) are polymerized in the presence of a diol/cationic catalyst for molecular weig~t control.

U.S. Patent No. 4,483,978 relates to ener~etic copolymers by copolymerization of azido monomers te.g., bis(azidomethyl)oxetane), wherein the N3 azido group i8 bonded directly to a ring carbon atom, with a cyclic oxide.

U.S. Patent Nos. 3,993,609 and 4,029,615 relate to polymeric cellular structures obtained by mixing an acid sensitive azo compound with an acidulous or acidic polymerizable ~edium, such as unsaturated polyesters and polymeric active resins containing one or more terminal and/or pendant functional groups that undergo free radical reaction.

U.S. Patent Nos. 3,645,917, 4,268,450 and 4,405,762 relate to polymers having pendant alkylazide side groups prepared by reaction of a polymer with a metal azide. In U.S. Patent No. 3,645,917, a polyether polymer i8 '2 ~ 3 :
prepared from epichlorohydrin, and then reacted with a metal azide (e.g., sodium azide) at 30OC to 150C to form azidomethyl groups pendant from the main polyether polymer backbone. Polyether and polyester polymers are disclosed in U.S. Patent No. 4,268,450 to be reacted with sodium azide at 100C to form energetic hydroxy-terminated azido polymer5 having pendant alkyl azide groups. In U.5. Patent No. 4,40S,762, 3,3-bischloromethyloxetane is polymerized to yield halomethyl polymer products having hydroxy functionality which are then reacted with metal azide to form poly(azidomethyl oxetanes), which are disclosed to be useful as energenic binders for (e.g.) explosives.

U.5. Patent No. 4,113,804 discloses compositions comprising polybutene, EPDM and polyolefin which are cross-linked by use of chemical free-radical generators or cross-linking agents which are disclosed to include a7rido formates (e.g., tetramethylenebis(azido formate)), aromatic polyamides (e.g., 4,4'-diphenylmethane diazide) and sulfonazides (e.g., p,p'-oxybis-(benzene sulfonyl azide).

European Patent Application 206,756 relates to olefin polymers such as polyisobutylene, polystyrene, polyoctene and polypropylene which are polymerized in the presence of a preformed catalyst complex of an organic acid or its ester and a Lewis acid, preferably boron trichloride. It is disclosed that the polymerization is believed to occur, e.g. in use of a catalyst complex of an ester and boron trichloride, by the opening of the e~ter bond and monomer in~ertion. The organic acids arQ
disclosed to be mono-, di- and tricarboxylic acids and acids containing chloride, formate, allylic, acrylic or methacrylic.

SUMMARY OF THE I~VENTION

The present invention relates to a direct synthesis of nitrogen-containing polymeric materials by a process wherein all reactants and catalysts are present at the initiation of polymerization. ~he polymer is terminally substituted by the nitrogen-containing functional groups.

Accordingly, the present invention relates to a method for direct synthesis by living cat~onic polymerization of polymeric materials which comprises providinq a cationically polymerizable monomer, and initiating polymerization in the presence of a suitable cationic polymerization catalyst and an initiator. The initiator is a pseudohalogen, preferably a nitrogen-containing initiator compound which includes a nitrogen-containing functional group. The nitrogen-containing functional group is preferably chemically bound to a release moiety. The ratio of moles of the nitrogen-containing functional groups to catalyst is less than 1:3.

The present invention includes preferred initiator bis(1-azido-1-~ethylethyl)benzene and the method to prepare such preferred initiator.

As the polymerization reaction proceeds, the nitrogen-containing functional group may be released fro~
the nitrogen-containing initiator compound to bind the electrophilic site of the developinq polymer and become a covalently bound nitrogen-containing functional group of the polymer. When the nitrogen-containing functional group separates from the nitrogen-containing initiator compound, it leaves behind a release moiety which is preferably a resonance stabilized structure capable of ::
. -.

2~11313 g delocalizing charge, thus aiding the departure of the nitrogen-containing functional group. This activity may be further aided if, as in other preferred embodiments, the nitrogen-containing functional group is bound to a secondary or tertiary carbon atom of the release moiety.

Preferred nitrogen-containing initiators include hydrocarbyl compounds and silyl compounds, sUbstituted with at least one nitrogen-containing group comprising azido (-N3), cyano also referred to as nitrile ~-CN), isocyanato (carbonylamino) (-NC0~, thiocarbonylamino (isothiocyanato) (-NCS), cyanato (-OCN), and thiocyanato (-SCN).

In certain preferred embodiments of the invention, polymerization is catalyzed by a Friedel-Crafts catalyst which is contacted under polymerization conditions with a mixture of the nitrogen-containing initiator with a suitable polymerizable monomer. The nitrogen-containing initiator and monomer are preferably admixed in the substantial absence of the Friedel-Crafts catalyst.

The process of the present invention is a "living polymerization" as defined. The living polymer i5 achieved by polymerizing the monomer with a catalyst to initiator ratio of greater than about 30:1, preferably greater than about 3:1.1, and more preferably greater than 4:1. Particularly useful ranges are greater than 6:1 and specifically greater than 6:1.1 with a most useful range of from 3:1.1 to 30:1, and more specifically 4:1 to 30:1 and 6:1 to 20:1. This results in a polymer with a narrow molecular weight distribution tMWD) (Rw/~n) also referred to as a low dispersity, preferably less than 1.5, more preferably le~s than 1.4, and typically ranging from 1.2 to 1.3. This is obtained directly from polymerization without resort to additional '`; `~ ~, steps to separate polymers at different molecular weights. The polymer made by the claimed process has as a terminal group the nitrogen-containing functional group. The molecular weight can be varied and can range from 300 or lower to 15,000,000 or higher with a specific range of from 300 to 15,000,000 and preferred ranges depending upon use.

The nitrogen containing end groups can be reacted to form a desired functional terminal group including amines to prepare new telechelic oligomers. Uses include lubricant dispersants, viscosity improvers, synthetic lubricating oils, and thermoplastic elastomers.

Where the initiator has more than one functional group, i.e., the polymer can have the plurality of arms ranging from 2 to 10 or more. This type of polymer is considered a "star polymer". The advantage is that each arm is substantially equal in length due to the low MMD.

An advantage of the polymerization method of the present invention is that the functionalization i9 obtained directly from the mixture of monomer, initiator, Lewis acid and solvent without the need of other functionalization effecting compounds such as electron donor type compounds disclosed in the art. The resulting polymer is characterized by the advantages of a high specificity of functionalization combined with a narrower molecular weight distribution. Additionally, the method of the present invention enables easy control over tha desirable molecular weight by ad~usting the initial monomer to initiator a concentration ratio without tba need of an electron donor.

The present invention includes a polymer co~po~ition having the formula:

R((M)p(Y))n R is selected from at least one group consisting of H, a hydrocarbyl group, and a hydrocarbyl-substituted silyl group. R can be alkyl, aryl, alkylaryl and arylalkyl. Y
is selected from at least one group consisting of an azido, cyano, carbonylamino, thiocarbonylamino, cyanato and thiocyanato. A preferred Y is an azido group. L and_ M is at least one repeat unit derived from a cationically polymerizable monomer. Useful monomers include straight and branched chain alpha olefins, isoolefins, alicyclic monoolefins, cycloaliphatic compounds, styrene derivatives, indene and derivatives thereof, and other monoolefins and heterocyclic monomers. "p" is an integer greater than 1 and preferably sufficient to attain a desired molecular weight. "n" is an integer of at least 1, preferably 1 to 10 and most preferably 1 to 2.

~AILED DESC~IPTION OF CERTAIN PREFER~E~ EMBODIMENTS

The following description is directed to preferred embodiments of the living polymer, method of preparation, functional reaction products, uses and related methods.
As will be illustrated from the preferred embodiment, the --present invention provides a way to obtain, at the sa~e time, complete functionalization of the polymer by a monofunctional pseudohalogen or halogenoid initiator by direct synthesis using living cationic polymerization. p~
When using a monofunctional initiator, the polymer product has a functionality of up to about 1, and preferably about 1. When using a bifunctional initiator, the polymer product has a functionality of up to about 2, and preferably about 2. The polymer has a narrow molecular weight di~tribution (MWD) or a low ~Z~ 1313 polydispersity index measured as weight average molecular weight divided by number average molecular weight. The MWD should ideally be l.O, preferably less than 1.5, preferably from about 1.0 up to about 1.5, more preferably about 1.0 to about 1.4, with preferred value3 typically at about 1.1 to about 1.4.

Preferred polymers produced in accordance with the method of the present invention are telechelic polymers.
The functional groups are derived from the initiator with at least one functional group preferably containing nitrogen. In the living polymerization process using an initiator having one functional nitrogen-containing group, the functionality of the polymer is close to the theoretical 1, and typically greater than O.7. Where the initiator contains more than one pseudohalide function the functionality would be expected to be close to a multiple of the number of functional groups. For example, an initiator containing two pseudohalide functional groups would be expected to have a ~unctionality of greater than 1.4 and preferably close to 2.

The foregoing and other aspects of the invention are provided by a process for producing polymers characterized in a living cationic polymerization. Th~
process comprises polymerization of a monomer in the presence of an initiator and a catalyst, preferably in a solvent under conditions which result in a living polymerization.

Nitroaen-Containina Initiator The nitrogen-containing compound employed a~
initiator in this invention can comprise at least on-! :........... ' ' ' . ` , .

'~111~1'3 member selected from the group consisting of (i)compounds of the formula:
R(Y)n (Ia) wherein R is hydrogen or a hydrocarbyl group, n is a positive integer, preferably an integer of from 1 to 10, more preferably 1 or 2 and Y is -N3, -CN, -NCO, -OC~N; --SC~N; or -NCS; and (ii) compounds of the formula:
. -R (Y)n (Ib~

wherein n and Y are as defined above, and R comprises ahydrocarbyl-substituted silyl group of the formula:

R
R li (Ic) R - .

wherein each R is the same or different and i~
hydrocarbyl.

Exemplary of R groups are alkyl of from 3 to 100 carbon atoms, preferably 4 to 20 carbon atoms, aryl of ~ ~
from 6 to 20 carbon atoms, preferably from 6 to 15 carbon -atoms, alkaryl and aralkyl of from 7 to 100 carbon atoms `;~
(e.g., 7 to 20 carbon atoms), and cycloaliphatic of from -3 to 20 carbon atoms, preferably from 3 to 12 carbon atoms. When n is 1, R in Formula (Ia) generally comprise an alkyl group of from 3 to 12 carbon atoms, preferably from 3 to 20 carbon atoms, such as propyl, butyl, pentyl, octyl, decyl, dodecyl, and the like can be a polymeric group.

2111~13 Most preferably R in Formula (Ia) comprises a moiety of the formula:

Rl R2 1 (IIa) l3 wherein R1, R2 and R3 are the same or different and are H
or hydrocarbyl (e.g., alkyl, aryl, ~lkaryl, aralkyl, heterocyclic or cycloalkyl) with the proviso that at least two of R1, R2, and R3 are hydrocarbyl. Most preferably all of R1, R2 and R3 are hydrocarbyl.
Exemplary of such secondary and tertiary alkyl groups are isopropyl, tert-~utyl, 1-methylpropyl, 1-ethylbutyl, 1,2-dimethylbutyl, and the like. Exemplary of such alkaryl Rl, R2 or R3 groups are ~CH2-, CH3~CH2-, -~C2H5 and the like. Exemplary of such R1, R~ or R3 groups are CH3~
(C~3)2~- and the like.

It will be understood that the hydrocarbyl-substituted nitrogen-containing initiators of Formula (Ia) can comprise a polymer, for example, a polyalkene, such as a C2 to C10 monoolefin homopolymer or a copolymer (e.g., polyisobutylene, ethylene-propylene copolymer), polydiene, such as hydrogenated or nonhydrogenated polyisoprene, polybutadiene and isoprene-butadiene, and aromatic-containing polymers (e.g., styrene-isoprene, styrene-butadiene, methyl-styrene-isoprene-butadiene polymers), ethylene-propylene-conjugated diene terpolymer having one or more Y-functional groups which can be added by grafting have been grafted.

Illustrative of hydrocarbyl compounds of Formula I(a) monosubstituted with azido (-N3), cyano (-CN), carbonylamino (-NCO), thiocarbonylamino (-NCS), cyanato .:. ~ ~. : . ; ~ . , . . : , . . .

2111~13 (-OCN), thiocyanato (-SCN) and groups are hydrazoic acid, HCN, HCNo, HCNS, ethylazide, tert-butylazide, isobutylazide, propylazide, isopropylazide, 2-ethylhexylazide, hexylazide, l,l-diethylheptylazide, benzylazide, phenylazide, tolylazide, xylylazide, cumylazide, cyclohexylazide, carbonylaminoethane, carbonylaminopropane, 1-carbonylamino-1,1,1-trimethyl-methane, 2-carbonylaminobutane, 2-carbonylamino-propane, 3-carbonylamino-2-methylheptane, 3-carbonylamino-3-ethyl-nonane, l-carbonylamino-1-phenylmethane, l-carbonylamino-~ -l-tolylmethane, 1-carbonylamino-1,1-dimethyl-1-phenylmethane, 1-carbonylamino-1-methyl-2-phenylethane, carbonylaminocyclohexane, thiocarbonylaminoethane, thiocarbonylaminopropane, l-thiocarbonyl-amino-1,1,1-trimethylmethane, 2-thiocarbonylaminobutane, 2-thiocarbonylaminopropane, 3-thiocarbonylaminomethyl-heptane, 3-thiocarbonylamino-3-ethylnonane, 1-thio-carbonylamino-l-phenyl-methane, l-thiocarbonylamino-l-tolyl-methane, l-thiocarbonylamino-l,l~dimethyl-1-phenyl-methane, l-thiocarbonylamino-l-methyl-2-phenylethane, thiocarbonylaminocyclohexane, cyanoethane, cyanopropane, 1-cyano-1,1,1-trimethylmethane, 2-cyanobutane, 2-cyano-propane, 3-cyanomethylheptane, 3-cyano-3-ethyl-nonane, 1-cyano-l-phenylmethane, 1-cyano-1-tolyl-methane, l-cyano-1,1-dimethyl-1-phenylmethane, 1-cyano-1,1-methyl-2~
phenylethane, cyanocyclohexane, cyanatoethane, cyanatopropane, l-cyanato-l,1,1-trimethylmethane, 2-cyanato-butane, 2-cyanatopropane, 3-cyanatomethyl-heptane, 3-cyanato-3-ethyl-nonane, 1 -cyanato-l-phenyl-methane, 1-cyanato-1-tolyl-methane, 1-cyanato- 1,1-dimethyl-l-phenylmethane, l-cyanato-1-methyl-2-phenyl-ethane, cyanatocyclohexane, thiocyanatoethane, thio-cyanatopropane, 1-thiocyanato-1,1,1-trimethylmethane, 2-thiocyanato-butane, 2-thiocyanato-propane, 3-thiocyanatomethyl-heptane, 3-thiocyanato-3-ethyl-nonane, l-thiocyanato-1-phenyl-methane, l-thiocyanato-l-tolyl-methane, 1-thiocyanato-1,1-dimethyl-1-phenyl-methane, 1-thiocyanato-1-methyl-2-phenylethane, thio-cyanatocyclo-hexane, isothiocyanatoethane, isothiocyanatopropane, 1-isothiocyanato-1,1,1-trimethyl-methane, 2-isothiocyanato-butane, 2-isothiocyanato-propane, 3-isothiocyanatomethyl-heptane, 3-isothiocyanato-3-ethyl-nonane, 1-isothiocyanato-1-phenyl-methane, l-isothiocyanato-1-tolyl-methane, 1-isothiccyanato-1,1-dimethyl-1-phenyl methane, 1-isothiocyanato-1- methyl-2- phenylethane, isothiocyanato-cyclohexane, and the like.

The carbonylamino (-NCO) and thiocarbonylamino (-NCS) substituted compounds are isocyanates and isothiocyanates, respectively.

Illustrative of the silyl compounds of Formula I(b1 are azidotrimethylsilane, azidotriethylsilana, azidoethyldimethylsilane, azidotriphenylsilane, azido-methyldiethylsilane, azidoethyldiphenylsilane, azido-trioctylsilane, azidotricumylsilane, cyanotrimethyl-silane, cyanotriethylsilane, cyanoethyldimethylsilane, cyanotriphenylsilane, cyanomethyldiethylsilane, cyano-ethyldiphenylsilane, cyanotrioctylsilane, cyanotri-cumylsilane, carbonylaminotrimethylsilane, carbonyl-aminotriethylsilane, carbonylaminoethyldimethylsilane, carbonylaminotriphenylsilane, carbonylaminomethyldiethyl-silane, carbonylaminoethyldiphenylsilane, carbonylamino-trioctylsilane, carbonylaminotricumylsilane, th$o-carbonylaminotrimethylsilane, thiocarbonylaminotriethyl-silane, thiocarbonylaminoethyldimethylsilane, th~o-carbonylaminotriphenylsilane, thiocarbonylaminomethyldi-ethylsilane, thiocarbonylaminoethyldiphenylsilane, thio-carbonylaminotrioctylsilane, thiocarbonylaminotricumyl-silane, cyanatotrimethylsilane, cyanatotriethylsilane, cyanatoethyldimethylsilane, cyanatotriphenylsilane, cyanatomethyldiethylsilane, cyanatoethyldiphenylsilane, , -, . .

~113~3 -- ~L7 cyanatotrioctylsilane, cyanatotricumylsilane, thio-cyanatotrimethylsilane, thiocyanatotriethylsilane, thiocyanatoethyldimethylsilane, thiocyanatotriphenyl-silane, thiocyanatomethyldiethylsilane, thio-cyanatoethyldiphenylsilane, thiocyanatotrioctylsilane, thiocyanatotricumylsilane, isothiocyanatotrimethyl-silane, isothiocyanatotriethylsilane, isothiocyanato-ethyldimethylsilane, isothiocyanatotriphenylsilane, - .
isothiocyanatomethyldiethylsilane, isothiocyanato-_ ethyldiphenylsilane, isothiocyanatotrioctylsilane, : -:
isothiocyanatotricumylsilane, and the like. -Useful as nitrogen-containing initiators include disubstituted compounds of the formula~

Y-Z-Y (III1 -wherein Y is as defined above, and Z comprises a R4 (i) :: :~
R5 R7 :
---C R4---C , (ii) ~ .
R6 A8 : ' R5 ~:
---C R4, or (iii) i R4 Si , (iv) 6 R8 . .

, ~ - .: ' ' : ;
~ , . ~ : . :

211~313 group wherein R5, R6, R7 and R8 are the same or different and comprise H or hydrocarbyl, e.g., al~yl of from 1 to 100 carbon atoms (e.g., methyl, ethyl, isopropyl, butyl and the like), cycloalkyl of from 3 to 10 carbon atoms (e.g., cyclohexyl, cyclobutyl and the like), aryl of fro~
6 to 20 carbon atoms (e.g., phenyl, naphthyl and the like)~ or aralkyl and alkaryl of from 7 to 20 carbon atoms (e.g., tolyl, cresyl, xylyl, benzyl, ethylbenzyl and the li~e), and R4 comprises ~(CH2)a-, or -Ar-, wherein a is an integer of from 3 to 20, and preferably 3 to 10, and wherein Ar is an arylene group of from 6 to 20 carbon atoms, or aryl-substituted arylene, e.g., Cl to C20 (preferably Cl to C10) alkyl mono- or disubstituted arylene group of from 7 to 40 carbon atoms (e.g., phenylene, naphthylene, mono- or dialkyl substituted derivatives of the foregoing, and the like).

Illustrative of compounds of Formula III
disubstituted with the above groups (i), (ii~ and (iii) are 2,4-bis(azido)-2,4-dimethylpentane, bis(azido)-methane, 1,2-bis(azido)-ethane, 1,3-bisazido-propane, 2,2-bis(azido)-propane, 2,3-bis(azido)-2,3-dimethyl-butane, 1,5-bis(azido)-pentane, 2,6-bis(azido)-heptane, 2,6-bis(azido)-2,6-dimethylheptane, bis(azido)benzene, bis(azidomethyl)benzene, bis(azidoethyl) benzene, bis(l-azidoethyl)benzene, bis-(1-azido-1-methylethyl)benzene, bis(2-azidopropyl) benzene, bis(azidomethyl)toluene, bis(azidomethyl) xylene, bis(l-azidoethyl)toluene, bis(l-azidoethyl)xylene, bis(1-azido-1-methylethyl)toluenQ, bis(1-azido-1-methylethyl)xylene, bis(azidophenyl) methane, bis(azido-ethylphenyl)methane, bis(azidomethyl-phenyl)methane, 2,2-bis(azidomethylphenyl) propanQ~
bis(1-azido-1-methylethylphenyl)methane, 2,4-bis(cyano)-2,4-dimethylpentane, bis(cyano)-methane, 1,2-bis(cyano)ethane, 1,3-bis-cyano-propane, 2,2-bis(cyano)propane, 2,3-bis-(cyano)-2,3-dimethyl-butane, 1,S-bis(cyano)-pentane, 2,6-bis(cyano)-heptane, 2,6-bis(cyano)-2,6-dimethylheptane, bis(cyano)benzene, bis(cyanomethyl)benzene, bis(cyanoethyl)benzene, bis(1-cyanoethyl)benzene, bis-(l-cyano-1-methylethyl)benzene, bis(2-cyanopropyl)benzene, bis(cyanomethyl)toluene, bis (cyanomethyl)xylene, bis(l-cyanoethyl)toluene, bi~
cyar.oethyl)xylene, bis(l-cyano-1-methylethyl)toluene, bis(l-cyano-l-methylethyl)xylene, bis(cyanophenyl) methane, bis(cyano-ethylphenyl) methane, b$s(cyano-methylphenyl)methane, 2,2-bis(cyanomethylphenyl) propane, bis(1-cyano-1-methylethylphenyl)methane, 2,4-bis~carbonylamino)-2,4-dimethylpentane, bis(carbonyl-amino)-methane, 1,2-bis(carbonylamino)-ethane, 1,3-bis(carbonylamino)-propane, 2,2-bis(carbonylamino)-propane, 2,3-bis(carbonylamino)-2,3-dimethylbutane, 1,5-bis(carbonylamino)-pentane, 2,6-bis(carbonylamino)-heptane, 2,6-bis(carbonylamino)-2,6-dimethylheptane, bis(carbonylamino)benzene, bis(carbonylaminomethyl) benzene, bis(carbonylaminoethyl) benzene, bis(l-carbonyl-aminoethyl)benzene, bis(l-carbonylamino-l-methylethyl) benzene, bis(2-carbonylaminopropyl)benzene, bis(carbonyl-aminomethyl)toluene, bis(carbonylamino-methyl)xylene, bis(1-carbonylaminoethyl)toluene, bis(l-carbonylamino-ethyl)xylene, bis(l-carbonylamino-1-methylethyl)toluene, bis(l-carbonylamino-1-methylethyl) xylene, bis(carbonyl-aminophenyl)methane, bis(carbonyl-amino-ethylphenyl) methane, bis(carbonylaminomethyl-phenyl)methane, 2,2-bis(carbonylaminoethylphenyl) propane, bistl carbonylamino-l-methylethylphenyl) methane, 2,4 bis(thiocarbonylamino)-2,4-dimethyl-pentane, bis(th~o-carbonylamino)-methane, 1,2-bis(thiocarbonylamino)-ethane, 1,3-bis(thiocarbonyl-amino)-propane, 2,2-bis(thiocarbonylamino)-propane, 2,3-bis(thiocarbonyl-amino)-2,3-dimethylbutane, 1,5-bis(thiocarbonylamino)-pentane, 2,6-bis(thiocarbonylamino)-heptane, 2,6-bis(thiocarbonylamino)-2,6-dimethylheptane, bis(thio-2111313 ~

carbonylamino)benzene, bis(thiocarbonylaminomethyl) :
benzene, bis(thiocarbonylaminoethyl)benzene, bis(l- :::
thiocarbonylaminoethyll benzene, bis(l-thiocaxbonylamino-l-methylethyl)benzene, bis(2-thiocarbonylamino-propyl)benzene, bis(thiocarbonylaminomethyl)toluene, bis(thiocarbonylaminomethyl)xylene, bis(l-thiocarbonyl aminoethyl)toluene, bis(1-thiocarbonylaminoethyl)xylene, bis(}-thiocarbonylamino-l-methylet ffl l)toluene, bis(l-thiocarbonylamino-l-methylethyl)xylene, bis(thiocarbonyl-aminophenyl)methane, bis(thiocarbonylaminoethylphenyl) methane, bis(thio-carbonylaminomothylphenyl)methane, 2,2-bis(thiocarbonylaminoethylphenyl)propane, bis(l-thiocarbonylamino-l-methylethyl-phenyl)methane, 2,4-bis(cyanato)-2,4-dimethylpentane, bis(cyanato)-methane, 1,2-bis(cyanato)-ethane, 1,3-biscyanato-propane, 2,2-bis(cyanato)-propane, 3-bis(cyanato)-2,3-dimethylbutane, 1,5-bis(cyanato)-pentane, 2,6-bis(cyanato)-heptane, 2,6-bis(cyanato)-2,6-dimethylheptane, bis(cyanato)benzene, bis(cyanato-methyl)benzene, bis(cyanatoethyl)benzene, bis(1-cyanatoethyl)benzene, bis(1-cyanato-1-methylethyl) benzene, bis(2-cyanatopropyl)benzene, bis(cyanatomethyl) toluene, bis(cyanatomethyl)xylene, bis(l-cyanatoethyl)toluene, bis(l-cyanatoethyl)xylene, bis(l-cyanato-1-methylethyl)toluene, bis(l-cyanato-1-methyl-ethyl)xylene, bis(cyanatophenyl)methane, bis(cyanato-ethylphenyl)methane, bis(cyanato-methylphenyl)methane, 2,2-bis(cyanatomethylphenyl) propane, bis(l-cyanato-1-methylethylphenyl)methane, 2,4-bis(thiocyanato)-2,4-dimethylpentane, bis(thio-cyanato)-methane, 1,2-bis(thiocyanato)-ethane, 1,3-bisthiocyanato-propane, 2,2-bis(thiocyanato)-propane, 2,3-bia(thiocyanato)-2,3-dimethylbutane, 1,5-bis(thiocyanato)-pentane, 2,6-bis(thiocyanato)-heptane, 2,6-bis(thiocyanato)-2,6-dimethylheptane, bis(thiocyanato)benzene, bis(thio-cyanatomethyl)benzene, bis(thiocyanatoethyl)benzene, bis(l-thiocyanato-ethyl)benzene, bis(l-thiocyanato-l-- 21 - : :
, methylethyl)benzene, bis(2-thiocyanatopropyl)benzene, b.is(thiocyanatomethyl~ toluene, bis(thiocyanato-methyl)xylene, bis(l-thiocyanatoethyl)toluene, bis(l-thiocyanatoethyl)xylene, bis(1-thiocyanato-1-methylethyl) toluene, bis(l-thiocyanato-1-methylethyl)xylene, bis(thiocyanatophenyl)methane, bis(thiocyanato~
ethylphenyl)methane, bis(thiocyanatomethylphenyl)methane, 2,2-bis(thiocyanatomethylphenyl)propane, bis(l-thio-cyanato-1-methylethylphenyl)methane, 2,4-bis(isothio-cyanato)-2,4-dimethylpentane, bis(isothiocyanato)-methane, 1,2-bis(isothiocyanato)-ethane, 1,3-bisisothiocyanato-propane, 2,2-bis(isothiocyanato)-propane, 2,3-bis(isothiocyanato)-2,3-dimethylbutane, 1,5 bis(isothiocyanato)-pentane, 2,6-bis(isothiocyanato)-heptane, 2,6-bis(isothiocyanato)-2,6-dimethylheptane, bis(isothiocyanato)benzene, bis(isothiocyanato-methyl)benzene, bis(isothiocyanatoethyl)benzene, bis(l-isothiocyanatoethyl)benzene, bis(l-isothiocyanato-l-methylethyl)benzene, bis(2-isothiocyanato-propyl)benzene, bis(isothiocyanatomethyl)toluene, bis(isothiocyanato-methyl)xylene, bis(1-isothio-cyanatoethyl)toluene, bis(l-i~othiocyanatoethyl)xylene, bis(1-isothiocyanato-1-methylethyl)toluene, bis~1-isothiocyanato-1-methylethyl) xylene, bis(isothio-cyanatophenyl)methane, bis(isothio-cyanatoethylphenyl) methane, bis(isothiocyanatomethyl-phenyl)methane, 2,2-bis(isothiocyanatomethylphenyl) propane, and the like.

Illustrative of the compunds of Formula III
disubstituted with the groups (iv) are bis(l-isothiocyanato-1-methylethylphenyl~methane, bis(azido-dimethylsilyl) methane, bis/azidodiethylsilyl) methane, 1,1-bis(azidodimethylsilyl) ethane, 1,2-bis azidodimethylsilyl) ethane, bis/azidoethyldimethyl-silyl) phenylmethane, 1,1-bis(azidodiethylmethylsilyl) -2-phenyl-ethane, bis(cyanodimethylsilyl) methane, ~1~1313 ~

bis/cyanodi-ethylsilyl) methane, 1,1-bis(cyanodimethylsilyl~ ethane, 1,2-bis (cyanodimethylsilyl) ethane, bis/cyanoethyldimethylsilyl) phenylmethane, l,l-bis(cyanodiethylmethylsilyl)-2-phenyl-ethane, bis(carbonylaminodimethylsilyl)methane, bis/
carbonyl-aminodiethylsilyl)methane, l,l-bis(carbonyl-amino-dimethylsilyl)ethane, 1,2-bis (carbonylamino-dimethyl-silyl)ethane, bis/carbonylaminoethyldimethyl-silyl)phenyl-methane, 1,1-bis(carbonylaminodiethyl-methylsilyl)-2-phenylethane, bis(thiocarbonylamino-dimethylsilyl) methane, bis/thiocarbonylaminodiethyl-silyl) methane, l,1-bis(thiocarbonylaminodimethylsilyl) ethane, 1,2-bis (thiocarbonylaminodimethylsilyl) ethane, bis/thio-carbonylaminoethyldimethylsilyl) phenylmethane, 1,1-bis(thiocarbonylaminodiethylmethylsilyl)-2-phenyl-ethane, bis(cyanatodimethylsilyl) methane, bis/cyanato-diethylsilyl) methane, l,l-bis(cyanatodimethylsilyl) ethane, 1,2-bis (cyanatodimethylsilyl) ethane, bis/cyanato-ethyldimethylsilyl) phenylmethane, 1,1-bis(cyanatodiethylmethylsilyl)-2-phenylethane, bis (thiocyanatodimethylsilyl)methane, bis/thiocyanato-diethylsilyl)methane, l,l-bis(thiocyanatodimethylsilyl3 ethane, 1,2-bis (thiocyanatodimethylsilyl) ethane, his/thiocyanatoethyldimethylsilyl) phenylmethane, 1,1-bis(thiocyanatodiethylmethylsilyl)-2-phenylethane, bis(isothiocyanatodimethylsilyl) methane, bis/isothio-cyanatodiethylsilyl) methane, l,1-bis(isothiocyanato-dimethylsilyl) ethane, 1,2-bis (icothiocyanatodimethyl-silyl) ethane, bis/isothiocyanatoethyldimethylsilyl) phenylmethane, l,1-bis(isothiocyanatodiethylmethyl-silyl) 2-phenylethane, and the like.

A preferred initiator of the present invention i~
bis(l-azido-l-methylethyl)benzene having the formula: ~ :

:
C,H ~ -N3 The bis(1-azido~1-methylethyl)benzene can be prepared by reacting dicumyl alcohol wit~ a halogen containing compound to form dicumyl halide. The dicumyl halide is reacted with an azide containing compound to form the bis(1-azido-1-methylethyl)benzene.

The halogen-containing compound is preferably a bromide or chloride and more preferably HCl, and t~e azide containing compound is preferably NaN3. T~Q
reactions can be conducted in the presence of suitable solvents under suitable conditions. The dicumyl alcohol can be reacted with HCl in a polar solvent such a~
methane dichloride under reflux conditions. The dicumyl chloride can be reacted with sodium azide in a solvent under reflux conditions, preferably with a weak Lawi~
acid catalyst such as ZnC12. The following preferred reactions have been successfully conducted:
~CH3 CIH3 CH~ve~t ~H3 ~ C~H3 HO-C~ ~ ~-OH + HCl 0C ~ Cl-C ~ Cl fH3 ~H3 so~ve~t Cl H3 ~ ~CH3 Cl-CI ~ Cl 2Na 3 R~ C~2 hr ~C ~ ~3 The ~is(l-azido-l-methylethyl)benzene is preferred for use as an initiator to make the living polymer, and particularly useful to make linear living polymer.

The method of the instant invention may be illustrated, for instance, by the production of polyisobutylene functionalized with terminal asido, cyano, carbonylamino or thiocarbonylamino groups. In 21~ 1313 preferred embodiments of the invention, isobutene monomer is provided in a low-boilinq, low-freezing alkyl halide solvent. An azido-providing species such a~ a substituted benzylic type azide such as cumyl azide may be added to the monomer.

Functionalization by the azide, cyano, carbonylamino, cyanato, thiocyanato, isothiocyanato, or thiocarbonylamino group can be obtained during th9 cationic polymerization of the selected monomer (e.g., isobutylene) in the liquid phase. In order to obtain this result, the azide, cyano, carbonylamino, cyanato, thiocyanato, isothiocyanato, or thiocarbonylamino group is introduced in the form of a suitably designed molecule including a release moiety enabling the Y- group to migrate to the electrophilic site of a growing polymer chain.

Without being bound, it is believed that the polymerization in accordance with the process of the present invention is a living cationic polymerization.
The criteria for such living polymerization are known in the art and are disclosed for example in Kennedy et al., Designed Polvmers by Carbocationic Macromolecular Engineering: Theory and Practice, Hanser Publishers, 1992, pp. 31 to 35. At page 32 it is disclosed th~t ideal living polymerization is one wherein chain tranafer and termination are absent. It is disclosed that in living polymerization the concentration of active propagating sites remains constant during the experiment (reaction) and provided initiation is faat the number average degree of polymerization increasea line~rly with the amount of monomer consumed. That is, the degree o~
polymerization is equal to the concentration of monomer consumed and incorporated in the polymer divided by t~e -initiator concentration. If the rate of initiation ia ~

equal to or higher than that of propagation, living polymerizations will yield molecular weight distributions very close to unity; i.e., Mw/Mn is about equal to 1.
This latter requirement is not disclosed to be part of the rigorous definition of living polymerization.
Initiation and propagation can be separated and controlled individually, for example, by first preparing a quantity of active centers and subsequently adding monomer to this seed or by continuously adding monomer t the active centers. The Kennedy reference provides a comprehensive classification of ideal living, a~ well a~
quasi-living and non-living cationic polymerization systems.

It is believed that in accordance with the present invention, N-containing initiators having Y- groups, which are mobile in the presence of Friedel-Crafts catalysts, provide functionalization (during polymerizatSon) of the growing polymer chain ends. Thi~
is believed to occur by reaction of the electrophilic site with the complex anion containing the Y~
constituent. The introduction of the initiator (also herein sometimes termed the "cocatalyst") simultaneously provides an initiation site and a functionalization system enabling the following reaction:
RN3 + mCH2=C(CH3)2 Cat ~ R-CH2-C(C~3)2m~N3 where R is the release moiety of the cocatalyst, N3 is the nitrogen-containing functional group, I'Cat." is, for instance, a metal halide catalyst, and m is the degree of polymerization.

~ he living polymerization in accordance with thQ
process of this invention is believed to proceed by t~e ~ormation of an ion pair of the selected nitrogen-.. . . . . . . . .. . . . . . . .. ' . . . . . .

containing initiator and Lewis acid catalyst, followed by monomer insertion. An alternative mechanism could bs insertion of the monomer into a strongly polarized covalent bond, according to the mechanism of pseudocationic polymerization. In the case of monofunctional N-containing initiators of this invention (e.g., ~c(CH3)2N3)~ the resulting product then theoretically contains functionality at each end. That i5, one end of the polymer corresponds to the "R" group of the nitrogen-containing initiator and the other corresponds to the "Y" group of the initiator. This can be illustrated by reference to the following equation:

~C(C~3)2-N3 ` t~C(C~3)2]+ [N3EADC]-M
~C(CH3)2-M-M-M... M-M-M-N3 wherein EADC represents ethyl aluminum dichloride and M
represents the selected c~tionically polymerizable monomer. ;

In the case of a difunctional initiator of this invention e.g., N3C(C~3)2tPhenYlene]C(c~3)2N3~ the resulting polymer product will theoretically contain a -y" functionality at each end of the polymer, and a "R~
group within the polymer chain, as illustrated by reference to the following equation:

i ., .

21113~

EADC
N3c(c~3)2[phenylene]c(cH3)2N3 N3c(cH3)2-M-M-~ -M-[phenylene]~ c(cn3~2N3 of course, the RYn initiator compound, when n > 2, is multifunctional and additional branching of the polymer can occur due to polymer growth at multiple sites on the intiators of this invention. In the living polymerization method of the present invention the polyolefin "M-M..." branches are ideally all of the sa~e length. The branches emanate from the R group in a star-like structure.

In the above reactions the Y-group (e.g., the -N3, azide group) in the N-containing initiator has sufficient mobility to be transferred to the growing chain end.
Preferably, the Lewis Acid selected to catalyze the polymerization is introduced at a concentration corresponding to greater than three times, preferably ~our and more preferably from four to twenty times, the molar equivalents of the Y functional group, i.e., azide or other N-containing group of this invention, charged to the polymerization zone.

The preferred N-containing initiators employed in this invention are those- in which the "Y" group is covalently bound to a secondary or tertiary carbon, and those in which the "R" release moiety is resonanc~
stabilized or otherwise capable of delocalizing charge.
Preferably the "R" release moiety is an allylic or benzylic species. As explained above, the initiator can be monofunctional, di- or multifunctional, and can contain more than one of the above Y functional groups, although it is preferred that di- or multifunctional 211~313 initiators contain only a single such type of "Y" group.
The functionality of the polymer product is then equal to one, two or more, accordingly. Preferred initiator molecules include l-azido-1-methylethyl benzene, and 2-azido-2-phenyl-propane in which the azide group is at the same time tertiary and of the benzylic type, and bis~1-azido-1-methylethyl)benzene. ~ydrazoic acid is also useful as the initiator molecule containing an azide group. In the latter case, the proton of the acid is th~
fragment on which polymerization is initiated (by cocatalysts), and the functionalization is the result of the termination reaction.

Particularly preferred is bis(1-azido-1-methylethyl)benzene, and the compounds derived therefrom where the two azide groups were replaced by any one of the members of the pseudohalide functions, it waR
possible to obtain the synthesis of end-capped oligomers in an ideal situation, i.e. specific functionalization with nitrogen-containing groups, low polydispersity and predetermined ~olecular weight, without the help of any substance of the electron donor type, provided that the ;
concentration of the Lewis acid is adjusted to a proper value which is higher than that of the nitrogen containing function.

The catalyst can comprise a Friedel-Crafts catalyst or other Lewis Acid cationic polymerization catalyst.
The Friedel-Crafts catalyst can comprise an organometallic compound of the formula:

R9nM' Tn"

wherein M' is a metal selected from the group consisting of Ti, Al, Sn, Fe and Zn, R9 i~ a hydrocarbyl group (preferably a C1 to C7 alkyl group, and most preferably a ,, .~ , , ... :: .

Cl to C4 al~yl group), T is a halo~en or mixture of halogens, preferably chlorine or bromine, and most preferably chlorine, or a group of atoms corresponding to the conjugated base of strong Bronsted acids such a~
C104 or CF3S03 , and wherein n' is an integer of from O
to ~v - 1) and n" is an integer of from 1, wherein v is the valence of M', with the proviso that (n' + n") < or 3 v. Preferred are organoaluminum halides, aluminum halides, boron trifluoride, and titantium halides. Most preferred are organoaluminum chlorides. The foregoing organometallic halide compounds are known in the art and can be prepared by conventional means, e.g., by the process described in U.S. Patent No. 4,151,113 and the references cited therein. Other Lewis Acid catalysts comprise halides (preferably chlorides or bromides) e.g.
B and As, such as BC13, BF3, AsFs, and the mixed halides thereof such as BClF2, and the various "sesqui"
derivatives of elements of Group IIIA of the Periodic Table, such as ~2(C2H5)3(CF3S03)3, A12(C2Hs)3C13, and the like. Preferred catalysts are diethylaluminum chloride, ethylaluminum dichloride. The preferred Lewis acids are amongst the relatively "weak" Lewis acids such as diethylaluminum chloride. Stronger Lewis acids, such as boron chloride or titanium tetrachloride, depending on the solvent and monomer used, are useful although not preferred since control of molecular weight and MMD is not as good as with the "weak" Lewis acids. When the Lewis acids are too weak, no polymerization is obser~ed.
Most preferred Friedel-Crafts Lewis acid catalysts are organohaluminum halides.

Although insoluble catalysts may be used, the catalyst is preferably soluble in the reaction medium, and the exact concentration of the catalyst depends on the concentration of the molecule containing the "Y"
group. Preferably, the Lewis acid catalyst and N-~111313 containing initiator are charged to the polymerization zone in moles of initiator to moles of Lewis Acid catalyst in a ratio of greater than 3.1 to 1, preferably from 4:1 to 30:1 and more preferably from 5:1 to 20:1.
Molecular weight of the product may be controlled by controlling the ratio of the moles of monomer "M" to moles of initiator "T". Molecular weight increases a3 this latter ratio increases.
:. ~
Suitable solvents include, but are not limited to, low-boiling alkyl halides, whether they are mono- or polyhalides, the requirement being a reasonably low freezing point to be used at the preferred polymerization temperature. Illustrative solvents include alkanes (generally C2 to C10 alkanes, including normal alkanes such as propane, normal butane, normal pentane, normal hexane, normal heptane, normal octane, normal nonane and normal decane, and branched alkanes including isobutane, isopentane, isohexane, 3-methylpentane, 2,2~
dimethylbutane, 2,3-dimethylbutane and the like), alkenes and alkenyl halides (such as vinyl chloride), carbon disul~ida, chloroform, ethylchloride, N-butyl chloride, methylene chloride, methylchloride, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, sulfur dioxide, acetic anhydride, carbon tetrachloride, nitroethane, acetonitrile, neopentane, benzene, toluene, methylcyclohexane, chlorobenzene, ethylidene dichloride, propyl dichloride, to name a few of the representative liquid diluents or solvents useful in cationic polymerizations. Mixed solvents can also be used. The preferred solvents are methyl and ethyl chlorid~, methylene dichloride and propyl chloride, hexane, heptane and purified petroleum ether.

Any cationically polymerizable monomers may be used, including straight and branched chain alpha olefins, 2~11313 isoolefins, alicyclic monoolefins, cycloaliphatic compounds, styrene derivatives, indene and derivatives, and other monoolefins and heterocyclic cationically polymerizable monomers identified in Joseph P. Kennedy "Cationic Polymerization of Olefins: A Critical Inventory" pages 39 to 53 (John Wiley & Sons, 1975).
Vinyl ethers can also be used.

Exemplary of useful cationic polymerizable monomer~
are ethylene-cyclopropane, 2-cyclopropylpropylene, 1,1-dicyclo-propylethylene, cyclopentene, methylenecyclo-propane, methylenecyclobutane, methylenecyclopentene, ethylene-cyclopentene, 3-methyl-cyclopentene, 1-methylcyclo-pentene, 3-cyclopentyl-prop-1-ene, cyclohexene, 1-methylcyclohexene, 3-methylcyclohexene, methylenecyclo-hexane, l-methyl-2-methylenecyclohexane, l-methyl-3-methylenecyclohexane, ethylenecyclohexaner 3-cyclohexyl-prop-l-ene, methyl-enecycloheptene, methylenecyclooctene, methylene-cyclotridecene, cyclopropane, ethylcyclo-propane, 3-cyclopropylpropane, 2-cyclopropylpropane, l,1-dimethylcyclopropane, 1,2-dimethylcyclopropane, bicyclo t3.1.0~hexane, bicyclo[4.1.0]heptane, bicyclo[5.1.0] octans, bicyclo[6.1.0~nonane, bicyclotlO.l.O]tridecane, l-methyl-bicyclot4.1.0]heptane, 2-methyl-bicyclo [4.1.0]heptane, 1-methyl-bicyclo~5.1.0~octane, 1-methyl-bicyclo[6.1.0]nonane, spiro[2.2]pentane, spiro [2.4]heptane, spiro[2.5]octane, spirol[2.6]nonane, spirot2.7]decane, spirot2.12]pentadecane, bicyclo [6.1.0]non-3-ene, bicyclo[2.2.1]hept-2 -ene, 5-methyl-bicyclo[2.2.1~hept-2-ene, 2-methylene-bicyclo[2.2.1]
heptane, 2-methylene-3,3-bimethyl-bicyclo~2.2.1] heptane, 2-ethylene-bicyclot2.2.1]heptane, 2 tl-methylethylene~
-bicyclo[2.2.1]heptane, 6-methyl-bicyclo[2.2.2~oct-2-ene, styrene, methylstyrene, ethylstyrene, dodecylstyrene, isopropylstyrene, tertiarybutylstyrene, indene, biocyclopentane, 1-methylindene, 2-methylindene, 3-methylindene, 5-methylindene, 6-methylindene, 7-methylindene, 1,1-dimethylindene, 2,3-dimethylindene, 4,7-dimethylindene, and the like. Particularly valuable polymers can be prepared from isoolefins of from 4 to 20 carbon atoms or mixtures thereof to produce homopolymers and copolymers. Examples of such unsaturatQd hydrocarbons include, but are not restricted to, isobutylene, 2-methylbutene, 3-methylbutene-1, 4~
methylpentene-l, and beta-pinene. Other cationically polymerizable monomers which may be employed include heterocyclic monomers such as oxazolines and others known to add onto polarized covalent bonds.
~ . , .
Mixtures of cationically polymerizable monomers can -~
be employed as feedstock to the polymerization zone if desired, e.g., copolymers, terpolymers and higher interpolymers can be prepared by employing a mixture of two, three or more of the above monomers. ~ ~
,~,, Preferred feedstocks to the polymerization zone -comprise pure isobutylene and mixed C4 hydrocarbon feedstocks containing isobutylene, such as a C4 cut resulting from the thermal or catalytic cracking operation of, for example, naphtha. Thus, suitable isobutylene feedstocks will typically contain at least 10%, and up to 100% isobutylene, by weight, based on th~
weight of the feed. In addition to isobutylene, conventional C4 cuts suitable for use as a feedstock which are of industrial importance typically will contain between about 10 and 40% butene-l, between about lO and 40% butene-2, between about 40 and 60% isobutane, between about 4 and 10% n-butane, and up to about 0.5 butadiene, all percentages being by weight based on the feed weight.
Feedstocks containing isobutylene may also contain other non-C4 polymerizable olefin monomers in minor amounts, 2111313 ~ ~

e.g., typically less than about 25%, preferably less than about 10%, and most preferably less than 5%, such as propadiene, propylene and C5 olefins.

The term "polyisobutene" as employed herein is intended to include not only homopolymers of isobutylene but also copolymers of isobutylene and one or more other C4 polymerizable monomers of conventional C4 cuts as well~
as non-C4 ethylenically unsaturated olefin monomers containing typically from about 3 to about 6, and preferably from about 3 to about 5 carbon atoms, provided such copolymers contain typically at least 50t, preferably at least 65%, and most preferably at least 80%
isobutylene units, by weight, based on the polymer number average molecular weight (Mn). The substantially selective polymerizability of isobutylene under the conditions specified herein ensures the aforedescribed minimum isobutylene content.

Preferably the polymerization medium i~
substantially free of substances which are capable o~
initiating the catalysts other than the selected N-containing initiator (or mixtures of initiators) of this invention. Therefore, the polymerization medium preferably should be substantially free of added conventionally employed cationic polymerization initiators or promoters (i.e., cocatalysts) such a~
water, alcohols, carboxylic acids and acid anhydride~, HF, ethers or mixtures thereof. ~he alcohols which should be excluded are straight or branched chain, aliphatic, aromatic, or mixed aliphatic/aromatic alcohol~
containing from 1 to 30 carbon atoms. Likewise, tbe carboxylic acid, acid anhydride and/or ether promoters to be excluded are halogen substituted or unsubstituted, straight or branched chain, aliphatic, aromatic or mixed aliphatic/aromatic acids and ether containing from about 1 to about 30 carbon atoms.

The polymerization reaction medium preferably contains less than about 20 weight ppm of water, and less than 5 weight ppm of mercaptans, ali of which can function as poisons to Lewis Acid catalysts. The olefin feed can be treated to achieve the above desired levels by conventional means, e.g., by use of mole sieves and_ caustic washing to remove mercaptans and water to the above, and dienes (if desired).

The polymerization reaction may be conducted batchwise or in semicontinuous or continuous operation in which continuous streams of ingredients are delivered to the reactor, and an overflow of a slurry or solution of polymer is taken out for the recovery of the polymer therefrom. The preferred mode of reaction, however, is on a continuous basis using a continuous flow stirred reactor wherein feed is continuously introduced into the reactor and product continuously removed from the reactor. Typically, the monomer feed rate and product removal rate can be controlled.

The amount of Lewis Acid catalyst employed in the process of the present invention can be controlled in conjunction with the reaction temperature to achieve the target number average molecular weight of polymer but is also sought to be minimized to reduce undesired isomerizations believed to be induced thereby. The lower the initiator concentration in the reaction phase, the higher will be the polymer molecular weight and vice versa. Control of the polymer molecular weight within defined limits of a selected target polymer molecular weight is particularly important when the polvmer is intended for use in lubricating oils as a dispersant.

~ he catalyst amount also affects the conversion of the olefin monomer and yield of polymer, with higher amounts of Lewis Acid catalyst typically achieving higher conversions and yields. Strong Lewis Acid catalyst can lead to isomerizations which reduce the functionality of the polymer, and can produce chain transfer. Thus, in the process of the present invention, a weaker or milder Lewis acid is preferred.

In view of the above, and of the fact that the Lewis Acid is complexed more or less strongly by the nitrogen-containing groups present in the reaction medium, the catalyst should be employed in sufficient amount to enable the reaction to be a "living" cationic polymerization. In other words, the preferred catalyst concentration corresponds to about the quantitative formation of complex between the catalyst and the nitrogen-containing compound. More specifically, the catalyst employed at a ratio of moles of Lewis Acid to equivalents of nitrogen-containing functional groups of more than 3:1.1, preferably more than 4:1, more preferably more than 6:1, with a preferred range of from 3:1.1 to 30:1, more preferably 4:1 to 20:1 and most preferably 6:1 to 10:1. When using bifunctional initiators, the Lewis acid to initiator molar ratios is preferably from 3:1 to 5:1.

The polymerization reaction is conducted in the liquid phase to induce linear or chain type polymerization in contradistinction to ring or branch formation. If a feed is used which is ga~eous under ambient conditions, it is preferred to control the reaction pressure and/or dissolve the feed in an inert solvent or liquid diluent, in order to maintain the feed in the liquid phase. Typical C4 cuts comprising the feed are liquid under pressure and do not need a solvent or diluent.

Where the selected Lewis Acid catalyst is normally a gas (e.g., 8F3, and the like) the catalyst is typically introduced into the reactor as gas which is partially or -~
completely dissolved in a pressurized liquid in the reactor. ~ ~
':
Polymerization pressures can range typically from about 25 to about 500, and preferably from about 100 to about 300, kpa.

The N-containing initiator can be introduced to the monomer feed, or to the reaction mixture, in liquid form preferably separately from the Lewis Acid catalyst.
Preferably, the monomer is not contacted with the Lewis Acid . catalyst in the absence of the N-containing initiator of this invention.

The temperature at which the polymerizations are caxried out is important, since temperatures which are too high tend to decrease the functionalization degree.
The usual polymerization temperature range is between about -100C and +10C. Preferably, the polymerizations are performed at a temperature below about -10C, preferably below -20C, and preferably between -80C and -20C., e.g. at a temperature of about -50C.

The liquid phase reaction mixture temperature is ;~
controlled by conventional means. The particular reaction temperature is selected to achieve the target living behavior, and preferably is not allowed to vary more than + or -5C from the selected value, while th~
catalyst andlor promoter feed rate is varied to achieve the desired Mn to compensate for variations in monomer distribution in the feed composition.

The polymerization reaction can be conducted batchwise, semi-continuously or completely continuously in the conventional manner. Preferably, the reactor contents are stirred to achieve even catalyst distribution therein.

Average polymerization times can vary from 10 to about 120, preferably from about lS to about 45 (e.g., about 20 to about 30), and most preferably from about 15 to about 25 minutes.

The quench materials used to achieve quench are conventional and include the same materials discussed above as conventional cationic polymerization initiators or promoters with the exception that excess quantities are employed in amounts sufficient to deactivate t~e catalyst. Thus, while any amount of quenching medium effective to deactivate the catalyst may be employed, it is contemplated that such effective amount be sufficient to achieve a molar ratio of quench medium to Lewis Acid catalyst of typically from about 1:1 to about 100:1, preferably from about 3:1 to about 50:1, and most preferably from about 10:1 to about 30:1.

Quench is conducted by introducing the quench medium into the polymer product. Typically, the polymer product is maintained under pressure during the quench sufficient to avoid vaporization of any gaseous Lewis Acid catalyst (if one is employed) and other components of the mixture.
The temperature of the quenching medium is not critical and, e.g., can comprise room temperature or lower.
... .

21~13~3 In a batch system, quench can be performed in the reactor or preferably on the product after it is withdrawn from the reactor. In a continuous system, the quench will typically be performed after it exits the reactor.

After quench, the polymerization product i8 typically subjected to conventional finishing steps which include a caustic/H20 wash to extract catalyst residue, a_ hydrocarbon/aqUeous phase separation step wherein deactivated and extracted Lewis Acid catalyst is isolated in the aqueous phase, and a water washing step to remove residual amounts of neutralized catalyst. The polymer is then typically stripped in a debutanizer to remove unreacted volatile monomers, followed by a further stripping procedure to remove light end polymer (e.g., C24 carbon polymer). The stripped polymer is then typically dried by N2.

The present invention includes a polymer composition having the formula:

R((M)p(Y))n (IV) R is selected from at least one group consisting of H, a hydrocarbyl group, and a hydrocarbyl-substituted silyl group. R can be alkyl, aryl, alkylaryl and arylalkyl. Y
is selected from at least one group consisting of an azido, cyano, carbonylamino, thiocarbonylamino, cyanato and thiocyanato. A preferred Y is an azido group. L and M is at least one repeat unit derived from a cationically polymerizable monomer. Useful monomers inelude straight and branched chain alpha olefins, isoolefins, alicyclic monoolefins, cycloaliphatic compounds, styreno derivatives, indene and derivatives thereof, and other monoolefins and heteroeyclic monomers. "p" is an integer ,;:

greater than 1 and preferably sufficient to attain a desired molecular weiqht. "n" is an integer of at least 1, preferably 1 to 10 and most preferably 1 to 2.

The novel polymers of this invention compris~
terminally substituted polymers derived from any of tho above-discussed cationically polymerizable monomers. ThQ
polymers will preferably contain at least 5 monomer units (M) per polymer chain, and will more usually bo characterized by number average molecular weights of at least 350, or less and up to 15,000,000 or more with a useful range of from 350 to 15,000,000. The molecular weight range can be determined for particular polymers.
However, preferred polymer generally range from 500 to 2,000,000 with derivatives of functionalized polymer used as lubricant additives generally up to 100,000 and with specific ranges of from 500 to 20,000 for use as dispersants and 20,000 to 100,000 for use as viscosity improvers.

The polymers of the present invention can be conducted in a manner and under conditions to attain various molecular weight polymers. The polymers can be conveniently characterized based on molecular weight range. Polymers and copolymers of low, intermediate and high molecular weights can be prepared.

Low molecular weight polymers are considered to be polymers having a number average molecular weight of 1eB8 than 20,000, preferably from 500 to 10,000, (e.g. from 2,000 to 8,000) and most preferably from 1,500 to 5,000.
The low molecular weights are number average molecular weights measured by vapor phase osmometry. Low molecular weight polymers are useful in forming dispersants for lubricant additives.

~: ~ , , - : - ., : - ~ . :

21113~3 Medium molecular weight materials having a n~mber average molecular weight range of from 20,000 to 200,000, preferably 25,000 to loO,OoO; and more preferably from 25,000 to 80,000 are useful for viscosity i~provers for lubricating oil compositions, adhesive coatings, tackifiers and sealants. The medium number average molecular weights can be determined by memhrane osmometry.

The higher molecular weight materials have a number average molecular weight range of greater than 200,000 to 15,000,000, and specific embodiment of 300,000 to 10,000,000 and more specifically 500,000 to 2,000,000.
These polymers are useful in polymeric compositions and blends including elastomeric compositions. ~igher molecular weight materials having number average molecular weights of from 20,000 to 15,000,000 can be measured by gel permeation chromatography with universal cal$bration, or by light scattering as recited in Billmeyer, Textbook of Polymer Science, Second Edition, pp. 81 - 84 (1971).

The values of the ratio Mw/Mn, also referred to a~
molecular weight distribution, (MWD) are not critical.
However, a typical maximum Mw/Mn value of about 1. 5 i8~ -preferred with typical ranges of about 1.1 up to about 1.4. The ideal MWD is 1Ø ~ -Useful olefin monomers from which nitrogen~
containing polyalkenes of the present invention can be derived are polymer$zable monoolefin monomers characterized by the presence of one or more groups having carbon-carbon unsaturated double bonds (i.e., >C=C<); that is, they are monoolefinic monomers such a~

. : -'~11313 ethylene, propylene, butene-1, isobutene, and octene-1 or polyolefinic monomers (usually diolefinic monomers) such as butadiene-1,3 and isoprene.

Although the polyalkenes may include aromatic groups (especially phenyl groups and lower alkyl- and/or lower alkoxy-substituted phenyl groups such as para-(tert-butyl)phenyl) and cycloaliphatic groups such as would be obtained from polymerizable cyclic olefins or cycloaliphatic substituted-polymerizable acrylic olefins, the polyalkenes usually will be free from such groups.
Again, because aromatic and cycloaliphatic groups can be present, the olefin monomers from which the polyalkene~
are prepared can contain aromatic and cycloaliphatic groups.

Specific examples of polyalkenes include polypropylenes, polybutenes, ethylene-propylene copolymers, ethylene-tert-butene, styrene-isobutene copolymers, isobutene-(paramethyl)styrene copolymers, copolymers of octene-1, copolymers of 3,3-dimethyl-pentene-1 with hexene-1, and copolymers of isobutene and styrene. More specific examples of such interpolymers include copolymer of 95% (by weight) of isobutene with 5S
(by weight) of styrene; terpolymer of 98% of isobutene with 1% of piperylene and 1% of chloroprene; terpolymer of 95% of isobutene with 2% of butene-1 and 3% of hexene-l; terpolymer of 60% of isobutene with 20% of pentene-l;
and 20% of octene-1; terpolymer of 90% of isobutene with 2S of cyclohexene and 8% of propylene; and copolymer of 80% of ethylene and 20% of propylene. The poly(isobutene)s obtained by polymerization of C4 refinery stream having a butene content of about 35 to about 75% by weight and an isobutene content of about 30 to about 60% by weight. These polybutenes contain predominantly (greater than about 80% of the total repeating units) of isobutene repeating units of the configuration:

ICHl C~l Also useful are poly-n-butenes made by the process of the present invention. A preferred source of n-butenes is petroleum feedstreams such as Raffinate II.
These feedstocks are disclosed in the art such as in U.S.
Patent No. 4,952,739, hereby incorporated by reference.
More specifically, Raffinate II feedstock useful in the process of this invention comprises a mixture of ~ressure liquefied C4 hydrocarbons which comprise less than about 5% (preferably less than about 4.9 wt. %, e.g. from about 0.1 to 4.9 wt. % and typically greater than 1 or 2 wt. %) isobutylene, and at least about 12 wt. % (preferably at least about 15 wt. %, e.g. from about 15 to about 85 wt.
%) total normal-butenes (i.e., butene-l, cis- and trans-butene-2), together with 10 to 70% n-butane, isobutane and less than about 0.8 wt. %, e.g. most preferably about 0% butadiene. Typically, there is about 20 to 50% of 1 butene and 5 to 35% of 2-butene. The C4 feedstrenm preferably is substantially free of sulfur contaminants (e.g., mercaptans) e.g. <20 wppm H2 and 5 wppm S. The low S levels are desired to avoid undesired side~
reactions with the monomer, polymer and catalyst components, and to avoid the needs to resort to added expense and technical difficultie~ in removing the sulfur contaminants from the polymers thereby formed. Further, the C4 feedstream is preferably substantially anhydrous, t~at is, it contains less than about 300 wppm wat~r, based on the C4 monomers in the feedstream. When Raffinate I is used in a process to make methyl tertiary 2111 ~13 butyl ether, the Raffinate II obtained has some methanol residue. The C4 feedstream preferably contains less than about lOo ppm of methanol. The C4 products other than butenes (e.g., saturated C4 hydrocarbons), functions as diluent or solvent in the reaction mixture and are a non-critical aspect of this invention. The process of the present invention has enabled a new class of polymers and copolymers to be made from Raffinate II feedstock rendering a substantially low value feedstream as a valuable new raw material.

The living polymers of the present invention will --comprise terminally substituent "Y" groups on one end, and a terminal "R" group on the other end when ~he nitrogen-containing initiator comprises a R-Y or R*-Y
compound. R and R are discussed above with regard to formulae (Ia, Ib and Ic). The polymers have the reacted ~ -functionality and molecular weight distribution.
Illustrative of the monosubstituted polymers of this invention, therefore, are those set forth in Table A
below:

~A~LE A
R-tpolyolefin]-Y
R~-tpolyolefin]-Y
R PolYolefin Y
H- polyisobutylene -N3 CH3 polyisobutylene -N3 C2H5- polyisobutylene -N3 2 polyisobutylene -N3 CH3~- polyisobutylene -N3 ~- polyisobutylene -N3 (CH3)2cH~-polyisobutylene -N3 2111~13 polyisobutylene -N3 (cH3)2- polyisobutylene -N3 ~C(CH3)(C2H5)- polyisobutylene -N3 ~CH2C(CH3)2- polyisobutylene -N3 (CH3)3Si- polyisobutylene -N3 (c2Hs)3si- polyisobutylene -N3 (CH3)2Si(c2H5) polyisobutylene -N3 (CH3)si(c2H5)2- polyisobutylene N
(C3H7)3si- polyisobutylene 3 ~si (CH3)2- polyisobutylene -N3 (~)2Si(CH3)~ polyisobutylene -N3 Si- polyisobutylene -N3 (C6H13)35i- polyisobutylene N3 (CgH17)3si- polyisobutylene N3 H- polybutylene -N
CH3 polybutylene -N3 C2H5- polybutylene -N3 ~CH2- polybutylene -N3 CH3~- polybutylene -N3 ~- polybutylene -N3 (CH3)2CH~- polybutylene .

polybutylene -N3 ~C(CH3)2- polybutylene -N3 ~C(CH3)(C2H5)- polybutylene -N3 ~CH2C(CH3)2- polybutylene -N3 (CH3)3Si- polybutylene -N3 (c2Hs)3si- polybutylene -N3 (CH3)2Si(c2H5) polybutylene -N3 (CH3)Si(c2H5)2- polybutylene -N3 ': . ' ~

:' . :

tC3H7)35i- polybutylene -N3 ~si(CH3)2- . polybutylene -N3 (~)2Si(CH3)- polybutylene -N3 Si- polybutylene -N3 ~C6H13)3Si- polybutylene -N3 (cgHl7)3si- polybutylene N
H- polypropylene -N3 CH3 polypropylene -N~
C2Hs- polypropylene -N3 ~CH2- polypropylene N3 ;;:~
CH3~- polypropylene -N3 ~- polypropylene -N3 :~
(cH3)2cH~- polypropylene -N3 \
polypropylene -N3 (CH3)2- polypropylene -N3 ~C(CH3)(C2H5) polypropylene -N3 ~CH2C(CH3)2- polypropylene -N3 (~H3)3si- polypropylene -N3 (C2Hs)3si- polypropylene -N3 (CH3)2Si(c2H5) polypropylene -N3 (CH3)Si(C2H5)2- polypropylene -N3 (c3H7)3si- polypropylene -N3 i(CH3)2~ polypropylene -N3 (~)25i(CH3)- polypropylene -N3 Si- polypropylene -N3 6H13)3Si- polypropylene -N3 (CgH17)3si- polypropylene -N3 H- polystyrene -N3 CH3 polystyrene -N3 C2Hs- polystyrene -N3 ~CH2- polystyrene -N3 CH3~- polystyrene -N3 ~- polystyrene -N3 (CH3)2cH~- polystyrene -N3 polystyrene -N3 ~c(CH3)2- polystyrene ~C(CH3)(C2H5) polystyrene -N3 ~CH2C(CH3)2- polystyrene N3 ::
(CH3)3Si- polystyrene N
(c2Hs)3si- polystyrene -N3 (CH3)2Si(c2H5)- polystyrene ~ -(CH3)Si(C2H5)2- polystyrene -N3 (C3H7)3si- polystyrene -N3 i(CH3)2- polystyrene -N3 (~)2Si(CH3)- polystyrene -N3 Si- polystyrene -N3 (C6H13)3si- polystyrene -N3 (C3~l7)3si- polystyrene -N3 H- polymethylstyrene -~3 CH3 polymethylstyrene N3 :
C2H5- polymethylstyrene N
~CH2- polymethylstyrene -N3 CH3~- polymethylstyrene N3 ~- poly~ethylstyrene -~3 ~.
(cH3)2cH~- polymethylstyrene -N3 polymethylstyrene -N3 (CH3)2- polymethylstyrene -N3 ~C(CH3)(C2H5)- polymethylstyrene -N3 ~CH2C(CH3)2- polymethylstyrene N
(CH3)3Si- polymethylstyrene -N3 (c2Hs)3si- polymethylstyrene -N3 (CH3)2Si(C2H5)- polymethylstyrene N3 (CH3)Si(C2H5)2- polymethylstyrene -N3 (c3H7)3si- polymethylstyrene -N3 ,,~ ., ,. .. ... , , ,~:, . . . . .. . .

~si(CH3)2- polymethylstyrene -N3 (~)2Si(CH3)- polymethylstyrene -N3 si- polymethylstyrene -N3 :
(C8H13)35i- polymethylstyrene -N3 :~
(CsHl7)3si- polymethylstyrene -N3 .~
H- polyisobutylene NCO ::
CH3 polyisobutylene -NCO
C2H5- polyisobutylene -NCO
~CH2- polyisobutylene -NCO
CH3~- polyisobutylene -NCO
~- polyisobutylene -NCO
(cH3)2cH~- polyisobutylene -NCO

polyisobutylene -NCO

~C~CH3)2- polyisobutylene -NCO
~C(cH3)(c2H5) polyisobutylene -NCO
~CH2C(CH3)2- polyisobutylene -NCO
(CH3)35i- polyisobutylene -NCO :::
(C2Hs)3si- polyisobutylene -NCO
(CH3)25i(C2H5)- polyisobutylene -NCO
(CH3) si (C2H5)2- polyisobutylene -NCO
(C3H7)3Si- polyisobutylene -NCO
~si(CH3)2~ polyisobutylene -NCO
(~)25i(CH3)- polyisobutylene -NCO
Si- polyisobutylene -NCO
(c6Hl3)3si- polyisobutylene -NCO
(C8H17)35i- polyisobutylene -NCO
H- polybutylene -NCO
CH3 polybutylene -NCO
C2Hs- polybutylene -NCO
~CH2- polybutylene -NCO
CH3~- polybutylene -NCO
~- polybutylene -NCO
(cH3)2cH~- polybutylene -NCO

polybutylene -NCO

~C(CH3)2- polybutylene -NCO
~C(CH3)~C2H5) polybutylene -NCO
~CH2C(CH3)2- polybutylene -NCO
(CH3)3Si- polybutylene -NCO
(C2Hs)3si- polybutylene -NCO
(CH3)2Si(c2H5) polybutylene -NCO
(cH3)Si(C2Hs)2~ polybutylene -NCO
(C3H7)3si- polybutylene -NCO
~si(CH3)2- polybutylene -NCO
[~)2si(CH3)- polybutylene -NCO
Si- polybutylene -NCO
(C6H13)3si- polybutylene -NCO
(CgH17)3si- polybutylene -NCO
H- polypropylene -NCO
CH3 polypropylene -NCO
C2Hs- polypropylene -NCO
~CH2- polypropylene -NCO
c~3~- polypropylene -NCO
~- polypropylene -NCO
(CH3)2cH~- polypropylene -NCO

~ ,:
polypropylene -NCO

(CH3)2- polypropylene -NCO
~C(CH3)(C2H5) polypropylene -NCO
~CH2C(CH3)2- polypropylene -NCO
(CH3)3Si- polypropylene -NCO
(c2Hs)3si- polypropylene -NCO
(CH3)2Si(c2H5) polypropylene -NCO
(CH3)Si(C2H5)2- polypropylene -NCO
(C3H7)35i- polypropylene -NCO

-: 2~i~ 313 .

~si(CH3)2~ polypropylene -NCO
(~) 2Si ( CH3 ) - polypropylene -NCO
si- polypropylene -NCO
(C6H13)35i polypropylene -NCO
(CgH17)3si- polypropylene -NCO
H- polystyrene -NCO
CH3 polystyrene -NCO
C2HS- polystyrene -NCO
~CH2- polystyrene -NCO
CH3~- polystyrene -NCO
~- polystyrene -NCO
(CH3)2cH~- polystyrene -NCO

polystyrene -NCO

~C(CH3)2- polystyrene -NCO
~C(CH3)(C2H5) polystyrene -NCO
~CH2C(CH3)2- polystyrene -NCO
(CH3)3Si- polystyrene -NCO
(c2Hs)3si- polystyrene -NCO
(CH3)2Si(c2H5)- polystyrene -NCO
(CH3) si (C2H5)2- polystyrene -NCO
(C3~7)35i- polystyrene -NCO
~Si(CH3)2- polystyrene -NCO
(~)25i(CH3)- polystyrene -NCO
Si~ polystyrene -NCO
(C6H13)3si- polystyrene -NCO
(CgH17)3si- polystyrene -NCO
H- polymethylstyrene -NCO
CH3 polymethylstyrene -NCO
C2HS- polymethylstyrene -NCO
~CH2- polymethylstyrene -NCO
CH3~- polymethylstyrene -NCO
~- polymethylstyrene -NCO
(CH3)2cH~- polymethylstyrene -NCO

2111~,13 ~:

- 50 - . -polymethylstyrene -NC0 ~ ~

~C(CH3)2- polymethylstyrene -NC0 ~:
~C(CH3)(C2H5) polymethylstyrene -NC0 ~CH2C(CH3)2- polymethylstyrene -NC0 (CH3)3Si- polymethylstyrene -NC0 (C2Hs)3si- polymethylstyrene -NC0 (CH3)2si(C2H5) polymethylstyrene -NC0 (CH3)Si(C2H5)2- polymethylstyrene -NC0 ~ :
(C3H7)3si- polymethylstyrene -NC0 : :
~si ( CH3)2- polymethylstyrene -NC0 (~)2si(CH3)- polymethylstyrene -NC0 Si- polymethylstyrene NC0 (C6H13)3Si- polymethylstyrene -NC0 (CeHl7)3si- polymethylstyrene -NC0 H- polyisobutylene -CN
CH3 polyisobutylene -CN :
c2Hs- polyisobutylene -CN
~CH2- polyisobutylene -CN
C~3~- polyisobutylene -CN
~- polyisobutylene -CN
(C~3)2CH~- polyisobutylene -CN

polyisobutylene -CN

~C(CH3)2- polyisobutylene -CN
~C(CH3)(C2H5)- polyisobutylene -CN
~CH2C(CH3)2- polyisobutylene -CN
(CH3)35i- polyisobutylene -CN
(C2Hs)3si- polyisobutylene -CN
(CH3)2Si(C2Hs)- polyisobutylene -CN
(CH3)Si(C2H5)2- polyisobutylene -CN
(c3H7)3si- polyisobutylene -CN

~ '.

11131~

~si(CH3)2- polyisobutylene -CN
(~) 2Si (CH3 ) - polyisobutylene -CN
Si- polyisobutylene -CN
(C6H13)3si- polyisobutylene -C~
(CBHl7)3si- polyisobutylene -CN
H- polybutylene -CN
CH3 polybutylene -CN
C2H5- polybutylene -CN-~CH2- polybutylene -CN
CH3~- polybutylene -CN
~- polybutylene -CN
(cH3)2cH~- polybutylene -CN

polybutylene -CN

(CH3)2- polybutylene -CN
~C(CH3)(C2H5) polybutylene -CN
~CH2C(CH3)2- polybutylene -CN
(CH3)3Si- polybutylene -CN
(c2Hs)3si- polybutylene -CN
(CH3)25i(C2H5) polybutylene -CN
(CH3)Si(C2H5)2- polybutylene -CN
(C3H7)3si- polybutylene -CN
i(CH3)2- polybutylene -CN
(~)2si(CH3)- polybutylene -CN
Si- polybutylene -CN
(C6H13)3Si- polybutylene -CN
(C8H17)3Si- polybutylene -CN : .
H- polypropylene -CN ~ ~-CH3 polypropylene -CN ~:
C2H5- polypropylene -CN
~CH2- polypropylene -CN
CH3~- polypropylene -CN
~- polypropylene -CN ~ -(cH3)2cH~- polypropylene -CN
. .

polypropylene -CN

~C(CH3)2- polypropylene -CN
~C(CH3)(C2H5) polypropylene -CN
~CH2C(CH3)2- polypropylene -CN
(CH3)3Si- polypropylene -CN
(C2H5)3si- polypropylene -CN
(CH3)25i(C2H5)- polypropylene -CN
(CH3)5i(C2H5)2- polypropylene -CN
(C3H7)3si- polypropylene -CN
~si(CH3)2~ polypropylene -CN
(~)25i(CH3)- polypropylene -CN
Si- polypropylene -CN
(C6H13)3si- polypropylene -CN
(CgH17)35i- polypropylene -CN
H- polystyrene -CN
CH3 polystyrene -CN
C2Hs- polystyrene -CN
~CH2- polystyrene -CN
CH3~- polystyrene -CN
~- polystyrene -CN
tCH3)2cH~- polystyrene -CN - ~`

polystyrene -CN -~
: ~:
~C(CH3)2- polystyrene -CN
~C(CH3)(C2H5)- polystyrene -CN
~CH2C(CH3)2- polystyrene -CN
(CH3)3Si- polystyrene -CN
(c2Hs)3si- polystyrene -CN
(CH3)2Si(c2H5) polystyrene -CN
(CH3)si(c2H5)2- polystyrene -CN
(C3H7)3si- polystyrene -CN

~' ~,., h: ; `' " .. ..

~si(CH3)2- polystyrene -CN
(~)2Si(CH3)- polystyrene -CN
Si- polystyrene -CN
(C6H13)3Si polystyrene -CN
(cgHl7)3si- polystyrene -CN
H- polymethylstyrene -CN
CH3 polymethylstyrene -CN
C2H5- polymethylstyrene -CN
~2- polymethylstyrene -CN
CH3~- polymethylstyrene -CN
~- polymethylstyrene -CN
(CH3)2CH~- polymethylstyrene -CN

polymethylstyrene -CN

~c(CH3)2- polymethylstyrene -CN
~C(CH3)(C2H5) polymethylstyrene -CN
~CH2C(CH3)2- polymethylstyrene -CN
(CH3)35i- polymethylstyrene -CN
(c2Hs)3si- polymethylstyrene -CN
(CH3)2Si(c2H5)- polymethylstyrene -CN ~::
(CH3)Si(C2H5)2- polymethylstyrene -CN ;~
(~3H7)3si- polymethylstyrene -CN
~si(CH3)2~ polymethylstyrene -CN
(~)25i(CH3)- polymethylstyrene -CN ~ ~
Si- polymethylstyrene -CN ~ ~:
(4H13)3si- polymethylstyrene -CN -~
(CgHl?)3si- polymethylstyrene -CN
H- polyisobutylene -OCN
CH3 polyisobutylene -OCN ~ :
C2H5- polyisobutylene -OCN
~CH2- polyisobutylene -OCN
CH3~- polyisobutylene -OCN

~- polyisobutylene -OCN
(CH3)2cH~- polyisobutylene -OCN

--` 2111313 polyisobutylene -OCN

~C(CH3)2- polyisobutylene -OCN
~C(CH3)(C2H5)- polyisobutylene -OCN
~CH2C(CH3)2- polyisobutylene -OCN
(CH3)3si- polyisobutylene -OCN
(C2Hs)3si- polyisobutylene -OCN
(CH3)2Si(C2H5)- polyisobutylene -OCN
(cH3)si(c2H5)2- polyisobutylene -OCN
(C3H7)3si- polyisobutylene -oCN
i(CH3)2- polyisobutylene -OCN ::
~)2Si(CH3)- polyisobutylene -OCN
Si- polyisobutylene -OCN
(C6Hl3)3si polyisobutylene -OCN
(C8H17)35i- polyisobutylene -OCN
H- polybutylene -OCN
CH3 polybutylene -OCN ~ -C2H5- polybutylene -OCN
~CH2- polybutylene -OC~
CH3~- polybutylene -OCN
~- polybutylene -OCN
(CH3)2cH~- polybutylene -OCN

polybutylene -OCN

~C(CH3)2- polybutylene -OCN :~
~C(CH3)(C2H5) polybutylene -OCN
~CH2C(C~3)2- polybutylene -OCN
(CH3)3Si- polybutylene -OCN
(c2Hs)3sl- polybutylene -OCN
(CH3)2si(C2H5) polybutylene -OCN
(CH3)si(c2H5)2- polybutylene -OCN
(C3H7)3si- polybutylene -OCN

211131~

~Si(CH3)2- polybutylene -OCN
t~)25i(CH3)- polybutylene -OCN
Si- polybutylene -OCN
(C6H13)3Si polybutylene -OCN
(C8H17)3Si polybutylene -OCN
H- polypropylene -OCN
CH3 polypropylene -OCN
C2H5- polypropylene -OC~
~CH2- polypropylene -QCN
CH3~- polypropylene -OCN
~- polypropylene -OCN
(cH3)2cH~- polypropylene -OCN

polypropylene -OCN

~C(CH3)2- polypropylene -OCN
~C(CH3)(C2H5) polypropylene -OCN
~CH2C(CH3)2- polypropylene -OCN
(CH3)3Si- polypropylene -OCN
2H5)35i- polypropylene -OCN
(CH3)2Si(C2H5)- polypropylene -ocN
(CH3)5i(C2H5)2- polypropylene -OCN
(c3H7)3si- polypropylene -OCN
~si(CH3)2~ polypropylene -OCN
(~)25i(CH3)- polypropylene -OCN
Si- polypropylene -OCN
(C6H13)3si- polypropylene -oCN
(C8H17)35i- polypropylene -OCN
H- poly~tyrene -OCN
CH3 polystyrene -OCN
C2H5- polystyrene -OCN

~CHz- polystyrene -OCN
CH3~- polystyrene -ocN
~- polystyrene -OCN
(CH3)2cH~- polystyrene -OCN

.. -, , ~ . " ,. ~ , - ,: : , polystyrene -OCN

~C(CH3)2- polystyrene -OCN
~C~CH3)(C2H5)- polystyrene -OCN
~CH2C(CH3)2- polystyrene -OCN
(CH3)3si- polystyrene -OCN
(c2Hs)3si- polystyrene -OCN
(CH3)2Si(C2HS)- polystyrene -OCN
(CH3)Si(C2H5)2- polystyrene -OCN
(C3H7)3si- polystyrene OCN
~si(CH3)2- polystyrene -OCN
(~)25i(CH3)- polystyrene -OCN
Si- polystyrene -OCN
(C6H13)3si polystyrene -OCN
(CgH17)3si- polystyrene -OCN
H- polymethylstyrene-OCN ~ :
CH3 polymethylstyrene-OCN
C2Hs- polymethylstyrene-OCN
~CH2- polymethylstyrene-OCN
CH3~- polymethylstyrene -OCN ~;~
~- polymethylstyrene -OCN
(CH3)2cH~- polymethylstyrene -oCN

polymethylstyrene -OCN

~C(CH3)2- polymethylstyrene -OCN
~C~CH3)(C2H5) polymethylstyrene -OCN
~CH2C(CH3)2- polymethylstyrene -OCN
(CH3)3Si- polymethylstyrene -OCN
(c2Hs)3si- polymethylstyrene -OCN
(CH3)2Si(c2H5) polymethylstyrene -OCN
(cH3)si(c2Hs)2- polymethylstyrene -OCN
(C3H7)3si- polymethylstyrene -OCN

~* ~ ,"~
!,."

~Si(CH3)2- polymethylstyrene -OCN
(~)2Si(CH3)- polymethylstyrene -OCN
Si- polymethylstyrene -OCN
(C6H13)3si polymethylstyrene -OCN
(CsH17)35i polymet~ylstyrene -OCN
H- polyisobutylene -SCN
CH3 polyisobutylene -SCN
C2H5- polyisobutylene -SCN
~CH2- polyi~obutylene -SCN
CH3~- polyisobutylene -SCN
~- polyisobutylene -SCN
(CH3)2CH~- polyisobutylene -SCN

polyisobutylene -SCN

~C(CH3)2- polyisobutylene -SCN
~C(CH3)(C2H5) polyisobutylene -SCN
~CH2C(CH3)2- polyisobutylene -SCN
(cH3)3si- polyisobutylene -SCN
(C2H5)3si- polyisobutylene -8CN
(CH3)2Si(C2H5)- polyisobutylene -SCN
(CH3)Si(C2H5)2- polyisobutylene -SCN
(c3H7)3si- polyisobutylene -SCN
~si(CH3)2~ polyisobutylene -SCN
(~)25i(CH3)- polyisobutylene -SCN
5i- polyisobutylene -SCN
(C6H13)3Si- poiyisobutylene -SCN
(C3H17)35i- polyisobutylene -SCN
H- polybutylene -SCN
CH3 polybutylene -SCN
C2H5- polybutylene -8CN

~CH2- polybutylene -SCN
CH3~- polybutylene -SCN
~- polybutylene -SCN
(CH3)2C~ polybutylene -SCN

polybutylene -SCN

~C(CH3)2- polybutylene -SCN
~C(CH3)(C2H5) polybutylene -~CN
~CH2C(CH3)2- polybutylene -SCN
(CH3)3Si- polybutylene -SCN
(c2Hs)3si- polybutylene -8CN ~-(CH3)2Si(C2H5)- polybutylene -SCN
(CH3)Si(C2H5)2- polybutylene -SCN ~ ~;
(C3H7)3si- polybutylene -SCN
i(CH3)2- polybutylene -SCN
(~)2Si(CH3)- polybutylene -SCN
5i- polybutylene -SCN
(4H13)3si- polybutylene -SCN
(C8H~7)3si- polybutylene -8CN
H- polypropylene -SCN
CH3 polypropylene -6CN
C2H5- polypropylene -SCN
~CH2- polypropylene -8CN
CH3~- polypropylene -SCN
~- polypropylene -SCN
(C83)2cH~- polypropylene -SCN

polypropylene -SCN

~C(CH3)2- polypropylene -SCN
~C(CH3)(C2H5)- polypropylene -SCN
~CH2C(CH3)2- polypropylene -SCN
(CH3)3Si- polypropylene -SCN
(C2Hg)3si- polypropylene -SCN
(CH3)2si(C2H5) polypropylene -SCN
(CH3)Si(C2H5)2- polypropylene -SCN
(C3H7)3Si- polypropylene -SCN

211131c) i(CH3)2- polypropylene -SCN
(~)25i(CH3)- polypropylene -SCN
Si- polypropylene -SCN -(C6H13)3Si- polypropylene -SCN
(C8H17)3Si- polypropylene -SCN
H- polystyrene -SCN
CH3 polystyrene -SCN ~;
C2H5- polystyrene -SCN
~CH2- polystyrene -SCN ~ ;
CH3~- polystyrene -5CN
~- polystyrene -SCN S
(CH3)2cH~- polystyrene -SCN

polystyrene -SCN

~C(CH3)2- polystyrene -SCN ~ . ~
~C(CH3)~C2H5) polystyrene -SCN : :
~CH2C(CH3)2- polystyrene -SCN
(CH3)35i- polystyrene -SCN
(C2Hs)35i- polystyrene -SCN
(CH3)2Si(C2H5) polystyrene -SCN ::
(CH3)Si(C2H5)2- polystyrene -SCN : ~
(C3H7)3si- polystyrene -SCN ~ ~:
i(CH3)2- polystyrene -SCN
(~)2si(CH3)- polystyrene -SCN
Si- polystyrene -SCN.
(C6H13)3Si- poiystyrene -SCN
(C8H17)35i- polystyrene -SCN
H- polymethylstyrene -SCN
CH3 polymethylstyrene -SCN
C2H5- polymethylstyrene -SCN
~CH2- polymethylstyrene -SCN
CH3~- polymethylstyrene -SCN
~- polymethylstyrene -SCN
(CH3)2cH~- polymethylstyrene -SCN

polymethylstyrene -SCN

~C(CH3)2- polymethylstyrene -SCN
~C(CH3)(C2Hs)- polymethylstyrene -SCN
~CH2C(CH3)2- polymethylstyrene -SCN
(CH3)3Si- polymethylstyrene -SCN
(c2Hs)3si- polymethylstyrene -SCN
(CH3)2Si(C2H5) polymethylstyrene -SCN
(CH3)Si(C2H5)2- polymethylstyrene -SCN
(c3H7)3si- polymethylstyrene -SCN
~si(cH3)2- polymethylstyrene -SCN ~:
(~)2si(CH3)- polymethylstyrene -SCN
Si- polymethylstyrene -SCN
(C6H13)3si- polymethylstyrene -SCN
(CgHl7)3si- polymethylstyrene -SCN
H- polyisobutylene -NCS
CH3 polyisobutylene -NCS
C2Hs- polyisobutylene -NCS
~CH2- polyisobutylene -NCS
CH3~- polyisobutylene -NCS
~- polyisobutylene -NCS
(CH3)2cH~- polyisobutylene -NCS

polyisobutylene -NCS

(CH3)2- polyisobutylene -NCS
~C(CH3)(C2H5)- polyisobutylene -NCS
~H2C~CH3)2- polyisobutylene -NCS
(CH3)3Si- polyisobutylene -NCS
(c2Hs)3si- polyisobutylene -NCS
(CH3)2Si(c2H5)- polyisobutylene -N~S
(cH3)si(c2H5)2- polyisobutylene -NCS
(C3H7)3si- polyisobutylene -NCS

211~3~

- 61 - ~ :

~si(CH3)2- polyisobutylene -NCS
(~)2Si(CH3)- polyisobutylene -NCS
Si- polyisobutylene -NCS :~
(C6H13)35i- polyisobutylene -NCS
(C8Hl7)3si- polyisobutylene -NCS -~
H- polybutylene -NCS : :
CH3 polybutylene -NCS
C2H5- polybutylene -NCS :
~CH2- polybutylene -NCS ~: :
CH3~- polybutylene -NCS
~- polybutylene -NCS :::
(CH3)2cH~- polybutylene -NCS

polybutylene -NCS :~
: ~ ' :' ~ -(CH3)2- polybutylene -NCS
~C(CH3)(C2H5)- polybutylene -NCS
~CH2C(CH3)2- polybutylene -NCS
(CH3)35i- polybutylene -NCS
(c2Hs)3si- polybutylene -NCS
(CH3)25i(C2HS)- polybutylene -NCS
(CH3)5i(C2H5)2- polybutylene -NCS -~
(C3H7)3si- polybutylene -NCS
i(CH3)2- polybutylene -NCS
(~)2Si(CH3)- polybutylene -NCS
Si- polybutylene -NCS
(C6H13)3si- polybutylene -NCS
(CgH17)3si- polybutylene -NCS
H- polypropylene -NCS
CH3 polypropylene -NCS
C2H5- polypropylene -NCS
~CH2- polypropylene -NCS
CH3~- polypropylene -NCS
~- polypropylene -NCS
(cH3)2cH~- polypropylene -NCS

21~ 1313 polypropylene -NCS

~C(CH3)2- polypropylene -NCS
~c(CH3)(c2H5)- polypropylene -NCS
~CH2C(CH3)2- polypropylene -NCS
(CH3)3Si- polypropylene -NCS
(C2Hs)3si- polypropylene -NCS
(CH3)2Si(c2H5)- polypropylene NCS -(CH3)Si(C2H5)2- polypropylene -NCS
(C3H~)3Si- polypropylene -NCS
~si(CH3)2- polypropylene -NCS
(~)25i(CH3)- polypropylene -NCS
Si- polypropylene -NCS
(C6H13)3Si- polypropylene -NCS
(C3H17)3si- polypropylene -NCS
H- polystyrene -NCS
CH3 polystyrene -NCS
C2H5- polystyrene -NCS
~CH2- polystyrene -NCS
CH3~- polystyrene -NCS
~- polystyrene -NCS
(CH3)2CH~- polystyrene -NCS

polystyrene -NCS

(CH3)2- polystyrene -NCS
~C(CH3)(C2H5) polystyrene -NCS
~CH2C(CH3)2- polystyrene -NCS
(CH3)3Si- poly~tyrene -NCS
(c2Hs)3si- polystyrene -NCS
(CH3)2Si(c2H5)- polystyrene -NCS
(CH3)Si(c2H5)2- poly~tyrene -NCS
(C3H7)3si- polystyrene -NCS

'~111313 - 63 - ~
:,, i(CH3)2- polystyrene -NCS
(~)2Si(CH3)- polystyrene -NCS
si- polystyrene -NCS ~.
(C6~l3)35i- polystyrene -NCS
(C8H17)35i- polystyrene -NCS
H- polymethylstyrene -NCS
CH3 polymethylstyrene -NCS
C2H5- polymethylstyrene -NCS :
~CH2- polymethylstyrene -NCS ~:
CH3~- polymethylstyrene -NCS
~- polymethylstyrene -NCS
(CH3)2CH~- polymethylstyrene -NCS

polymethylstyrene -NCS

~C(CH3)2- polymethylstyrene -NCS
~C(CH3)(C2H5) polymethylstyrene -NCS
~CH2C(CH3)2- polymethylstyrene -NCS
(CH3)3si- polymethylstyrene -NCS
(c2Hs)3si- polymethylstyrene -NCS
(CH3)2Si(C2H5)- polymethylstyrene -NCS
(CH3)Si(C2H5)2- polymethylstyrene -NCS
(C3H7)3si- polymethylstyrene -NCS
i(CH3)2- polymethylstyrene -NCS
(~)25i(CH3)- polymethylstyrene -NCS
Si- polymethylstyrene -NCS
(4Hl3)3S$- polymethylstyrene -NCS
(CgH17)3si- polymethylstyrene -NCS

When a poly-functional initiator is employed, such as the bifunctional initiator of Formula III abova, the polymers will comprise terminal Y-groups on each end of the polymer and a "R" group within the polymer chain, -211~313 e.g., substantially at the center of the polymer chain.
Illustrative of the poly-substituted polymers of this invention therefore are those set forth in Table B below:

TABLE B
y-tpolyolefin~-R-tpolyolefin]-y Pol~olefin ~ y polyi~obutylene -C3H6- -N3 polyisobutylene -C4H8- -N3 polyisobutylene -C5Hlo~ -N3 polyisobutylene -C6H12- -N3 polyisobutylene -C8H16- -N3 polyisobutylene -CloH2o- -N3 polyisobutylene -C12H24- -N3 polyisobutylene -C18H36- -N3 polyisobutylene -C(Me)2CH2C(Me)2- -N3 polyisobutylene -CH(Et)C3H6- -N3 polyisobutylene -C(Et12C2H4C(Et)2- -N3 polyisobutylene -Si(Me)2CH2Si(Me)~- -N3 polyisobutylene -Si(Et)(Me)C2H5Si(Et)(Me)- -N3 polyisobutylene -Si(Et)2C3H6Si(Et)2- -N3 polyisobutylene -~(Et)- -N3 polyisobutylene -CH2CH(~)- -N3 polybutylene -C3H6- -N3 polybutylene -C4H8- -N3 polybutylene -C5Hlo-polybutylene -C6H12- -N3 polybutylene -C8H16- -N3 polybutylene -cloH20- -N3 polybutylene -C12H24- -N3 polybutylene -C18H36- -N3 polybutylene -C(Me)2CH2C(Me)2- -N3 polybutylene -CH(Et)C3H6- 3 polybutylene -C(Et)2C2H4C(Et)2- -N3 polybutylene -Si(Me)2CH2Si(Me)2- -N3 A ~ C- ~

polybutylene -Si(Et)(Me)C2HsSi(Et)(Me)- -N3 polybutylene -Si(Et)2C3H6Si(Et)2- -N3 polybutylene -~(Et)- -N3 polybutylene -CH2CH(~)- -N3 polypropylene -C3H6- N3 polypropylene -C4H8- -N3 polypropylene -C5H1o- -N3 polypropylene -C6H12- -N3 polypropylene -C8H16- -N3 polypropylene -ClOH20 -N3 polypropylene -C12H24- -N3 polypropylene -C18H36 -N3 polypropylene -c(Me)2cH2ctMe)2- -N3 polypropylene -CH(Et)C3H6- -N3 polypropylene -C(Et)2C2H4C(Et)2- N3 polypropylene -Si(Me)2CH2Si(Me)2- -N3 polypropylene -si(Et)(Me)c2Hssi(Et)(Me)- -N3 polypropylene -Sl(Et)2C3H6Si(Et)2- -N3 polypropylene -~(Et)- -N3 polypropylene -CH2CH(~)- -N3 polystyrene -C3H6- -N3 polystyrene -C4H8- -N3 polystyrene -C5H1o- -N3 polystyrene -C6H12- -N3 polystyrene -C8H16- N3 polystyrene -ClOH20 -N3 polystyrene -C12H24- -N3 polystyrene -C18H36- -N3 polystyrene -C(Me)2CH2C(Me)2- -N3 polystyrene -CH(Et)C3H6- -N3 polystyrene -C(Et)2C2H4C(Et)2- -N3 polystyrene -Sl(Me)2CH2Si(Me)2~ -N3 polystyrene -Si(Et)(Me)C2H5Si(Et)(Me)- -N3 polystyrene -Si(Et)2C3H6Si(Et)2- -N3 polystyrene -~(Et)- -N3 polystyrene -CH2CH(~)- -N3 21113~3 polymethylstyrene -C3H6- -N3 polymethylstyrene -C4H8- -N3 polymethylstyrene -C5Hlo~ -N3 polymethylstyrene -C6H12- -N3 polymethylstyrene -C8H16- -N3 polymethylstyrene -ClOH20- -N3 polymethylstyrene -ClzH24~ -N3 polymethylstyrene -C18H36- -N3 polymethylstyrene -C(Me)2CH2C(~e)2- -N3 polymethylstyrene -CH(Et)C3H6- -N3 polymethylstyrene -C(Et)2C2H4C(Et~2- -N3 polymethylstyrene -si (Me)2CH25i(Me)2~ -N3 polymethylstyrene -si(Et)(Me)c2Hssi(Et)(Me)- -N3 polymethylstyrene -si (Et~2C3H65i(Et)2- -N3 polymethylstyrene -~(Et)- -N3 polymethylstyrene -CH2CH(~)- -N3 polyisobutylene -C3H6- -NCO
polyisobutylene -C4Hg- -NCO
polyisobutylene -C5H1o- -NCO
polyisobutylene -C6H12- -NCO
polyisobutylene -CgH16- -NCO
polyisobutylene -CloH2o- -NCO
polyisobutylene -C12H24- -NCO
polyisobutylene -C18H36- -NCO
polyisobutylene -C(Me)2CH2C(Me)2- -NCO
polyisobutylene -CH(Et)C3H6- -NCO
polyisobutylene -C(Et)2C2H4c(Et)2- -NCO
polyisobutylene -si (Me)2cH2si(Me)2- -NCO
polyisobutylene -Si(Et)(Me)C2H55i(Et)(Me)- -NCO
polyisobutylene -Si(Et)2C3H65i(Et)2- -NCO
polyisobutylene -~(Et)- -NCO
polyisobutylene -CH2CH(~)- -NCO
polybutylene -C3H6- -NCO
polybutylene -C4HB- -NCO
polybutylene -CsHlo- -NCO
polybutylene -C6H12- -NCO

21113~3 polybutylene -CgH16- -NCO
polybutylene -cloH20~ -NCO
polybutylene -C12H24- -NCO
polybutylene -clgH36- -NCO
polybutylene -C(Me)2CH2C(Me)2- -NCO
polybutylene -CH(Et)C3H6- -NCO
polybutylene -C(Et)2C2H4C(Et)2- -NCO
polybutylene -Si(Me)2CH2Si(Me)2- -NCO
polybutylene -Si(Et)(Me)C2HsSi(Et)(Me)- -NCO
polybutylene -Si(Et)2C3H6Si(Et)2- -NCO
polybutylene -~(Et)- -NCO
polybutylene -CH2CH(~ NCO
polypropylene -C3H6- -NCO
polypropylene -C4Hg- -NCO
polypropylene -CsHlo- -NCO
polypropylene -C6H12- -NCO
polypropylene -CgH16- -NCO
polypropylene -CloH2o- -NCO
polypropylene -C12H24- -NCO
polypropylene -C18H36 -NCO
polypropylene -C(Me)2CH2C(Me)2- -NCO
polypropylene -CH(Et)c3H6- -NCO
polypropylene -C(Et)2C2H4C(Et)2- -NCO
polypropylene -si (Me)2CH2Si(Me)2- -NCO
polypropylene -Sl(Et)(Me)C2H5Si(Et)(Me)- -NCO
polypropylene -Sl(Et)2C3H6Si(Et)2- -NCO
polypropylene -O(Et)- -NCO
polypropylene -CH2CH(~)- -NCO
polystyrene -C3H6- -NCO
polystyrene -C4Hg- -NCO
polystyrene -CsHlo- -NCO
polystyrene -C6H12- -NCO
polystyrene -C8H16- -NCO
polystyrene -ClOH20- -NCO
polystyrene -C12H24- -NCO
polystyrene -C18H36- -NCO

.: : :~ . : -~" . . . .

polystyrene -C(Me)2CH2C(Me)2~ -NCO
polystyrene -CH(Et)C3H6- -NCO
polystyrene -C(Et)2C2H4C(Et)2- -NCO
polystyrene -Si(Me)2CH2Si(Me)2- -NCO
polystyrene -Si(Et)(Me)C2HsSi(Et)(Me)- -NCO
polystyrene -si(Et)2c3H6si(Et)2- -NCO
polystyrene -~(Et)- -NCO
polystyrene -CH2CH~)- -NCO
polymethylstyrene -C3H6- -NCO
polymethylstyrene -C4H8- -NCO
polymethylstyrene -C5Hlo- -NCO
polymethylstyrene -C6H12- -NCO
polymethylstyrene -C8H16- -NOO
polymethylstyrene -ClOH20- -NCO
polymethylstyrene -C12H24- -NCO
polymethylstyrene -C18H36- -NCO
polymethylstyrene -C~Me)2CH2C(Me)2- -NCO
polymethylstyrene -CH(Et)C3H6- -NCO
polymethylstyrene -C(Et)2C2H4C(Et)2- -NCO
polymethylstyrene -si (Me)2CH2Si(Me)2~ -NCO
polymethylstyrene -Si(Et)(Me)C2HsSi(Et)(Me)- -NCO
polymethylstyrene -Si(Et)2C3H6Si(Et)2- -NCO
polymethylstyrene -~(Et)- -NCO
polymethylstyrene -CH2CH(~)- -NCO
polyisobutylene -C3H6- -NCS
polyisobutylene -C4H8- -NCS
polyisobutylene -C5H10- -NCS
polyisobutylene -C6H12- -NCS
polyisobutylene -CgH16- -NCS
polyisobutylene -CloH2o- -NCS
polyisobutylene -C12H24- -NCS
polyisobutylene -C18H36- -NCS
polyisobutylene -c(Me)2cH2c(Me)2- -NCS
polyisobutylene -CH(Et)C3H6- -NCS
polyisobutylene -C(Et)2C2H4C(Et)2- -NCS
polyisobutylene -S~(Me)2CH2Si(Me)2- -NCS

.
..

21~1313 polyisobutylene -Si(Et)(Me)C2HsSi(Et)(Me)~ -NCS
polyisobutylene -Si(Et)2C3H6Si(Et)2- -NCS
polyisobutylene -~(Et)- -NCS
polyisobutylene -CH2CH(~ NCS
polybutylene -C3H6- -NCS
polybutylene -C4Hg- -NCS
polybutylene -CsHlo- -NCS
polybutylene -C6H12- -NCS
polybutylene -CgH16- -NCS
polybutylene -ClOH20- -NCS
polybutylene -C12H24- -NCS
polybutylene -C18H36- -NCS
polybutylene -C(Me)2CH2C(Me~2~ -NCS
polybutylene -CH(Et)C3H6- -NCS
polybutylene -C(Et)2C2H4C(Et)2- -NCS
polybutylene -si (Me)2CH2Si(Me)2~ -NCS
polybutylene -Si(Et)(Me)C2HsSi(Et)(Me)~ -NCS
polybutylene -Si(Et)2C3H6Si(Et)2- -NCS
polybutylene -~(Et)- -NCS
polybutylene -CH2CH(~)- -NCS
polypropylene -C3H6- -NCS
polypropylene -C4Hg- -NCS
polypropylene -CsH1o- -NCS
polypropylene -C6H12- -NCS
polypropylene -CgH16- -NCS
polypropylene -ClOH20- -NCS
polypropylene -C~2H24- -NCS
polypropylene -C18H36- -NCS
polypropylene -c(Me)2cH2c(Me)2- -NCS
polypropylene -CH(Et)C3H6- -NCS
polypropylene -C(Et)2C2H4C(Et)2- -NCS
polypropylene -Si(Me)2CH2Si(Me)2~ -NCS
polypropylene -Si(Et)(Me)C2H5Si(Et)(Me)- -NCS
polypropylene -Si(Et)2C3H6Si(Et)2- -NCS
polypropylene -~(Et)- -NCS
polypropylene -CH2CH(~)- -NCS

polystyrene -C3H6- -NCS
polystyrene -C4H8- -NCS
polystyrene -C5Hlo- -NCS
polystyrene -C6H12- -NCS
polystyrene -C8H16- -NCS
polystyrene -CloH2o- -NCS
polystyrene -C12H24- -NCS
polystyrene -C18H36- -NCS
polystyrene -C(Me?2CH2C(Me)2- -NCS
polystyrene -CH(Et)C3H6- -NCS
polystyrene -C(Et)2C2H4C(Et)2- -NCS
polystyrene -si (Me)2CH2Si(Me)2~ -NCS
polystyrene -Si(Et)(Me)C2H5Si(Et)(Me)- -NCS
polystyrene -si(Et)2C3H6Si(Et)2~ -NCS
polystyrene -~(Et)- -NCS
polystyrene -CH2CH(~)- -NCS
polymethylstyrene -C3H6- -NCS
polymethylstyrene -C4H8- -NCS
polymethylstyrene -C5Hlo- -NCS
polymethylstyrene -4 H12- -NCS
polymethylstyrene -C8H16- -NCS
polymethylstyrene -cloH20- -NCS
polymethylstyrene -C12H24- -NCS
polymethylstyrene -C18H36- -NCS
polymethylstyrene -C(Me)2CH2C(Me)2- -NCS
polymethylstyrene -CH(Et)C3H6- -NCS
polymethylstyrene -C(Et)2C2H4C(Et)2- -NCS
polymethylstyrene -si(Me)2CH2Si(Me)2- -NCS
polymethylstyrene -Si(Et)(Me)C2H5Si(Et)(Me)- -NCS
polymethylstyrene -Si(Et)2C3H6Si(Et)2- -NCS
polymethylstyrene -~(Et)- -NCS
polymethylstyrene -CH2CH~)- -NCS
polyisobutylene -C3H6- -OCN
polyisobutylene -C4H8- -OCN
polyisobutylene -C5Hlo- -OCN
polyisobutylene -C6H12- -OCN

, .. , .. ; , :

,: ' -` , ~
.. : , ' ' ` ~ ` , ' :.
.:',:. ~ ' : ' :

~1~131~

polyi~obutylene -C8H16- -OCN
polyisobutylene -CloH20- -OCN
polyisobutylene -C12H24- -OCN
polyisobutylene -C18H36- -OCN
polyisobutylene -C(Me)2CH2C(Me)2~ -OCN
polyisobutylene -CH(Et)C3H6- -OCN
polyisobutylene -c(Et)2c2H4c(Et~2- -OCN
polyisobutylene -Si(Me)2CH2Si(Me)2- -oCN
polyisobutylene -Si(Et)(Me)C2H5Si(Et)(Me)- -OCN
polyisobutylene -Si(Et)2C3H6Si(Et)2- -OCN
polyisobutylene -~(Et)- -OCN
polyisobutylene -CH2CH(~ OCN
polybutylene -C3H6- -OCN
polybutylene -C4H8- -OCN
polybutylene -C5Hlo- -OCN
polybutylene -C6H12- -OCN
polybutylene -C8H16- -OCN
polybutylene -C10H20 -OCN
polybutylene -C12H24- -OCN
polybutylene -ClgH36- -OCN
polybutylene -C(Me)2CH2C(Me)2- -OCN
polybutylene -CH(Et)C3H6- -OCN
polybutylene -C(Et)2C2H4C(Et)2- -OCN
polybutylene -Si(Me)2CH2Si(Me)2- -OCN
polybutylene -Si(Et)(Me)C2H5Si(Et)(Me)- -OCN
polybutylene -Si(Et)2C3H6Si[Et)2- -OCN
polybutylene -~(Et)- -OCN
polybutylene -CH2CH(~)- -OCN
polypropylene -C3H6- -OCN
polypropylene -C4H8- -OCN
polypropylene -C5Hlo~ -OCN
polypropylene -C6H12- -OCN
polypropylene -C8H16- -OCN
polypropylene -C10H20- -OCN
polypropylene -C12H24- - -OCN
polypropylene -C18H36- -OCN

~i, . , - , :,: : , . ~ ~ .
-: ~ . . . :
. .,:. .
, ,-. . .

polypropylene -C(Me)2CH2C(Me)2- -OCN
polypropylene -CH(Et)C3H6- -OCN
polypropylene -C(Et)2C2H4C(Et)2- -OCN
polypropylene -Si(Me)2CH25i(Me)2~ -OCN
polypropylene -si (Et)(Me)C2HsSi(Et)(Me)~ -OCN
polypropylene -Si(Et)2C3H6Si(Et)2- OCN
polypropylene -~(Et)- -OCN
polypropylene -CH2CH(~)- -OCN
polystyrene -C3H6- -OCN
polystyrene -C4H8- -OCN
polystyrene -CsHlo- -OCN
polystyrene -C6H12- -OCN
polystyrene -C8H16- -OCN
polystyrene -ClOH20- -OCN
polystyrene C12H24- -OCN
polystyrene -C18H36- -OCN
polystyrene -C(Me)2CH2C(Me)2~ -OCN
polystyrene -CH(Et)C3H6- -OCN
polystyrene -C(Et)2C2H4C(Et)2- -OCN
polystyrene -Si(Me)2CH2Si(Me)2- -OCN
polystyrene -Si(Et)(Me)C2HsSi(Et)(Me)- -OCN
polystyrene -si (Et)2C3H65i(Et)2- -OCN
polystyrene -~(Et)- -OCN
polystyrene -CH2CH(~)- -OCN
polymethylstyrene -C3H6- -OCN
polymethylstyrene -C4Hg- -OCN
polymethylstyrene -C5Hlo~ -OCN
polymethylstyrene -C6H12- -OCN
polymethylstyrene -CgH16- -OCN
polymethylstyrene -C10H20- -OCN
polymethylstyrene -C12H24- -OCN
polymethylstyrene -C18H36- -OCN
polymethylstyrene -C(Me)2CH2C(Me)2- -OCN
polymethylstyrene -CH(Et)C3H6 -OCN
polymethylstyrene -C(Et)2C2H4C(Et)2- -OCN
polymethylstyrene -Si(Me)2C~2Si(Me)2- -OCN

t .,~p~ * ~ ~h~ ..... ~.~,.. ~: ~

polymethylstyrene -Si(Et)(Me)C2HsSi(Et)(Me)- -OCN
polymethylstyrene -Si(Et)2C3H65i(Et)2- -OCN
polymethylstyrene -~(Et)- -OCN
polymethylstyrene -CH2CH(~)- -OCN
polyisobutylene -C3H6- -SCN
polyisobutylene -C4Hg- -SCN
polyisobutylene -C5H1o~ -SCN
polyisobutylene -C6H12- -SCN
polyisobutylene -CgH16- -SCN
polyisobutylene -CloH2o- -SCN
polyisobutylene -C12H24- -SCN
polyisobutylene -C18H36- -SCN
polyisobutylene -C(Me)2C~2C(Me)2~ -SCN
polyisobutylene -CH(Et)C3H6- -SCN
polyisobutylene -C(Et)2C2H4C(Et)2- -SCN
polyisobutylene -Si(Me)2CH2Si(Me)2~ -SCN
polyisobutylene -Si(Et)(Me)C2HsSi(Et)(Me)- -SCN
polyisobutylene -Si(Et)2C3H6Si(Et)2- -SCN
polyisobutylene -~(Et)- -SCN
polyisobutylene -CH2CH(~)- -SCN
polybutylene -C3H6- -SCN
polybutylene -C4H8- -SCN
polybutylene -CsH1o- -SCN
polybutylene -C6H12- -SCN
polybutylene -C8H16- -SCN
polybutylene -ClOH20- -SCN
polybutylene -C12H24- -SCN
polybutylene -C18H36- -SCN
polybutylene -C(Me)2CH2C(Me)2- -SCN
polybutylene -CH(Et)C3H6- -SCN
polybutylene -C(Et)2C2H4C(Et)2- -SCN
polybutylene -Si(Me)2CH2Si(Me)2- -SCN
polybutylene -Si(Et)(Me)C2H5Si(Et)(Me)- -SCN
polybutylene -Si(Et)2C3H6Si(Et)2- -SCN
polybutylene -~(Et)- -SCN
polybutylene -CH2CH(~)- -SCN

, : , polypropylene -C3H6- -SCN
polypropylene -C4H8- -SCN
polypropylene -C5H1o~ -SCN
polypropylene -C6H12- -SCN
polypropylene -C8H16- -5CN
polypropylene -ClOH20- -SCN
polypropylene -C12H24 -SCN
polypropylene -C18H36 -SCN
polypropylene -C(Me)2CH2C(Me)2- -SCN
polypropylene -CH(Et)C3H6- -SCN
polypropylene -C(Et)2C2H4C(Et)2- -SCN
polypropylene -Si(Me)2CH2Si(Me)2- -SCN
polypropylene -Si(Et)(Me)C2HsSi(Et)(Me)- -SCN
polypropylene -Si(Et)2C3H6Si(Et)2- -SCN
polypropylene -~(Et) -SCN
polypropylene -CH2CH(~)- -SCN
polystyrene -C3H6- -SCN
polystyrene -C4Hg- -SCN
polystyrene -C5H1o- -SCN
polystyrene -C6H12- -SCN
polystyrene -C8H16- -SCN
polystyrene -cloH20- -SCN
polystyrene -C12H24- -SCN
polystyrene -C18H36- -SCN
polystyrene -C(Me)2CH2c(Me)2 -SCN
polystyrene -CH(Et)C3H6- -SCN
polystyrene -C(Et)2C2H4C(Et)2- -SCN
polystyrene -Sl(Me)2CH2Si(Me)2~ -SCN
polystyrene -Si(Et)(Me)C2H5Si(Et)(Me)- -SCN
polystyrene -Si(Et)2C3H6Si(Et)2- -SCN
polystyrene -~(Et)- -SCN
polystyrene -CH2CH(~)- -SCN
polymethylstyrene -C3H6- -SCN
polymethylstyrene -C4H8- -SCN
polymethylstyrene -C5Hlo~ -SCN
polymethylstyrene -C6H12- -SCN

21113~3 polymethylstyrene -C8H16- -SCN
polymethylstyrene -CloH20- -SCN
polymethylstyrene -C12H24- -SCN
polymethylstyrene -C18H36- -SCN
polymethylstyrene -C(Me)2CH2C(Me)2- -SCN
polymethylstyrene -CH(Et)C3H6- -SCN
polymethylstyrene -C(Et)2C2H4C(Et)2- -SCN
polymethylstyrene -Si(Me)2CH2Si(Me)2~ -SCN
polymet~ylstyrene -Si(Et)~Me~C2H5Si(Et)(Me)- -SCN
polymethylstyrene -Si(Et)2C3H6Si(Et)2- -SCN
polymethylstyrene -~(Et)- -SCN
polymethylstyrene -CH2CH(~)- -SCN
polyisobutylene -C3H6- -CN
polyisobutylene -C4H8- -CN
polyisobutylene -C5Hlo- -CN
polyisobutylene -C6H12- -CN
polyisobutylene -C8H16- -CN
polyisobutylene -ClOH20- -CN
polyisobutylene -C12H24- -CN
polyisobutylene -C18H36- -CN
polyisobutylene -C(Me)2CH2C(Me)2- -CN
polyisobutylene -CH(Et)C3H6- -CN
polyisobutylene -C(Et)2C2H4C(Et)2- -CN
polyisobutylene -Si(Me)2CH25i(Me)2~ -CN
polyisobutylene -si(Et)(Me)c2HssitEt)(Me)- -CN
polyisobutylene -Si(Et)2C3H6Si(Et)2- -CN
polyisobutylene -~(Et)- -CN
polyisobutylene -CH2CH(~)- -CN
polybutylene -C3H6- -CN
polybutylene -C4H8- -CN
polybutylene -C5Hlo- -CN
polybutylene -C6H12- -CN
polybutylene -C8H16- -CN
polybutylene -ClOH20- -CN
polybutylene -C12H24- -CN
polybutylene -clgH36- -CN

... , ~, . " , .. .. . . . ...

21~ 1313 - 76 - ~:

polybutylene -c(Me)2cH2c(Me)2- -CN
polybutylene -CH(Et)C3H6- -CN
polybutylene -C(Et)2C2H4C(Et)2- -CN
polybutylene -Si(Me)2CH2Si(Me)2- -CN
polybutylene -Si(Et)(Me)C2HsSi(Et)(Me)- -CN
polybutylene -Si(Et)2C3H6Si(Et)2- -CN
polybutylene -~(Et)- -CN
polybutylene -CH2CH(~)- -CN
polypropylene -C3H6- -CN
polypropylene -C4H8- -CN
polypropylene -C5Hlo~ -CN
polypropylene -C6Hlz- -CN
polypropylene -C8H16- -CN
polypropylene -ClOH20- -CN
polypropylene -C12H24- -CN
polypropylene -C18H36- -CN
polypropylene -C(Me)2CH2C(Me)2- -CN
polypropylene -CH(Et)C3H6- -CN
polypropylene -C(Et)2C2H4C(Et)2- -CN
polypropylene -Si(Me)2CH25i(Me)2- -CN
polypropylene -Si(Et)(Me)C2HsSi(Et)(Me)- -CN
polypropylene -Si(Et)2C3H6Si(Et)2- -CN
polypropylene -~(Et)- -CN
polypropylene -CH2CH(~)- -CN
polystyrene -C3H6- -CN
polystyrene -C4H8- -CN
polystyrene -C5Hlo~ -CN
polystyrene -C6H12- -CN
polystyrene -C8H16- -CN
polystyrene -ClOH20- -CN
polystyrene -C12H24- -CN
polystyrene -C18H36- -CN
polystyrene -C(Me)2CH2C(Me)2- -CN
polystyrene -CH(Et)C3H6- -CN
polystyrene -C(Et)2C2H4C(Et)2- -CN
polystyrene -Si(Me)2CH2Si(Me)2- -CN

polystyrene -Si(Et)(Me)C2HsSi(Et)(Me)~ -CN
polystyrene -si(Et)2c3H6si(Et)2- CN
polystyrene -~(Et)- -CN
polystyrene -CH2CH(~- -CN
polymethylstyrene -C3H6- -CN
polymethylstyrene -C4H8- -CN
polymethylstyrene -CsHlo- -CN
polymethylstyrene -C6H12- -CN
polymethylstyrene -C8H16- -CN
polymethylstyrene -ClOH20- -CN
polymethylstyrene -C12H24- CN
polymethylstyrena -C18H36- -CN
polymethylstyrene -C(Me)2CH2C(Me)2- -CN
polymethylstyrene -CH(Et)C3H6- -CN
polymethylstyrene -C(Et)2C2H4ctEt)2- -CN
polymethylstyrene -si(Me)2CH25i(Me)2~-CN
polymethylstyrene -Si(Et)(~e)C2HsSi(Et)(Me)~ -CN
polymethylstyrene -Sl(Et)2C3H6Si(Et)2- CN
polymethylstyrene -~(Et)- -CN
polymethylstyrene -CH2CH(~)- -CN

The nitrogen functionalized polymeric material of the present invention are useful by incorporation and dissolution into an oleaginous material such as fuels and lubricating oils. When the polymers of this invention are used in normally liquid petroleum fuels such as middle distillates boiling from about 65C to 430C, including kerosene, diesel fuels, home heating fuel oil, jet fuels, etc., a concentration of the polymers in the fuel in the range of typically from about 0.001 to about o.S, and preferably 0.005 to about O.lS wt. %, based on the total weight of the composition, will usually be employed. When the polymers of this invention are usad in lubricating oils, a concentration of the polymers in ' ' ' ; ~ " ' ~ ' ~
'~ ' " : ' ~ ,' ~ " ' ' ' ' , :

the lubricating oil in the range of from about 0.01 to lS
wt. %, and preferably 0.5 to about 10 wt. %, ba~ed on the total weight of the lubricating composition, will usually be employed. The polymers may be employed in lubricating oil compositions which employ a ba~e oil in which the polvmers are dissolved or dispersed. Such base oils m~y be natural or synthetic. Base oils suitable for use in preparing the lubricating oil compositions of the present invention include those conventionally employed as _ crankcase lubricating oils for spark-ignited and compression-ignited internal combustion engines, such a~
automobile and truck engines, marine and railroad die~el engines, and the like. Advantageous results are also achieved by employing the polymers of the present invention in base oils conventionally employed in andlor adapted for use as power transmitting fluids such as automatic transmission fluids, tractor fluids, universal tractor fluids and hydraulic fluids, heavy duty hydraulic fluids, power steering fluids and the like. Gaar lubricants, industrial oils, pump oils and other lubricating oil -ompositions can also benefit from the incorporation therein of the polymers of the present invention. These lubricating oil formulations conventionally contain several different types of additives that will supply the characteristics that are required in the formulations. Among these types of additives are included viscosity index improvers, antioxidants, corrosion inhibitors, detergents, dispersants, pour point depressants, antiwear agents, friction modifiers, etc. ~ ;

The polymers of this invention are also useful a~
polymerization additives, e.g. as cross-linking agents and polymerization comonomers, and the polymers can be employed to prepare molded or extruded articles such as films. The polymers of this invention are also useful 2111'~13 components for the synthesis of block copolymers and star copolymers. These polymer m~terials c~n be used as compatibilizer or as thermoplastic elastomers.

Functionalization The polymers of the present invention include~
functional reaction products of the above-recited polymers containing nitrogen groups, particularly -N3, -NCO, -OCN, -SCN, -CN and -NCS groups. Such functional reaction products are the reaction product of the nitrogen functional groups of the nitrogen-containing polymer with a functional reactant compound. This is illustrated by the reaction of -N3 (azido) containing polymer derived from formula IV, where -Y is -N3, i.Q., (R(M)p(-N3))n where R, M, p and n are as defined above.
For illustration purposes n shall equal one.

The azido R(M)p-N3 can be reacted to form functional reaction product polymers containing the following functional groups:

.,..;

": . ~ ' ' . ... . .

N\ /N (1) R2 --C = C -R2 1 R(M)p\ ~ \ N (2) R22 /C = C R23 ;

O

R(M)pNR24R25;

R(M)pcsN;

R(M)p-OH;

R(M)pNCO; ~6) R(M)pR26coNR27R28;

R(~)p N (8) ~:
R29R30 - C \C - R31R32; .

R(M)pN; (9) :~ ~
.' ' ' ,`' .
R(M)pCH=NH; (10) R(M)pN=NR(M)p; ~11) .

R(M)pR33NBX2; and (12) R(M)pNR33 (13) -'~
': : -21~131~

wherein R20 to R33 are the same or different and can be selected from hydrogen, a hydrocarbyl group and a substituted hydrocarbyl group. R20 to R33 can be -~, and alkyl, aryl, alkylaryl, or arylalkyl group, X iB a halide, preferably a chloride group. Useful R20 to R33 alkyl groups include C1 to C22 hydrocarbyl groups with methyl, ethyl, propyl and butyl groups being particularly useful.

Reactions of azides to prepare the above function~l reactant product polymers include those of types known in the art. Typically, they can be conducted under mild conditions in a suitable solvent. A useful solvent i~
tetrahydrofuran (THF) at 0C - 100C and about atmosphere.
- .. :
The above functional reactant azide polymeric compounds can be prepared according to methods analogous to those disclosed.

Bastide et al., Cycloaddition di~olaire-1l3 aux alcvnes, Bulletin De La Societe Chimigue De France No~.
7-8, pp. 2555 - 2579 (1973), hereby incorporaed by reference, discloses a variety of reactions of azides beginning at p. 2574. A useful reaction of the present invention to form a polymer is triazole as follows:
R20-C~C-R21 + R(M)pN

( )P\N/ ~ N/ \N ~ ( )P
R20 - C=C R21 or R20 C-C R21 (l) (triazole) Such triazole are useful as lubricant additives.

, - .,.. - ~ - ,,, , . . ~ .. ~ :

.- . . ~ . - ::
~- : : , ::. ~ - - - :. -- . - .. :: - .: . , - .. : . .

2~11313 Bastide et al., Cycloaddition dipolaire-1,3 aux alcynes, Bulletin De La Societe Chimique De France, Nos.
9-10, pp. 2871 - 2887 (1973), hereby incorporated ffl reference, discloses a variety of reactions including the reactions of triazoles. A useful reaction of the present invention is the reaction of an anhydride, preSerably maleic anhydride with a triazole.
N ~ ~ (M)p ~C=C~ ~ N \ ~ (M)p N~ ~
O=C\ /C=O + N\ ~ ~ ~C=C~ (2) o HC=CH O=C\ /C=O

Compounds of formula (2) are useful as aditives to lubricant compositions. They can be further reacted with alcohols, metals, metal compounds and amines to form ~
polymeric compounds which are also useful as lubricant - ~-additives. -Xazankov et al., J. org. Chem. USSR 77,451 (1975) discloses the replacement of azo compounds. A useful -replacement reaction involving the azide functionalized p -~
polymer of the present invention follows~
:, .
R(M)p-N3 + NR24R25 ~ R(M)p-NR24~25 (3) Preferably at least one of R24 and R25 is an -H group.
With a preferred embodiment of formula (3) being R(M)pNH2. This amine can be used as an additive for lubricants. The conversion of azidQs to nitrile~ iS
disclosed in the Bull. Chem. Soc. of Japan, 49 p. 506 (1976) and the J. Org. Chem., Vol. 44, No. 16, p. 2951 (1976) hereby incorporated by reference. A useful reaction to decompose an azide of the present invention follows:

R(M)PCH2N3 cat-alyst' R~M)p-C~N (4) the R(M)pC--N can be further reacted to fzrm an amine, i.e., with H2 to form R(M)pCNH2 (4)1 The catalyst can be Pd or those referred to in the above publications. The amine is useful as an additive for lubricating oils.
... ., , ,:
An alternative and preferred method of producing amine derivatized polymer from azido functionalized polymer is by reducing the azido group to form an amine group. The reduction is preferably accomplished by reducing the azido functionalized polymer in the presence of a reducing catalyst to form the amine. Useful reducing catalysts include LiAlH4, CaH2 and the like, with LiAlH4 most preferred. The reaction is preferably conducted in a suitable solvent for the polymer and the catalyst. A preferred solvent is a polar solvent such a tetrahydrofuran (THF). The reaction can be conducted at room temperature or under reflux conditions.

Knudsen et al., A Convenient One-SteD Conversion_ Aromatic Nitro ComDounds to Phenols, J. org. Chem., Vol.
39, No. 23, 1974, discloses conversion of phenolic azido to esters. A useful reaction of the present invention follows:

R(M~pN3 + KOH THF ~ R(M)pOH (5) Other hydroxyl type bases and solvents for the base and polymer can be used with KOH preferred. The polymer containing hydroxyl group can be reacted with acids, i.e.

carboxylic acids to form esters which are useful as additives for iubricating oil compositions.

Isocyanates can be formed by the reaction of azides and C0 as disclosed in J. Am. Chem. soc. 90, 3295 (1968).
A useful reaction of the present invention follows.

R(M)pN3 +CO ~ R(M)pNCO (6) The R(M)pNCO can be reacted with an amine to form R(M)pNR26coNR27R28 which is useful as a lubricant additive. Preferably R26 is -H, and at least one of R27 and R28 is -H.
:: - ::~
~itrogens can be formed from azides by decomposing by heat or light. ~
:; ~-:'' ::
heat or R(M)pN3 light R(M)pN + N2 ( ) - ;
The J. Am. Soc. Chem. Comm., 1160 (1922) and Anderson et al., Addition of Nitrenes to Acetvlene. An~
aromaticitv of 1-H-Azirines, Chemical Communications, 147 (1969) discloses chemistry related to the addition of nitrenes to acetylenes. The nitrene reacts with a compound having a carbon-carbon double bond as follows.
A useful reaction of the present invention R(IMN)P

R(M)pN + R29R30-c=cR3lR32 ~ R29R30c-~cR3lR

21113~3 The nitrenes of formula (9) can rearrange to form imines. This tvpe of chemistry is reviewed in Moriarty et al., T~e Direct and Photosensitized Decomposition of Al~vl Azides, Tetrahedron, 26, 1379 (1970) and J. A~.
Chem. Soc. 93, 1537 (1971). A useful rearrangement reaction of the present invention follows:

R(M)pCH2-N ~ RCH s NH (10) Dimerization reactions of nitrenes are reviewed in Smith, in Lwowsku; Nitrenes, Ref. 200, p. 112, pp. 405 -419. A useful reaction of the present invention follows~

2R(M)pN ~ R(M)pN = R(M)pN (11) The J. Am. Chem. Soc. 94, p. 2114 (1973) and 95, 2394 (1973) disclose the reaction of azides with chloroboranes to form secondary amines. Useful reactions of the present invention follow:

R(M)p~X2 + R33N3 ~ R~M)pR33NBX2 (12 R(M)pR33N~X2 + H20 + X + OH- ~ RNHR33 (13) R(M)pBX + RN3 ~ RNHR (14) The functionalized reactant product polymer can be used as a dispersant if the functional group contain~ the reguisite polar group. However, derivatives of various of the functionalized polymers can be formed. T~ese derivatized polymers have the requisite properties for uses such as dispersants and viscosity modifiers.

Derivatization Reactant functional groups of the functionalized polymer can be reacted with derivative compounds to form derivatized polymers. The derivative compound comprises at least one reactive derivative group. The derivatized compound preferably contains at least one additional group which ~akes the derivatized group polar or reactive. Such derivatized polymers can contain amine~
groups, carboxyl groups or groups derived from reactive metal or reactive metal compounds. Various of the functional reactant product polymers can be further chemically modified to improve the polymer properties or impact desirability properties not otherwise present. A
chemical moiety can be directly or indirectly reacted at various of the nitrogen-containing functional reactant groups included in formulae (1) to (14). Such modified, derivatized compounds include the reaction product of formula (2), particularly wherein the anhydride is maleic anhydride with derivative compounds, and formula (6) isocyanato with compounds containing carboxyl group~
The functionalized polymer having the amine groups of formulae (3) and (14), and alcohol groups of formula (5) can be used as directly, i.e. as dispersants or V.I.
improvers for lubricating oil compositions or further derivatized with carboxyl-containing derivative compounds.

The derivatized polymer can include the reaction product of the above recited functionalized polymer (i.e.
formula (2)) with a nucleophilic reactant such as amines, alcohols, amino-alcohols and mixtures thereof to form oil soluble salts, amides, imides, oxazoline and esters of mono- and dicarboxylic acids, esters or anhydrides. The derivatized polymers are us~ful as lubricant dispersants which maintain oil insolubles, resulting from oxidation ~111313 during use, in suspension in the fluid thus preventing sludge flocculation and precipitation.

The compounds useful as dispersants generally are characterized by a "polar" group attached to a relatively high molecular weight hydrocarbon chain. The "polar"
group generally contains up to 10 wt. %, and typically from 0.1 to 5 wt. %, one or more of the elements nitrogen, oxygen, sulfur and phosphorus. The solubilizing chains are generally higher in molecular weight than those employed with the metallic ba~ed dispersants, but in some instances they may be quite similar. various types of dispersants can be made using the derivatized polymer of the present invention and are suitable for use in the lubricant compositions. T~e following are illustrative:

1. Reaction products of carboxylic acid or anhydride functionalized reactant polymer , i.e. formula (2) of the present invention (or derivatives thereof) derivatized with nitrogen-containing compounds such a~
amine, organic hydroxy compounds such as phenols and alcohols, and/or basic inorganic materials. More specifically, nitrogen- or ester-containing dispersants comprise members selected from the group consisting o~
oil-soluble salts, amides, imides, oxazolines and esters, or mixtures thereof, of the polymer of the present invention, functionalized (i.e. substituted with) mono-and dicarboxylic acids or anhydride or ester derivatives thereof.

2. Reaction products of the acid or anhydr~de derivatized polymer (formula (2)) of the present invention which have been halogenated.

21113~3 3. Reaction products, or isocyanato derivatized polymer (formula (6)) to form urea, and alcohols to forc urethanes. Such reactions are typically conducted by mixing the component with or without solvents (depending on molecular weight) at ambient conditions. Reference is made to Morton, Rubber Technoloon~ 2nd Ed., Chapter 17, pp. 440. Van Nostrand Reinhold Co. (1973), hereby incorporated by reference.

The derivatized living polymer can also be used to make ash and ashless type detergents. Typically, the living polymer for use as a detergent is an alkyl polymer having a number average molecular weight of from about 300 to 900. The ash-producing detergents are exemplified by oil-soluble neutral and basic salts of alkali or alkaline earth metals with alkyl derivatized polymers sulfonic acids, carboxylic acids, or organic phosphorus acids characterized by at least one direct carbon-to~
phosphorus linkage such a~ those prepared by ths derivatized olefin polymer of the present invention with a phosphorizing agent such as phosphorus trichloride, phosphorus heptasulfide, phosphorus pentasulfide, phosphorus trichloride and sulfur, white phosphorus and a sulfur halide, or phosphorothioic chloride. The most commonly used salts of such acids are those of sodium, potassium, lithium, calcium, magnesium, strontium and barium.

The term "basic salt" is used to designate metal salts wherein the metal is present in stoichiometrically larger amounts than the derivatized polymer, such as with maleic anhydride (or acid). The commonly employed methods for preparing the basic salts involve heating a mineral oil solution of the polymer with a stoichiometric excess of a metal neutralizing a~ent such as metal oxide, hydroxide, carbonate, bicarbonate, or sulfide at a temperature of about sOoc and filtering the resulting mass. The use of a "promoter" in the neutralization step to aid the incorporation of a large excess of metal likewise is known. Examples of compounds useful as the promoter include phenolic substance such as phenol, napthol, alkylphenol, thiophenol, sulfurized alkylphenol, and condensation products of formaldehyde with a phenolic substance; alcohols such as metbanol, 2-propanol, octyl ~
alcohol, cellosolve, ethylene glycol, stearyl alcohol,_ and cyclohexyl alcohol; and amines such as aniline, phenylenediamine, phenyl-beta-napthylamine, and dodecylamine. A particularly effective method for preparing the basic salts comprises mixing an acid with an excess of a basic alkaline earth metal neutralizing agent and at least one alcohol promoter, and carbonating the mixture at an elevated temperature such as 60C to 2000C. This class of materials is discussed further hereinabove in connection with detergents and metal rust inhibitors.

Preferred ash-producing detergents which can be derived from the functionalized reactant polymer of the present invention include the metal salts of sulfonic acid derivatives, preferably wherein the polymer is an alkyl compound, alkyl phenols, sulfurized alkyl phenols, alkyl salicylates, alkyl naphthenates and other oil soluble mono- and dicarboxylic acids. Highly basic (viz, overbased) metal salts, such as highly basic alkaline earth metal alkyl sulfonates (especially Ca and Mg salts) are frequently used as detergents. They are usually produced by heating a mixture comprising an oil-soluble sulfonate or alkaryl sulfonic acid, with an excess of alkaline earth metal compound above that required for complete neutralization of any sulfonic acid present, and thereafter forming a dispersed carbonate complex by reacting the excess metal with carbon dioxide to provide ~111313 the desired overbasing. The sulfonic acids are typically obtained by the sulfonation of alkyl substituted aromatic hydrocarbons such as those obtained from the fractionation of petroleum by distillation and/or extraction or by the alkylation of aromatic hydrocarbons as for example those obtained by alkylating benzene, toluene, xylene, naphthalene, diphenyl and the halogen derivatives such as chlorobenzene, chlorotoluene and chloronaphthalene. The alkylation may be carried out in the presence of a catalyst with acid derivatized polymer.

The alkaline earth metal compounds which may be used in neutralizing these alkaryl sulfonic acids to provide the sulfonates includes the oxides and hydroxides, alkoxides, carbonates, carboxylate, sulfide, hydrosulfide, nitrate, borates and ethers of magnesium, calcium, and barium. Examples are calcium oxide, calcium hydroxide, magnesium acetate and magnesium borate. AB
noted, the alkaline earth metal compound is used in excess of that required to complete neutralization of the alkaryl sulfonic acids. Generally, the amount ranges from about 100 to about 220%, although it is preferred to use at least 125% of the stoichiometric amount of metal required for complete neutralization.

Various other preparations of basic alkaline earth metal alkaryl sulfonates are known, such a~ those described in U.S. Patents 3,150,088 and 3,150,089, wherein overbasing is accomplished by hydrolysis of an alkoxide-carbonate complex with the alkaryl sulfonate in a hydrocarbon solvent/diluent oil.

Amine ComDounds Useful amine compounds for derivatizing polymers having functional groups or reactive derivative group~
comprise at least one a~ine and can comprise one or more additional amines or other reactive or polar groups.
Where the reactant functional group is a carbnxylic acid, ester or derivative thereof, or an isocyanato, it re~cts with the amine to form an amide. Where the functional group is a halide the amine reacts to displace ithe halide. Where the reaction functional group i~ an isocyanate it reacts with an amine to form a urea, and an alcohol to form a urethane.

Amine compounds useful as nucleophilic reactants for reaction with the functionalized polymer of the present invention include those disclosed in U.S. Patent No~.
3,445,441, 5,017,299 and 5,102,566, all hereby incorporated by reference. Preferred amine compounds include mono- and (preferably) polyamines, of about 2 to 60, preferably 2 to 40 (e.g. 3 to 20), total carbon atoms of about 1 to 12, preferably 3 to 12, and most preferably 3 to 9 nitrogen atoms in the molecule. These amines may be hydrocarbyl a~ines or may be hydrocarbyl amine~
including other groups, e.g., hydroxy groups, alkoxy qroups, amide groups, nitriles, imidazoline groups, and the like. Hydroxy amines with 1 to 6 hydroxy groups, preferably l to 3 hydroxy groups, are particularly useful. Preferred amines are aliphatic saturated amine~, including those of the general formulas:
R3S_N_R36, and (lS) l37 . . ~ . . - . ., , : : . ~ . :

R35-N-tc~2)r ~ N-(CH2)r ~ I R (16) ;

t wherein R35, R36, R37 and R38 are independently selected :
from the group consisting of hydrogen; Cl to C2S straight or branched chain alkyl radicals; C1 to C12 alkoxy; C2 to C6 alkylene radicals; C2 to C12 hydroxy amino alkylene radicals; and C1 to C12 alkylamino C2 to C6 alkylene radicals; and wherein R38 can additionally comprise a moiety of the formula~

(CH2) '- N ~ H (17) R36 - : -wherein R36 i8 as defined above, and wherein r and r' can be the same or a d$fferent number of from 2 to 6, preferably 2 to 4; and t and t' can be the same or .
different and are numbers of from O to 10, preferably 2 to 7, and most preferably about 3 to 7. Preferably, the sum of t and t' is not greater than 15. To assure a facile reaction, it is preferred that R35, R36, R37, R38, r, r', t and t' be selected in a manner sufficient to provide the compounds of Formulas (15) and (16) with typically at least 1 primary or secondary amine group, preferably at least 2 primary or secondary amine groups.
This can be achieved by selecting at least 1 of said R35, ~:
R36, R37 and R38 groups to be hydrogen or by letting t in Formula 16 be at least 1 when R38 is H or when the formula (17) moiety possesse~ a secondary amino group.
The most preferred amine of the above formulae are :~
represented by Formula 6 and contain at least 2 primary ~ :
amine groups and at least 1, and preferably at least 3, -: :
secondary amine groups. . .

~ ' ~

21~1313 Non-limiting examples of suitable amine compounds include: 1,2-diaminoethane; 1,3-diaminopropane; 1,4-diaminobutane; 1,6-diaminohexane; polyethylene amines such as diethylene triamine; triethylene tetramine;
tetraethylene pentamine; polypropylene amines such as 1,2-propylene diamine; di-(1,2-propylene)triamine; di-(1,3-propylene)triamine; N,N-dimethyl-1,3-diaminopropane;-N,N-di-(2-aminoethyl) ethylene diamine; N,N-di-(2-hydroxyethyl)-1,3-propylene diamine; 3-~
dodecyloxypropylamine; N-dodecyl-1,3-propane diamine;
tris hydroxymethylaminomethane (THAM); diisopropanol amine; diethanol amine; triethanol amine; mono-, di-, and tri-tallow amines; amino morpholines such as N-(3-aminopropyl)morpholine; and mixtures thereof. Monoamines include methyl ethyl amine, methyl octadecyl amines, anilines, diethylol amine, dipropyl amine, etc.

Other useful amine compounds include: alicyclic diamines such as 1,4-di(aminomethyl) cyclohexane, and heterocyclic nitrogen compounds such as imidazolines, and N-aminoalkyl piperazines of the general formula:
(18) N ~ NN - (C~z)pl]~ ~ (C~2)p2 - N~ ~3N

wherein P1 and P2 are the same or different and are each ~ ;
integers of from 1 to 4, and nl, n2 and n3 are t~e same ;~-~
or different and are each integers of from 1 to 3. Non-limiting examples of such amines include 2-pentadecyl imidazoline; N-(2-aminoethyl) piperazine; etc.

Commercial mixtures of amine compounds may advantageously be used. For example, one process for preparing alkylene amines involves the reaction of an 21113~ 3 - 94 - :

alkylene dihalide (such as ethylene dichloride or propylene dichloride) with ammonia, which results in a complex mixture of alkylene amines wherein pairs of nitrogens are joined by alkylene groups, forming such compounds as diethylene triamine, triethylenetetramine, tetraethylene pentamine and isomeric piperazines. Low c06t poly(ethyleneamine) compounds averaging about 5 to 7 nitrogen atoms per molecule are available commercially under trade names such as "Polyamine H", "Polyamine 400", "Dow Polyamine E-100", etc.

Useful amines also include polyoxyalXylene polyamines such as those of the formula:

NH2 alkylene-(------O------alkylenc )m--NH2 (19) where m has a value of about 3 to 70 and preferably 10 to 35; and the formula:

~39-( alkylene-(---o---alkylene---)n - NH2)a (20) where n has a value of about 1 to 40 with the provision that the sum of all the n values is from about 3 to about 70 and preferably from about 6 to about 35, and R39 i8 a polyvalent saturated hydrocarbon radical of up to 10 carbon atoms wherein the number of substituents on the :- :~
R38 group is represented by the value of "a", which i~ a ~ -number of from 3 to 6. The alkylene groups in either ~:
formula (19) or (20) may be straight or branched chains containing about 2 to 7, and preferably about 2 to 4 :~
carbon atoms. ~ ~

The polyoxyalkylene polyamineq of formulas tl9) or ~ :
(20) above, preferably polyoxyalkylene diamines and :~:
polyoxyalkylene triOamines, may have average molecular weights ranging from about 200 to about 4,000 and .

~11131~

preferably from about 400 to about 2,000. The preferred polyoxyalkylene polyamines include the polyoxyethylens and polyoxypropylene diamines and the polyoxypropylene triamines having average molecular weights ranging from about 200 to 2,000. The polyoxyalkylene polyamines are commercially available and may be obtained, for example, from the Jefferson Chemical Company, Inc. under the trade name "Jeffamines D-230, D-400, D-1000, D-2000, T-403, etc.

A particularly useful class of amines are the polyamido and related amines disclosed in U.S. Patent Nos. 4,857,217; 4,963,275 and 4,956,107, the disclosures of which are herey incorporated by reference, which comprise reaction products of a polyamine and an alpha, beta unsaturated compound of the formula: .

R40 C = C - C - Y (21) :

wherein X is sulfur or oxygen, Y i9 -oR43, SR43, or 43(R44) and R40 R41 R42, R43 and R44 are the s~me ~ -or dif~erent and are hydrogen or substituted or unsubstituted hydrocarbyl. Any polyamine, whether :-aliphatic, cycloaliphatic, aromatic, heterocyclic, etc., can be employed provided it is capable of adding acros~
the acrylic double bond and amidifying with, for ex~mple, the carbonyl group (-C(o)-) of the acrylate-type compound of formula X, or with the thiocarbonyl group (-C(S)-) of the thioacrylate-type compound of formula (21).
When R40 R41 R42 R43 or R44 in Formula (21) are hydrocarbyl, these groups can comprise alkyl, cycloalkyl, aryl, alkaryl, aralkyl or. heterocyclic, which can be substituted with groups which are substantially inert to any component of the reaction mixture under conditions sele~ted for preparation of the amido-amine. Such substituent groups include hydroxy, halide (e.g., Cl, Fl, I, Br~, -SH and alkylthio. When one or more of R40 through R44 are alkyl, such alkyl groups can be straight or branched chain, and will generally contain from 1 to 20, more usually from 1 to 10, and preferably from 1 to 4, carbon atoms. Illustrative of such alkyl groups are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tridecyl, hexadecyl, octadecyl and the like. When one or more of R40 through R44 are aryl, the aryl group will generally contain from 6 to 10 carbon atoms (e.g., phenyl, naphthyl).
,, :
When one or more of R40 through R44 are alkaryl, the al~aryl group will generally contain from about 7 to 20 car~on atoms, and preferably from 7 to 12 carbon atoms.
Illustrative of such alkaryl groups are tolyl, m-ethylphenyl, o-ethyltolyl, and m-hexyltolyl. When one or more of R40 through R44 are aralkyl, the aryl component generally consists of phenyl or (Cl to C6) alkyl-substituted phenol and the alkyl component generally contains from 1 to 12 carbon atom~, and preferably from 1 to 6 carbon atom~. Examples of such aralkyl groups are benzyl, o-ethylbenzyl, and 4-isobutylbenzyl. When one or more of R40 through R44 are cycloalkyl, the cycloalkyl group will generally contain from 3 to 12 carbon atoms, and preferably from 3 to 6 carbon atoms. Illustrative of such cycloalkyl groups are cyclopropyl, cyclobutyl, cyclohexyl, cyclooctyl, and cyclododecyl. When one or more of R40 through R44 are heterocyclic, the heterocyclic group generally consists of a compound having at least one ring of 6 to 12 members in which on-or more ring carbon atoms is replaced by oxygen or nitrogen. Examples of such heterocyclic groups are furyl, pyranyl, pyridyl, piperidyl, dioxanyl, tetrahydrofurvl, pyrazinyl and 1,4-oxazinyl.

- . ... . . . . .

211~ 313 The alpha, beta ethylenically unsaturated carboxylate compounds employed herein have the followiny formula:

R41 R42 o R4 o C = ~ oR4 3 (22) wherein R40, R41, R42 and R43 are the sa~e or different-and are hydrogen or substituted or unsubstituted hydrocarbyl as defined above. Examples of such alpha, beta-ethylenically unsaturated carboxylate compounds of formula (22) are acrylic acid, methacrylic acid, the methyl, ethyl, isopropyl, n-butyl, and isobutyl esters of acrylic and methacrylic acids, 2-butenoic acid, 2-hexenoic acid, 2-decenoic acid, 3-methyl-2-heptenoic acid, 3-methyl-2-butenoic acid, 3-phenyl-2-propenoic acid, 3-cyclohexyl-2-butenoic acid, 2-methyl-2-butenoic acid, 2-propyl-2-propenoic acid, 2-isopropyl-2-hexenoic acid, 2,3-dimethyl-2-butenoic acid, 3-cyclohexyl-2-methyl-2-pentenoic acid, 2-propenoic acid, methyl 2-propenoate, methyl 2-methyl-2-propenoate, methyl 2-butenoate, ethyl 2-hexenoate, isopropyl 2-decenoate, phenyl 2-pentenoate, tertiary butyl 2-propenoate, octadecyl 2-propenoate, dodecyl 2-decenoate, cyclopropyl 2,3-dimethyl-2-butenoate, methyl 3-phenyl-2-propenoate and the like.

The alpha, beta ethylenically unsaturated carboxylate thioester compounds employed herein have the following formula:

R40 _ C = C IC. SR43 (23) ". .. . .,. ~ . ~ . ,. . ... , . . . ~ .

: - . .. i - , : ... . . .
, . .:

,: - . . : - . :

wherein R40, R41, R42 and R43 are the same or different and are hydrogen or substituted or un~ubstituted hydrocarbyl as defined above. Examples of such alpha, beta-ethylenically unsaturated carboxylate thioesters of formula (23) are methylmercapto 2-butenoate, ethylmercapto 2-hexenoate, i~opropylmercapto 2-decenoate, phenylmercapto 2-pentenoate, tertiary butylmercapto 2-propenoate, octadecylmercapto 2-propenoate, dodecylmercapto 2-decenoate, cyclopropylmercapto 2,3-dimethyl-2-butenoate, methylmercapto 3-phenyl-2-propenoate, methylmercapto 2-propenoate, methylmercapto 2-methyl-2-propenoate and the like.

The alpha, beta-ethylenically unsaturated : :~
carboxyamide compounds employed herein have the following : ~ :
formula~
~' - .
R4 1 R4 2 o R40 1 = C C NR43(R44) (241 h ein R40 R41 R~2 R43 and R44 are the same or dif~erent and are hydrogen or substituted or unsubstituted hydrocarbyl as defined above. Examples of alpha, beta-ethylenically unsaturated carboxyamides of formula (24) are 2-butenamide, 2-hexenamide, 2- ~ :
decenamide, 3-methyl-2-heptenamide, 3-methyl-2-butenamide, 3-phenyl-2-propenamide, 3-cyclohexyl-2-butenamide, 2-methyl-2-butenamide, 2-propyl-2-propenamide, 2-isopropyl-2-hexenamide, 2,3-dimethyl-2-butenamide, 3-cyclohexyl-2-methyl-2-pentenamide, N-methyl 2-butenamide, N,N-diethyl 2-hexenamide, N-isopropyl 2-decenamide, N-phenyl 2-pentenamide, N-tertiary butyl 2-propenamide, N-octadecyl 2-propenamide, N-Nodidodecyl 2-decenamide, N-cyclopropyl 2,3-dimethyl-2-butenamide, N-methyl 3-phenyl-2-propenamide, 2-propenamide, 2-methyl-2-propenamide, 2-ethyl-2-propenamide and the like.
~'.

,. -: :..... - - .:-The alpha, beta ethylenically unsatur~ted thiocarboxylate compounds employed herein have the following formula R40 _ C = C C---oR43 ~25) wherein R40, R4l, R42 and R43 are the same or di~ferent and are hydrogen or substituted or unsubstituted hydrocarbyl as defined above Examples of alpha, beta~
ethylenically unsaturated thiocarboxylate compounds of formula (15) are 2-butenthioic acid, 2-hexenthioic acid, 2-decenthioic acid, 3-methyl-2-heptenthioic acid, 3-methyl-2-butenthioic acid, 3-phenyl-2-propenthioic acid, 3-cyclohexyl-2-butenthioic acid, 2-methyl-2-butenthioic acid, 2-propyl-2-propenthioic acid, 2-isopropyl-2-hexenthioic acid, 2,3-dimethyl-2-butenthioic acid, 3-cyclohexyl-2-methyl-2-pententhioic acid, 2-propenthioic acid, methyl 2-propenthioate, methyl 2-methyl 2-propenthioate, methyl 2-butenthioate, ethyl 2-hexenthioate, isopropyl 2-decenthioate, phenyl 2-pententhioate, tertiary butyl 2-propenthioate, octad~cyl 2-propenthioate, dodecyl 2-decenthioate, cyclopropyl 2,3-dimethyl-2-butenthioate, methyl 3-phenyl-2-propenthioate and the like The alpha, beta ethylenically unsaturated dithioic acid and acid e~ter compounds employed herein have the following formula R40 _ C = C IC SR43 (26) 21113~ 3 wherein R40, R41, R42 and R43, are the same or different and are hydrogen or substituted or unsubstituted hydrocarbyl as defined above. Examples of alpha, beta-ethylenically unsaturated dithioic acids and acid esters of formula (26) are 2-butendithioic acid, 2-hexendithioic acid, 2-decendithioic acid, 3-methyl-2-heptendithioic acid, 3-methyl-2-butendithioic acid, 3-phenyl-2-propendithioic acid, 3-cyclohexy1-2-butendithioic acid, 2-methyl-2-butendithioic a~id, 2-propyl-2-propendith~oic acid, 2-isopropyl-2-hexendithioic acid, 2,3-dimethyl-2-butendithioic acid, 3-cyclo- hexyl-2-methyl-2~
pentendithioic acid, 2-propendithioic acid, methyl 2-propendithioate, methyl 2-methyl 2-propendithioate, methyl 2-butendithioate, ethyl 2-hexendithioate, isopropyl 2-decendithioate, phenyl 2-pentendithioate, tertiary butyl 2-propendithioate, octadecyl 2-propendithioate, dodecyl 2-decendithioate, cyclopropyl 2,3-dimethyl-2-butendithioate, methyl 3-phenyl-2-propendithioate and the like.

The alpha, beta ethylenically unsatur~ted thiocarboxyamide compounds employed herein have the following formula:

R40 1 = C C NR43(R44~ (27) h in R40 R41 R42 R43 and R44 are the same or different and are hydrogen or substituted or unsubstituted hydrocarbyl as derined above. Examples o~
alpha, beta-ethylenically unsaturated thiocarboxyamides Or formula (27) are 2-butenthioamide, 2-hexenthio~mide, 2-decenthioamide, 3-methyl-2-heptenthioamide, 3-methyl-2-butenthioamide, 3-phenyl-2-propenthioamide, 3-cyclohexyl-2-butenthioamide, 2-methyl-2-butenthioamide, 2-propyl-2-propenthioamide, 2-isopropyl-2-hexenthioamide, 2,3-211131~

dimethyl-2-butenthloamide, 3-cyclohexy1-2-methyl-2-pententhioamide, N-methyl 2-butenthioamide, N,N-diethyl 2-hexenthioamide, N-isopropyl 2-decenthioamide, N-phenyl 2-pententhioamide, N-tertiary butyl 2-propenthioamide, N- ;
octadecyl 2-propenthioamide, N-N-didodecyl 2-decenthioamide, N-cyclopropyl 2,3-dimethyl-2-butenthioamide, N-methyl 3-phenyl-2-propenthioamide, 2-propenthioamide, 2-methyl-2-propenthioamide, 2-ethyl-2-~
propenthioamide and the like.

Preferred compounds for reaction with the polyamines in accordance with this invention are lower alkyl ester~
of acrylic and (lower alkyl) suDstituted acrylic acid.
Illustrative of such preferred compounds are compounds of the formula:

R42 o CH2 C l oR43 (28) where R42 is hydrogen or a C1 to C4 alkyl group, such as methyl, and R43 is hydrogen or a Cl to C4 alkyl group, capable of being removed so as to form an amido group, for example, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, aryl, hexyl, etc. In the preferred embodiments these compounds are acrylic and methacrylic esters such as methyl or ethyl acrylate, methyl or ethyl methacrylate. When the selected alpha, beta-unsaturated compound comprises a compound of formula (21) wherein X is oxygen, the re~ulting reaction product with the polyamine contains at least one amido linkage (-C(O)N~) and such materials are herein termed "amido-amines". Similarly, when the selQcted alpha, beta unsaturated compound of formula (21) comprises a compound wherein X is sulfur, the re~ulting reaction product with the polyamine contains thioamide linkage (-C(S)N<) and these materials are herein termed "thioamido-amine~".

` ~111313 For convenience, the following discussion is directed to the preparation and use of amido-amines, although it will be understood that such discussion is also applicable to the thioamido-amines.

The type of amido-amine formed varies with reaction conditions. For example, a more linear amido-amine is ~ormed where substantially equimolar amounts of the unsaturated carboxylate and polyamine are reacted. The presence of excesses of the ethylenically unsaturated reactant of formula (21) tends to yield an amido-amino which is more cross-linked than that obtained where substantially equimolar amounts of reactants are employed. Where, for economic or other reasons, a cross-linked amido-amine using excess a~ine i~ desired~
generally a molar excess of the ethylenically unsaturatod reactant of about at least 10%, such as 10 to 300~, or greater, for example, 25 to 200%, is employed. For more efficient cross-linking an excess o~ carboxylated material should preferably be used since a cleaner reaction ensues. For example, a molar excess of about lO
to 100% or greater such as 10 to 50S, but preferably an excess of 30 to 50%, of the carboxylated material.
Larger excess can be employed if desired.

In summary, without considering other factors, equimolar amounts of reactants tend to produce a more linear amido-amine whereas excess of the formula (22) reactant tends to yield a more cross-linked amido-amine.
It should be noted that the higher the polyamine (i.o., in greater the number of amino groups on the molecule) the greater tho statistical probability of cross-linking since, for example, a tetraalkylenopentamino, such as tetraethylene pentamine 211~313 NH2(CH2CH2N)4H

has more labile hydrogens than ethylene diamine.

These amido-amine adducts so formed are characterized by both amido and amino groups. In their simplest embodiments they may be represented by units of the following idealized formula:

N-(-A N-)n4 CH2---CH C (29) wherein the R45's, which may be the same or different, are hydrogen or a substituted group, such as a hydrocarbon group, for example, alkyl, alkenyl, alkynyl, aryl, etc., and A is a moiety of the polyamine which, for example, may be aryl, cycloalkyl, alkyl, etc., and n4 is an integer such as 1 to 10 or greater.

The above simplified formula represents a linear amido-amine polymer. However, cross-linked polymers m~y also be formed by employing certain conditions since the polymer has labile hydrogens which can further react with either the unsaturated moiety by adding across the double bond or by amidifying with a carboxylate group.

Preferably, however, the amido-amines are not cross-linked to any substantial degree, and more preferably are substantially linear.

Preferably, the polyamine reactant contains at least one primary amine, and more preferably from 2 to 4 primary amines, group per molecule, and the polyamine and the unsaturated reactant of formula (21) are contacted in ~, .. . ... . . . . . ..

` 21~1~13 an amount of from about 1 to 10, more preferably from about 2 to 6, and most preferably from about 3 to 5, equivalents of primary amine in the polyamine reactant per ~ole of the unsaturated reactant of formula (21).

The reaction between the selected polyamine and acrylate-type compound is carried out at any suitable temperature. Temperatures up to the decomposition points of reactants and products can be employed. In practice, one generally carries out the reaction by heating the reactants below 100C, such as 80C to 90C, for a suitable period of ti~e, such as a few hours. Where an acrylic-type ester is employed, the progress of the reaction can be judged by the removal of the alcohol in forming the amide.

During the early part of the reaction, alcohol is removed quite readily below 100C in the case of low boiling alcohols such as methanol or ethanol. AB the reaction slows, the temperature is raised to push the polymerization to completion and the temperature may be raised to 150C toward the end of the reaction. Removal of alcohol is a convenient method of judging the progress and completion of the reaction which is generally continued until no more alcohol is evolved. Based on removal of alcohol, the yields are generally stoichiometric. In more difficult reactions, yields of at least 95% are generally obtained.

Similarly, it will be understood that the reaction of an ethylenically unsaturated carboxylate thioester of formula (23) liberates the corresponding HSR43 compound (e.g., H2S when R43 i8 hydrogen) a~ a by-product, and of formula (24) liberates the corresponding HNR43 (R44 compound (e.g., ammonia when R43 and R44 are each hydrogen) as a by-product.

2:1 113~3 The reaction time to form an amido-amine material can vary widely depending on a wide variety of factors.
For example, there is a relationship between time and temperature. In general, lower temperature demands longer times. Usually, reaction times of from about 2 to 30 hours, such as 5 to 25 hours, and preferably 3 to 10 hours will be employed. Although one can employ a solvent, the reaction can be run without the use of any_ solvent. In fact, where a high degree of cross-linking is desired, it is preferably to avoid the use of a solvent and most particularly to avoid a polar solvent such as water. However, taking into consideration the effect of solvent on the reaction, where desired, any suitable solvent can be e~ployed, whether organic or inorganic, polar or non-polar.

A~ an example of the amido-amine adducts, the reaction of tetraethylene pentaamine (TEPA) with methyl methacrylate can be illustrated as follows~

R (Eq. 1) H2N[CH2CH2NH~3CH2C82NH2 + C82 = CHC-OCH3 7 H2N[CH2CH2NH]3CH2CH2NHCH2CH2CNHCH2CH2[NHCH2CH2]3NH2 The amine compound can be reacted with the functionalized polymer by haating an oil ~olution containing 5 to 95 wt. % of functionalized polymer to about 100C to 200C, preferably 125C to 175C, generally for 1 to 10, e.g. 2 to 6 hours until the desired amount of water is removed. The heating is preferably carried out to favor formation of imides or mixtures of imide and amides, rather than amides and . -salts. Reaction ratios of dicarboxylic acid material to equivalents of amine as well as the other nucleophilic reactants described herein can vary considerably, depending upon the reactants and type of bonds formed.
Generally from 0.1 to 1.0, preferably about 0.2 to 0.6, e.g. 0.4 to 0.6, moles of functionalized groups present in the functionalized polymer is used, per equivalent of nucleophilic reactant, e.g. amine. For example, for imide formation, about 0.8 mole of a pentamine (having two primary amino groups and 5 equivalents of nitrogen per molecule) is preferably used to convert polymer functionalized with succinic anhydride into a mixture of amides and imides, i.e. preferably the pentamine is used in an amount sufficient to provide about 0.8 mole (that is (2) (1.6)/[0.8 x 5] mole) of carboxy functional groups ~;
(o.4 moles of succinic groups) per nitrogen equivalent of the amine.

Tris(hydroxymethyl) amino methane (T~AM) can be reacted with the aforesaid runctionalized polymers to form amides, imides or ester type additives as taught by U.K. 984,409, or to form oxazoline compounds and borated oxazoline compounds as described, for example, in U.S.
Patent Nos. 4,102,798; 4,116,876 and 4,113,639.

Derivativized Polvmers From AlcohQls `~

The polymers of the present invention f~nctionalized with acid groups, i.e. formula (2), can be reacted with alcohols to form esters. The alcohols may be aliphat~c compounds such as monohydric and polyhydric alcohol~ or aromatic compounds such as phenols and naphthol~. T~e polymer containing isocyanato functionality reacted with alcohols to form urethanes. Following are useful alcohols.

~111313 The aromatic hydroxy compounds from which the esters may ~e derived are illustrated by the following specific examples: phenol, ~eta-naphthol, alpha-naphthol, cresol, resorcinol, catechol, p,p'di-hydroxybiphenyl, 2-chlorophenol, 2,4-dibutylphenol, propene tetramer-substituted phenol, didodecylphenol, 4,4'-methylene-bis-phenol, alpha-decyl-beta-naphthol, polyisobutene (molecular weight of 10~0)-substituted phenol, thQ
condensation product of heptylphenol wit~ 0.5 mole of formaldehyde, the condensation product of octyl-phenol with acetone, di(hydroxyphenyl)-oxide, di(hydroxy-phenyl)sulfide, di(hydroxyphenyl)disulfide, and 4-cyclo-hexylphenol. Phenol and alkylated phenols having up to three alkyl substituents are preferred.

The alcohols from which the e~ters may be derived preferably contain up to about 40 aliphatic carbon atoms.
They may be monohydric alcohols such as methanols, ethanol, isooctanol, dodecanol, cyclohexanol, cyclopentanol, behenyl alcohol, hexatriacontanol, neopentyl alcohol, isobutyl alcohol, benzyl alcohol, beta-phenyl-ethyl alcohol, 2-methylcyclohexanol, beta~
chloroethanol, monomethyl ether of ethylene glycol, monobutyl ether of ethylene glycol, monopropyl ether of diethylene glycol, monododecyl ether of triethylene glycol, monooleate of ethylene glycol, monostearate of diethylene glycol, secpentyl alcohol, tertbutyl alcohol, 5-bromo-dodecanol, nitro-octadecanol and dioleate o~
glycerol. The polyhydric alcohols preferably contain from 2 to about 10 hydroxy radicals. They are illustrated by, for example, ethylene glycol, dlethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, dibutylene glycol, tributylene glycol, and other alkylene glycols in which the alkylene radical contains from 2 to about 8 : ~: .. : , - .. . .... .

21~1313 carbon atoms. Other useful polyhydric alcohols include glycerol, monooleate of glycerol, monostearate of glycerol, monomethyl ether of glycerol, pentaerythritol, s,lo-dihydroxy stearic acid, methyl ester of 9,10-dihydroxy stearic acid, 1,2-butanediol, 2~3-hexanediol~
2,4-hexanediol, penacol, erythritol, arabitol, sorbitol, mannitol, 1,2-cyclo-hexanediol, and xylene glycol.
Carbohydrates such as sugars, starches, cellulose, etc., likewise may yield the esters of this invention. The carbohydrates may be exemplified by a glucose, fructoQe, sucrose, rhamnose, mannose, glyceraldehyde, and galactose.

A useful class of polyhydric alcohols are those having at least three hydroxy radicals, some of which have been esterif$ed with a monocarboxylic acid h~ving from about 8 to about 30 carbon atoms, such as octanoic acid, oleic acid, stearic acid, linoleic acid, dodecanoic acid, or tall oil acid. Examples of such partially esterified polyhydric alcohols are the monooleate of sorbitol, distearate of sorbitol, monooleate of glycerol, monostearate of glycerol, di-dodecanoate of erythritol.

The esters and urethanes may also be derived from unsaturated alcohols such as allyl alcohol, cinnamyl alcohol, propargyl alcohol, 1-cyclohexene-3-ol, an oleyl alcohol. Still another class of the alcohols capable of yielding the esters of this invention comprise the ether-alcohols and amino-alcohols including, for example, the oxyalkylene-, oxyarylene-, amino-alkylene-, and amino-arylene-substituted alcohols having one or more oxyalkylene, amino-alkylene or amino-arylene oxyarylene radicals. They are exemplified by Cellosolve, carbitol, phenoxyethanol, heptylphenyl-(oxypropylene)6-H, octyl-(oxyethylene)30-H, phenyl-(oxyoctylene)2-H, mono(heptyl-phenyl-oxypropylene)-substituted glycerol, poly(styrene ~ , 2 ~ 1 3 oxide), aminoethanol, 3-amino ethyl-pentanol, di(hydroxyethyl) amine, p-amino-phenol, tri(hydroxypropyl)amine, N-hydroxyethyl ethylene diamine, N,N,N',N'-tetrahydroxy-trimethylene diamine, and the like. For the most part, the ether-alcohols having up to about 150 oxyalkylene radicals in which the alkylene radical contains from 1 to about 8 carbon atoms are preferred.

The esters may be diesters, e.g., of succinic acid~
or acidic esters, i.e., partially esterified polyhydric alcohols or phenols, i.e., esters having free alcoholic or phenolic hydroxyl radicals. Mixtures of the above-illustrated esters likewise are contemplated within the scope of the invention.

The esters may be prepared by one of several methods. The ~ethod which is preferred becau~e of convenience and superior properties of the esters it produces, involves the reaction of a suitable alcohol or phenol with the acid or anhydride (i.e., functionalizod polymer succinic anhydride). The esterification is usually carried out at a temperature above about lOO-C, preferably between 150C and 300C.

The water formed as a by-product i~ removed by distillation as the esterification proceeds. A solvent may be used in the esterification to facilitate mixing and temperature control. It also facilitates the removal of water from the reaction mixture. The useful solvents include xylene, toluene, diphenyl ether, chlorobenzene, and mineral oil.

A modification of the above process involving dicarboxylic acid involves the replacement of, for example, the succinic anhydride with the corresponding succinic acid as a functionalized co~pound. However, succinic acids readily undergo dehydration at temperatures above about 100C and are thus converted to their anhydrides which are then esterified by the reaction with the alcohol reactant. In this regard, succinic acids appear to be the substantial equivalents of their anhydrides in the process.

The relative proportions of the carboxylic acid or isocyanato functionalized polymer and the hydroxy reactant which are to be used depend to a large measure upon the type of the product desired, the functionality of the functionalized polymer, and the nu~ber of hydroxyl groups present in the molecule of the hydroxy reactant.
For instance, the formation of a half ester of a succinic acid, i.e., one in which only one of the two acid radicals is esterified, involves the use of one mole of a monohydric alcohol for each mole of the succinic functional group, whereas the formation of a d~ester of a succinic acid involves the use of two moles of the alcohol for each mole of the acid functional group. on the other hand, one mole of a hexahydric alcohol may combine with as many as six moles of a di-acid to form an e~ter in which each of the six hydroxyl radicals of the alcohol is esterified with one of the two acid radicals of the succinic acid. Thus, the maximum proportion of functional groups to be used with a polyhydric alcohol is determined by the number of hydroxyl groups present in the molecule of the hydroxy reactant. Esters obtained by the reaction of stoichiometric amounts of the acid reactant and hydroxy reactant are preferred.

In some instances, it is advantageous to carry out the esterification in the pre~ence of a catalyst such as sulfuric acid, pyridine hydrochloride, hydrochloric acid, benzenesulfonic acid, p-toluenesulfonic acid, pAosphoric acid, or any other known esterification catalyst. Th~
amount of the catalyst in the reaction mAy be as little as 0.01% (by weight of the reaction mixture), more often from about 0.1% to about 5%.

Ester derivatives likewise may be obtained by the reaction of acid or anhydride functionalized polymer with epoxide or a mixture of an epoxide and water. Such reaction is similar to one involving the acid or anhydride with a glycol. For instance, the product mny be prepared by the reaction of a functionalized polymer with alkylene oxide to yield half esters, monoesters or diesters.

Epoxides which are commonly available for use in such reaction include, for example, ethylene oxide, propylene oxide, styrene oxide, 1,2-butylene oxide, 2,3-butylene oxide, epichlorohydrin, cyclohexene oxide, 1,2-octylene oxide, epoxidized soya bean oil, met~yl ester of 9,10-epoxy-stearic acid, and butadiene monoepoxide.
Preferred epoxides are the alkylene oxides in which the alkylene radical has from 2 to about 8 carbon atoms; or the epoxidized fatty acid esters in which the fatty acid radical has up to about 30 carbon atoms and the ester radical is derived from a lower alcohol having up to about 8 carbon atoms.

In lieu of the acid functionalized polymer, a polymer functionalized with lactone acid or a acid h~lide may be used in the processes illustrated above for preparing the ester derivative~ of this invention. Such acid halides may be acid dibromides, acid dichlorides, acid monochlorides, and acid monobromides.

Where the carboxylic derivative compositions produced are eRters, such esters include acidic e~ters '~111313 and neutral esters. Acidic esters are those in which less than all of the functional groups in the functionalized polymer are esterified, and hence posse~s at least one free functional group. Obviously, acid esters are easily prepared by using an amount of alcohol insuf$icient to esterify all of the functional groups of -;
the functionalized polymer.

The functionalized, e.g. acid functionalized, polymer of this invention are reacted with the alcohols according to conventional esterification technique~.
This normally involves heating the functionalized polymer with the alcohol, optionally in the presence of a ~ i~
normally liquid, substantially inert, organic liquid solvent/diluent and/or in the presence of esterification catalyst. Temperatures of at least about 100C up to the decomposition point are used (the decomposition point having been defined hereinbefore). m is temperature ~s u~ually within the range of about 100C up to about 300C
with temperatures of about 140C to 250C often being employed.

Many issued patents disclose procedures for react~nq high molecular weight carboxylic acids with alcohols to produce acidic esters and neutral esters. These saoe techniques are applicable to preparing esters from the functionalized polymer of this invention and the alcohols described above. All that is required is that t~e acylating reagents of this invention are substituted for the high molecular weight carboxylic acid acylating agents discussed in these patents, u~ually on an equivalent weight ba~is. The following U.S. Patents are expressly incorporated herein by reference for th ir disclosure of suitable methods for reacting the acylatinq reagents of this invention with the alcohols describQd ., ., - . .. .

: ~ , : . .

~111313 above: U.S. Patent Nos. 3,331,775; 3,381,022; 3,522,179;
3,542,680; 3,697,428 and 3,755,169.

Derivatized Polvmers From Reactive Metals/~etaL-~ompounds U~eful reactive metals or reactive m~tal compounds are those which will form metal salts or metal-containing complexes with the functionalized polymer. Metal complexes are typically achieved by reacting the carboxyl functionalized polvmers with amines and/or alcohols as discussed above, and also with complex forming reactants either during or subsequent to amination.

Reactive metal compounds for use in the formation of complexes with the reaction products of functionalized polymer and amines include those disclosed in U.S. Patent No. 3,306,908. Complex-forming metal reactants include the nitrates, nitrites, halides, c~rboxylates, phosphates, phosphites, sulfates, sulfites, carbonates, borate~, and oxides of cadmium a~ well as metals having atomic numbers from 24 to 30 (including chromium, manganese, iron, cobalt, nickel, copper and zinc). The~e metals are the so-called transition or coordination metals, i.e., they are capable of forming complexe~ by means of their secondary or coordination valence.
Specific examples of the complex-forming metal compounds useful as the metal reactant are cobaltous nitrate, cobaltous oxide, cobaltic oxide, cobalt nitrite, cobaltic phosphate, cobaltous chloride, cobaltic chloride, cobaltous carbonate, chromous acetate, chromic aCQtate~
chromic bromide, chromous chloride, chromic fluoride, chromous oxide, chromium dioxide, chromic oxide, chromic sulfite, chromous sulfate heptahydrate, chromic sulfate, chromic formate, chromic hexanoate, chromium oxychloride, chromic phosphite, manganous acetate, manganous benzoate, ~111313 . .
manganous carbonate, ~anganese dichloride, manganese trichloride, manganous citrate, manganous form~te, manganous nitrate, manganous oxalate, manganefie monooxide, manganese dioxide, manganese trioxide, manganese heptoxide, manganic phosphate, manganous pyrophosphate, manganic metaphosphate, manganous hypophosphite, manqanous . valerate, ferrous acetate, ferric benzoate, ferrous bromide, ferrous carbonate, ~erric formate, ferrous lactate, ferrous nitrate, ferrous oxide, ferric oxide, ferric hypophosphite, ferric sulfate, ferrous sulfite, ferric hydrosulfite, nickel dibromide, nickel dichloride, nickel nitrate, nickel dioleate, nickel stearate, nickel sulfite, cupric propionate, cupric acetate, cupric metaborate, cupric benzoate, cupric formate, cupric laurate, cupric nitrite;
cupric oxychloride, cupric palmitate, cupric salicylate, zinc benzoate, zinc borate, zinc bromide, zinc chromate, zinc dichromate, zinc iodide, zinc lactate, zinc nitratQ, zinc oxide, zinc stearate, zinc sulfite, cndmium benzoate, cadmium carbonate, cadmium butyrate, cadmium chloroacetate, cadmium fumerate, cadmium nitrate, cadmium dihydrogenphosphate, cadmium sulfite, and cadmium oxide.
Hydrates of the above compounds are especially convenient for use in the process of this invention.

U.5. Patent No. 3,306,908 is expressly incorporated herein by reference for its discussion of reactive motal compounds suitable for forming such complexes and its disclosure of processes for preparing the complexes.
~asically, those processes are applicable to the carboxylic derivative compositions of the functionali8sd polymer of this invention with the amines as described above by substituting, or on an eguivalent basis, the functionalized polymer of this invention wit~ the high molecular weight carboxylic acid functionalized polymer disclosed in U.S. Patent No_ 3,306,908.

~111313 U.S. Patent No. Re. 26,433 discloses metals useful in preparing salts from acid functionalized polymer and/or an amine derivatized polymer as de~cribed hereinabove. Metal salts are prepared, according to this patent, from alkali metals, alkaline earth metals, zinc, cadmium, lead, cobalt and nickel. Examples of a re~ctive metal compound suitable for use are sodium oxide, sodium hydroxide, sodium carbonate, sodium methylate, sodiu~
propylate, sodium pentylate, sodium phenoxide, potassium oxide, potassium hydroxide, potassium chrbonate, potassium methylate, potassium pentylate, potassium phenoxide, lithium oxide, lithium hydroxide, lithium carbonate, lithium pentylate, calcium oxide, calciu~
hydroxide, calcium carbonate, calcium methylate, calcium ethylate, calcium propylate, calcium chloride, calcium fluoride, calcium pentylate, calcium phenoxide, calcium nitrate, barium oxide, barium hydroxide, bar$u~
carbonate, barium chloride, barium fluoride, barium methylate, barium propylate, barium pentylate, barium nitrate, magnesium oxide, magnesium hydroxide, magne~ium carbonate, m~gnesium ethylate, magnesium propy~ate, magnesium chloride, magnesium bromide, barium, iodide, magnesium phenoxide, zinc oxide, zinc hydroxide, zinc carbonate, zinc methylate, zinc propylate, zinc pentylate, zinc chloride, zinc fluoride, zinc nitrate trihydrate, cadmium oxide, cadmium hydroxide, cadmium carbonate, cadmium methylate, cadmium propylate, cadmium chloride, cadmium bromide, cadmium fluoride, lead oxide, lead hydroxide, lead carbonate, le~d ethylate, lead pentylate, lead chloride, lead fluoride, lead iodide, lead nitrate, nickel oxide, nickel hydroxide, nickel carbonate, nickel chloride, nickel bromide, nickel fluoride, nickel methylate, nickel pentylate, n~ckel nitrate hexahydrate, cobalt oxide, cobalt hydroxide, cobaltous bromide, cobaltous chloride, cobalt butylate, cobaltous nitrate hexahydrate, etc. The above metal compounds are merely illustrative of those useful in this invention and t~e invention is not to be con5idered as limited to such.
.
U.S. Patent No. Re. 26,433 is expressly incorporated herein by reference for its disclosure of u8eful reactive metal compounds as, and processes ~or, utilizing these compounds in the formation of salts. Again, in applying the teachings of this patent to the present invention, it is only necessary to substitute the functionalized polymer of this invention on an equivalent weight basis for the high molecular weight carboxylic acylating agents disclosed in this reissue patent.

U.S. Patent No. 3,271,310 discloses the preparation of metal salt of high molecular weight carboxylic a~id material, in particular alkenyl succinic acids which can be adopted to make the present functionalized polymer.
The metal salts disclosed therein are acid salts, neutral salts, and basic salts. Among the illustrative reactive metal compounds used to prepare the acidic, neutral and basic salts of the acid functionalized polymer are those disclosed in U.S. Patent No. 3,271,310 including lithium oxide, lithium hydroxide, lithium carbonate, lithium pentylate, sodium oxide, sodium hydroxide, sodium carbonate, sodium methylate, sodium propylate, ~odium phenoxide, potassium oxide, potassium hydroxide, potassium carbonate, potas~ium methylate, silver oxide, silver carbonate, magne~ium oxide, magnesium hydroxide, magnesium carbonate, magne~ium ethylate, magne~ium propylate, magnesium phenoxide, calcium oxide, calcium hydroxide, calcium carbonate, calcium methylate, calcium propylate, calcium pentylate, zinc oxide, zinc hydroxide, zinc carbonate, zinc propylate, strontium oxide, strontium hydroxide, cadmium oxide, cadmium hydroxide, 2111~13 cadmium carbonate, cadmium ethylate, barium oxide, barium hydroxide, barium hydrate, barium carbonate, barium ethylate, bariumi pentylate, aluminum oxide, aluminum propylate, lead oxide, lead hydroxide, lead c~rbonate, tin oxide, tin butylate, cobalt oxide, cobalt hydroxide, cobalt carbonate, cobalt pentylate, nickel oxide, nickel hydroxide, and nickel carbonate. The present invention is not to be considered as limited to the use of the above metal compounds; they are presented merely to illustrate the metal compounds included within the invention.

U.s. Patent No. 3,271,310 is expressly incorporated herein by reference for its disclosure of suitable reactive metal compounds suitable for forming salts of the functionalized polymer of this invention ac well aai illustrative processes for preparing salts of these reagents. As will be apparent, the processes of U.S.
Patent No. 3,271,310 are applicable to this invention merely by substituting on an equivalent weight basis, the functionalized polymer of this invention for the high molecular weight carboxylic acids of the patent.

From the foregoing description, it is apparent that the appropriate functionalized reactive polymer of this invention can be reacted with any individual amine, alcohol, reactive metal, reactive metal compound or any combination of two or more of any of these; that is, for example, one or more amines, one or more alcohols, one or more reactive metals or reactive metal compounds, or a mixture of any of these. The mixture can be a mixture of two or more amines, a mixture of two or more alcohoLs, a mixture of two or more metals or reactive metal compounds, or a mixture of two or more components selected from amines and alcohols, from amines and reactive metals or reactive metal compounds, from ~111313 : ~

alcohols and reactive metal compounds, or one or more components from each of the amines, alcohols, and reactive metals or reactive metal compounds.
Furthermore, the appropriate functionalized polymer of this invention can be reacted with the amines, alcohols, reactive metals, reactive metal compounds, or mixtures thereof, as described a~ove, simultaneously (concurrently) or sequentially in any order of reaction.

Canadian Patent No. 956,397 is expressly incorporated herein by reference for its disclosure of procedures which can be used for reacting the functionalized polymer of this invention with amines, alcohols, reactive metals and reactive metal compounds, or mixtures of these, sequentially and simultaneously.
All that is required to apply the processes of that patent to this invention is to substitute, on an equivalent weight basis, the functionalized polymer o~
this invention for the high molecular weight carboxylic acid. Carboxylic acid derivatives of this invention prepared utilizing the processes disclosed in the Canadian patent constitute a preferred class of carboxylic acids or carboxylic acid derivative compositions. The following U.S. Patents are also incorporated herein by reference, being counterparts of the incorporated Canadian patent, for the same reasons given for incorporating the Canadian patent: U.S. Patent Nos. 3,836,469; 3,836,470; 3,836,471; 3,838,050;
3,838,052; 3,879,308; 3,957,854 and 3,957,855.

Post Treatment Another aspect of this invention involves the post treatment of derivatized polymers. The processes for post-treating the functionalized or derivatized polymers useful as dispersant materials are analogous to the post-treating processes used with respect to conventional dispersants and multi-functional viscosity index improvers useful as dispersants of the prior art.
Accordingly, the same reaction conditions, ratio of reactants and the like can be used. Reference is made to U.S. Patent No. 5,017,199.

Derivatized polymers can bQ post-treated with such_ reagents as urea, thiourea, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, nitriles, epoxides, boron compounds, phosphorus compounds or the like. Exemplary materials of this kind are described in the following U.S. Patent Nos.
3,036,003; 3,200,107; 3,254,025; 3,278,550; 3,281,428;
3,282,955; 3,366,569; 3,373,111; 3,442,808; 3,455,832;
3,493,520; 3,513,093; 3,539,633; 3,579,450; 3,600,372;
3,639,242; 3,649,659; 3,703,536 and 3,708,522, which are herein incorporated by reference.

The amine derivatized polymers o~ the present invention as described above cAn be post-treated, particularly for use as dispersants and viscosity index improvers by contacting said polymers with one or more post-treating reagents selected from the group consisting of boron oxide, boron oxide hydrate, boron halides, boron acids, esters of boron acids, carbon disul~ide, sulfur, sulfur chlorides, alkenyl cyanides, aldehydes, ketones, urea, thiourea, guanidine, dicyanodiamide, hydrocarbyl phosphates, hydrocarbyl phosphites, hydrocarbyl thiophosphates, hydrocarbyl thiophosphite~, phosphorus sulfides, phosphorus oxides, phosphoric acid, hydrocarbyl thiocyanates, hydrocarbyl isocyanates, hydrocarbyl isothiocyantes, epoxides, episulfides, formaldehyde or formaldehyde-producing compounds plus phenols, and sulfur plus phenols, and Cl to C30 hydrocarbyl substituted ~ ~ -~1~1313 succinic acids and anhydrides (e.g., succinic anhydride, dodecyl succinic anhydride and the like), fu~aric acid, itaconic acid, maleic acid, maleic anhydride, chloromaleic acid, chloromaleic anhydride, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, and lower alkyl (e.g., C1 to C4 al~yl) acid esters of the foregoing, e.g., methyl maleate, ethyl fumarate, methyl fumarate, and the like.

For example, the amine derivatized polymers can be treated with a boron compound selected from the cla~s consisting of boron oxide, boron halides, boron acids and esters of boron acids in an amount to provide from about o.l atomic proportion of boron for each mole of said nitrogen composition to about 20 atomic proportions of boron for each atomic proportion of nitrogen of s~id nitrogen composition. Borated derivatized polymers useful as dispersants can contain from about O.OS to 2.0 wt. %, e.g. 0.05 to 0.7 wt. % boron based on the total weight of said borated nitrogen-containing dispersant compound. The boron, which appears to be in the product as dehydrated boric acid polymers ~primarily (HB02)3), is believed to attach to the derivatized polymer as amine salts, e.g., the metaborate salt of said amine derivatized polymer.

~ reating is readily carried out by adding from about 0.05 to 4, e.g. 1 to 3 wt. % (based on the weight of said nitrogen compound) of said boron compound, preferably boric acid which is most usually added as a slurry to said nitrogen compound and heating with stirring at from about 135C to 190C, e.g. 140C to 170C, for from 1 to hours followed by nitrogen stripping at said temperature ranges.

: ', Since post-treating processes involving the use of these post-treating reagents is known insofar a~
application to high molecular weight nitrogen-containing dispersants of the prior art, further descriptions of these processes herein is unnecessary. In order to apply the prior art processes to the compositions of t~ia invention, all that is necessary is t~at reaction conditions, ratio of reactants, and the like as described in the prior art, be applied to the novel composition o~
this invention. The following U.S. patents are expressly incorporated herein by reference for their disclosure o~
post-treating processes and post-treating reagents applicable to the compositions of this invention: U.S.
Patent Nos . 3,087,936; 3,200,107; 3,254,025; 3,256,185;
3,278,550; 3,281,428; 3,282,955; 3,284,410; 3,338,832;
3,344,069; 3,366,569; 3,373,111; 3,367,943; 3,403,102;
3,428,561; 3,502,677; 3,513,093; 3,533,945; 3,541,012;
3,Ç39,242; 3,708,522; 3,859,318; 3,865,813; 3,470,098;
3,369,021; 3,184,411; 3,185,645; 3,245,908; 3,245,909;
3,245,910; 3,573,205; 3,692,681; 3,749,695; 3,865,740;
3,954,639; 3,458,530; 3,390,086; 3,367,943; 3,185,704;
3,551,466; 3,415,750; 3,312,619; 3,280,034; 3,718,663;
3,652,616; UX Patent No. 1, 085,903; UK Patent No.
1,162,436; U.S. Patent ~o. 3,558,743.

The derivatized polymers of the present invention can also be treated with polymerizable lactones (such as epsilon-caprolactone) to form dispersant adducts having the moiety -~C~O)(C2)zO]mH~ wherein z i~ a number of from 4 to 8 (e.g., 5 to ~) and m has an average value of from about O to 100 (e.g., 0.2 to 20). The functionallzed or derivatized polymers of this invention, particularly for ~ `;
use a~ a dispersant, can be post-treated with a C5 to Cg lactone, e.g., epsilon-caprolactone, by heating a mixture of the polymers and lactone in a reaction vessel in thQ
absence of a solvent at a temperature of about 50C to ,: - .

~111313 about 200c, more preferably from about 75C to about 180C, and most preferably from about 90C to about 160C, for a sufficient period of time to ef~ect reaction. Optionally, a solvent for the lactone, dispersant material and/or the resulting adduct may be employed to control viscosity and/or the reaction rates.

In one preferred embodiment, the Cs to Cg lactone, e.g., epsilon-caprolactone, is reacted with a nitrogen containing polymer (i.e., dispersant) in a 1:1 mole ratio of lactone to dispersant material. In practice, the ratio of lactone to polymer may vary considerably a~ a means of controlling the length of the sequence of the lactone units in the adduct. For example, the mole ratio of the lactone to the dispersant material may vary from about 10:1 to about 0.1:1, more preferably from about 5:1 to about 0.2:1, and most preferably from about 2:1 to aboùt 0.4:1. It is preferable to maintain the average degree of polymerization of the lactone monomer below about 00, with a degree of polymerization on the order or from about 0.2 to about 50 being preferred, and ~rom about 0.2 to about 20 being more preferred. For optimum dispersant performance the nitrogen containing polymer a~
a dispersant, sequences of from about 1 to about 5 lactone units in a row are preferred.

Catalysts useful in the promotion of the lactone-dispersant material reaction~ are selected from the group consisting of stannous octanoate, stannous hexanoate, tetrabutyl titanate, a variety of organic-based acid catalysts and amine catalysts, a~ described on page 266, and forward, in a book chapter authored by R. D. Lundberg and E. F. Cox, entitled "Xinetics and Mechanisms of Polymerization: Rlng Opening Polymerization", edited by Frisch and Reegen, published by Marcel Dekker in 1969, wherein stannous octanoate is an especially preferred ~ ':' : : . j ,. . - :

-: : :, - ` .
~ : . . .~ : .:

catalyst. The catalyst is added to the reaction mixture at a concentration level of about 50 to about lO,oOo parts per weight of catalyst per one million parts of the total reaction mixture.

Lubricatina Compositions The above discussions relate to a variety o~ --materials including the polymer per se, t~e functionalized polymer, the derivatized polymer, and post-treated derivatized polymer.

The polymer per se hac a variety of utilities depending on its molecular weight including synthetic ba~e oil (for lower molecular weights~, adhesive coatings for intermediate molecular weights, and as elastomeric compositions for high molecular weights, e.g. films, extrudates, composites, and the liXe. -~

The functionalized polymer, in addition to acting as intermediates for dispersant and in multifunctional viscosity improvers (MFVI) manufacture, c~n be used as molding release agents, molding agents, metal working lubricants, point thickeners, and the like.

The primary utility for all the above described materials, from polymer all the way through post-treated derivatized polymer is as an additive for oleaginou~
compositions. For ease of discussion the above-mentioned ~aterials are collectively and individually referred to herein as "additives" when u~o in the context of an oleaginous composition containing such "additives".

Accordingly, the additives of the present invention can be used by incorporation and dissolution into an 21~.131~

oleaginous material such as fuels and lubricating oils.
~hen the additives of this invention are used in normally liquid petroleum fuels such as middle distillates boiling from about 65C to 430C, including kerosene, diesel fuels, home heating fuel oil, jet fuels, etc., a concentration of the additives in the fuel in the range of typically from about 0.001 to about 0.5, and preferably 0.005 to about 0.15 wt. %, baced on the total weight of the composition, will usually be employed.
Useful compositions and additives are disclosed in U.S.
Patent No. 5,102,566, hereby incorporated by reference.

The additives of the present invention find their primary utility in lubricating oil compositions which employ a base oil in which the additives are dissolved or dispersed therein. Such base oils may be natural or synthetic. Base oils suitable for use in preparing the lubricating oil compositions of the present invention include those conventionally employed as crankcase lubricating oils for spark-ignited and compression-ignited internal combu~tion engines, such as automob$1e and truck engines, marine and railroad diesel engines, and the like. Advantageous results are also achieved by employing the additive mixtures of the present invention in base oils conventionally employed in and/or adapted for use as power transmitting fluids, universal tractor fluids and hydraulic fluids, heavy duty hydraulic fluids, power steering fluids and the like. Gear lubricants, industrial oils, pump oils and other lubricating oil compositions can also benefit from the incorporation therein of the additives of the present invention.

These lubricating oil formulations conventionally contain several different types of additives that will supply the characteristics that are reguired in t~e formulations. Among these types of additives are .. . .. :: - , . .

,. : ~ . .. - . :
: . ~ ~ ., . :.
. ::~. -211~31~

included viscosity index improvers, antioxidants, corrosion inhibitors, detergents, dispersants, pour point depressants, antiwear agents, friction modifiers, etc.

The additives of the present invention, particularly those adapted for use as dispersants and viscosity modifiers, can be incorporated into a lubricating oil in any convenient way. Thus, they can be added directly to the oil by dispersing or dissolving the same in the oil at the desired level of concentrations of the additive.
Such blending into the additional lube oil can occur at room temperature or elevated temperatures.
Alternatively, the additives can be blended with a suitable oil-soluble solvent and base oil to form a concentrate, and then blending the concentrate with a lubricating oil basestock to obtain the flnal formulation. Such dispersant concentrates will typically contain (on an active ingredient (A.I.) ba~is) from about 10 to about 80 wt. %, ty~pically about 20 to about 60 wt.
%, and preferably from about 40 to about 50 wt. %
additive, and typically from about 40 to 80 wt. %, preferably from about 40 to 60 wt. % base oil, i.Q., hydrocarbon oil based on the concentrate weight. The lubricating oil basestock for the additive typically is adapted to perform a selected function by ~he incorporation of additional additives therein to form lubricating oil compositions (i.e., formulations).

Usually these concentrates may be diluted with 3 to 100, e.g., 5 to 40 parts by weight of lubricating oil, per part by weight of the additive package, in forming finished lubricants, e.g. crankcase motor oils. T~e purpose of concentrates, of course, is to make the handling of the various materials less difficult and awkward as well as to facilitate solution or dispersion in t~e final blend. Thus, the additive of the presnt :: :

2~11313 invention and formulations containing them would usually be employed in the form of a 40 to 50 wt~ % concentrate, for example, in a lubricating oil fraction.

The additives of the present invention will be generally used in admixture with a lube oil basestock, comprising an oil of lubricating vi8cosity, including natural and synthetic lubricating oils and mixture~
thereof. Useful oils are described in U.S. Patent Nos.
5,017,299 and 5,084,197.

Natural oils include animal oils and vegetable oil~
(e.g., castor, lard oil) liquid petroleum oils and -hydrorefined, solvent-treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic and mixed paraffinic-naphthenic types. Oils of lubricating viscosity derived from coal or shale are also useful base oils.

Synthetic lubricating oils include hydrocarbon oils and halosubstituted hydrocarbon oils such as polymerized and interpolymerized olefins (e.g., polybutylene~, polypropylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, etc.) poly(hexenes), poly(l-octenes), poly(1-decense), etc. and mixtures thereof;
alkylbenzenes (e.g., dodecyl-benzenes, tetradecyl-benzenes, dinonylbenzenes, di-(2-ethylhexyl)-benzenQs, etc.); polyphenyls (e.g., biphenyls, terphenyls, alkylated diphenyl ethers and a}kylated diphenyl sulfidQs and the derivatives, analogs and homologs thereof and tho like.

Alkylene oxide polymers and interpolymers and derivatives thereof where the terminal hydroxyl group8 have been modified by e~terification, etherification, etc., constitute another class of known synthetic .. . ..

~111313 lubricating oils. These are exemplified by polyoxyalkylene polymers prepared by polymerization of ethylene oxide or propylene oxide, the alkyl and aryl ethers of these polyoxyalkylene polymers (e.g., methyl-poly isopropylene glycol ether having an average molecular weight of 1000, diphenyl ether of polyethylene glycol having a molecular weight of 500 to 1,000, diethyl ether of polypropylene glycol having a molecular weight of 1,000 to 1,500; and mono- and polycarboxylic esters thereof, for example, the acetic acid esters, mixed C3 to C8 fatty acid e~ters and C13 Oxo acid diester of tetraethylene glycol.

Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebasic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkylmalonic acids, alkenyl malonic acids) with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethy}ene glycol, diethylene glycol monoether, propylene glycol). Specific examples of the~e 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 complex ester formed by reacting 1 mole of sebacic acid with 2 moles of tetraethylene glycol and 2 moles of 2-ethylhexanoic acid.

Esters useful as synthetic oils also include tho~e made from C5 to cl2 monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol.

, ., , . ~ ; . ~ .. . . . .

~-" 211~3~.3 Silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxysiloxane oils and silicate oils comprise another useful class of synthetic lubricants; they include tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl)silicate, tetra-(4-methyl-2-ethylhexyl)silicate, tetra-(p-tert-butylphenyl)silicate, hexa-(4-methyl-2-pentoxy) disiloxane, poly(methyl)siloxanes and poly(methyl-_ phenyl)siloxanes. Other synthetic lubricating oils include liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, diethyl ester of decylphosphonic acid) and polymeric tetrahydrofurans.

Unrefined, refined and rerefined oils can be used in the lubricants of the present invention. Unrefined oils are those obtained directly from a natural or synthetic source without further purification treatment. For example, a shale oil obtained directly from retortin~
operations, a petroleum oil obtained directly from distillation or ester oil obtained directly from an esterification process and used without further treatment would be an unrefined oil. Refined oils are similar to the unrefined oils except they have been further treated in one or more purification steps to improve one or more properties. Many such purification techniques, such as distillation, solvent extraction, acid or b~se extraction, filtration and percolation are known to those skilled in the art. Rerefined oils are obtained by processes similar to those used to obtain refined oils applied to refined oils which have been already used ~n service. Such rereflned oils are also known as reclaimed or reprocessed oils and often are additionally proces~ed by techniques for re~oval of spent additives and oil breakdown products.

.

Additional Formulation ComDonents ' ~
As indicated above, the additives of thQ pre~ent invention may be mixed with other types of additive~- ~
selected to perform at least one desired function. -Typical of such functions are detergentJinhibitor, viscosity modification, wear inhibitor, oxidation inhibitor, corrosion inhibitor, friction modifier, foam inhibitor, rust inhibitor, demulsifier, lube oil flow~ ~-improvers, and seal swell control. Each class of such additional additives is discussed in more detail below. ;
~.~
Deter~ent/Inbibitor Metal-containing detergents which can also act aB
rust inhibitors are known as "detergent/inhibitors" or simply "DI". DI's include the metal salts of sulphonic acids, alkyl phenols, sulphurized alkyl phenols, alkyl salicylates, naphthenates, and other oil soluble mono-and dicarboxylic acids as well as metal-containing complexes thereof. Usually these metal-containing DI'~
are used in lubricating oil in amounts of about 0.01 to 10, e.g. 0.1 to 5 wt. %, based on the weight of the total lubricating composition. Marine diesel lubricating oils typically employ such metal-containing rust inhibitors and detergents in amounts of up to about 20 wt. %.

Metal detergent/inhibitors are generally basic (viz, overbased) alkali or alkaline earth metal salt~ (or mixtures thereof, e.g. mixtures of Ca and Mg salts) of one or more organic sulfonic acid (generally a petroleum sulfonic acid or a synthetically prepared alkaryl sulfonic acid), petroleum naphthenic acids, alkyl bonzene ^~

sulfonic acids, alkyl phenols, alkylene-bis-phenols, oil soluble fatty acids and the like, such as are described in U.S. Patent Nos. 2,501,731; 2,616,904; 2,616,905;
2,616,906; 2,616,911; 2,616,924; 2,616,925; 2,617,049;
2,777,874; 3,027,325; 3,256,186; 3,2~2,835; 3,384,585;
3,373,108; 3,30S,308; 3,365,396; 3,342,733; 3,320,162;
3,312,618; 3,3~8,809 and 3,562,159 the disclosures of which are hereby incorporated by reference. Among the petroleum sulfonates, the most useful products are tho~
prepared by the sulfonation of suitable petroleum fractions with subsequent removal of acid sludge and purification. Synthetic alkaryl sulfonic acids are usually prepared from alkylated benzenes such as the Friedel-Crafts reaction product of benzene and a polymer such as tetrapropylene, C18 to Cz4 hydrocarbon polymer, etc. Suitable acids may also be obtained by sulfonation of alkylated derivatives of such compounds as diphenylene oxide thianthrene, phenolthioxine, diphenylene sulfide, phenothiazine, diphenyl oxide, diphenyl sulfide, diphenylamine, cyclohexane, decahydro naphthalene and the like.

The terms "basic salt" and "overbased salt" are used to designate metal salts wherein the metal is present in stoichiometrically larger amounts than the acid radical.

As used in this discussion, the term "complex"
refers to basic metal salts which contain metal in an amount in excess of that present in a neutral or norm~l metal salt. The "base number" of a complex is the number of milligrams of KOH to which one gram of the complex is equivalent as measured by titration.

The commonly employed methods for preparinq the basic salts involve heating a mineral oil solution of the normal metal salt of the acid with a metal neutralizing agent. The use of a "promoter" in the neutralization step to aid the incorporation of a large excess of m~tal is known and is preferred for the preparation of such compositions.

Examples of compounds useful as the promoter include phenolic substances such as phenol, naphthol, alkyl phenols, thiophenol, sulfurized alkyl phenols, and condensation products of formaldehyde with a phenolic substance; alcohols such as methanol, 2-propanol, octanol, cellosolve, carbitol, ethylene glycol, stearyl alcohol and cyclohexanol; and amines such as aniline, phenylene diamine, phenothiazine, phenol beta-naphthylamine and dodecylamine.

The alkali and alkaline earth metal compounds which may be used in neutralizing these acids to provide the metal salts include the oxides and hydroxides, al~oxides, carbonates, carboxylate, sulfide, hydrosulfide, nitrate, borates and ethers of magnesium, calcium, and barium.
Examples are calcium oxide, calcium hydroxide, magnesium acetate and magnesium borate. As noted, the alkaline earth metal compound is used in excess of that required to complete neutralization of the alkaryl sulfonic acids.
Generally, the amount ranges from about 100 to 220%, although it is preferred to use at least 125%, of the stoichiometric amount of metal required for complete neutralization.

Various other preparations of basic alkaline earth metal alkaryl sulfonates are known, such as U.S. PatQnt Nos. 3,150,088 and 3,150,089 wherein overbasing is accomplished by hydrolysis of an alkoxide-carbonatQ
complex with the alkaryl sulfonate in a hydrocarbon solvent-diluent oil.

, ,. . . - : .. : ~:

.

~1~131~

An example, convenient process for tha preparation of the metal-containing complexes employs an oil-soluble sulfonic acid, such as a synthetically prepared didodecylbenzene sulfonic acid, which is mixed with an excess of lime (e.g., 10 equivalents per equivalent o~
the acid) and a promoter such as methanol, heptylphenol, or mixture thereof, and a solvent such as mineral oil, at 50C to 150C and the process mass is then carbonated until a homogeneous ma6s is obtained. Complexes o~
sulfonic acids, carboxylic acids, and mixtures thereof are obtainable by processes such as are described in U.S.
Patent No. 3, 312, 618 . Another example is the preparation of a magnesium sulfonate normal magnesium salt thereof, an excess of magnesium oxide, water, and preferably also an alcohol such as methanol.

The carboxylic acids useful for preparing sulfonate carboxylate complexes, and carboxylate complexes, i.e., those obtainable from processes such as the above wherein a mixture of sulfonic acid and carboxylic acid or a carboxylic acid alone is used in lieu of the sulfonic acid, are oil-soluble acids and include primarily fatty acids which have at least about 12 aliphatic carbon atom~
and not more than about 24 aliphatic carbon atoms.
Examples of these acids include: palmitic, stearic, myristic, oleic, linoleic, dodecanoic, behenic, etc.
Cyclic carboxylic acids may also be employed. T~ese include aromatic and cycloaliphatic acids. The aromatic acids are those containing a benzenoid structure (i.e., benzene, naphthalene, etc.) and an oil-solubilizing radical or radicals having a total oS at least about lS
to 18 carbon atoms, preferably from about 15 to about 200 carbon atoms. Examples of the aromatic acids include:
stearyl-benzoic acid, phenyl stearic acid, mono- or polywax-substituted benzoic or naphthoic acids wherein the wax group consists of at least about 18 carbon atoms, ~ , .

cetyl hydroxybenzoic acids, etc. The cycloaliphatic acids contemplated have at least about 12, usually up to about 30 carbon atoms. Examples of such acids are petroleum naphthenic acids, cetyl cyclohexane carboxylic acids, dilauryl decahydro naphthalene carboxylic acids, dioctyl cyclopentane carboxylic acids, etc. The thiocarboxylic acid analogs of the above acids, wherein one or both of the oxygen atoms of the carboxyl group are replaced by sulfur, are also contemplated.

The ratio of t~e sulfonic acid to the carboxylic acid in mixtures is typically at least l:l (on a chemical equivalent basis) and is usually less than 5 preferably from 1:1 to 2:1.

Usually, the basic composition obtained according to the above-described method is treated with carbon dioxide until its total base number tTBN) is less than about 50, as determined by ASTM procedure D-2896. In many instances, it is advantageous to form the basic product by adding a Ca or Mg base portionwise and carbonating after the addition of each portion. Products with very high metal ratios (10 or above) can be obtained by this method. As used herein, the term "metal ratio" refers to the ratio of total equivalents of alkaline earth metal in the sulfonate complex to equivalents of sulfonic acid anion therein. For example, a normal sulfonate has a metal ratio of 1.0 and a calcium sulfonate complex containing twice as much calcium as the normal salt has a metal ratio of 2Ø The overbased metal detergent compositions usually have metal ratios of at le~st about 1.1, for example, from about 1.1 to about 30, with metal ratios of from about 2 to 20 being preferred.

Neutral metal sulfonates are freguently used as rust inhibitors. Polyvalent metal alkyl salicylate, 211131~

naphthenate and phenate matarials are known additives for lubricating oil compositions to improve their high temperature performance and to counteract deposition of carbonaceous matter on pistons (U.S. Patent No.
2,744,069). They can be milkylene or sulfur bridged~

The sulfurized metal phenates represent a preferred class of phenates, and can be considered the "metal salt of a phenol sulfide" which thus refers to a metal salt whether neutral or basic, of a compound typified by the general formula (30):

(30) 46 ~46 ~46 ~S~Sx~

where x = 1 or 2, n = 0, 1 or 2; or a polymeric form o~
such a compound, where R46 is an alkyl radical, n and x are each integers from 1 to 4, and the average number of carbon atoms in all of the R46 groùps is at least about 9 in order to ensure adequate solubility in oil. The individual R46 groups may each contain from 5 to 40, preferably 8 to 20, carbon atoms. The metal salt i8 prepared by reacting an alkyl phenol sulfide with a sufficient quantity of metal containing material to impart the desired alkalinity to the sulfurized metal phenate.

Regardless of the manner in which they are preparod, the sulfurized alkyl phenols which are useful genorally contain from about 2 to about 14 wt. %, preferably about 4 to about 12 wt. % sulfur based on the weight of sulfurized alkyl phenol.
.

:- : :. : : .
-:: - . . ::

21113~

The sulfurized alkyl phenol may also be converted by reaction with a metal containing ~aterial including oxides, hydroxides and complexes in an amount sufficient to neutralize said phenol and, if desired, to overbase the product to a de~ired alkalinity by procedures well known in the art. Preferred is a process of neutralization utilizing a solution of metal in a glycol ~
ether. -The neutral or normal sulfurized metal phenates arethose in which the ratio of metal to phenol nucleus is about 1:2. The "overbased" or "basic" sulfurized metal phenates are sulfurized metal phenates wherein the ratio of metal to phenol is greater than that of stoichiometric, e.g. basic sulfurized metal dodecyl phenate, has a metal content up to and greater than 100%
in excess of the metal present in the corresponding normal sulfurized metal phenates wherein the excess metal ~~
is produced in oil-soluble or dispersible form (as by ~ -reaction with C02).

Magnesium and calcium containing detergents, although beneficial in other respects, can increase the tendency of the lubricating oil to oxidize. ~his is especially true of the highly basic sulphonates. ;
~ .
The magnesium and/or calcium is generally present as basic or neutral detergents such as the sulphonates and phenates.

Viscositv Modifiers A viscosity index (V.I.) i~prover, also referred to as viscosity modifier, is typically employed in multi-. ~ . .: , I,, - . : : . :

21~1313 grade automobile engine lubricatinq oils. Viscosity modifiers impart high and low temperature operability to the lubricating oil and permit it to remain relatively viscous at elevated temperatures and also exhibit acceptable viscosity or fluidity at low temperature~.
Viscosity modifiers are generally high molecular weight hydrocarbon polymers including polyesters. The viscosity modifiers may include derivatized polymers recited above which include various properties or functions, including dispersancy properties. These oil soluble viscosity modifying polymers will generally have nu~oer average molecular weights of from 103 to 106, preferably 104 to lo6/ e.g., 20,000 to 250,000, as determined by gel permeation chromatography or osmometry.

Examples of suitable hydrocarbon polymers which can be used as viscosity improvers include homopolymers and copolymers of two or more monomers of C2 to C~O, e.g. C2 to c8 olefins, including both alpha olefins and internal olefins, which may be straight or branched, aliphatic, aromatic, alkyl-aromatic, cycloaliphatic, etc.
Frequently they will be of ethylene with C3 to C
olefins, particularly preferred being the copolymers of ethylene and propylene. Other polymers can be used such as polyisobutylenes, homopolymers and copolymers of C
and higher alpha olefins, atactic polypropylene, hydrogenated polymers and copolymers and terpolymers of styrene, e.g. with isoprene and/or butadiene and hydrogenated derivatives thereof. The polymer may b-degraded in molecular weight, for example, by mastication, extrusion, oxidation or thermal degradation, and it may be oxidized and contain oxygen. Also included are derivatized polymers such as post-grafted interpolymers of ethylene-propylene with an active monomer such as maleic anhydride which may be further reacted with an alcohol, or amine, e.g. an alkylene polyamine or hydroxy amine, e.g., see U.S. Patent Nos.
4,089,794: 4,160,739 and 4~137,185; or copolymers of ethylene and propylene reacted or grafted with nitrogen compounds such as shown in U.S. Patent Nos. 4,068,056;
4,068,058; 4,146,489 and 4,149,984.

Useful hydrocarbon polymers include ethylene copolymers containing from 15 to 90 wt. % ethylene, preferably 30 to 80 wt. % of ethylene and 10 to 8S wt. %~
preferably 20 to 70 wt. % of one or more C3 to C28, preferably C3 to Clg, more preferably C3 to C8, alpha-olefins. While not essential, such copolymers preferably have a degree of crystallinity of less than 25 wt. %, aB
determined by X-ray and differential scanning calorimetry. Copolymers of ethylene and propylene or ethylene and butene are most preferred. Other alpha-olefins suitable in place of propylene to form the copolymer, or to be used in combination with ethylene and propylene, to form a terpolymer, tetrapolymer, etc., include l-butene, 1-pentene, l-hexene, l-heptene, 1-octene, 1-nonene, 1-decene, etc.; also branched chain alpha-olefins, such as 4-methyl-1-pentene, 4-methyl-1-hexene, 5-methylpentene-1, 4,4-dimethyl-1-pentene, and 6-methylheptene-1, etc., and mixtures thereof.

Terpolymers, tetrapolymers, etc., of ethylene, said C3 to C28 alpha-olefin, and a non-conjugated diolefin or mixtures of such diolefins may also be used. The amount of the non-conjugated diolefin generally rangea from about 0.5 to 20 mole %, preferably from about 1 to about 7 mole %, based on the total amount of ethylene and alpha-olefin present.

The polyester V.I. improvers are generally polymers of esters of ethylenically unsaturated C3 to C8 mono- and ,... - - ..- .,, ... ~ .....

..

~11313 dicarboxylic acids such as methacrylic and acrylic acids, maleic acid, maleic anhydride, fumaric acid, etc.

Examples of unsaturated esters that may be used include those of aliphatic saturated mono alcohols of at least 1 carbon atom and preferably of from 12 to 20 carbon atoms, such a~ decyl acrylate, lauryl acrylate, stearyl acrylate, eicosanyl acrylate, docosanyl acrylate, decyl methacrylate, diamyl fumarate, lauryl methacrylate, cetyl methacrylate, stearyl methacrylate, and the like and mixtures thereof.

Other esters include the vinyl alcohol esters of C2 to c22 fatty or mono carboxylic acids, preferably saturated such as vinyl acetate, vinyl laurate, vinyl palmitate, vinyl stearate, vinyl oleate, and the like and mixtures thereof. Copolymers of vinyl alcohol esters with unsaturated acid esters such as the copolymer of vinyl acetate with dialkyl fumarates, can also be u~ed.

The esters may be copolymerized with still other unsaturated monomers such as olefins, e.g. 0.2 to 5 mole~
f C2 to C20 aliphatic or aromatic olefin per mole of unsaturated ester, or per mole of unsaturated acid or anhydride followed by esterification. For example, copolymers or styrene with maleic anhydride esterified with alcohols and amines are known, e.g., see U.S. Patent No. 3,702,300.

Such ester polymers may be grafted with, or the e~ter copolymerized with, polymerizable unsatUratQd nitrogen-containing monomers to impart dispersancy to the V.I. improvers. Examples of suitable un~aturated nitrogen-containing monomers include those containinq 4 to 20 carbon atoms such as amino substituted olefins as p-(beta-diethylaminoethyl)styrene; basic nitrogen-containing heterocycles carrying a polymerizable ethylenically unsaturated substituent, e.g. the vinyl pyridines and the vinyl alkyl pyridines such as 2-vinyl-5-ethyl pyridine, 2-methyl-5-vinyl pyridine, 2-vinyl-pyridine, 4-vinylpyridine, 3-vinyl-pyridine, 3-methyl-5-vinyl-pyridine, 4-methyl-2-vinyl-pyridine, 4-ethyl-2-vinyl-pyridine and 2-butyl 1-5-vinyl-pyridine and the ;
like. N-vinyl lactams are al80 suitable, e.g. N-vinyl ~
pyrrolidones or N-vinyl piperidones. Tne vinyl_ pyrrolidones are preferred and are exemplified by N-vinyl pyrrolidone, N-(1-methylvinyl) pyrrolidone, N-vinyl-5-methyl pyrrolidone, N-vinyl-3, 3-dimethylpyrrolidone, N-vinyl-5-ethyl pyrrolidone, etc.

Such nitrogen- and e~ter-containing polymeric viscosity index improver dispersants are generally employed in concentraions of from about O.OS to 10 wt. S
in the fully formulated oil, and preferably from about 0.1 to 5 wt. %, and more preferably from about 0.5 to 3 -wt. S can reduce (e.g., to about 0.5 wt. %) the amount of the ashless dispersant employed to provide the required dispersancy to the oil formulation.

Antiwear Aaents Antiwear agents, as their name implies, reduce wQar of moving metallic parts. Representative of conventional antiwear agents which may be used include, for ex~ple, phosphorous compounds such as zinc dialkyl dithiophosphates, and the zinc diaryl dithiopho~phate-.

Suitable phosphates include dihydrocarbyl dithiophosphates, wherein the hydrocarbyl groups contain an average of at least 3 carbon atoms. Particularly useful are metal salts of at least one dihydrocarbyl dithiophosphoric acid wherein the hydrocarbyl groups contain an average of at least 3 carbon atoms. The acids from which the dihydrocarbyl dithiophosphates can be derived can be illustrated by acids of the formula:

S : .
R470-P-S-H ~
~.48 1 wherein R47 and R48 are the same or different and are alkyl, cycloalkyl, aralkyl, alkaryl or substituted -~
substantially hydrocarbon radical derivatives of any of the above groups, and wherein the R47 and R48 groups in the acid each have, on average, at least 3 carbon ato~s.

By "substantially hydrocarbon" is meant radicals containing substituent groups (e.g., 1 to 4 substituent groups per radical moiety) such as ether, ester, nitro or halogen which do not materially affect the hydrocarbon character of the radical.

Specific examples of suitable R47 and R48 radicals include isopropyl,isobutyl, n-butyl, sec-butyl, n-hexyl, heptyl, 2-ethylhexyl, diisobutyl, isooctyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, butylphenyl,o,p-depentylphenyl, octylphenyl, polyi80-butene-(molecular weight 350)-substituted phenyl, tetrapropylene-substituted phenyl,beta-octylbutyl-naphthyl, cyclopentyl, cyclohexyl, phenyl, chlorophenyl, o-dichlorophenyl, bromophenyl, naphthenyl, 2-methylcyclohexyl, benzyl, chlorobenzyl, chloropentyl,~
dichlorophenyl, nitrophenyl, dichlorodecyl ~nd xenylradicals. Al~yl radicals having about 3 to 30 carbon atoms, and aryl radicals having about 6 to 30 21113~3 carbon atoms, are preferred. Particularly preferred R47 and R48 radicals are alkyl of 4 to ~8 carbons.

~ he phosphorodithioic acids are readily obtainable by the reaction of phosphorus pentasulfide and an alcohol or phenol. The reaction involve~ mixing, at a temperature o~ about 20C to 200C, 4 mole~ o~ the alcohol or phenol with one mole of phosphorus pentasulfide. Hydrogen sulfide i8 liberated as the reaction takes place. Mixtures of alcohols, phenols or both can be employed, e.g., mixtures of C3 to C
alkanols, C6 to C30 aromatic alcohols, etc.

The metals useful to make the phosphorous salts include Group I metals, Group II metals, aluminum, lead~
tin, molybdenum, manganese, cobalt and nickel. Zlnc i~
the preferred metal. Examples of metal compounds which may be reacted with the acid include lithium oxide, lithium hydroxide, lithium carbonate, lithium pentylate, ~odium oxide, sodium hydroxide, sodium carbonate, sodium methylate, sodium propylate, sodium phenoxide, potas~ium oxide, pota~ium hydroxide, potassium c~rbonate, potassium methylate, silver oxide, 3ilver carbonate, magnesium oxide, magnesium hydroxide, magne~ium carbonate, magnesium ethylate, magnesium propylate, magne6ium phenoxide, calcium oxide, calcium hydroxide, calciu~ carbonate, calcium methylate, calcium propylate, calcium pentylate, zinc oxide, zinc hydroxide, zinc carbonate, zinc propylate, strontium oxide, strontium hydroxide, cadmium oxide, cadmium hydroxide, cadmiu~
carbonate, cadmium ethylate, barium oxide, barium hydroxide, barium hydrate, barium carbonate, barium ethylate, barium pentylate, aluminum oxide, aluminum propylate, lead oxide, lead hydroxide, lead carbonate, tin oxide, tin butylate, cobalt oxide, cobalt hydroxide, cobalt carbonate, cobalt pentylate, nickel oxide, nickel hydroxide and nickel carbonate.

In some instances, the incorporation of certain ingredients, particularly carboxylic acids or metal carboxylates such as small amounts of the metal acetate or acetic ac~d u3ed in conjunction with the metal reactant will facilitate the reaction and result in an improved product. For example, the use of up to about 5%
of zinc acetate in co~bination with the required amount of zinc oxide facilitates the formation of a z~nc phosphorodithioate.
, ~
The preparation of metal phosphorodithioates is well known in the art and is described in a large number of issued patents, including U.S. Patent Nos. 3,293,181;
3,397,145; 3,396,109 and 3,442,804, the disclosure~ o~
which are hereby incorporated by reference insofar as the preparation of ~etal salts of organic phosphorodithioic acids useful in this invention are described.

Also useful as antiwear additives are auine derivatives of dithiophosphoric acid compounds, such a~
are described in U.S. Patent No. 3,637,499, the di6closure of which is hereby incorporated by reference in its entirety.

The zinc salts are most commonly used as antiwear additives in lubricating oil in amounts of 0.1 to 10, preferably 0.2 to 2 wt. %, based upon the total weight Or the lubricating oil composition. They may ba prepared ln accordance with known techniques by first forming a dithiophosphoric acid, usually by reaction of an alcohol o- a phenol with P2Ss and then neutralizing t~
dithiophosphoric acid with a suitable zinc compound.

Mixtures of alcohols may be used including mixtures of primary and secondary alcohols, secondary generally for imparting improved antiwear properties, and primary for thermal stability. Mixtures of the two are particularly useful. In general, any basic or neutral zinc compound could be used ~ut the oxide~, hydroxide~
and carbonates are most generally employed. Commercial additives frequently contain an exces of zinc due to use of an excess of the ba~ic zinc co~pound in ths neutralization reaction.

The zinc dihydrocarbyl dithiophosphate are oil soluble salts of dihydrocar~yl esters of dithiophosphoric acids and may be represented by the following formula:

_--R490-P_~_ I Zn oR5 wherein R49 and R50 are described the same as R47 and R48 respectively.

Suitable antiwear agents also comprise the phosphorous- and sulfur-containing product mixtures described in U.S. Application Serial No. 210,831 filed on June 24, 198a by Ryer and Gutierrez and the Continuation-in-Part thereof: U.S. Serial No. 370,315, filed June 22, 1989, the disclosures thereof are incorporated herein by reference.

In a preferred embodiment of the phosphorous- and sulfur-containing product mixtures disclosed in s~id commonly assigned applic~tions, the following three components, namely: (1) organic phosphite ester, t21 ,, ,~. ...... ... .... .. . . . .

hydrocarbyl thioalkanol, and (3) heterodialkanol are reacted in admixture, preferably in simultaneous admixture. Preferred hydrocarbyl thioalkanol re~ctants include C8 to C18 thioethanols. Preferred heterodialkanols are thiodialkanols. Representative thiodialkanols include 2,2'-thiodiethanol; 3,3~-thiodipropanol; thio-bis ethoxy-ethanol;
thiobisisopropoxyisopropanol; and mixtures thereof.

Oxidation Inhibitors Oxidation inhibitors reduce the tendency of mineral oils to deteriorate in service, which deterioration can be evidenced by the products of oxidation such as sludge and varnish-like deposits on the metal surfaces and by viscosity growth.

Useful antioxidant materials include oil soluble phenolic co~pounds, oil soluble sulfurized organic compounds, oil soluble amine antioxidants, oil ~oluble organo borates, oil soluble organo phosphite~, oil soluble organophosphates, oil soluble organo dithiophosphates and mixtures thereof. Preferably such antioxidants are metal-free (that is, free of metals which are capable of generating sulfated ash), and therefore are most preferably ashless (having a sulfated a~h value of not greater than 1 wt. % SASH, as determined by ASTMD874).

Illustrative of oil soluble phenolic compounds are alkylated monophenols, alkylated hydroquinon~s, hydroxylated thiodiphenyl ethers, alkylid-nebis phenols, benzyl compounds, acylaminophenols, and e~ters and amides of hindered phenol-substituted alkanoic acids.

211~ 313 ExamDles of Phe~ol~c Antioxidants 1. Alkylated monophenols 2,6-di-tert-butyl-4-methylphenol; 2,6-di-tert-butylphenol; 2-tert-butyl-4,6 dimethylphenol; 2,6-di-tertbutyl-4-ethylphenol; 2,6-ditert-butyl-4-ethylphenol; 2,6-di-tert-butyl-4-n-butyl-phenol; 2,6-di-tertbutyl-4-isobutylphenol; 2,6-dicyclo-pentyl-4-methylphenol; 2-(alpha-methylcyclohexyl)-4,6-_ dimethylphenol; 2,6-dioctadecyl-4-methylphenol; 2,4,6-tricyclohexylphenol; 2,6-di-tert-butyl-4-methoxymethyl-phenol; o-tert-butylphenol.

2. Alkylated hydroquinoneæ 2,6-di-tert-butyl-4-methoxyphenol; 2,5-di-tertbutyl-hydroquinone; 2,5-di-tert-amylhydroquinone; 2,6-di-phenyl-4-octadecyloxy-phenol.

3. Hydroxylated thiodiphenyl ethers 2,2'-thiobis(6-tert-butyl-4-methyl-phenol); 2,2'-thiobis(4-octylphenol); 4,4'-thiobis(6-tert-butyl-3-methylphenol);
4,4'-thiobis(6-tert-butyl-2-methylphenol).

4. Alkylidenebisphenolc 2,2'-methylenebis(6-tert-butyl-4-methylphenol); 2,2'-methylenebis(6-tert-butyl-4-ethylphenol); 2,2'-methylenebist4-methyl-6-(alpha-methyl-cyclohexyl)-phenol); 2,2'-methylenebis(4-methyl-6-cyclo-hexylphenol); 2,2'-methylenebis(6-nonyl-4-methylphenol);
2,2'-methylenebis(4,6-di-tert-butyl-phenol); 2,2'-methyl-idenebis(4,6-di-tert-butylphenol); 2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol); 2,2'-methylenebist6-alpha-methylbenzyl)-4-nonylphenol~; 2,2'-methylenebis[6-(~lpha, alpha-dimethylbenzyl)-4-nonyl-phenol]; 4,4'-methylene-bis~2,6-di-tert-butylphenol), 4,4'-methylenebis(6-tert-butyl-2-methylphenol); 1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)butane; 2,6-d~(3-tert-butyl-5-methyl-2-.
. . .

2~113~3 hydroxybenzyl)-4-methylphenol; l~lr3-tris(5-tert-butyl-4 hydroxy-2-methylphenyl)-3-n-dodecylmercapobutane;
ethylene glycol bist3,3-bis(3'-tert-butyl-4'-hydroxylphenyl)butyrate]; di(3-tert-butyl-4-hydroxy-5-methylphenyl)dicyclopentadiene; dit2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tertbutyl-4-methylpheny]terephthalate.

5. Benzyl compounds 1~3~5-tris(3~5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethyl-benzene; di(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide; 3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetic acid isooctyl ester; bis(4-tert-butyl-3-hydroxy-2,6-dimethyl-benzyl)dithio-terephthalate; 1,3,5-tris(3,5-di-tertbutyl-4-hydroxy-benzyl)isocyanuratel,3,5-tris(4-tertbutyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate; 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid dioctadecyl e6ter 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid mono-ethyl eoter calcium salt.

6. Acylaminophenols 4-hydroxylauric acid anilide;
4-hydroxystearic acid anillde; 2,4-bis-octylmercapto-6-(3,5-di-tert-butyl-4-hydroxyanilino)-s-triazine; N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamic acid octyl ester.

7. Esters o~ beta-(3,5-di-tert-butyl-4-hydroxy-phenyl)propionic acid with mono- or polyhydric alcoholo, e.g. with methanol; octadecanol; 1,6-hexanediol;
neopentyl glycol; thiodiethylene glycol; diethylen glycol; triethylene glycol; pentaerythritol;
tris(hydroxy-ethyl)i~ocyanurate; and di(hydroxyethyl) oxalic acid diamide.

8. Esters of beta-(5-tert-butyl-4-hydroxy-3-msthylphenyl)propionic acid with mono- or polyhydric alcoholo, e.g. with methanol; octadecanol; 1,6-'.

hexanediol; neopentyl glycol; thiodiethylene glycol;
diethylene glycol; triethylene glycol; pentaerythritol;
tris(hydroxyethyl)isocyanurate; and di(hydroyethyl)oxalic acid diamide.

9. Amides of beta -(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, e.g., N,N'-di(3,5-di-tert-butyl-4-hydroxyphenyl-pro-prionyl)heXamethylenediamine;
N~N~-di(3~5-di-tert-butyl-4-hydroxyphenylpropionyl) trimethylenediamine; N,N'-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine.

Oil soluble sulfurized organic compounds include those represented by the for~ula:

R Sx4R

wherein s represents sulfur, X4 is a whole number having a value of from 1 to about 10, and R51 and R52 m3y be the same or different organic groups. The organic groups may be hydrocarbon groups or substituted hydrocarbon groups containing alkyl, aryl, aralkyl, alkaryl, alkanoate, thiazole, imidazole, phosphorothionate, beta-ketoalkyl groups, etc. The substantially hydrocarbon groups may contain other substituents such as halogen, amino, hydroxyl, ~ercapto, alkoxy, aryloxy, thio, nitro, sulfonic acid, carboxylic acid, carboxylic acid e~ter, etc.

Specific examples of types of sulfurized compositions which are u~eful oxidation inhibitor~
include aromatic, alkyl or alkenyl sulfides and .
polysulfides, sulfurized olefins, sulfurized carboxylic acid esters, sulfurized e~ter olefins, sulfurized oil, and mixtures thereof. Ths preparation of such oil-soluble sulfurized compositions is described in the art, ., : . ~ ~ . , . ~

211131~

and u.S. Patent No. 4,612,129 is incorporated herein by reference in its entirety for its disclosure of such preparations; including the type and amount of reactants and catalyst~ (or promoters), temperatures and other process conditions, and product purification and recovery techniques (e.g., decoloring, f~ltering, and other solias and impurity removal steps). The sulfurized organic compounds may be aromatic and alkyl sulfides such as dibenzyl sulfide, dixylyl sulfide, dicetylsulfide, diparaffin wax sulfide and polysulfide, cracked wax oleu~
sulfides, etc.

Examples of dialkenyl sulfides are described in U.S.
Patent No. 2,446,072. Examples of sulfides of this type include 6,6'-dithiobis(5-methyl-4-nonene), 2-butenyl monosulfideand disulfide, and 2-methyl-2-butenyl monosulfide and disulfide.

Representative sulfurized olefins include sulfurized olefins prepared by the reaction of an olefin (preferably containing 3 to 6 carbon atoms) or a lower molecular weight polyolefin derived therefrom, with a sulfur-containing compound such as sulfur, sulfur monochloridQ
and/or sulfur dichloride, hydrogen sulfide, stc.
Isobutene, propylene and their dimers, trimers and tetramers, and mixtures thereof are especially preferred olefinic compounds. Of these ccmpounds, isobutylene and diisobutylene are particularly desirable because of thQir availability and the particularly high sulfur-containing compositions which can be prepared therefrom.

Ths sulfurized organic compounds may be sulfurizQd oils which may be prepared by treating natural or synthetic oils including mineral oils, lard oil, carboxylic acid e~ters derived from aliphatic alcohols and fatty acids or aliphatic carboxylic acids (e.g~, r~....... . ~ ..

;-' . ` . - ~ i - ` ' 211~ 31~

myristyl oleate and oleyl oleate) sperm whale oil and synthetic sperm whale oil substitutes and cynthetic unsaturated esters or glycerides.

The sulfurized fatty acid esters can be prepared by reacting sulfur, sulfur monochloride, and/or sulfur dichloride with an unsaturated fatty ester at elevated temperatures. Typical esters include Cl to C20 aLkyl esters of C8 to C24 unsaturated fatty acids such as-palmitoleic, oleic, ricinoleic, petroselic, vaccenic, linoleic, linolenic, oleostearic, licanic, ~tc.
Sulfurized fatty acid esters prepared from mixed unsaturated fatty acid esters such as are obtained from animal fats and vegetable oils such as tall oil, linsQed oil, olive oil, castor oil, peanut oil, rape oil, fish oil, sperm oil, etc. also are useful. Specific examples of the fatty esters which can be sulfurized include lauryl talate, methyl oleate, ethyl oleate, lauryl oleate, cetyl oleate, cetyl linoleate, lauryl ricinoleate, oleolinoleate, oleostaarate, and al~yl glycerides.

Another class of organic sulfur-containing compounds includes sulfurized aliphatic e~ters of an olefinic monodicarboxylic acid. For example, aliphatic alcohols of from 1 to 30 carbon atoms can be used to esterify monocarboxylic acids such as acrylic acid, methacrylic acid, 2,4-pentadienic acid, etc. or fumaric acid, maleic acid, muconic acid, etc. Sulfurization of these e~ter~ i~
conducted with elemental sulfur, sulfur monochloride and/or sulfur dichloride.

Another class of sulfurized organic compounds include diester sulfides. ~ypical die~ters include the butyl, amyl, hexyl, heptyl, octyl, nonyl, d-cyl, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, . ~, . - . - :

stearyl, lauryl, andeicosyl; diesters of thiodialkanoic acids such as propionic, butanoic, pentanoic and hexanoie acids. of the diester sulfides, a specific example is dilauryl,3,3'-thiodipropionate.

Other suitable sulfurized organic eompound antioxidants inelude those derived from a partieular type of cyelic or bieyelic olefin whieh is a Dlels-Alder adduet of at least one dienophile with at least one aliphatic conjugated diene. The sulfurized Diels-Alder adducts can be prepared by reaeting various sulfurizinq agents with the Dlels-Alder adducts as described more fully below. Typically, the sulfurizing agent is sulfur.

The Diels-Alder adduets are a well-known, art-reeognized class of compounds prepared by the diene synthesis of Diels-Alder reaetion. A summary of the prior art relating to this elass of eompounds i~ found in the Russian monograph, "Dienovyi Sintes~, Izdatelstwo .A
Akademii Nauk SSSR, 1963 by A. S. Onischenko.
(Tran~lated into the English language by L. Mandel a~ A.
S. Onisehenko, "Diene Synthesi~", N.Y., Daniel Davey and Co., Ine., 1964). Thi~ monograph and referenees eitod therein are ineorporated by referenee into the present speeification.

Still further, sulfurized organie eompounds inelude at least one sulfurized terpene compound or a eomposition prepared by sulfurizing a mixture eomprising at least one terpene and at least one other olefinie eompound.

The term "terpene eompound" a~ u~ed in the speeifieation and claims i~ intended to inelude the various isomerie terpene hydroearbons having the empirieal formula C1oH16, sueh as eontained in turpentine, pine oil and dipentenes, and the various ;. . :~ . - : . :1 : ' .` .. ' ~11 1313 synthetic and naturally occurring oxygen-containing derivatives. Mixtures of these various compounds generally will be utilized, especially when natural products such as pine oil and turpentine are used. Plne oil, for example, which is obtained by de~tructi~e distillation of waste pinewood with super-heated steam comprise~ a mixture of terpene derivative~ such as alpha-terpineol, beta-terpineol, alpha-fenchol~ c~mphor, ~
borneol/isoborneol, fenchone, e~tragole, dihydro alpha-terpineol, anethole, and other monoterpene hydrocarbons.
The specific ratios and amounts of the various components in a given pine oil will depend upon thQ particular source and the degree of purification. A group of pine oil-derived products are available commercially from Hercules Incorporated. The pine oil products generally known a~ terpene alcohols available from Hercule~
Incorporated are particularly useful in the preparation of this class of sulfurized products. Examples of such products include alpha-Terpineol containing about 95 to 97% of alpha-terpineol, a high purity tertiary terpene alcohol mixture typically containing 96.3% of tertiary alcohols; Terpineol 318 Prime which is a mixture of isomeric terpineols obtained by dehydration of terpene hydrate and contains about 60 to 65 wt. % of alpha-terpineol and 15 to 20% beta-terpineol, and 18 to 20% of other tertiary terpene alcohols. Other mixtures and grades of u~eful pine oil products also are available from Hercules under such de~ignations as Yarmor 302, Herco pine oil, Yarmor 302W, Yarmor F and Yarmor 60.

The above terpene compounds may be sulfurized terpene compounds, sulfurized mixtures of terpeno compounds or mixtures of at least one terpene compound and at least one sulfurized terpene compound. Sulfuriz~d terpene compounds can be prepared by sulfurizing terpene compounds with sulfur, sulfur halides, or mixtures o~

, ............ . .

' ! ..,. . ' .. ~ : .
"'~; , :.. . . . '', "''' ' ''' sulfur dioxide with hydrogen sulfide. Also, the sulfurization of various terpene compounds has been described in the prior art. For example, the sulfurization of pine oil is described in U.S. Patent No.
2,012,446.

The other olefinic compound which may be combined with the terpene compound and sulfurized may be any oS
several olefinic compounds such ag those described earlier.

The other olefin used in combination with the terpene also may be an unsaturated fatty acid, an unsaturated fatty acid ester, mixtures thereof, or mixtures t~ereof with the olefins described above. The term "fatty acid~ as used herein refers to acids which may be obtained by ~ydrolysis of naturally occurring vegetable or animal fats or oils. These fatty acids usually contain from 16 to 20 carbon atoms and are mixtures of saturated and unsaturated fatty acids. The unsaturated fatty acids generally contained in the naturally occurring vegetable or animal fats and oils may contain one or more double bonds and such acids include palmitoleic acid, oleic acid, linoleic acid, linolenic acid, and erucic acid. The unsaturated fatty acids may comprise mixtures of acids such as those obtained from naturally occurring animal and vegetable oils such as lard oil, tall oil, peanut oil, soybean oil, cottonseed oil, sunflower seed oil, or wheat germ oil. Tall oil is a mixture of rosin acids, mninly abietic acid, and unsaturated fatty acids, mainly oleic and linoleic acids.
Tall oil is a by-product of the sulfate process for the manufacture of wood pulp.

The most particularly preferred unsaturated fatty acid esters are the fatty oils, that is, naturally . . . . ., . .... ;~ . ~ .. ..

. . : . , :: ~ .

21~1313 occurring esters of glycerol with the fatty acids described above, and synthetic e~ters of similar structure. Examples of naturally occurring fats and oils containing unsaturation include animal fats such as Neat's foot oil, lard oil, depot fat, beef tallow, etc.
Examples of naturally occurring vegetable oils include cottonseed oil, corn oil, poppyseed oil, safflower oil, sesame oil, soybean oil, sunflower seed oil and wheat germ oil. _ The fatty acid esters which are useful also may be ~:
prepared from aliphatic olefinic acids of the type described above such as oleic acid, linoleic acid, linolenic acid, and behenic acid by reaction with ;~
alcohols and polyols. Examples of aliphatic alcohols ~:
which may be reacted with the above-identified acids include monohydric alcohols such as methanol, ethanol, n-propanol, isopropanol, the butanols, etc.; and polyhydric alcohols including ethylene glycol, propylene glycol, trimethylene glycol, neopentyl glycol, glycerol, etc.

The sul~urized derivatives of the other olefin compounds can be prepared by methods known in the art utilizing sulfurizing reagents such as sulfur, sulfur halides or mixtures of sulfur or sulfur dioxide with ffl drogen sulfide.

Exemplary of aminé antioxidants are phenyl-substituted and phenylene-substituted amines, N-nitro phenylhydroxylamine, isoindoline compounds, phosphinodithioic acid-vinyl carboxylate adducts, phosphorodithioate e~ter-aldehyde reaction products, phosphorodithioate-alkylene oxide reaction products, silyl esters of terephthalic acid, bis-1,3-alkylamino-2-propanol, anthranilamide compounds, anthranilic acid esters, alpha-methyl styrenated aromatic amines, aromat$c , . -.. ,., ., ~ ".

: . . .

21113~3 - 1~4 -amines and substituted benzophenones, aminoguanidines, peroxide-treated phenothiazine, N-7substituted phenothiazines and triazines, 3-tertiary alkyl-substituted phenothiazines, alkylated diphenyl-aimine~, 4-alkylphenyl-1-alkyl-2-naphthylamines, di-benzazepine compounds, fluorinated aromatic amines, alkylated polyhydroxy benzenoid compounds, substituted indans, dimethyl octadecylphosphonate-arylimino di-alkanol copolymers and substituted benzo-diazoborole.

Exam~les of Amine Antioxidants N,N'-diisopropyl-p-phenylenediamine; N,N'-di-sec-butyl-p-phenylenediamine; N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine; N,N'-bis(l-ethyl-3-methylpentyl)-p-phenylenediamine; N,N'-bis(l-methylheptyl)-p-phenyl-enediamine; N,N'-diphenyl-p-phenylenediamine; N,N'-di-(naphthyl-2)-p-phenylenediamine; N-isopropyl-N'-phenyl-p-phenylenediamine; N-(1,3-dimethylbutyl)-N'-phenyl-n-phenylenediamine; N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine; N-cyclohexyl-N'-phenyl-p-phenyl-enediamine; 4-(p-toluenesulfonamido)diphenylamine; N,N'-dimethyl-N,N'-di-sec-butyl-p-phenylenediamine diphenyl-amine; 4-isopropoxydiphenylamine; N-phenyl-1-naphthylamine; N-phenyl-2-naphthylamine; octylated diphenylamine; 4-n-butylaminophenol; 4-butyryl-aminophenol; 4-nonanoyiaminophenol; 4-dodecanoyl-aminophenol; 4-octadecanoylaminophenol; di-(4-methoxy-phenyl)amine; di-tert-butyl-4-dimethylaminomethylphenol;
2,4'-diaminodiphenylmethane; 4,4'-diaminophenylmethane;
N,N,N',N'-tetramethyl-4,4'-diaminodiphenylmethanQ; 1,2-dit(2-methylphenyl)amino]ethane; 1,2-di(phenylamino)-propane; (o-tolyl)biguanide; di~4-(1',3'-dimethyl-butyl)phenyl~amine; tert-octylated N-phenyl-1-napthyl-7~-; ~ - . `:~
r~
;.,. . : ,.

~11131~

amino; and mixture of mono- and dialkylated tert-butyl-/tert-octyldiphenylamines.

Oil soluble organo-borate, phosphate and phosphite anti-oxidants include alkyl- and aryl- (and mixed al~yl, aryl) substituted borates, alkyl- and aryl- (and mixed alkyl, aryl) substituted phosphates, alkyl- and aryl-(and mixed alkyl, aryl) substituted phosphites, and~
alkyl- and aryl- (and mixed alkyl, aryl) substitutedL
dithiophosphates such as O,O,S-trialkyl dithiophosphates, O,O,S-triaryldithiophosphates and dithiophosphates having mixed substitution by alkyl andaryl groups, phosphorothionyl sulfide, phosphorus-containing silane, polyphenylene sulfide, amine salts of phosphinic acid and quinone phosphates.

A preferred class of anti-oxidants includes the sulfurized alkyl-substituted hydroxyaromatic compounds.
Sulfurized alkyl-3ubstituted hydroxyaromatic compounds and the methods of preparing them are known in the art and are disclosed, for example, in the following U.S.
Patents (which are incorporated by reference herein):
U.S. Patent Nos. 2,139,766; 2,198,828; 2,230,542;
2,836,565; 3,285,854; 3,538,166; 3,844,956; 3,951,830 and 4,115,287.

In general, the sulfurized alkyl-substituted hydroxyaromatic compounds may be prepared by reacting an alkyl-substituted hydroxyaromatic compound with a sulfurizing agent such a~ elemental sulfur, a sulfur halide (e.g., sulfurmonochloride or sulfur dichloride), a mixture of hydrogen sulfid~ and sulfur dioxide, or the like. The preferred sulfurizing agents are sulfur and the sulfur halides, and especially the sulfur chlorides, with sulfur dichloride (SC12)being especially preferred.

21~l~31~

The alkyl-substituted hydroxyaromatic compounds which are sulfurized to produce antioxidant are generally compounds containing at least one hydroxy group (e.g., from 1 to 3 hydroxy groupa) and at least one alkyl radical (e.g., from 1 to 3 alkyl radical3) attached to the same aromatic ring. The alkyl radical ordinarily contains about 3 to 100, and preferably about 6 to 20, carbon atoms. The alkyl-substituted hydroxy aromatic compound may contain more than one hydroxy group a~
exemplified by alkyl resorcinols, hydroquinones and catechols, or it may contain more than one alkyl radical;
but normally it contains only one of each. Compounds in which the alkyl and hydroxy groups are ortho, meta and para to each other, and mixtures of such compounds, are within the scope of the invention. Illustrative alkyl-substituted hydroxyaromatic compounds are n-propylphenol, isopropylphenol, n-butylphenol, t-butylphenol, hexylphenol, heptylphenol, octylphenol, nonylphenol, n-dodecylphenol, (propenetetramer)-substituted phenol, octadecylphenol, eicosylphenol, polybutene (molecular weight about 10001-substituted phenol, n-dodecylre orcinol and 2,4-di-t-butylphenol, and the alkyl-~ubstituted catechols corresponding to the foregoing. Also included are methylene-bridged alkyl-substituted hydroxyaromatic compounds of the type which may be prepared by the reaction of an alkyl-substituted hydroxyaromatic compound with formaldehyde or a formaldehyde-yielding reagent such as trioxane or paraformaldehyde.

The sulfurized alkyl-substituted hydroxy-aromatic compound is typically prepared by reactlng the alkyl-substituted hydroxyaromatic compound with the sulfurizing agent at a temperature within the range of about lOO-C to 250C. The reaction may take place in a ~ubstantially inert diluent such as tolusne, xylene, petroleum naphtha, ~11131~

, mineral oil, Cellosolve or the like. If the sulfurizing agent is a sulfur halide, and especially if no diluent is used, it is frequently preferred to remove acidic materials such as hydrogen halides by vacuum stripping the reaction mixture or blowing it with an inert gas such as nitrogen. If the sulfurizing agent is sulfur, it is frequently advantageous to blow the sulfurized product with an inert gas such as nitrogen or air so as to remove sulfur oxides and the like.

Also useful herein are antioxidants disclosed in the following U.S. Patents, the disclosures of which are herein incorporated by reference in their entirety: U.S.
Patent Nos. 3,451,166; 3,458,495; 3,470,099; 3,511,780;
3,687,848; 3,770,854; 3,850,822; 3,876,733; 3,929,654;
4,115,237; 4,136,041; 4,153,562; 4,367,152 and 4,737,301.

The most preferred antioxidants include oil soluble copper compounds. The copper may be blended into the oil as any suitable oil soluble copper compound. ~y oil soluble we mean the compound is oil soluble under normal blending conditions in the oil or additive package. The copper compound may be in the cuprous or cupric form.
The copper may be in the form of the copper dihydrocarbyl thio- or dithiophosphates wherein copper may be substituted for zinc in the compounds and reactions described above although 1 mole of cuprous or cupric oxide may be reacted with 1 or 2 moles of the dithiophosphoric acid, respectively. Alternatively, the copper may be added as the copper salt of a synthetic or natural carboxylic acid. Exsmples include C10 to C18 fatty acids such as stearic or palmitic, but unsaturated acids such as oleic or branched carboxylic acids such as napthenic acids of molecular weight from 200 to 500 or synthetic carboxylic acids are preferred because of the improved handling and solubility properties of the resulting copper carboxylates. Also useful are oil soluble copper dithiocarbamates of the general formula (RR'NCSS) ncu, where n is 1 or 2 and R and R' are the same or different hydrocarbyl radicals containing from 1 to 18 and preferably 2 to 12 carbon atoms and including radicals such as alkyl, alkenyl, aryl, aralkyl, alkaryl and cycloaliphatic radicals. Particularly preferred as R
and R' groups are alkyl groups of 2 to 8 carbon atoms.
~hus, the radicals may, for example, be ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, amyl, n-hexyl, i-hexyl, n-heptyl, n-octyl, decyl, dodecyl, octadecyl, 2-ethylhexyl, phenyl, butylphenyl, cyclohexyl, methylcyclopentyl, propenyl, butenyl, etc. In order to obtain oil solubility, the total number of carbon atoms (i.e., R and R') will generally be about 5 or greater.
Copper sulphonates, phenates, and acetylacetonates may also be used.

Exemplary of useful copper compound ianti-oxidants are copper (CuI and/or CuII) salts of alkenyl carboxylic acids or anhydrides such as succinic acids or anhydrides.
The salts themselves may be basic, neutral or acidic.
They may be formed by reacting (a) any of t~e functionalized polymers which are useful as dispersants section, which have at least one free carboxylic acid (or anhydride) group with (b) a reactive metal compound.
Suitable acid (or anhydride) reactive metal compounds include those such as cupric or cuprous hydroxide~, oxides, acetates, borates, and carbonates or basic copper carbonate.

Examples of the metal salts are Cu salts of poly-n-butene succinic anhydride (hereinafter referred to as Cu-PNBSA) polyisobutenyl succinic anhydride (hereinafter referred to as Cu-PIBSA), and Cu salts of poly-n-butene or polyisobutenyl succinic acid. Preferably, the selected metal employed is its divalent form, e.g., Cu +
2. The preferred substrates are polyalkenyl carboxylic acids in which the alkenyl group has a molecular w~i~ht greater than about 700. The alkenyl group desirably has a Mn from about 900 to 1,500, and up to 5,000. These materials can be dissolved in a solvent, such as a mineral oil, and heated in the presence of a water solution (or slurry) oS the metal bearing material.
Heating may take place between 70C and about Z00C_ Temperatures of 110C to 140C are entirely adequate. It may be necessary, depending upon the salt produced, not to allow the reaction to remain at a temperature above about 140C for an extended period of time, e.g., longer than 5 hours, or decomposition of the salt may occur.

The copper antioxidants (e.g., Cu-PIBSA, Cu-PNB, Cu-oleate, or mixtures thereof) will be generally employed in an amount of from about 50 to 500 ppm by weight of the metal, in the final lubricating or fuel composition.

The copper antioxidants are inexpensive and are ef~ective at low concentrations and therefore do not add substantially to the cost of the product. The results obtained are frequently better than those obtained with previously used antioxidants, which are expensive and used in higher concentrations. In the amounts employed, the copper compounds do not interfere with the performance of other components of the lubricating composition, in many instances, completely satisfactory results are obtained when the copper compound is the sole antioxidant in addition to the ZDDP. The copper compounds can be utilized to replace part or all of the need for supplementary antioxidants. Thus, for particularly severe conditions it may be desirable to include a supplementary, conventional antioxidant.
However, the amounts of supplementary antioxidant ~11131~ ~

required are small, far less than the amount required in the absence of the copper compound.

While a~y effective amount of the copper antioxidant can be incorporated into the lubricating oil composition, it is contemplated that such effective amounts be sufficient to provide said lube oil composition with an amount of the copper antioxidant of from about S to 500 (more preferably 10 to 200, still more preferably 10 to 180, and most preferably 20 to 130 (e.g., 90 to 120)) ppm of added copper based on the weight of the ll~bricating oil composition. of course, the preferred amount may depend, amongst other factors, on the quality of the basestock lubricatinq oil.

Corrosion Inhibitors Corrosion inhibitors, also known as anti-corrosive agents, reduce the degradation of the metallic parts contacted by the lubricating oil composition.
Illustrative of corrosion inhibitors are phosphosulfurized hydrocarbons and the products obtained by reaction of a phosphosulfurized hydro~arbon with an alkaline earth metal oxide or hydroxide, preferably in the presence of an alkylated phenol or of an alkylphenol thioester, and also preferably in the presence of carbon dioxide. Phosphosulfurized hydrocarbons are prepared by reacting a suitable hydrocarbon such as a terpene, a heavy petroleum fraction of a C2 to C6 olefin polymer such as polyisobutylene, with from 5 to 30 wt. % of a sulfide of phosphorus for 1/2 to 15 hours, at a temperature in the range of 65C to 315C.
Neutralization of the phosphosulfurized hydrocarbon may be effected in the manner taught in U.S. Patent No.
2,969,324.

... ~ . . . . ~ .......... . ......................... .

: . . . . , .~ . , .... ~ -.. ~ . - . . .. . , . . . :

Other suitable corrosion inhibitors include copper corrosion inhibitors comprising hydrocarhyl-thio-distributed derivatives of 1,3,4-thiadiazole, e.g., C2 to C30; alkyl, aryl, cycloalkyl, aralkyl and alkaryl-mono-, di-, tri-, tetra- or thio-substituted derivatives thereof.

Representative examples of such materials included_ 2,5-bis~octylthio)-1,3,4-thiadiazole; 2,5-bis(octyl-dithio)-1,3,4-thiadiazole; 2,5-bis(octyltrithio)-1,3,4-thiadiazole; 2,5-bis(octyltetrithio)-1,3,4-thiadiazole;
2,5-bis(nonylthio)-1,3,4-thiadiazole; 2,5-bis(dodecyl-dithio)-1,3,4-thiadiazole; 2-dodecyldithio-5-phenyl-dithio-1,3,4-thiadiazole; 2,5-bis(cyclohexyl dithio)-1,3,4-thiadiazole; and mixtures thereof.

Preferred copper corrosion inhibitors are the derivative of -1,3,4-thiadiazoles such as those described in U.S. Patent Nos. 2,719,12S, 2,719,126 and 3,087,932;
especially preferred is the compound 2,5-bis(t-octyldithio)-1,3,4-thiadiazole commercially available as Amoco 150, and 2,5-bis(t-nonyldithio)-1,3,4-thiadiazole, commercially available as Amoco 158.

The preparation of such materials is further described in U.S. Patent Nos. 2,719,125, 2,719,126, 3,087,932 and 4,410,436, the disclosures of which are hereby incorporated by reference.

Corrosion inhibitors also include copper lead ~-bearing corrosion inhibitors. Typically such compounds are the thiadiazole polysulphides containing from 5 to 50 carbon atoms, their derivatives and polymers thereof.
Preferred materials are the derivatives of 1,3,4-thiadiazoles such as those described in U.S. Patent Nos.

~111313 2,719,125; 2,719,126 and 3,087,932; especially preferred is the compound 2,5 bis(t-octadithio)-l, 3, 4-thiadiazole, commercially available as Amoco 150. Other similar materials also suitable are described in U.S. Patent Nos.
3,821,236; 3,904,537; 4,097,387; 4,107,059; 4,136,043;
4,188,299 and 4,193,882.

Other suitable corrosion inhibitors are the thio and polythio sulphenamides of thiadiazoles such as those described in U.K. Patent Specification 1,560,830. T~ese compounds can be included in the lubricating composition in an amount from 0.01 to 10, preferably 0.1 to 5.0 wt. %
based on the weight of the composition.

Friction Modifiers Friction modifiers serve to impart the proper friction characteristics to lubricating oil compositions such as automatic transmission fluids. Representative examples of suitable friction modifiers are found in U.S.
Patent No. 3,933,659 which discloses fatty acid esters and amides; U.S. Patent No. 4,176,074 which describes molybdenum complexes of polyisobutenyl succinic anhydride-amino alkanols; U.S. Patent No. 4,105,571 which discloses glycerol esters of dimerized fatty acids; U.S.
Patent No. 3,779,928 which discloses alkane phosphonic acid salts; U.S. Patent No. 3,778,375 which discloses reaction products of a phosphonate with an oleamide; U.S.
Patent No. 3,852,205 which discloses S-carboxy-alkylene hydrocarbyl succinimide, S-carboxy alkylene hydrocarbyl succinamic acid and mixtures thereof; U.S. Patent No.
3,879,306 which discloses N-(hydroxyalkyl) alkenyl-succinamic acids or succinimides; U.S. Patent No.
3,932,290 which discloses reaction products of di-(lower alkyl) phosphites and epoxides; and U.S. Patent No.

.:' . . : ~ : ' ' - ' :. ' -, ": : :, t. . ~

211~3~

4,028,258 which discloses the alkylene oxide adduct of phosphosulfurized N-(hydroxyalkyl) alkenyl succinimides.
The disclosures of the above references are herein incorporated by reference. Preferred friction modifiers include hydroxy amines as disclosed in U.S. Patent No.
5,078,893 and the thioether hydroxy amines as disclosed in U.S. Serial No. 211,428 filed June 24, 1988; glycerol mono and dioleates; and succinate esters, or metal salts thereof, of hydrocarbyl substituted succinic acids or anhydrides and thiobis alkanols such as described in U.S.
Patent No. 4,344,8S3; and amide friction modifiers such as the reaction product of isostearic acid tetraethylene pentamine as disclosed in U.S. Serial No. 425,939 filed Octobed 24, 1989 all of which are herein incorporated by reference.

Anti-Foamants Foam control can be provided by an antifoamant of the polysiloxane type, e.g. silicone oil and polydimethyl siloxane.

Rust Inhibitors organic, oil-soluble compounds useful as rust inhibitors comprise nonionic surfactants such as polyoxyalkylene polyols and esters thereof, and anionic surfactants such as salts of alkyl sulfonic acids. Such anti-rust compounds are known and c~n be made by conventional means. Nonionic surfactants, useful a~
anti-rust additives in the oleaginous compositions, usually owe their surfactant properties to a number of weak stabilizing groups such as ether linkages. Nonionic anti-rust agents containing ether linkages can be made by 21~131~

alkoxylating organic substrates containing active hydrogens with an excess of the lower alkylene oxides (such as ethylene and propylene oxides) until the desired number of alkoxy groups have been placed in the molecule.

The preferred rust inhibitors are polyoxyalkylene polyols and derivatives thereof. This class of materials are commercially available from various sources: Pluronic Polyols from Wyandotte Chemicals Corporation; Polyglycol 112-2, a liquid triol derived from ethylene oxide and propylene oxide available from Dow Chemical Co.; and Tergitol, dodecylphenyl or monophenyl polyethylene glycol ethers, and Ucon, polyalkylene glycols and derivatives, both available from Union Carbide Corp. These are but a ~;
few of the commercial products suitable as rust inhibitors. ~ ;
-In addition to the polyols per se, the esters thereof obtained by reacting the polyols with various carboxylic acids are also suitable. Acids useful in preparing these esters are lauric acid, stearic acid, succinic acid, and alkyl- or alkenyl-substituted succinic acids wherein the alkyl or alkenyl group contains up to about 20 carbon atoms.
' ' '~:
The preferred polyols are prepared as block polymers. Thus, a hydroxy-substituted compound, R-(OH)n (wherein n is l to 6, and R is the residue of a mono- or polyhydric alcohol, phenol, naphthol, etc.) is reacted with propylene oxide to form a hydrophobic base. This base is then reacted with ethylene oxide to provide a hydrophylic portion re~ulting in a molecule having both hydrophobic and hydrophylic portions. The relative sizes of these portions can be adjusted by regulating the ratio of reactants, time of reaction, etc., as is obvious to those skilled in the art. Typically, the ethylene oxide t .. . .

~111313 units will comprise from about 10% to about 40%, and prefera~ly from about 10% to about 15% by weight of the molecule. The number averaye molecular weight of the polyol is from about 2,500 to 4,500. The polyols having a molecular weight of about 4,000 with about lOS
attributable to ethylene oxide units are particularly preferred.

Thus it is within the skill of the art to prepare_ polyols whose molecules are characterized by hydrophobic and hydrophylic moieties which are present in a ratio rendering rust inhibitors suitable for use in any lubricant composition regardless of differences in the base oils and the presence of other additives.

If more oil-solubility is needed in a given lubricating composition, the hydrophobic portion can be increased and/or the hydrophylic portion decreased. If greater oil-in-water emulsion breaking ability i8 ~:~
required, the hydrophylic and/or hydrophobic portions can be adjusted to accomplish this.

Compounds illustrative of R-(OH)n include alkylene -;
polyols such as the alkylene glycols, alkylene triols, alkylene tetrols, etc., such as ethylene glycol, propylene glycol, glycerol, pentaerythritol, sorbitol, mannitol, and the like. Aromatic hydroxy compounds such as alkylated mono- and polyhydric phenols and naphthols can also be used, e.g., heptylphenol, dodecylphenol, etc.

Useful rust inhibitors also include alkoxylated fatty amines, amides, alcohols and the like, including such alkoxylated fatty acid derivatives treated with Cg to C16 alkyl-substituted phenols (such as the mono- and di-heptyl, octyl, nonyl, decyl, undecyl, dodecyl and tridecyl phenols), as described in U.S. Patent No.

. ................ . ~ . . .
, ~, . ~ .. .. . ... - - ~

~111313 - 166 - -~

3,849,501, which is also hereby incorporated by reference in its entirety.

Demulsifie~s Suitable demulsifiers include the esters disclosed in U.S. Patent Nos. 3,098,827 and 2,674,619, herein incorporated by reference.
. :
' :
Lube Oil_Flow ImDrovers Lubricating oil flow improvers (LOFI) include all those additives which modify the size, number, and growth ~-~
of wax crystals in lube oils or fuels in such a way a to impart improved low temperature handling, pumpability, and/or vehicle operability as measured by such tests as `~
pour point and mini rotary viscometry (MRV). The majority of flow improvers are polymers or contain polymers. These polymers are generally of two types, either backbone or sidechain.

The backbone variety, such as the ethylene-vinyl acetates (EVA), have various lengths of methylene segments randomly distributed in the backbone of the polymer, which associate or cocrystallize with the wax crystals inhibiting further crystal growth due to branches and non-crystallizable segments in the polymer.

The sidechain type polymers, wh$ch are the predominant variety used as LOFI's, have methylene segments as the sidechain~, preferably as straight side-chains. The polymers work similarly to the backbone type except the sidechains have been found more effective in treating isoparaffins as well as n-paraffins found in 21~13~3 lube oils. Representative of this type of polymer are C8 to Cl8 dialkylfumarate/vinyl acetate copolymers, polyacrylates, polymethacrylates, and esterified styrene-maleic anhydride copolymers.

Seal Swell Aqents Seal swellants include mineral oils of the type that provoke swelling of engine seals, including aliphatic alcohols of 8 to 13 carbon atoms such as tridecyl alcohol, with a preferred seal swellant being characterized as an oil-soluble, saturated, aliphatic or aromatic hydrocarbon ester of from 10 to 60 carbon atomC
and 2 to 4 linkages, e.g., dihexyl phthalate, as are ~ ~ ~
described in U.S. Patent No. 3,974,081. ~ -Some of the above additives can provide a ~;
multiplicity of effects e.g., a dispers~nt oxidation inhibitor. This approach is well known and need not be further elaborated herein.

Compositions, when containing these additives typically are blended into the base oil in amounts which are effective to provide their normal attendant function.
Representative effective amounts of such additives are illustrated as follows: ~ ~
~ ::

;,. ; . : ,. ~ ,, , ., , .. . ~. ~, 2111~13 (~road) (Preferred) Com~ositions wt % _ wt %
V.I. Improver 1-12 1-4 Corrosion Inhibitor 0.01-3 0.01-1.5 Oxidation Inhibitor 0.01-5 0.01-1.5 Dispersant 0.1-10 0.1-5 Lube Oil Flow Improver 0.01-2 0.01-1.5 Detergents and Rust 0.01-6 0.01-3 Inhibitors Pour Point Depressant 0.01-1.5 0.01-1.5 Anti-~oaming Agents 0.001-0.1 0.001-0.01 ~ :
Antiwear Agents 0.001-5 0.001-1.5 Seal Swellant 0.1-8 0.1-4 :
Friction Modifiers 0.01-3 0.01-1.5 : :
Lubricating Base Oil Balance Balance ~
::
When other additives are employed, it may be -::
desirable, although not necessary, to prepare additive concentrates comprising concentrated solutions or dispersions of the subjçct additives of this invention (in concentrate amounts hereinabove described), together with one or more of said other additives (said concentrate when constituting an additive mixture bQing referred to herein as an additive-package) whereby several additives can be added simultaneously to the base oil to form the lubricating oil composition. Dissolution of the additive concentrate into the lubricating oil may be facilitated by solvents and by mixing accompanied with mild heating, but this is not essential. The concentrate or additive-package will typically be formulated to contain the additives in proper amounts to provide the desired concentration in the final formulation when the additive-package is combined with a predetermined amount of base lubricant. Thus, the subject additives of the present invention can be added to small amounts of base oil or other compatible solvents along with other desirable additives to form additive-packages containing active ingredients in collective amounts of typically from about 2.5 to about 90%, and preferably from about 15 to about 75%, and most preferably from about 2S to about i , , .

. ~ . - - ~ . . - . , . ~ :
.. . ... . . . .

~1113~3 60% by weight additives in the appropriate proportions with the remainder being base oil.

The final formulations may employ typically about 10 wt. % of the additive-package with the remainder being base oil.

All of said weight percents expressed herein (unless ~
otherwise indicated) are based on active ingredient~
(A.I.) content of the additive, and/or upon the total -weight of any additive-package, or formulation which will be the sum of the A.I. weight of each additive plus the - -~
weight of total oil or diluent.
: :
The following examples illustrate the invention.
The examples were conducted in a batch polymerization ;~
employing a cooled reactor dipped in an external cold bath.

EXAMPLES

Exam~le 1 (ComDarative) In a three necked round bottom 250 ml flask, equipped with a magnetic stirrer, Teflon (PTFE) taps and rubber cap for the introduction of some of the reactaDts by a syringe, connected to a vacuum line, 0.73 g of l-azido-l-methylethyl benzene were introduced followed by 100 ml of methylene dichloride. This solvent w~s previously dried by storage under vacuum after purification over phosphorous pentoxide. The reactor wa~
pumped off and 12 ml of isobutylene, previously dried under calcium hydride, were condensed inside the flask.
The reactor was then cooled down to -50C, and 11 ml of a 211131'3 one molar solution of diethylaluminum chloride in heptane were introduced by a syringe through a rubber cap. The system was allowed to stand for 50 minutes and quenching was carried out by the introduction of 10 ml of methanol.
The mixture was then treated by 100 ml o~ heptane filtrated to eliminate cataly~t residues and concentrated. Polyisobutylene polymer (PIB) was collected ~y precipitation in acetone, filtrated and dried under secondary vacuum to constant weight. The yield (7.2 g) was considered as complete and the polymer was analyzed by NMR and infrared spectroscopy and size exclusion chromatography (SEC). Using the peak at 2,100 cm 1 on the infrared spectrum characteristic of the azide group, and by comparison with the peaks at 1,475, 1,390 and 1,365 cm 1 characteristic of polyisobutylene and used as internal standard, and using the average number molecular weight (Mn = 1600) determined by size exclusion chromatography which was calibrated with known samples, an azide group functionality was found equal to 0.9 allowing to conclude that there is nearly one azide group per macromolecule. The polydispersity (~n/Mw) index was found equal to 1.5. Using the NMR spectrum, the aromatic nuclei content of the polymer was determined and was found to correspond to 1,500 g of polymer per mole of aromatic nucleus. This resulted in the calculation of an aromatic functionality of 1.07, supporting the conclusion that there was one aromatic nucleus per macromolecule within experimental accuracy. The monomer to initiator azido group ratio was 135/4.53 = 29.8 is the degree of polymerization. The calculated molecular weight o~ the PIB plus end groups was 1668 + 161 = 1829. The measured molecular weight was Mn - 1600. The initiator azido group to catalyst molar ratio was calculated to ~e -N3:catalyst = 1:2.43.

211131~

This example is provided for comparison with Examples 2 - 5. The initiator in Example 1 was l-azido-1-methylethyl benzene while that in Examples 2 - 5 waC
bis(l-azido-1-methylethyl)benzene. Additionally, Comparative Exa~ple 1 was carried out in such conditions that the molar ratio of Lewis acid to azide group is equal to 2.43, that is to say lower than 3. It shows that the average number molecular weight is close to, but lower than the theoretical one which could be calculated from the M:I molar ratio (Mn cal = 1829). The experimental molecular weight of 1,600 falls outside of ~ -the desired range. This example illustrates what is happening just above the upper limit of about 1:3 of the useful range for the ratio of pseudohalide group to Lewis acid, showing that the system begins to deviate from the apparently living behavior. Examples 2 - 5 below show the results when the molar ratio pseudohalide to Lewis acid group is within the desired range.

~amDle 2 -In a three necked double walled reactor, equipped with a magnetic stirrer, Teflon taps and rubber cap for the introduction of some of the reactants by a syringe, connected to a vacuum line and cooled to -50C, 2.2 mmole of bis(l-azido-l-methylethyl)benzene were introduced under nitrogen. The reactor was then pumped off and 100 ml of methylene dichloride were introduced by condensation, followed by 60 mmole of isobutylene (5.3 ml at -10C). When the temperature of the reaction medium was stabilized at -50C, 18 mmole of diethylaluminum chloride were introduced as 18 ml of a molar solution of this Lewis acid in heptane. The system was allowed to stand at this temperature for S0 minutes. The reaction medium was then quenched using 5 ml of methanol. The 211131~

mixture was then treated by 100 ml of heptane filtrated to eliminate catalyst residues and concentrated.
Polyisobutylene polymer was collected by precipitation in acetone, filtrated and dried under secondary vacuum to constant weight. T~e yield was complete and the polymer was analyzed by NMR and infrared spectroscopy and size exclusion chromatography (SEC). Ucing the peak at 2100 cm 1 on the infrared spectrum characteristic of the azide group, and by comparison with the peaks at 1,475, 1,390 and 1,365 cm 1 characteristic of polyisobutylene and used as internal standard, and using the average number molecular weight (Mn = 16SO) determined by size exclusion chromatography which was calibrated with known samples, an azide group functionality was found equal to 2.0 allowing to conclude that there are 2 azide groups per macromolecule. The polydispersity index was found equal to 1.3. On the NMR spectrum, the aromatic nuclei content of the polymer was determined and was found to correspond to 1,500 g of polymer per mole of aromatic nucleus. This figure resulted in the calculation of an aromatic functionality of 1.09, supporting the conclusion that there was one aromatic nucleus per macromolecule within experimental acc~racy. The monomer to initiator azido group ratio was 60:2.2 which corresponds to a degree of polymerization of 27.27. The calculated molecular weight was (27.27 x 56) + 244 = 1,771. The measured molecular weight was 1,650. The initiator to catalyst ratio was 2.2:18 = 1:8.18, and -N3:cat was 1:4.09. The results support apparently living polymer having substantially no chain transfer reactions.

ExamDle 3 . . .
Using the same technology as in the case of Example 2, 2.2 mmoles of bis(1-azido-1-methylethyl)-benzene were ~1113~3 - 173 ~

introduced followed by 90 mmole of isobutylene and 18 mmoles of diethylaluminum chloride. The yield was complete and the polymer was analyzed ~y NMR and infrared spectroscopy and size exclusion chromatography (SEC), as in the case of Example 2. Using the average number molecular weight (Mn = 2350) determined by size exclusion chromatography, an azide group functionality was found equal to 2.07 allowing to conclude that there are -approximately 2 azide groups per m cromolecule. T~
polydispersity index was found equal to 1.3. ~y NMR
spectroscopy, the aromatic nuclei content of the polymer was found to correspond to 2,200 g of polymer per mole of aromatic nucleus. This figure resulted in the calculation of an aromatic functionality of 1.08, supporting the conclusion that there was one aromatic nucleus per macromolecule within experimental accuracy.
The monomer to initiator azido group ratio is 90:2.2 which corresponds to a degree of polymerization of 40.90.
This calculated molecular weight w~s ~-(40.90 x 56) + 244 = 2,S35. The measured molecular weight was 2,350. The initiator to catalyst ratio WAs 2.2:18 = 1:8.18, and -N3:cat was 1:4.09.

Exam~le 4 Using the same technology as in the case of Example 2, 2.2 mmoles of bis(1-azido-1-methylethyl)benzene were introduced followed by 160 mmole of isobutylene and 18 mmoles of diethylaluminum chloride. The yield wa~
complete and the polymer was analyzed by NMR and infrared spectroscopy and size exclusion chromatography (SEC), a~
in the case of Example 2. Usinq the average number molecular weight (Mn = 4250) determined by size exclusion chromatoqraphy, an azide group functionality was found equal to 2.10 allowing to conclude that there was about 2 .

Xill3~3 - 174 ~

azide groups per macromolecule. A polydispersity index of 1.2 was found. The aromatic nuclei content of the polymer was found to correspond to 4,SOo g of polymer per mole of aromatic nucleus. This figure resulted in the calculation of an aromatic functionality of 0.95, supporting the conclusion that there was one aromatic nucleus per macromolecule within experimental accuracy.
The monomer to initiator azido group ratio is 160:2.2 which corresponds to a degree of polymerization of 72.73.
The calculated molecular weight was 4,317. The measured molecular weight was 4,250. The initiator to catalyst ratio was 2.2:18 = 1:8.18, and -N3:cat was 1:4.09.

Exam~le 5 Using the same technology as in the case of Example 2, 2.2 mmoles of bis(1-azido-1-methylethyl)-~enzene were introduced followed by 215 mmoles of isobutylene and 18 mmole of diethylaluminum chloride. The yield wa8 complete and the polymer was analyzed by NMR and infrared spectroscopy and size exclusion chromatography (SEC), as in the case of Example 2. Using the average number molecular weight (Mn = 5,,450) determined by size exclusion chromatography and the function content measured by infrared spectroscopy, an azide group functionality was found equal to 2.12 allowing to conclude that there was about 2 azide groups per macromolecule. The polydispersity index was 1.3. ThQ
aromatic nuclei content of the polymer was found to correspond to 5,900 g of polymer per mole of aromatic nucleus. This figure resulted in the calculation o~ an aromatic functionality of 0.94, supporting the conclusion that there was one aromatic nucleus per macromolecule within experimental accuracy. The monomer to initiator azido group ratio is 215:2.2 which corresponds to a . . ~ ~ . , ~ . -;:. .,.- . .~ . . . ~ . .

degree of polymerization of 97.73. The calculated molecular weight is 5,717. The measured molecular weight was s,450. The initiator to catalyst ratio was 2:2:18 =
1:8.1, and -N3:cat was 1:4.09.

~x~mDle 6 (ComDarative) Using the same technology as in the case of Example 2, 1 mmoles of bistl-azido-l-methylethyl)benzene (0.24 g) was introduced followed by 103 mmole of isobutylene (9.2 ml) and 6 mmole of titanium tetrachloride. The yield wa~
nearly complete (90%), and the polymer was analyzed by NMR and infrared spectroscopy and size exclusion chromatography (SEC), as in the case of Example 2. Using the average number molecular weight (Mn = 5,300) determined by size exclusion chromatography and the function content measured by infrared spectroscopy, an azide group functionality was found equal to 1.7 allowing to conclude that there are about 2 azide groups per macro~olecule. T~e polydispersity index was 1.7. The aromatic nuclei content of the polymer was found to correspond to 5,600 g of polymer per mole of aromatic nucleus. This figure resulted in the calculation of an aromatic functionality of 0.95, supporting the conclusion that there was one aromatic nucleus per macromolecule within experimental accuracy. The monomer to initiator azido group ratio was 103:1 which corresponds to a degree of polymerization of 103. The calculated molecular weight was 6,012. The measured molecular weight was 5,300. The initiator to catalyst ratio was 1:6, and -N3:cat was 1:3.

~ - - , , -, . ~ .

ExamDle 7 (com~arative) Using the same technology as in the case of Example 2, 4.3 mmole of bis(1-azido-1-methylethyl)benzene ~1.05 g) were introduced followed by 103 mmole of isobutylene (9.2 ml) and 80 ml of methylene dichloride, so that the total volume of reaction medium was about 100 ml. Then 9.4 mmole of boron trichloride as a 9.3 ml of a one molar solution in methylene dichloride was introduced. The_ polymerization was carried out at -70C. The yield was nearly complete (92%), and the polymer was analyzed by NMR and infrared spectroscopy and size exclusion chromatography (SEC), as in the case of Example 2. Using the average number molecular weight (Mn = 2,100) determined by size exclusion chromatography, an azide group functionality was found equal to 2.1 allowing to conclude that there are about 2 azide groups per macromolecule. The polydispersity index was 1.8. The monomer to initiator azido group ratio was 103:4.3 which ;; `-corresponds to a degree of polymerization of 23.95. The calculated molecular weight was 1,585. The measured molecular weight was 2,100. The initiator to catalyst ratio was 4:3:9.4, and -N3:cat was 1:2.10.

This Comparative example shows that with a molar ratio of BC13 to azide group above 1:3, the system had a loss of living behavior. Possible side reactions induced by the strong Lewis acid include dehydroazidation of the initiator.

Exam~le 8 A three necked round bottom 250 ml flask, equipped with a magnetic stirrer, Teflon taps and rubber cap for the introduction of some of the reactants by a syringe, -::. - ' : ' : , . ~ ~ :

was connected to a vacuum line. The reactor was then flushed with dry nitrogen and 47 mg of bis-l~4-(l-azido-l-methylethyl)benzene were introduced, followed by 9o ml of methylene dichloride. This solvent was previously dried by distillation over phosphorous pentoxide and stored under vacuum before use. The reactor wa~ rapidly pumped off and 7.5 ml of isobutylene, previously dried under calcium hydride, were condensed inside the fla~k. -The reactor was then cooled down to -50C, and 1.5 ml of a one molar solution of diethylaluminum chloride in heptane were introduced by a syringe through a rubber cap. Thus, the isobutene concentration was 0.84 mole/l, the concentration of initiator was 1.9.10 3 mole/l and the diethylaluminum chloride was 1.5.10 2 mole/l.
Accordingly, the molar ratio Lewis acid/azide group was 3.95. The system was allowed to stand for 50 mm before quenching by the introduction of 10 ml of methanol. The mixture was then treated with 100 ml of heptane and filtrated to eliminate catalyst residues and concentrated. The polymer was collected by precipitation in acetone, filtrated and dried under secondary vacuum to constant weight. The yield (4.7 g) was considered a~ -complete and the polymer was analyzed by NMR and infrared spectroscopy and size exclusion chromatography (SEC). -~
Using the peak at 2,100 cm 1 on the inSrared spectrum characteristic of the azide group, and by comparison with the peaks at 1,475, 1,390 and 1,365 cm 1 characteristic of polyisobutylene and used as internal standards, and using the average number molecular weight (Mn = 24,300) determined by size exclusion chromatography which was calibrated with known samples, an azide group functionality was found equal to 2.0 allowing to concludQ
that there is two azide groups per macromolecule. The polydispersity index was found to be 1.3. On the NMR
spectrum, the aromatic nuclei content of the polymer wa~
determined and was found to correspond to one aromatic ~1~1313 nucleus per macromolecule within experimental accuracy.
The theoretical molecular weight (Mn cal) was 25,001 which is close to the experimental one is a good indication that t~e system behaves as a living system.
The monomer to initiator azido group ratio was 0.84:0.0019 which corresponds to a degree of polymerization of 442. The calculated molecular weight was 25,001 and the measured molecular we~.ght was 24,300.
The initiator to catalyst ratio was 1.9 x 10 3:1.5 x 10 2 = 1:7.89, and -N3:cat was 1:3.95.
.
The results of the Examples 1 - 8 are summarized on ~able 1, with "M" being moles of monomer, "I" moles of initiator, "Cat." moles of catalyst, "-N3" moles of azide functional group, "Mn cal" calculated number average molecular weight, "~n m" measured number average molecular weight, "DRn" the difference between "Rn cal" and "~n m", and "MWD" molecular weight distribution also called polydispersity index. The calculated or theoretical molecular weight Mn cal was determined from the molar ratio of initial monom~r soncentration "Mo" to initial initiator concentration ~-"Io" plus the molecular weight of initiator "In. (~h - -cal = Mo/Io + I).
Table 1 Ex. M/I I/CAT -N31CAT Mn cal Mn m DMn %
1* 29.8 1~2.43 1/2.43 1829 1600 229 12.5 1.5 2 27.27 1/8.18 1/4.09 1771 1650 121 6.8 1.3 3 40.90 1/8.18 1/4.09 2535 2350 185 7.2 1.3 4 72.73 1/8.18 1/4.09 4317 4250 67 1.6 1.2 97.73 1/8.18 1/4.09 5717 5420 267 4.7 1.3 6* 103.0 1/6 1/3 6012 5300 712 11.8 1.7 7* 24.0 1/2.19 1/1.10 1585 2100 515 32.5 1.8 8 442 1/7.89 1/3.95 25001 24300 701 2.8 1.3 * Comparative Examples ~1113~3 Example 9 A three necked round bottom 250 ml flask, equipped with a magnetic stirrer and small graduated capillary tubes for the handling of small quantities of isobutylene, Teflon taps and rubber cap for the introduction of some of the reactants by a syringe, was connected to a vacuum line. The reactor was then flu~hed with dry nitrogen and o.OS3 g of bi~ 4~ azido-l-methylethyl)benzene were introduced, followed by approximately 97 ml of methylene dichloride. ~his ~ -solvent was previously dried by distillation over phosphorous pentoxide and stored under vacuum before use.
The reactor was rapidly pumped off and 1.0 ml of isobutylene, previously dried under calcium hydride, was condensed inside the flask. The reactor was then cooled down to -50C, and 1.7 ml of a one molar solution of diethylaluminum chloride in heptane were introduced by a ~-syringe through a rubber cap. Thus, the isobutene -concentration was 0.11 mole/l, the concentration of ~
initiator was 2.2.10 3 mole/l and the diethylaluminum ~ - -chloride was 1.7.10 2 mole/l. Accordingly, the molar ratio Lewis acid/azide group was around 3.9. The system was allowed to stand for 50 minutes before the sampling of approximately 10 ml of the reaction medium. Quenching of the sample was carried out by the introduction of 1 ml of methanol. The resulting mixture was discarded for further analysis.

After sampling, a new charge of 0.32 ml of isobutylene was added in the reactor kept at -50C. T~Q
concentration of monomer units (previous polymer + new charge) was then 0.15 mole/l. The system was allowed to stand at -50C for a new period of 50 minutes and quenched. The sa~ple was then treated by 10 ml of heptane filtrated to eliminate catalyst residues and : :- ,. ~- ~ . :: .

~111313 concentrated. The final polymer, containing the polvmer produced after the introduction of the second charge of monomer, was collected by precipitation in acetone, filtrated and dried under secondary vacuum to constant weight. The yield was considered as complete and the polymer was analysed by NMR and infrared spectroscopy and size exclusion chromatography (SEC).

The number average molecular weight (Mn) was 3,05Q
for the initial sample, and Mn = 4,062 for the final polymer, was determined ~y size exclusion chromatography which was calibrated with known samples. This wag compared with the theoretical calculated molecular weight determined based on the molar monomer to diazide ratio (Mn = 3,044 and 4,440) respectively for the sample and the main polymer). The subsequent polymerization agreement between the measured and calculated molecular weights shows living polymeric behavior. Using the peak at 2,100 cm 1 on the infrared spectrum characteristic of the azide group, and by comparison with the peaks at 1,475, 1,390 and 1,365 cm 1 characteristic of polyisobutylene and used as internal standard, an azide group functionality was found equal to 2.0 for both samples, indicating that there are two azide groups per macromolecule. The polydispersity index was found equal to 1.3 and 1.4 respectively for the initial sample and the final polymer. On the NMR spectrum, the aromatic nuclei content of the polymers was determined and wa~
found to correspond to one aromatic nucleus per macromolecule within experimental accuracy. This incremental monomer addition technique was carried out within the useful range for the molar ratio of 3.9 of Lewis acid to pseudohalide group. This example demonstrates the apparently living character of the system since the addition of monomer resulted in continuing polymerization.

' ' : .': . ' :' ... ~ - .

Claims (64)

1. A method for the direct synthesis of polymeric materials functionalized with nitrogen-containing functional groups, comprising the steps of providing a cationically polymerizable monomer, and initiating polymerization by the addition of a cationic polymerization catalyst, in the presence of a nitrogen-containing initiator compound having said nitrogen-containing functional group chemically bound to a release moiety, wherein the ratio of moles of catalyst to nitrogen-containing functional groups is greater than about 3:1.

2. The method according to claim 1 wherein said nitrogen-containing functional group is at least one species selected from the group consisting of -N3, -NCO, -OCN, -SCN, -CN and -NCS.

3. The method according to claim 1 wherein the ratio of moles said catalyst to nitrogen-containing functional groups is from about 4:1 to about 30:1.

4. The method according to claim 1 wherein said nitrogen-containing functional group is covalently bound to a tertiary or secondary carbon of said release moiety.

5. The method according to claim 1 wherein said release moiety is resonance stabilized.

6. The method according to claim 5 wherein said release moiety is an allylic, benzylic, or tertiary aliphatic moiety.

7. The method according to claim 1 wherein said polymerizable monomer is selected from the group consisting of isobutene, styrene, and cationically polymerizable heterocyclic monomers.

8. The method according to claim 1 wherein said polymerization takes place at a temperature below about -20°C.

9. The method according to claim 8 wherein said polymerization takes place at a temperature between about -80°C and about -20°C.

10. The method according to claim 9 wherein said polymerization takes place at a temperature of about -50°C.

11. The method according to claim 1 wherein said equivalent ratio of catalyst to nitrogen-containing initiator compound is about 4:1 to about 10:1.

12. The method according to claim 11 wherein said ratio is about 4:1.

13. The method according to claim 1 wherein the polymer composition has a molecular weight distribution of less than 1,5.

14. A method for the direct synthesis of polymeric materials functionalized with nitrogen-containing functional groups, comprising the steps of providing a cationically polymerizable monomer, and initiating polymerization by the addition of a cationic polymerization catalyst, in the presence of hydrazoic acid as a nitrogen-containing initiator having a nitrogen-containing functional group chemically bound to a release moiety, wherein the ratio of moles of catalyst to nitrogen-containing functional groups is greater than about 4:1, said polymerization occurring at a temperature of from about -80°C to about -20°C.

15. A method for the direct synthesis of polymeric materials functionalized with nitrogen-containing functional groups, comprising the steps of providing a cationically polymerizable monomer, and initiating polymerization by the addition of a cationic polymerization catalyst, in the presence of bis(1-azido-1-methylethyl)benzene as a nitrogen-containing initiator having a nitrogen-containing functional group chemically bound to a release moiety, wherein the ratio of moles of catalyst to nitrogen-containing functional groups is greater than about 4:1.

16. The method according to claim 15 wherein said ratio is between about 4:1 and about 10:1, and said monomer is isobutylene.

17. The method according to claim 15 wherein the polymer composition has a molecular weight distribution of less than 1.5.

18. A method for direct synthesis of polymers functionalized with nitrogen-containing functional groups comprising the steps of mixing a Friedel-Crafts catalyst with a nitrogen-containing initiator compound including said nitrogen-containing functional group chemically bound to a release moiety, then contacting a polymerizable monomer with an amount of the catalyst/initiator compound mixture effective to initiate polymerization, wherein the ratio of moles of catalyst to nitrogen-containing functional groups is greater than about 4:1, and wherein said nitrogen-containing functional group is at least one species selected from the group consisting of -N3, -CN, -NC -NCO, -OCN, -SCN, and -NCS.

19. The method according to claim 18 wherein said release moiety comprises a resonance stabilized species, said nitrogen-containing functional group is covalently bound to a tertiary or secondary carbon of said release moiety, said polymerization is conducted at a temperature of from about -20°C to about -80°C, and the ratio of moles of catalyst to nitrogen-containing functional groups is from about 4:1 to about 20:1.

20. The method according to claim 18 wherein said nitrogen-containing initiator compound is an allylic or benzylic compound.

21. The method according to claim 18 wherein the polymer composition has a molecular weight distribution of less than 1.5.

22. A method for direct synthesis of polymers functionalized with nitrogen-containing functional groups comprising the steps of mixing a Friedel-Crafts catalyst with an azide-containing initiator, then contacting a polymerizable monomer with an amount of the catalyst/azide mixture effective to initiate polymerization, wherein said monomer is isobutylene, wherein the ratio of moles of catalyst to nitrogen-containing functional groups is greater than about 4:1, and wherein said polymerization proceeds at a temperature of from about -80°C to about -20°C.

23. The method according to claim 22 wherein said monomer is isobutylene, and said ratio of catalyst to initiator is about 4:1.

24. The method according to claim 22 wherein the polymer composition has a molecular weight distribution of less than 1.5.

25. A method for the synthesis of azide-functionalized polymers comprising the steps of providing a polymerizable monomer and initiating polymerization, by the addition of a Friedel-Crafts catalyst, in the presence of a resonance-stabilized azide-containing initiator compound whose azide group is covalently bound to a tertiary or secondary carbon atom, said polymerization being conducted at a temperature below about -20°C, wherein the ratio of molar equivalents of Friedel-Crafts catalyst to azide group is greater than about 4:1.

26. The method according to claim 25 wherein said ratio is from about 4:1 to about 10:1, wherein said polymerization proceeds at a temperature of between about -20°C and about -80°C, and said azide-containing compound is an allylic or benzylic compound.

27. The method according to claim 26 wherein said ratio is about 4:1, said polymerization proceeds at a temperature of about -50°C, and said azide-containing compound is bis(1-azido-1-methylethyl)benzene.

28. The method according to claim 25 wherein the polymer composition has a molecular weight distribution of less than 1.5.

29. A method for direct synthesis of polymeric materials functionalized with nitrogen-containing functional groups, comprising the steps of providing a cationically polymerizable monomer, and initiating polymerization by the addition of a cationic polymerization catalyst, in the presence of a nitrogen-containing initiator compound having nitrogen-containinq functional groups chemically bound to a release moiety, wherein the ratio of moles of catalyst to nitrogen-containing functional groups is greater than about 4:1, wherein said nitrogen-containing functional group iB at least one species selected from the group consisting of -N3, -NCO, -OCN, -SCN, -CN and -NCS, and wherein said polymerization takes place at a temperature below about -_ 20°C.

30. The method according to claim 29 wherein the polymer composition has a molecular weight distribution of less than 1.5.

31. A polymer composition having the formula:
R((M)p(Y)) n wherein R is selected from at least one group consisting of H, a hydrocarbyl group, and a hydrocarbyl-substituted group;

Y is selected from at least one group consisting of an azido, cyano, carbonylamino, thiocarbonylamino, cyanato, and thiocyanato;

M is at least one repeat unit derived from a cationically polymerizable monomer;

p is an integer greater than one; and n is an integer of at least one.

32. The polymer composition according to claim 31 having a molecular weight distribution of less than 1.5.

33. The polymer composition according to claim 31 wherein R comprises a hydrocarbyl substituted silyl group of the formula:

34. The polymer composition according to claim 31 wherein R is selected from the group consisting of: alkyl of from 3 to 100 carbon atoms, aryl of from 6 to 20 carbon atoms, alkaryl and aralkyl of from 7 to 100 carbon atoms, and cycloaliphatic of from 3 to 20 carbon atoms.

35. The polymer composition according to claim 34 wherein R is selected from the group consisting of: alkyl of from 4 to 20 carbon atoms, aryl of from 6 to 15 carbon atoms, alkaryl and aralkyl of from 7 to 20 carbon atoms, and cycloaliphatic of from 3 to 12 carbon atoms.

36. The polymer composition according to claim 31 wherein R has the formula:
wherein R1, R2 and R3 are the same or different and are H
or hydrocarbyl selected from the group consisting of alkyl, aryl, alkaryl, aralkyl, heterocyclic or cycloalkyl with the proviso that at least two of R1, R2 and R3 are hydrocarbyl.

37. The polymer composition according to claim 31, 33 or 36 wherein R is selected from the group consisting of .PHI.CH2-, CH3.PHI.CH2- C2H5.PHI.-, CH3.PHI.-, (CH3)-2.PHI.-.

38. The polymer composition according to claim 36 wherein R is selected from the group consisting of isopropyl, tert-butyl, 1-methylpropyl, 1-ethylbutyl, and 1,2-dimethylbutyl.

39. The polymer composition according to claim 31 wherein the cationically polymerizable monomer is selected from the group consisting of straight and branched chain alpha olefins, isoolefins, alicyclic monoolefins, cycloaliphatic compounds, styrene derivatives, indene and derivatives thereof.

40. The polymer composition according to claim 39 wherein the cationically polymerizable monomer is selected from the group consisting of isoolefins of from 4 to 20 carbon atoms and mixtures thereof.

41. The polymer composition according to claim 40 wherein the cationically polymerizable monomer is selected from the group consisting of isobutylene, 2-methylbutene, 3-methylbutene-1, 4-methylpentene-1, and beta-pinene.

42. The polymer composition according to claim 39 wherein the cationically polymerizable monomer is selected from the group consisting of oxazolines.

43. The polymer composition according to claim 39 wherein the cationically polymerizable monomer is selected from the group consisting of vinyl ethers, ethylene-cyclopropane, 2-cyclopropylpropylene, 1,1-dicyclopropylethylene, cyclopentene, methylenecyclo-propane, methylenecyclobutane, methylenecyclopentene, ethylenecyclopentene, 3-methyl-cyclopentene, 1-methylcyclopentene, 3-cyclopentyl-prop-1-ene, cyclohexene, 1-methylcyclohexene, 3-methylcyclohexene, methylenecyclohexane, 1-methyl-2-methylenecyclohexane, 1-methyl-3-methylenecyclohexane, ethylenecyclohexane, 3-cyclohexyl-prop-l-ene, methyl-enecycloheptene, methylene-cyclooctene, methylene-cyclotridecene, cyclopropane, ethylcyclopropane, 3-cyclopropylpropane, 2-cyclopropylpropane, l,l-dimethylcyclopropane, 1,2-dimethylcyclopropane, bicyclo(3.1.0)hexane, bicyclo(4.1.0)heptane, bicyclo(5.1.0) octane, bicyclo(6.1.0)nonane, bi)cyclo(10.1.0)tridecane, 1-methyl-bicyclo(4.1.0)heptane, 2-methyl-bicyclo (4.1.0)heptane, 1-methyl-bicyclo(5.1.0)octane, l-methyl-bicyclo(6.1.0)nonane, spiro(2.2)pentane, spiro (2.4)heptane, spiro(2.5)octane, spirol[2.6]nonane, spiro[2.7]decane, spiro[2.12]pentadecane, bicyclo(6.1.0) non-3-ene, bicyclo(2.2.1)hept-2-ene, 5-methyl-bicyclo(2.2.1)hept-2-ene, 2-methylene-bicyclo(2.2.1) heptane, 2-methylene-3,3-bimethyl-bicyclo(2.2.1) heptane, 2-ethylene-bicyclo(2.2.1)heptane, 2(1-methylethylene)-bicyclo(2.2.1)heptane, 6-methyl-bicyclo(2.2.2)oct-2-ene, styrene, methylstyrene, ethylstyrene, dodecylstyrene, isopropylstyrene, tertiarybutylstyrene, indene, biocyclopentane, l-methylindene, 2-methylindene, 3-methylindene, 5-methylindene, 6-methylindene, 7-methylindene, l,l-dimethylindene, 2,3-dimethylindene, and 4,7-dimethylindene.

44. The polymer composition according to claim 39 wherein n is from 1 to 10.

45. The polymer composition according to claim 44 wherein n is from 1 to 2.

46. The polymer composition according to claim 31 wherein p is from 1 to 1,000,000.

47. The polymer composition according to claim 46 wherein p is from 25 to 10,000.

48. The polymer composition according to claim 31 having a number average molecular weight of from 350 to 15,000,000.

49. The polymer composition according to claim 48 having a number average molecular weight of from 350 to 2,000,000.

50. The polymer composition according to claim 49 having a number average molecular weight of from 350 to 1,000,000.

51. The polymer composition according to claim 50 having a number average molecular weight of from 350 to 1,000,000.

52. The polymer composition according to claim 51 having a number average molecular weight of from 350 to 100,000.

53. The polymer composition according to claim 52 having a number average molecular weight of from 20,000 to 100,000.

54. The polymer composition according to claim 52 having a number average molecular weight of from 500 to 20,000.

55. Polymeric material or polymer composition of claims 1, 14, 15, 22, 25, 29, or 31 wherein the nitrogen containing functional group is further reacted to form a reactant functional group selected from carboxyl groups, cyanate groups, amine groups, hydroxyl groups, triazole groups, nitrile groups, nitrene groups and dimerized nitrene groups.

56. Polymeric material or polymeric composition of claim 55 further comprising the reaction product of at least one reactant functional group and a derivative reactant compound.

57. Polymeric material or polymeric composition of claim 56 wherein the derivative reactant compound is selected from the group consisting of amines, alcohols and metal salts.

58. Polymeric material or polymeric composition of claim 57 wherein the reactant functional group is selected from the group consisting of at least one carboxyl group selected from mono- or dicarboxylic acids, anhydride or acid ester, and the derivative reactant compound comprises at least one hydroxy or amine containing compound.

59. Polymeric material or polymeric composition of claims 1, 14, 15, 22, 25, 29, or 31 wherein the nitrogen containing functional group is an azide which is reacted to form an amine group.

60. A compound having the formula:

61. A method comprising the steps of:

reacting dicumyl alcohol having the formula;

with a halogen (x) containing compound to form dicumyl halide having the formula ;and reacting the dicumyl halide with an azide containing compound to form bis(1-azido-1-methylethyl)benzene having the formula;

62. The method as recited in claim 62 wherein the halogen is chlorine.

63. The method as recited in claim 62 wherein the halogen containing compound is HCl.

64. The method as recited in claim 62 wherein the azide containing compound is NaN3.