WO1997006192A1 - Functionalized polystyrene/polydiene copolymers and processes for making same - Google Patents

Abstract

Functionalized polystyrene/polydiene copolymers are prepared with a protected functional organometallic initiator of the formula (II): M-Rn-Z-J-[A(R1R2R3)]x wherein M is an alkali metal; R is a saturated or unsaturated hydrocarbyl group derived by incorporation of a compound selected from the group consisting of conjugated diene hydrocarbons, alkenylsubstituted aromatic hydrocarbons, and mixtures thereof; n is an integer from 0 to 5; Z is a branched or straight chain hydrocarbon group which contains 3-25 carbon atoms, optionally containing aryl or substituted aryl groups; A is an element selected from carbon and silicon; J is oxygen, sulfur, or nitrogen; R?1, R2, and R3¿ are each independently selected from hydrogen, alkyl, substituted alkyl groups containing lower alkyl, lower alkylthio, and lower dialkylamino groups, aryl or substituted aryl groups containing lower alkyl, lower alkylthio, and lower dialkylamino groups, and cycloalkyl and substituted cycloalkyl containing 5 to 12 carbon atoms; and X is dependent on the valence of J and varies from one when J is oxygen or sulfur to two when J is nitrogen, to form a mono-protected, mono-functionalized living copolymer.

Description

FUNCTIONALIZED POLYSTYRENE/POLYDIENE COPOLYMERS AND PROCESSES FOR MAKING SAME

Cross-Reference to Related Applications

This application is related to commonly owned copending Provisional Application Serial No. 60/001,842, filed August 3, 1995, and claims the benefit of its earlier filing date under 35 U.S.C. 119 (e) .

Field of the Invention

This invention relates to novel functionalized copolymers and processes for producing the same. More particularly, the invention relates novel functionalized polystyrene/polydiene copolymers, and to processes for the anionic polymerization of monomers to produce the same.

Background of the Invention Living polymerizations can provide advantages over other polymerization techniques, such as well- defined polymer structures and low degrees of compositional heterogeneity. Many of the variables that affect polymer properties can be controlled, including molecular weight, molecular weight distribution, copolymer composition and microstructure, stereochemistry, branching and chain end functionality. Living anionic polymerization of styrene and diene monomers was first described by Szwarc and his coworkers. See M. Szwarc, Nature 178, 1169 (1956) and M. Szwarc, et al . , J^".Am. Chem.Soc. 78, 2656 (1956) . Many useful materials can be prepared by anionically polymerizing olefinic-containing monomers, such as styrene and dienes, in the presence of an organo-alkali metal initiator. For example, conventionally, conjugated dienes and styrene monomers are anionically polymerized using lithium initiators, such as sec- and tert-butyllithium. The resultant polymer, which has an active alkali metal end group, can thereafter be reacted with a reagent which will couple the polymer molecules or replace the alkali metal with a functional group.

While alkyllithium initiators can be useful to prepare mono-functional polymers, di-functional, or telechelic, polymers cannot be produced using these initiators. Telechelic polymers are polymers that contain two functional groups per molecule at the termini of the polymer. Such polymers have found wide utility in many applications. For instance, telechelic polymers have been employed as rocket fuel binders, in coatings and sealants and in adhesives. In addition, polymers that contain two hydroxyl groups per molecule can be co-polymerized with appropriate materials to form segmented polyesters, polyurethanes, polycarbonates, and polyamides (see U.S. Patent No. 4,994,526) .

A variety of polymerization techniques, such as cationic and free radical polymerizations, have been employed to prepare telechelic polymers. However, functionality can be best controlled with anionic polymerization. An early approach to the preparation of telechelic polymers is described in D.N. Schulz, et al, J. Polym. Sci . , Polym. Chem. Ed. 12, 153 (1974), which describes the reaction of a hydroxy protected initiator with butadiene. The resultant living anion was quenched with ethylene oxide to afford mono-protected di-hydroxy polybutadiene. While excellent functionality (f = 1.87-2.02) was achieved by this process, the protected initiator was insoluble in hydrocarbon solution. Therefore, the reaction was conducted in diethyl ether, and as a result, relatively high 1,2 microstructure (31-54%) was obtained. Another approach that has been employed to prepare telechelic polymers is the generation and subsequent functionalization of a "dilithium initiator" . A dilithium initiator is typically prepared by the addition of two equivalents of secondary butyllithium to meta-diisopropenylbenzene. The dilithium initiator is then reacted with a conjugated diene, such as butadiene or isoprene, to form a polymer chain with two anionic sites. The resultant polymer chain is then reacted with two equivalents of a functionalizing agent, such as ethylene oxide. While useful, gelation is frequently observed during the functionalization step. This leads to lower capping efficiency (see, for example, U.S. Patent No. 5,393,843, Example 1, wherein the capping efficiency was only 82%) . Additional details of this gelation phenomenon are described in U.S. Patent No. 5,478,899. Further, this dilithium approach can only afford telechelic polymers with the same functional group on each end of the polymer chain. Great Britain published patent application

2,241,239, published August 28, 1991, describes a novel approach for producing telechelic polymers in hydrocarbon solution. Telechelic polymers were prepared using monofunctional silyl ether initiators containing alkali metal end groups that were soluble in hydrocarbon solutions. These monofunctional silyl ether initiators were demonstrated to be useful in producing dihydroxy (telechelic) polybutadienes having desirable characteristics, such as a molecular weight of typically 1,000 to 10,000, a 1,4 microstructure content of typically 90%, and the like. Summarv of the Invention

The present invention provides novel alkenylsubstituted aromatic/polydiene copolymers, preferably polystyrene/polyisoprene or polybutadiene copolymers, including functionalized, telechelic, hetero-telechelic, and multi-branched and star copolymers thereof, and processes for preparing the same. The copolymers can be block, tapered or random copolymers. The novel copolymers of the invention can have good functionalization, from about one for mono¬ functional copolymers, and about 2 for telechelic copolymers. The novel copolymers of the invention have applications in a variety of areas, and are particularly useful as viscosity modifiers for lubricants, for example, a viscosity index improving additive having a "built-in" compatibilizing functional group having dispersant properties for motor oils.

The present invention also provides processes for anionic copolymerization of alkenylsubstituted aromatic hydrocarbon and diene monomers to produce the copolymers of the invention. The copolymers of the invention are prepared using protected functionalized initiators. Block copolymers can be provided by sequentially reacting monomers selected from conjugated diene hydrocarbons and alkenylsubstituted aromatic hydrocarbons . Tapered copolymers can be prepared by reacting a mixture of monomers selected from conjugated diene hydrocarbons and alkenylsubstituted aromatic hydrocarbons. Still further, random copolymers can be prepared by reacting a mixture of monomers selected from conjugated diene hydrocarbons and alkenylsubstituted aromatic hydrocarbons, in the presence of a polar modifier.

The resultant living copolymer can be quenched, for example with acidic methanol, to afford a protected copolymer with a functional group at the initiating chain end thereof . Removal of the protecting group results in a functionalized copolymer. Alternatively, the resultant living copolymer can be quenched with various functionalizing agents, such as ethylene oxide, carbon dioxide, epichlorohydrin, and the like, to afford a mono- protected telechelic copolymer. The functional groups on the termini of the polymer can be the same (such as two hydroxyl groups) or different (such as one hydroxyl group and one amino group) . The copolymers can optionally be hydrogenated to remove aliphatic unsaturations. The protecting group can also be removed to provide telechelic or heterotelechelic copolymers, either before or after the optional hydrogenation.

Protected, functionalized star polymers can also prepared by coupling the living polymer with known coupling agents such as silicon tetrachloride, tin tetrachloride, isomers of divinylbenzene, and the like. Subsequent deprotection affords functionalized stars. In contrast to star polymers of the prior art, the molecular architecture of compounds of the present invention can be precisely controlled. For example, each arm of the multi-arm polymer can contain a functional group (protected or non-protected) , and the functional groups (and/or protecting groups) can be the same or different, through use of mixtures of initiators with different protected functionalities to initiate polymerization. The star polymers can also include both functional and non-functional ends by using combinations of protected functional initiators and alkyllithium initiators to initiate polymerization. The nature of the functional group and/or protecting group and/or non-functional group can be varied simply by changing the initiator, and the ratio of one functional group to another functional group, or of one functional group to a non-functional group, can be adjusted by simply varying the ratio of initiators to one another. Further, monomer identity, monomer composition and molecular weight of both functional and non-functional arms can be independently manipulated by varying the monomer charged by each initiator. Still further, the number of polymer arms can be adjusted by varying the nature of the coupling agent, and the ratio of living polymer to the coupling agent.

Detailed Description of the Invention The copolymers of the present invention can be represented generally by following formula:

FG-(Q)_d-R_n-Z-J- [Ad^R³)], (I) wherein:

FG is H or a protected or non-protected functional group;

Q is a saturated or unsaturated hydrocarbyl group derived by incorporation of a conjugated diene hydrocarbon and an alkenylsubstituted aromatic hydrocarbon, sequentially or as a mixture thereof; d is an integer from 10 to 4000;

R is a saturated or unsaturated hydrocarbyl group derived by incorporation of a compound selected from the group consisting of conjugated diene hydrocarbons, alkenylsubstituted aromatic hydrocarbons, and mixtures thereof; n is an integer from 0 to 5;

Z is a branched or straight chain hydrocarbon group which contains 3-25 carbon atoms, optionally containing aryl or substituted aryl groupε; J is oxygen, sulfur, or nitrogen;

[A(R^XR²R³)]_X is a protecting group, wherein A is an element selected from Group IVa of the Periodic Table of Elements;

R¹, R², and R³ are each independently selected from the group consisting of hydrogen, alkyl, substituted alkyl groups containing lower alkyl, lower alkylthio, and lower dialkylamino groups, aryl or substituted aryl groups containing lower alkyl, lower alkylthio, and lower dialkylamino groups, and cycloalkyl and substituted cycloalkyl containing 5 to 12 carbon atoms; and x is dependent on the valence of J and varies from one when J is oxygen or sulfur to two when J is nitrogen.

Removal of the protecting group (deprotection) produces polymers with oxygen, sulfur or nitrogen functional groups on the ends of the polymers . The residual aliphatic unsaturation can be optionally removed by hydrogenation before or after removal of the protecting groups. These functional groups can then participate in various copolymerization reactions by reaction of the functional groups on the ends of the polymer with selected difunctional or polyfunctional comonomers and/or linking or coupling agents, as described in more detail below. The alkenylsubstituted aromatic hydrocarbon and conjugated diene to be anionically copolymerized are chosen from the group of unsaturated organic compounds that can be polymerized anionically (i.e. in a reaction initiated by an organo-alkali metal) . Examples of polymerizable alkenylsubstituted aromatic hydrocarbons include, but are not limited to, styrene, alpha-methylstyrene, vinyltoluene, 2-vinylpyridine, 4- vinylpyridine, 1-vinylnaphthalene, 2-vinylnaphthalene, 1-alpha-methylvinylnaphthalene, 2-alpha- methylvinylnaphthalene, 1, 2-diphenyl-4-methyl-1-hexene and mixtures of these, as well as alkyl, cycloalkyl, aryl, alkylaryl and arylalkyl derivatives thereof in which the total number of carbon atoms in the combined hydrocarbon constituents iε generally not greater than 18. Examples of these latter compounds include 3- methylεtyrene, 3, 5-diethylεtyrene, 4-tert-butylstyrene, 2-ethyl-4-benzylstyrene, 4-phenylstyrene, 4-p- tolylstyrene, 2,4-divinyltoluene and 4, 5-dimethyl-1- vinylnaphthalene. U.S. Patent No. 3,377,404, incorporated herein by reference in its entirety, discloses suitable additional alkenylsubstituted aromatic compounds.

The conjugated diene is preferably a 1,3- diene. Examples of suitable conjugated diene hydrocarbons include, but are not limited to, 1,3- butadiene, isoprene, 2, 3-dimethyl-1, 3-butadiene, 1,3- pentadiene, myrcene, 2-methyl-3-ethyl-1, 3-butadiene, 2- methyl-3-ethyl-l, 3-pentadiene, 1, 3-hexadiene, 2-methyl- 1, 3-hexadiene, 1, 3-heptadiene, 3-methyl-1, 3-heptadiene, 1, 3-octadiene, 3-butyl-l, 3-octadiene, 3 ,4-dimethyl-l, 3- hexadiene, 3-n-propyl-1, 3-pentadiene, 4, 5-diethyl-1, 3- octadiene, 2, 4-diethyl-l, 3-butadiene, 2, 3-di-n-propyl- 1, 3-butadiene, and 2-methyl-3-isopropyl-1, 3-butadiene. The copolymers of the present invention can be prepared by the sequential reaction of conjugated alkadienes and alkenylsubstituted aromatic hydrocarbons with protected functional organolithium initiators to form a mono-protected mono-functional living block copolymer. Alternatively, novel copolymers of the invention can be prepared by the reaction of the protected functional organolithium initiator with a mixture of conjugated alkadienes and alkenylsubstituted aromatic hydrocarbons to form a mono-protected mono¬ functional living tapered or random copolymer.

The mono-protected mono-functional living copolymer can be quenched or terminated by addition of a suitable proton donor, such as water, methanol, isopropanol, acetic acid, and the like, to provide a mono-functional copolymer. Alternatively, polymerization can be followed by functionalization of the resultant living anion with a suitable electrophile to provide a mono-protected, di-functional polymer. The di-functional copolymer may be telechelic, i.e., contain two functional groups, which are the same, per molecule at the termini of the polymer. The copolymer can also be hetero-telechelic, having different functionalities at opposite ends of the polymer chain. This is represented schematically by the formula A B, wherein A and B are different functional groups.

A telechelic di-protected di-functional copolymer having random, tapered or sequential blocks can be formed by reacting the living copolymer with a difunctional linking agent, such as ethylbenzoate, xylene dibromide or dimethyldichlorosilane. In the case of the sequential or tapered block copolymer, this linking reaction will result in a telechelic difunctional triblock copolymer, with di-protected di- functionality.

The product polymer can be hydrogenated, either before or after removing the protecting group.

Electrophiles that are useful in functionalizing the polymeric living copolymer include, but are not limited to, alkylene oxides, such as ethylene oxide, propylene oxide, styrene oxide, and oxetane; oxygen; sulfur; carbon dioxide; halogens such as chlorine, bromine and iodine; haloalkyltrialkoxysilanes, alkenylhalosilanes, and omega-alkenylarylhalosilanes, such as chlorotrimethylsilane and styrenyldimethyl chlorosilane; sulfonated compounds, such as 1,3-propane sultone; amides, including cyclic amides, such as caprolactam, N-benzylidene trimethylsilylamide, and dimethyl formamide; silicon acetals; 1,5- diazabicyclo [3.1.0] hexane; allyl halides, such as allyl bromide and allyl chloride; methacryloyl chloride; amineε, including primary, εecondary, tertiary and cyclic amineε, such as 3- (dimethylamino) -propyl chloride and N- (benzylidene) trimethylsilylamine; epihalohydrins, such as epichlorohydrin, epibromohydrin, and epiiodohydrin, and other materials as known in the art to be useful for terminating or end capping polymers. These and other useful functionalizing agents are described, for example, in U.S. Patent Nos. 3,786,116 and 4,409,357, the entire disclosure of each of which is incorporated herein by reference. As noted above, the copolymer optionally is hydrogenated, either before after removal of the protecting group.

Exemplary organolithium initiators useful in the present invention include initiators εelected from the group consiεting of omega- ( tert-alkoxy) -l- alkyllithiums, omega- (tert-alkoxy) -1-alkyllithiums chain extended with conjugated alkadienes, alkenylsubstituted aromatic hydrocarbons, and mixtures thereof, omega- (tert-alkylthio) -1-alkyllithiums, omega- ( tert-alkylthio) -1-alkyllithiums chain extended with conjugated alkadienes, alkenylsubstituted aromatic hydrocarbons, and mixtures thereof, omega- ( tert- butyldimethylsilyloxy) -1-alkyllithiums, omega- ( tert- butyldimethylsilylthio) -1-alkyllithiums, omega-

(dialkylamino) -1-alkyllithiums, omega- (dialkylamino) -1- alkyllithiumε chain-extended with conjugated alkadienes, alkenylsubstituted aromatic hydrocarbons, and mixtureε thereof, and omega- (bis- tert- alkylsilylamino) -1-alkyllithiums.

Initiators useful (II) in the preparation of polymers of the present invention are also represented by the following formula:

M-R_n-Z-J-[A(R¹R²R³)]_X (II) wherein M is an alkali metal, R is a saturated or unsaturated hydrocarbyl group derived by incorporation of a compound selected from the group consisting of conjugated diene hydrocarbons, alkenylsubstituted aromatic hydrocarbons, and mixtures thereof; n is an integer from 0 to 5; Z is a branched or straight chain hydrocarbon group which containε 3-25 carbon atomε, optionally containing aryl or substituted aryl groups; J iε a hetero atom, e . g. , oxygen, sulfur, or nitrogen; A is an element selected from Group IVa of the Periodic Table of Elements; R¹, R², and R³ are each independently selected from hydrogen, alkyl, substituted alkyl groups containing lower alkyl, lower alkylthio, and lower dialkylamino groupε, aryl or εubεtituted aryl groupε containing lower alkyl, lower alkylthio, and lower dialkylamino groups, and cycloalkyl and subεtituted cycloalkyl containing 5 to 12 carbon atoms; and x is dependent on the valence of J and varies from one when J is oxygen or sulfur to two when J is nitrogen.

Theεe initiators can be prepared by reaction of protected organolithium compounds of the following formula: M-Z-J-[A(R¹R²R³)]_X (III) wherein each of M, Z, J, A, R¹, R², R³, and x are the same as defined above, with conjugated alkadienes (such as butadiene or isoprene) , alkenylsubstituted aromatic hydrocarbons (such as styrene or alpha-methylstyrene) , and mixtureε thereof, to form an extended hydrocarbon chain between M and Z in Formula (III) , which extended chain iε denoted as R_n in Formula (II) .

The compounds of Formula (III) can be prepared by first reacting in an inert solvent a selected tertiary amino-1-haloalkane, omega-hydroxy- protected-1-haloalkane or omega-thio-protected-1- haloalkane, depending on whether J is to be N, O or S, (the alkyl portions of the haloalkyi groupε contain 3 to 25 carbon atoms) with an alkali metal, preferably lithium, at a temperature between about 35°C and about

130°C, preferably at the solvent reflux temperature, to form a protected monofunctional alkali metal initiator (of Formula III) , which is then optionally reacted with a one or more conjugated diene hydrocarbonε, one or more alkenylεubstituted aromatic hydrocarbons, or mixtureε of one or more dienes with one or more alkenylsubεtituted aromatic hydrocarbons, in a predominantly alkane, cycloalkane, or aromatic reaction solvent, which solvent containε 5 to 10 carbon atoms, and mixtures of such solvents to produce a monofunctional initiator with an extended chain or tether between the metal atom (M) and element (J) in Formula (II) above and mixtures thereof with compounds of Formula (III) . R in Formula (II) is preferably derived from conjugated 1,3-dienes. While A in the protecting group [A(R¹R²R³)] of the formulae above can be any of the elements in Group IVa of the Periodic Table of the Elements, carbon and εilicon currently appear the most useful, especially when polymerizing conjugated dienes.

Incorporation of R groups into the M-Z linkage to form the compounds of Formula (II) above involves addition of compounds of the Formula

M-Z-J- [A R^R³) ]_x where the symbols have the meanings ascribed above, across the carbon to carbon double bonds in compounds selected from the consisting of one or more conjugated diene hydrocarbons, one or more alkenylsubstituted aromatic hydrocarbons, or mixtures of one or more dienes with one or more alkenylsubstituted aromatic hydrocarbons, to produce new carbon-lithium bonds of an allylic or benzylic nature, much like those found in a propagating polyalkadiene or polyarylethylene polymer chain derived by anionic initiation of the polymerization of conjugated dienes or arylethylenes . Theεe new carbon-lithium bonds are now activated toward polymerization and so are much more efficient in promoting polymerization than the precursor M-Z (M=Li) bonds, themselves.

Tertiary amino-1-haloalkanes uεeful in practicing this invention include compounds of the following general structureε :

X-Z-N[A(R¹R²R³) ]₂ and

wherein X is halogen, preferably chlorine or bromine; Z is a branched or straight chain hydrocarbon tether or connecting group which contains 3-25 carbon atoms, which tether may also contain aryl or substituted aryl groups; A is an element εelected from Group IVa of the Periodic Table of the Elements; R¹, R², and R³ are independently defined as hydrogen, alkyl, substituted alkyl groups containing lower alkyl, lower alkylthio, and lower dialkylamino groups, aryl or substituted aryl groups containing lower alkyl, lower alkylthio, and lower dialkylamino groups, or cycloalkyl and substituted cycloalkyl groups containing 5 to 12 carbon atoms; and m is an integer from 1 to 7, and their employment as initiators in the anionic polymerization of olefin containing monomers in an inert, hydrocarbon solvent optionally containing a Lewis base. The process reacts selected tertiary amino-1-haloalkaneε whoεe alkyl groupε contain 3 to 25 carbon atoms, with alkali metal, preferably lithium, at a temperature between about 35°C and about 130°C, preferably at the reflux temperature of an alkane, cycloalkane or aromatic reaction solvent containing 5 to 10 carbon atoms and mixtures of such solvents. Anionic polymerizations employing the tertiary amine initiators are conducted in an inert solvent, preferably a non-polar solvent, optionally containing an ethereal modifier, using an olefinic monomer which iε an alkenylεubstituted aromatic hydrocarbon or a 1,3-diene at a temperature of about - 30°C to about 150°C. The polymerization reaction proceeds from initiation to propagation and is finally terminated with appropriate reagents so that the polymer is mono-functionally or di-functionally terminated. The polymers may have a molecular weight range of about 1000 to 50,000 but the molecular weight can be higher. Typically 5 to 50 milli-moles of initiator is used per mole of monomer.

Tertiary amino-1-haloalkanes useful in the practice of this invention include, but are not limited to, 3- (N,N-dimethylamino) -1-propyl halide, 3-(N,N- dimethylamino) -2-methyl-1-propyl halide, 3-(N,N- dimethylamino) -2, 2-dimethyl-1-propyl halide, 4-(N,N- dimethylamino) -1-butyl halide, 5- (N,N-dimethylamino) -1- pentyl halide, 6- (N,N-dimethylamino) -1-hexyl halide, 3- (N,N-diethylamino) -1-propyl halide, 3-(N,N- diethylamino) -2-methyl-1-propyl halide, 3-(N,N- diethylamino) -2, 2-dimethyl-1-propyl halide, 4-(N,N- diethylamino) -1-butyl halide, 5- (N,N-diethylamino) -1- pentyl halide, 6- (N,N-diethylamino) -1-hexyl halide, 3- (N-ethyl-N-methylamino) -1-propyl halide, 3- (N-ethyl-N- methylamino) -2-methyl-1-propyl halide, 3- (N-ethyl-N- methylamino) -2, 2-dimethyl-1-propyl halide, 4- (N-ethyl- N-methylamino) -1-butyl halide, 5- (N-ethyl-N- methylamino) -1-pentyl halide, 6- (N-ethyl-N- methylamino) -1-hexyl halide, 3- (piperidino) -1-propyl halide, 3- (piperidino) -2-methyl-1-propyl halide, 3- (piperidino) -2, 2-dimethyl-1-propyl halide, 4- (piperidino) -1-butyl halide, 5- (piperidino) -1-pentyl halide, 6- (piperidino) -1-hexyl halide, 3- (pyrrolidino) - 1-propyl halide, 3- (pyrrolidino) -2-methyl-1-propyl halide, 3- (pyrrolidino) -2, 2-dimethyl-1-propyl halide, 4- (pyrrolidino) -1-butyl halide, 5- (pyrrolidino) -1- pentyl halide, 6- (pyrrolidino) -1-hexyl halide, 3- (hexamethyleneimino) -1-propyl halide, 3-

(hexamethyleneimino) -2-methyl-1-propyl halide, 3- (hexamethyleneimino) -2, 2-dimethyl-1-propyl halide, 4- (hexamethyleneimino) -1-butyl halide, 5- (hexamethyleneimino) -1-pentyl halide, 6- (hexamethyleneimino) -1-hexyl halide, 3- (N-isopropyl-N- methyl) -1-propyl halide, 2- (N-isopropyl-N-methyl) -2- methyl-1-propyl halide, 3- (N-isopropyl-N-methyl) -2, 2- dimethyl-1-propyl halide, and 4- (N-isopropyl-N-methyl) - 1-butyl halide. The halo- or halide group is preferably selected from chlorine and bromine.

Omega-hydroxy-protected-1-haloalkaneε useful in producing monofunctional ether initiators useful in practicing this invention have the following general structure:

X-Z-O- [C(R^XR²R³) ] wherein X is halogen, preferably chlorine or bromine; Z is a branched or straight chain hydrocarbon group which contains 3-25 carbon atoms, optionally containing aryl or substituted aryl groups; and R¹, R², and R³ are independently defined as hydrogen, alkyl, subεtituted alkyl groups containing lower alkyl, lower alkylthio, and lower dialkylamino groups, aryl or substituted aryl groups containing lower alkyl, lower alkylthio, and lower dialkylamino groups, or cycloalkyl and substituted cycloalkyl groups containing 5 to 12 carbon atoms, and their employment as initiators in the anionic polymerization of olefin containing monomers in an inert, hydrocarbon solvent optionally containing a Lewis base. The process reacts selected omega-hydroxy- protected-1-haloalkaneε whose alkyl groups contain 3 to 25 carbon atoms, with alkali metal, preferably lithium, at a temperature between about 35°C and about 130°C, preferably at the reflux temperature of an alkane, cycloalkane or aromatic reaction solvent containing 5 to 10 carbon atoms and mixtures of such solventε. Anionic polymerizations employing the monofunctional ether initiators are conducted in an inert solvent, preferably a non-polar solvent, optionally containing an ethereal modifier, using an olefinic monomer which is an alkenylsubstituted aromatic hydrocarbon or a 1,3-diene at a temperature of about -30°C to about 150°C. The polymerization reaction proceeds from initiation to propagation and is finally terminated with appropriate reagents so that the polymer is mono-functionally or di-functionally terminated. The polymers may have a molecular weight range of about 1000 to 50,000 but the molecular weight can be higher. Typically 5 to 50 milli-moles of initiator is uεed per mole of monomer.

The precursor omega-protected-1-haloalkanes (halides) can be prepared from the corresponding haloalcohol by standard literature methods. For example, 3- (1, 1-dimethylethoxy) -1-chloropropane can be synthesized by the reaction of 3-chloro-1-propanol with 2-methylpropene according to the method of A. Alexakis, M. Gardette, and S. Colin, Tetrahedron Letters, 29, 1988, 2951. The method of B. Figadere, X. Franck and A. Cave, Tetrahedron Letters, 3_4, 1993, 5893, which involves the reaction of the appropriate alcohol with

2-methyl-2-butene catalyzed by boron trifluoride etherate, can be employed for the preparation of the t- amyl ethers. The alkoxy, alkylthio or dialkylamino substituted ethers, for example 6- [3- (methylthio) -1- propyloxy] -1-chlorohexane, can be synthesized by reaction of the corresponding substituted alcohol, for instance 3-methylthio-1-propanol, with an alpha-bromo- omega-chloroalkane, for inεtance 1-bromo-6-hexane, according to the method of J. Almena, F. Foubelo and M. Yus, Tetrahedron, 51, 1995, 11883. The compound 4-

(methoxy) -1-chlorobutane, and the higher analogs, can be syntheεized by the ring opening reaction of tetrahydrofuran with thionyl chloride and methanol, according to the procedure of T. Ferrari and P. Vogel, SYNLETT, 1991, 233. The triphenylmethyl protected compounds, for example 3- (triphenyl ethoxy) -1- chloropropane, can be prepared by the reaction of the haloalcohol with triphenylmethylchloride, according to the method of S. K. Chaudhary and 0. Hernandez, Tetrahedron Letters, 1979, 95.

Omega-hydroxy-protected-1-haloalkanes prepared in accordance with this earlier process useful in practicing this invention include, but are not limited to, 3- (1, 1-dimethylethoxy) -1-propyl halide, 3- (1, 1-dimethylethoxy) -2-methyl-1-propyl halide, 3- (1,1- dimethylethoxy) -2, 2-dimethyl-1-propyl halide, 4- (1,1- dimethylethoxy) -1-butyl halide, 5- (1, 1-dimethylethoxy) - 1-pentyl halide, 6- (1, 1-dimethylethoxy) -1-hexyl halide, 8- (1, 1-dimethylethoxy) -1-octyl halide, 3- (1,1- dimethylpropoxy) -1-propyl halide, 3- (1,1- dimethylpropoxy) -2-methyl-1-propyl halide, 3- (1,1- dimethylpropoxy) -2, 2-dimethyl-1-propyl halide, 4- (1,1- dimethylpropoxy) -1-butyl halide, 5- (1,1- dimethylpropoxy) -1-pentyl halide, 6- (1,1- dimethylpropoxy) -1-hexyl halide, 8- (1,1- dimethylpropoxy) -1-octyl halide, 4- (methoxy) -1-butyl halide, 4- (ethoxy) -1-butyl halide, 4- (propyloxy) -1- butyl halide, 4- (1-methylethoxy) -1-butyl halide, 3-

(triphenylmethoxy) -2, 2-dimethyl-1-propyl halide, 4-

(triphenylmethoxy) -1-butyl halide, 3- [3-

(dimethylamino) -1-propyloxy] -1-propyl halide, 3- [2- (dimethylamino) -1-ethoxy] -1-propyl halide, 3- [2- (diethylamino) -1-ethoxy] -1-propyl halide, 3- [2- (diiεopropyl) amino) -1-ethoxy] -1-propyl halide, 3- [2- (1- piperidino) -1-ethoxy] -1-propyl halide, 3- [2- (1- pyrrolidino) -1-ethoxy] -1-propyl halide, 4-[3- (dimethylamino) -1-propyloxy] -1-butyl halide, 6- [2- (1- piperidino) -1-ethoxy] -1-hexyl halide, 3- [2- (methoxy) -1- ethoxy] -1-propyl halide, 3- [2- (ethoxy) -1-ethoxy] -1- propyl halide, 4- [2- (methoxy) -1-ethoxy] -1-butyl halide, 5- [2- (ethoxy) -1-ethoxy] -1-pentyl halide, 3-[3- (methylthio) -1-propyloxy] -1-propyl halide, 3-[4- (methylthio) -1-butyloxy] -1-propyl halide, 3- (methylthiomethoxy) -1-propyl halide, 6- [3- (methylthio) - 1-propyloxy] -1-hexyl halide, 3- [4- (methoxy) -benzyloxy] - 1-propyl halide, 3- [4- (1, 1-dimethylethoxy) -benzyloxy] - 1-propyl halide, 3- [2, 4- (dimethoxy) -benzyloxy] -1-propyl halide, 8- [4- (methoxy) -benzyloxy] -1-octyl halide, 4- [4- (methylthio) -benzyloxy] -1-butyl halide, 3- [4-

(dimethylamino) -benzyloxy] -1-propyl halide, 6- [4- (dimethylamino) -benzyloxy] -1-hexyl halide, 5- (triphenylmethoxy) -1-pentyl halide, 6- (triphenylmethoxy) -1-hexyl halide, and 8- (triphenylmethoxy) -1-octyl halide. The halo- or halide group is preferably selected from chlorine and bromine. U.S. Patent 5,362,699 discloεeε a proceεε for the preparation of hydrocarbon εolutionε of monofunctional ether initiators derived from omega- hydroxy-silyl-protected-1-haloalkaneε of the following general structure:

X-Z-O- [Si (R-^R³) ] wherein X is halogen, preferably chlorine or bromine; Z iε a branched or εtraight chain hydrocarbon group which contains 3-25 carbon atoms, optionally containing aryl or substituted aryl groups; and R¹, R², and R³ are independently defined aε εaturated and unεaturated aliphatic and aromatic radicals, and their employment as initiators in the anionic polymerization of olefin containing monomers in an inert, hydrocarbon solvent optionally containing a Lewis base. The process reacts selected omega-hydroxy-protected-1-haloalkanes whose alkyl groups contain 3 to 25 carbon atoms, with lithium metal at a temperature between about 25°C and about 40°C, in an alkane or cycloalkane reaction solvent containing 5 to 10 carbon atoms and mixtures of such solventε.

Anionic polymerizations employing the monofunctional siloxy ether initiatorε are conducted in an inert εolvent, preferably a non-polar εolvent, optionally containing an ethereal modifier, using an olefinic monomer which is an alkenylsubstituted aromatic hydrocarbon or a 1,3-diene at a temperature of about -30°C to about 150°C. The polymerization reaction proceeds from initiation to propagation and is finally terminated with appropriate reagents εo that the polymer iε mono-functionally or di-functionally terminated. The polymerε may have a molecular weight range of about 1000 to 50,000 but the molecular weight can be higher. Typically 5 to 50 milli-moles of initiator is used per mole of monomer. Omega-silyl-protected-1-haloalkanes prepared in accordance with thiε earlier process useful in practicing this invention include, but are not limited to, 3- (t-butyldimethylεilyloxy) -1-propyl halide, 3-(t- butyldimethyl-εilyloxy) - 2-methyl-1-propyl halide, 3-(t- butyldi ethylεilyloxy) -2, 2-dimethyl-1-propyl halide, 4- (t-butyldimethylsilyloxy) -1-butyl halide, 5- (t- butyldimethyl-εilyloxy) -1-pentyl halide, 6- (t- butyldimethylεilyloxy) -1-hexyl halide, 8- (t- butyldimethylεilyloxy) -1-octyl halide, 3 - (t- butyldiphenylylεilyloxy) -1-propyl halide, 3 - (t- butyldiphenylylεilyloxy) -2-methyl-1-propyl halide, 3 - (t-butyldiphenylylsilyloxy) -2, 2-dimethyl-1-propyl halide, 4 - (t-butyldiphenylylsilyloxy) -1-butyl halide, 6- (t-butyldiphenylsilyloxy) -1-hexyl halide and 3- (trimethylεilyloxy) -2, 2-dimethyl-1-propyl halide. The halo- or halide group is preferably εelected from chlorine and bromine.

Monofunctional thioether initiatorε uεeful in the practice of thiε invention can be derived from omega-thio-protected-1-haloalkanes of the following general structure:

X-Z-S- [A(R¹R²R³) ] wherein X is halogen, preferably chlorine or bromine; Z is a branched or straight chain hydrocarbon group which contains 3-25 carbon atoms, optionally containing aryl or substituted aryl groups; [A(R¹R²R³)] is a protecting group in which A is an element selected from Group IVa of the Periodic Table of the Elementε; and R¹, R², and R³ are independently defined aε hydrogen, alkyl, substituted alkyl groups containing lower alkyl, lower alkylthio, and lower dialkylamino groups, aryl or substituted aryl groups containing lower alkyl, lower alkylthio, and lower dialkylamino groups, or cycloalkyl and substituted cycloalkyl groups containing 5 to 12 carbon atoms, and their employment as initiators in the anionic polymerization of olefin containing monomers in an inert, hydrocarbon solvent optionally containing a Lewis base. The process reacts selected omega- thioprotected-1-haloalkyls whose alkyl groups contain 3 to 25 carbon atoms, with alkali metal, preferably lithium, at a temperature between about 35°C and about 130°C, preferably at the reflux temperature of an alkane, cycloalkane or aromatic reaction solvent containing 5 to 10 carbon atoms and mixtures of such solventε.

Anionic polymerizations employing the monofunctional thioether initiators are conducted in an inert solvent, preferably a non-polar solvent, optionally containing an ethereal modifier, using an olefinic monomer which is an alkenylsubεtituted aromatic hydrocarbon or a 1,3-diene at a temperature of about -30°C to about 150°C. The polymerization reaction proceedε from initiation to propagation and iε finally terminated with appropriate reagentε so that the polymer is mono-functionally or di-functionally terminated. The polymers may have a molecular weight range of about 1000 to 50,000 but the molecular weight can be higher. Typically 5 to 50 milli-moles of initiator iε uεed per mole of monomer.

The initiator precurεor, omega-thio- protected-1-haloalkaneε (halideε) , can be prepared from the corresponding halothiol by standard literature methods. For example, 3- (1, 1-dimethylethylthio) -1- propylchloride can be syntheεized by the reaction of 3- chloro-1-propanthiol with 2-methylpropene according to the method of A. Alexakis, M. Gardette, and S. Colin, Tetrahedron Letters, 29_., 1988, 2951. Alternatively, reaction of 1, 1-dimethylethylthiol with l-bromo-3- chloropropane and a baεe affordε 3- (1,1- dimethylethylthio) -1-propylchloride. The method of B. Figadere, X. Franck and A. Cave, Tetrahedron Letters, 34 , 1993, 5893, which involves the reaction of the appropriate thiol with 2-methyl-2-butene catalyzed by boron trifluoride etherate, can be employed for the preparation of the t-amyl ethers. Additionally, 5- (cyclohexylthio) -1-pentylhalide and the like, can be prepared by the method of J. Almena, F. Foubelo, and M. Yus, Tetrahedron, 5JL, 1995, 11883. Thiε synthesis involves the reaction of the appropriate thiol with an alkyllithium, then reaction of the lithium salt with the corresponding alpha, omega dihalide. 3- (Methylthio) -1-propylchloride can be prepared by chlorination of the corresponding alcohol with thionyl chloride, as taught by D. F. Taber and Y. Wang, J. Org,

Chem., _.58_., 1993, 6470. Methoxymethylthio compounds, such as 6- (methoxymethylthio) -1-hexylchloride, can be prepared by the reaction of the omega-chloro-thiol with bromochloromethane, methanol, and potasεium hydroxide, by the method of F. D. Toste and I. W. J. Still,

Synlett, 1995, 159. T-Butyldimethylsilyl protected compounds, for example 4- (t-butyldimethylsilylthio) -1- butylhalide, can be prepared from t- butyldimethylchloroεilane, and the correεponding thiol, according to the method described in U.S. Patent No.

5,493,044.

Omega-thio-protected 1-haloalkanes prepared in accordance with this earlier procesε uεeful in practicing thiε invention include, but are not limited to, 3- (methylthio) -1-propylhalide, 3- (methylthio) -2- methyl-1-propylhalide, 3- (methylthio) -2, 2-dimethyl-l- propylhalide, 4- (methylthio) -1-butylhalide, 5- (methylthio) -1-pentylhalide, 6- (methylthio) -1- hexylhalide, 8- (methylthio) -1-octylhalide, 3-

(methoxymethylthio) -1-propylhalide, 3-

(methoxymethylthio) -2-methyl-l-propylhalide, 3- (methoxymethylthio) -2, 2-dimethyl-1-propylhalide, 4-

(methoxymethylthio) -1-butylhalide, 5-

(methoxymethylthio) -1-pentylhalide, 6-

(methoxymethylthio) -1-hexylhalide, 8-

(methoxymethylthio) -1-octylhalide, 3- (1, 1- dimethylethylthio) -1-propylhalide, 3- (1,1- dimethylethylthio) -2-methyl-l-propylhalide, 3- (1,1- dimethylethylthio) -2, 2-dimethyl-1-propylhalide, 4- (1,1- dimethylethylthio) -1-butylhalide, 5- (1,1- dimethylethylthio) -1-pentylhalide, 6- (1,1- dimethylethylthio) -1-hexylhalide, 8- (1,1- dimethylethylthio) -1-octylhalide, 3- (1, 1- dimethylpropylthio) -1-propylhalide, 3- (1,1- dimethylpropylthio) -2-methyl-l-propylhalide, 3- (1,1- dimethylpropylthio) -2, 2-dimethyl-1-propylhalide, 4- (1, 1-dimethylpropylthio) -1-butylhalide, 5-(l,l- dimethylpropylthio) -1-pentylhalide, 6- (1,1- dimethylpropylthio) -1-hexylhalide, 8- (1,1- dimethylpropylthio) -1-octylhalide, 3- (cyclopentylthio) - 1-propylhalide, 3- (cyclopentylthio) -2-methyl-l- propylhalide, 3- (cyclopentylthio) -2, 2-dimethyl-l- propylhalide, 4- (cyclopentylthio) -1-butylhalide, 5- (cyclopentylthio) -1-pentylhalide, 6- (cyclopentylthio) - 1-hexylhalide, 8- (cyclopentylthio) -1-octylhalide, 3- (cyclohexylthio) -1-propylhalide, 3- (cyclohexylthio) -2- methyl-1-propylhalide, 3- (cyclohexylthio) -2, 2-dimethyl- 1-propylhalide, 4- (cyclohexylthio) -1-butylhalide, 5- (cyclohexylthio) -1-pentylhalide, 6- (cyclohexylthio) -1- hexylhalide, 8- (cyclohexylthio) -1-octylhalide, 3-(t- butyldimethylsilylthio) -1-propylhalide, 3- (t- butyldimethylsilylthio) -2-methyl-l-propylhalide, 3-(t- butyldimethylsilylthio) -2, 2-dimethyl-l-propylhalide, 3- (t-butyldimethylεilylthio) -2-methyl-1-propylhalide, 4- (t-butyldimethylεilylthio) -1-butylhalide, 6- (t- butyldimethylεilylthio) -1-hexylhalide and 3- (trimethylεilylthio) -2, 2-dimethyl-l-propylhalide. The halo- or halide group is preferably selected from chlorine and bromine.

Examples of functionalized organolithium initiators (II) include, but are not limited to, tert- alkoxy-alkyllithiumε such aε 3- (1, 1-dimethylethoxy) -1- propyllithium and its more hydrocarbon-soluble isoprene chain-extended oligomeric analog (n=2) , 3-(tert- butyldimethylsilyloxy) -1-propyllithium (n=0) , tert- alkylthio-alkyllithiums such as 3- (1,1- dimethylethylthio) -1-propyllithium and its more hydrocarbon-εoluble isoprene chain-extended oligomeric analog (n=2) , 3- (dimethylamino) -1-propyllithium and its more hydrocarbon-soluble isoprene chain-extended oligomeric analog (n=2) and 3-(di-tert- butyldimethylεilylamino) -1-propyllithium, and mixtures thereof. Further examples of protected functionalized initiators that may be employed in this invention include, but are not limited to, 3- (1,1- dimethylethoxy) -1-propyllithium, 3- (1,1- dimethylethoxy) -2-methyl-l-propyllithium, 3- (1,1- dimethylethoxy) -2, 2-dimethyl-1-propyllithium, 4- (1,1- dimethylethoxy) -1-butyllithium, 5- (1, 1-dimethylethoxy) - 1-pentyllithium, 6- (1, 1-dimethylethoxy) -1-hexyllithium, 8- (1, 1-dimethylethoxy) -1-octyllithium, 3- (1,1- dimethylpropoxy) -1-propyllithium, 3- (1,1- dimethylpropoxy) -2-methyl-1-propyllithium, 3- (1,1- dimethylpropoxy) -2, 2-dimethyl-l-propyllithium, 4- (1,1- dimethylpropoxy) -1-butyllithium, 5- (1,1- dimethylpropoxy) -1-pentyllithium, 6- (1,1- dimethylpropoxy) -1-hexyllithium, 8- (1,1- dimethylpropoxy) -1-octyllithium, 3- (t- butyldimethylsilyloxy) -1-propyllithium, 3-(t- butyldimethylεilyloxy) -2-methyl-l-propyllithium, 3- (t- butyldimethylεilyloxy) -2, 2-dimethyl-l-propyllithium, 4- (t-butyldimethylsilyloxy) -1-butyllithium, 5- (t- butyldimethylεilyloxy) -1-pentyllithium, 6- (t- butyldimethylsilyloxy) -1-hexyllithium, 8- (t- butyldimethylsilyloxy) -1-octyllithium and 3- (trimethylsilyloxy) -2, 2-dimethyl-1-propyllithium, 3- (dimethylamino) -1-propyllithium, 3- (dimethylamino) -2- methyl-1-propyllithium, 3- (dimethylamino) -2, 2-dimethyl- 1-propyllithium, 4- (dimethylamino) -1-butyllithium, 5- (dimethylamino) -1-pentyllithium, 6- (dimethylamino) -1- hexyllithium, 8- (dimethylamino) -1-propyllithium, 4-

(ethoxy) -1-butyllithium, 4- (propyloxy) -1-butyllithium, 4- (1-methylethoxy) -1-butyllithium, 3- (triphenylmethoxy) -2, 2-dimethyl-l-propyllithium, 4- (triphenylmethoxy) -1-butyllithium, 3- [3- (dimethylamino) -1-propyloxy] -1-propyllithium, 3- [2- (dimethylamino) -1-ethoxy] -1-propyllithium, 3- [2- (diethylamino) -1-ethoxy] -1-propyllithium, 3- [2- (diiεopropyl) amino) -1-ethoxy] -1-propyllithium, 3- [2- (1- piperidino) -1-ethoxy] -1-propyllithium, 3- [2- (1- pyrrolidino) -1-ethoxy] -1-propyllithium, 4- [3-

(dimethylamino) -1-propyloxy] -1-butyllithium, 6- [2- (1- piperidino) -1-ethoxy] -1-hexyllithium, 3- [2- (methoxy) -1- ethoxy] -1-propyllithium, 3- [2- (ethoxy) -1-ethoxy] -1- propyllithium, 4- [2- (methoxy) -1-ethoxy] -1-butyllithium, 5- [2- (ethoxy) -1-ethoxy] -1-pentyllithium, 3- [3-

(methylthio) -1-propyloxy] -1-propyllithium, 3- [4- (methylthio) -1-butyloxy] -1-propyllithium, 3- (methylthiomethoxy) -1-propyllithium, 6- [3- (methylthio) - 1-propyloxy] -1-hexyllithium, 3- [4- (methoxy) -benzyloxy] - 1-propyllithium, 3- [4- (1, 1-dimethylethoxy) -benzyloxy] -

1-propyllithium, 3- [2,4- (dimethoxy) -benzyloxy] -1- propyllithium, 8- [4- (methoxy) -benzyloxy] -1- octyllithium, 4- [4- (methylthio) -benzyloxy] -1- butyllithium, 3- [4- (dimethylamino) -benzyloxy] -1- propyllithium, 6- [4- (dimethylamino) -benzyloxy] -1- hexyllithium, 5- (triphenylmethoxy) -1-pentyllithium, 6- (triphenylmethoxy) -1-hexyllithium, and 8- (triphenylmethoxy) -1-octyllithium, 3- (hexamethyleneimino) -1-propyllithium, 4- (hexamethyleneimino) -1-butyllithium, 5- (hexamethyleneimino) -1-pentyllithium, 6- (hexamethyleneimino) -1-hexyllithium, 8- (hexamethyleneimino) -1-octyllithium, 3- (t- butyldimethylεilylthio) -1-propyllithium, 3- (t- butyldimethylεilylthio) -2-methyl-l-propyllithium, 3- (t- butyldimethylsilylthio) -2, 2-dimethyl-l-propyllithium, 4- (t-butyldimethylsilylthio) -1-butyllithium, 6- (t- butyldimethylsilylthio) -1-hexyllithium, 3- (trimethylsilylthio) -2, 2-dimethyl-1-propyllithium, 3- (1, 1-dimethylethylthio) -1-propyllithium, 3- (1, 1- dimethylethylthio) -2-methyl-1-propyllithium, 3- (1,1- dimethylethylthio) -2,2-dimethyl-1-propyllithium, 4- (1, 1-dimethylethylthio) -1-butyllithium, 5- (1, 1- dimethylethylthio) -1-pentyllithium, 6- (1, 1- dimethylethylthio) -1-hexyllithium, 8- (1, 1- dimethylethylthio) -1-octyllithium, 3- (1,1- dimethylpropylthio) -1-propyllithium, 3- (1,1- dimethylpropylthio) -2-methyl-l-propyllithium, 3- (1,1- dimethylpropylthio) -2, 2-dimethyl-l-propyllithium, 4- (1, 1-dimethylpropylthio) -1-butyllithium, 5- (1, 1- dimethylpropylthio) -1-pentyllithium, 6- (1, 1- dimethylpropylthio) -1-hexyllithium, and 8-(l,l- dimethylpropylthio) -1-octyllithium and their more hydrocarbon soluble conjugated alkadiene, alkenylsubstituted aromatic hydrocarbon, and mixtures thereof, chain extended oligomeric analogs (n = 1-5) . Functionalized copolymers of Formula (I) can be further reacted with other comonomers such as di- or polyesters, di- or polyiisocyanates, di-, poly-, or cyclic amides, di- and polycarboxylic acids, and di- and polyols in the presence of a strong acid catalyst to εimultaneouεly deprotect the functional copolymer and polymerize both functional ends thereof to produce novel segmented block polymers. Alternatively, functionalized copolymers of Formula (I) can be reacted with other comonomers in the absence of a strong acid catalyst to yield block copolymers, while maintaining the integrity of the protective group to provide a functional block copolymer. Still another alternative is to remove the protective group of the functional copolymer of Formula (I) and to polymerize a functional block copolymer of the preceding sentence with the same or other comonomers to produce novel segmented block polymers.

The polymerization solvent can be an inert solvent such as a hydrocarbon. Solvents useful in practicing this invention include, but are not limited to, inert liquid alkanes, cycloalkanes and aromatic solvents such as alkanes and cycloalkanes containing five to ten carbon atoms, such as pentane, hexane, cyclohexane, methylcyclohexane, heptane, methylcycloheptane, octane, decane and the like, and aromatic solvents containing six to ten carbon atomε εuch as toluene, ethylbenzene, p-xylene, m-xylene, o- xylene, n-propylbenzene, isopropylbenzene, n- butylbenzene, and the like.

Polar solvents can also be used, including, but not limited to, diethyl ether, dibutyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, methyl tert- butyl ether, diazabicyclo [2.2.2] octane, triethylamine, tributylamine, N,N,N' ,N' -tetramethylethylene diamine (TMEDA) , and 1, 2-dimethoxyethane (glyme) . Polar solvents (modifiers) can also be added to the polymerization reaction to alter the microstructure of the resulting polymer or to promote functionalization or randomization. The amount of the polar modifier added depends on the vinyl content desired, the nature of the monomer, the temperature of the polymerization, and the identity of the polar modifier.

The εkilled artiεan will appreciate that copolymerization of a mixture of alkenylεubstituted aromatic monomers and conjugated diene monomers in a hydrocarbon solvent resultε in the preferential incorporation of the conjugated diene compound to form tapered (or graded) block copolymerε with compoεitional heterogeneity incorporated intramolecularly along the polymer chain. The monomer sequence distribution can be described schematically by (1) below: -[-A-]_n-[-A/B-]-[-B-]_m- or - [-A-] „-- [-A-→B-] - [-B-]_m- wherein A is a saturated or unsaturated hydrocarbyl group derived by incorporation of a conjugated diene; n represents the equivalents of A employed primarily in the initial block εegment; B is an aromatic substituted saturated hydrocarbyl group derived by incorporation of an alkenylsubstituted aromatic hydrocarbon; and m represents the equivalents of B employed primarily in the εecond block εegment.

This sequence is reversed when a mixture of alkenylsubstituted aromatic hydrocarbons and conjugated dienes is polymerized in a polar solvent. Accordingly, the alkenylsubεtituted aromatic hydrocarbon is preferentially incorporated to form a tapered (or graded) block copolymer, schematically illustrated by (2) below:

- t-A-]_n- [-A/B-] -[-B-]_m- or -[-A-]_n--[-A-→B-]- [-B-]_m- wherein A is an aromatic substituted saturated hydrocarbyl group derived by incorporation of an alkenylsubεtituted aromatic subεtituted hydrocarbon; n repreεentε the equivalentε of A employed primarily in the initial block εegment; B is a saturated or unsaturated hydrocarbyl group derived by incorporation of a conjugated diene; and m represents the equivalents of B employed primarily in the second block segment.

A telechelic di-protected functional copolymer having random, tapered or sequential blocks can be formed by reacting the living copolymer with a difunctional linking agent, such as ethylbenzoate, xylene dibromide or dimethyldichlorosilane. In the caεe of the εequential or tapered block copolymer, this linking reaction results in a telechelic triblock copolymer with protected functionality. These triblock polymers may optionally be hydrogenated before or after removal of the protecting groups to produce saturated difunctional polymers. In the case of protected hydroxy functional polymerε, the deprotection will yield a telechelic dihydroxyl functional polymer which may then be further reacted with bisphenol A and phosgene, caprolactam and adipic acid, hexamethylene diamine and adipic acid, dimethyl terephthalate and 1,4-butane diol, or diphenylmethane diisocyanate, which would produce, respectively, sequential pentablock polymers with blocks of polyamide, polyeεter and polyurethane attached to the εelectively deprotected telechelic functional polydiene/polyarylethylene or polyolefin/polyarylethylene triblocks.

As noted above, if desired, the protecting groups can be removed from the copolymer. Deprotection can be performed either prior to or after the optional hydrogenation of the residual aliphatic unsaturation. For example, to remove tert-alkyl-protected groups, the protected polymer can be mixed with Amberlyst^® 15 ion exchange resin and heated at an elevated temperature, for example 150°C, until deprotection is complete. Tert-alkyl-protected groupε can also be removed by reaction of the polymer with para-toluensulfonic acid, trifluoroacetic acid, or trimethylsilyliodide. Additional methods of deprotection of the tert-alkyl protecting groups can be found in T.W. Greene and

P.G.M. Wuts, Protective Groups in Organic Synthesis, Second Edition, Wiley, New York, 1991, page 41.

Tert-butyldimethylsilyl protecting groupε can be removed by treatment of the copolymer with acid, such as hydrochloric acid, acetic acid, para- toluensulfonic acid, or Dowex^® 50W-X8. Alternatively, a source of fluoride ions, for instance tetra-n- butylammonium fluoride, potasεium fluoride and 18- crown-6, or pyridine-hydrofluoric acid complex, can be employed for deprotection of the tert- butyldimethylsilyl protecting groups. Additional methods of deprotection of the tert-butyldimethylsilyl protecting groups can be found in T.W. Greene and P.G.M. Wuts, Protective Groups in Organic Synthesis, Second Edition, Wiley, New York, 1991, pages 80-83. In addition, protecting groups can be selectively removed from the polymer, i.e., deprotecting conditions can be selected so as to remove at least one protecting group without removing other dissimilar protecting groups, by proper selection of deprotecting reagents and conditions. The following table details representative experimental conditions capable of selectively removing protecting groups (more labile) while maintaining the integrity of other different protecting groups (more stable) . Labile Stable Conditions t-butyldimethylsilyl t-butyl tetrabutylammonium fluoride t-butyldimethylsilyl t-butyl 1 N HCL t-butyldimethylsilyl dialkylamino tetrabutylammonium fluoride t-butyldimethylsilyl dialkylamino 1 N HCL t-butyl dialkylamino Amberlyst^® resin t-amyl dialkylamino Amberlyst^® resin trimethylsilyl t-butyl tetrabutylammonium fluoride trimethylsilyl t-butyl 1 N HCl trimethylsilyl dialkylamino tetrabutylammonium fluoride trimethylsilyl dialkylamino 1 N HCl

The progress of the deprotection reactions can be monitored by conventional analytical techniques, such as Thin Layer Chromatography (TLC) , Nuclear Magnetic Resonance (NMR) spectroεcopy, or InfraRed (IR) spectroscopy. Exampleε of methodε to hydrogenate the copolymerε of this invention are described in U.S. Patent Nos. 4,970,254, 5,166,277, 5,393,843 and 5,496,898, the entire disclosure of each of which is incorporated by reference. The hydrogenation of the copolymer is conducted in si tu, or in a suitable solvent, such as hexane, cyclohexane or heptane. This solution is contacted with hydrogen gas in the presence of a catalyst, such as a nickel catalyεt . The hydrogenation iε typically performed at temperatures from 25°C to 150°C, with a archetypal hydrogen preεsure of 15 pεig to 1000 pεig. The progress of this hydrogenation can be monitored by InfraRed (IR) spectroscopy or Nuclear Magnetic Resonance (NMR) spectroscopy. The hydrogenation reaction is conducted until at least 90% of the aliphatic unsaturation has been saturated. The hydrogenated copolymer is then recovered by conventional procedures, such as removal of the catalyst with aqueous acid wash, followed by εolvent removal or precipitation of the copolymer.

In another aspect of the invention, multi- branched or star-εhaped polymerε which include alkenylεubεtituted aromatic- and conjugated diene-based compounds are also provided, including multi-branched or star-shaped polymers with protected functional groups, their optionally hydrogenated analogues, and the polymers produced by removal of the protecting groups . The star polymerε in this aspect of the invention can be produced using the functional initiators (II) described above (singly or combinations thereof) , which, by design, incorporate the versatility of functional branch end star polymers. For example, hydroxy-, thio-, or amino-terminated functional branches can be copolymerized with comonomers, such as organic diacids (such as carboxylic acids) , diisocyanates, and the like. The copolymers can also include non-functional branches in the polymer. This can provide improved impact resistance in molecules resulting from further copolymerization of the star- shaped polymers of the invention with other functional comonomers, for example, reεultant polyester and/or polyamide molecules .

Novel multi-branched or star-shaped polymerε having functional ends can be produced by polymerizing the alkenylsubstituted aromatic hydrocarbons and conjugated dienes as a mixture or sequentially as described above with protected functional organolithium initiators of Formula (II) (singly or as combinations thereof to provide arms having different protecting groups and/or different functional groups) , and subsequently reacting the resulting copolymer with multifunctional linking agents. This can lead to polymer anion chain lengths of approximately the εame εize.

Examples of useful linking or coupling agents include halosilaneε, εuch as silicon tetrachloride and methyl trichlorosilane; halostannanes, such as tin tetrachloride; phoεphorus halides, such as phosphorus trichloride; and isomeric (mixtures of ortho, meta and para) dialkenylaryls and isomeric di- and trivinylaryls, εuch as 1, 2-divinylbenzene, 1,3- divinylbenzene, 1,4-divinylbenzene, 1,2,4- trivinylbenzeneε, 1, 3-divinylnaphthaleneε, 1,8- divinylnaphthalene, 1, 2-diisopropenylbenzene, 1,3- diiεopropenylbenzene, 1, 4-diiεopropenylbenzene, 1,3,5- trivinylnaphthalene, and other εuitable materialε known in the art to be useful for coupling polymers, as well as mixtureε of coupling agentε. See also U.S. Patent Nos. 3,639,517 and 5,489,649, and R.P. Zelinski et al in J.Polym.Sci. , A3, 93, (1965) for these and additional coupling agents. Mixtures of coupling agents can also be used. Generally, the amount of coupling agent used is εuch that the molar ratio of protected living polymer anions to coupling agents ranges from 1:1 to 24:1. This linking process is described, for example, in U.S. Patent No. 4,409,357 and by L.J. Fetters in Macromolecules, £,732 (1976) . These radiating multi-arm polymers with protected functionality on the ends of the arms may be optionally hydrogenated before or after removal of the protecting groups. The star polymers thus formed may have hydroxyl, thio, and/or amino functional branch ends. Nonfunctional initiators (such as n- butyllithium, sec-butyllithium, and tert-butyllithium) may also be mixed with the functional initiators of Formula (II) to provide non-functional branch ends as well, which can serve to modify the physical properties of these star-shaped or radiating polymerε, especially after their further copolymerization with other functional monomers, such as organic diacids or organic diisocyanates.

Alternatively, novel multi-branched or star- shaped polymers possesεing functional endε which may be the εame or different, and/or both functional and non¬ functional endε, may be produced by separately polymerizing alkenylsubstituted aromatic hydrocarbons and conjugated dienes with protected functional initiators (II) and/or with non-functional organolithium initiators, subsequently mixing the resulting separately produced anions, treating the resulting mixture with multifunctional linking agents, and optionally hydrogenating before or after optionally deprotecting the functional ends of the polymer. This alternative method allows for control of the molecular weight of the arms of the star polymer (for example, different polymer anion chain lengths can be produced) and provides for a more selective control of the physical properties of the resultant polymers.

If deεired, the protecting groups can be removed from the arms of the star polymer, prior to or after the optional hydrogenation of the residual unsaturation of the armε, using the techniques described above. This includes selective deprotection when diεεimilarly protected functional groupε are preεent, aε detailed above.

Molecular weightε of the reεulting linked or coupled polymerε can vary depending on the molecular weight of the polymer anion and the number of potential functional linking groupε on a coupling agent. The εizes of the branches of the linked polymer can be the same or vary.

A wide variety of symmetrically and asymmetrically functional polymers may be produced by reacting the living copolymer resulting from the copolymerization of alkenylsubstituted aromatic and conjugated dienes described above with various functionalizing agents. For example, addition of carbon dioxide (see J. Polym . Sci . , Polym . Chem . 30, 2349 (1992)) to a living copolymer produced using the protected functional initiator 3- ( tert-butoxy) -1- propyllithium, chain-extended with two equivalents of isoprene, would produce a polymer with one protected hydroxyl and one carboxyl group. The living copolymer may also be reacted with 1,5 diazabicyclo- (3.1.0) hexane as described in U.S. Patent No. 4,753,991 to produce a polymer with one protected hydroxyl and one amino group. A polymer with one protected hydroxyl group and one protected amino group can be prepared by reaction of the living copolymer with a protected amino propyl bromide, see Macromolecules, ________ 939 (1990) , or with N- (benzylidene) trimethylsilylamine (see British Polymer Journal, 22_., 249 (1990)) . Reaction of the living copolymer with oxetane or substituted oxetanes (see U.S. Patent No. 5,391,637) would afford a copolymer which contained one protected hydroxyl and a hydroxyl group. A polymer with two protected hydroxyl groups can be prepared by reaction of the living copolymer with a εilicon derived acetal, see U.S. Patent No. 5,478,899.

Other asymmetrically substituted polymers may be produced having epoxy or isocyanate groups at one end, for example, by reacting the lithium salt of a protected hydroxy-terminated living copolymer (before hydrolysiε) , with epichlorohydrin or, by reacting the living copolymer itself with an equivalent of a diisocyanate, such as methylene 4, 4-diphenyl diisocyanate (2/1 NCO/OH) . These unsymmetrically εubεtituted polymerε could then be further reacted with other comonomers either with or without simultaneouε deprotection as described below.

The polar functional groups of the polymer chain ends allow the polymers of this invention to alter the surface properties of polymers like polyethylene (including high density polyethylene, low density polyethylene and linear low density polyethylene) , polypropylene, polyisobutylene and copolymers and blends thereof. When the polymers of thiε invention are blended with non-polar polyolefins, the polar functional groups on the chain ends, being incompatible with the non-polar polyolefin, will phase separate and migrate to the surface of the polyolefin. The functional polymers of the invention can be added in amounts ranging from 1 to 25% by weight based on the weight of the polyolefin. Properties such as εurface adheεion are thus greatly enhanced, leading to improved adhesion of pigments in printing inks for labelε, compoεite layering, and other adheεive applicationε . An alternative approach to modification of polymer εurfaceε to alter propertieε by introduction of functional groupε has been the use of chemical reagents such as alkyllithiums (see, for example, A.J. Dias, K-W Lee, and T.J. McCarthy, Rubber & Plastics News, 18-20, October 31, 1988, and A.J. Dias and T.J. McCarthy, Macromolecules, 20, 1437 (1987)) . Protected monohydroxy copolymers alone and in their hydrogenated forms can be uεed aε base materials to lend flexibility and higher impact strength in a number of formulas to produce coatings, sealantε, binders and block copolymers with polyesters, polyamides and polycarbonates as described in UK Patent Application GB2270317A and in "Polytail" data sheetε and brochureε (Mitεubiεhi Kaεei America) .

In the preεence of acidic catalyεtε uεed to promote the formation of many of theεe block copolymer resins, the protective group of the hydrogenated polymer is removed as well, allowing the exposed hydroxyl grouping in the base polymer molecule to simultaneously participate in the block copolymer reaction.

For example, hydrogenated hydroxy-terminated copolymers may be reacted with bisphenol A and phosgene in the presence of appropriate catalysts with simultaneouε deprotection to yield a polycarbonate alternating block copolymer. The reεulting productε are useful as molding resinε, for example, to prepare interior components for automobiles.

A segmented polyamide-hydrogenated block copolymer is also useful as a molding composition to prepare exterior automotive components and can be prepared by reacting a hydrogenated hydroxy-terminated copolymer with, for example, caprolactam and adipic acid in the presence of a suitable catalyst .

A segmented polyester-hydrogenated block copolymer is produced by reaction of hydrogenated hydroxy-terminated copolymer with dimethyl terephthalate and a suitable acidic catalyst. Again, the products are useful as molding compounds for exterior automotive components. Isocyanate-terminated prepolymers can be produced from hydrogenated hydroxy-terminated copolymers by reaction with εuitable diisocyanates (2/1 NCO/OH) as above and which can be further reacted with diols and additional diisocyanates to form segmented polyurethanes useful for water based, low VOC coatings. Inclusion of acid functional diols, such as dimethylolpropionic acid, in the polyurethane introduces pendant carboxyl groups which can be neutralized with tertiary amines to afford water dispersable polyolefin/polyurethane segmented polymers, useful for water based coatingε. Thiε same principle could be applied to acrylic polymers made with tertiary amine functional monomers included, which could be made by free radical polymerization following reacting the hydroxyl groups at the terminal ends of the polymer with acryloyi chloride or methacryloyl chloride. Segmented polyurethane prepolymers may be mixed with tackifying resins and used as a moisture-curable sealant, caulk or coating.

Another posεible application in coatingε would be the uεe of new dendrimerε, baεed on the uεe of the polymer with hydroxyl functionality at the termini thereof to form the core for dendritic hybrid macromolecules based on condensation or addition polymerizations, utilizing the hydroxyl functionality as the initiating site (see, for example Gitsov and Frechet, American Chemical Society PMSE Preprints, Volume 73, August 1995.

Yet another application includes use as toughening polymers for epoxy compoεiteε, utilizing the polymer core with the hydroxyl groups converted to half esters by reaction with anhydrides. These epoxy reactive polymers can then be utilized as reactants with epoxy resins and amines in composite systems. Reacting the hydroxyl functional polymers into unsaturated polyesterε provides a new polymer toughening system for polyester molding compounds for automotive and other uses. For a review of the use of linear polymers for toughening of epoxieε and polyesters, see "Rubber-Toughened Plastics", Edited By C.Keith Riew, ACS Advances in Chemistry Series ,#222. Cathodic electrodepositable coatings may be prepared from epoxy functional polymers described above by reacting with epoxy reεins in the presence of excess amine or polyamine, to completely react all the epoxy groups, distilling off excess amine, and neutralizing the resulting epoxy-amine adduct with water soluble organic or inorganic acids to form water soluble, quartemary ammonium containing polymer saltε (εee for reference, U.S. Patent Noε. 3,617,458, 3,619,398, 3,682,814, 3,891,527, 3,947,348, and 4 , 093 , 594) . Alternatively, the above epoxy-amine polymer adductε may be converted to quartemary phoεphonium or εulfonium ion containing polymerε, aε deεcribed in U.S. Patent No. 3,935,087.

An acrylate-terminated prepolymer curable by free-radical processes can be prepared from the hydrogenated hydroxy-terminated copolymer by reaction with a diisocyanate (2NCO/OH) followed by further reaction with hydroxyethyl acrylate in the preεence of a basic reagent.

Another likely application for acrylate or methacrylate terminated hydrogenated polymers includes use as viscoεity index (V.I.) improvers. Using carboxyl functional monomers, such as acrylic acid and methacrylic acid, and/or amine functional monomers such as acrylamide, along with free radical initiators in further polymerizations, can result in the formation of polymer segments at the periphery of each termini with amine or other functionalities which, in addition to the advantageous properties of the polymers as V.I. improvers, combines the ability to add functionality to the polymers for dispersant properties (see, for example, U.S. Patent Nos. 5,496,898, 4,575,530, 4,486,573, 5,290,874, and 5, 290, 868) . The versatility of the hydroxyl functional polymers of this invention, and the wide range of different segmented polymers (polyethers, polyesters, polyamides, polycarbonates, polyurethanes, etc.) which can be initiated at the hydroxyl groups, leads to numerous posεible applicationε as compatibilizerε for polymer blendε and alloys. In addition to the use of such blends for new applications, much recent interest is generated in the uεe of compatibilizers to facilitate polymer waste recycling.

Alternatively, protecting groupε may be removed, either before or after optional hydrogenation of the aliphatic unεaturation, then the hydroxy terminated polymer may be reacted with functional comonomers to produce novel copolymers using these and other processes . Thus, for example, a hydroxy terminated polymer may be hydrogenated, and then reacted with ethylene oxide in the presence of potassium tert-butoxide to produce a poly(ethylene oxide) -hydrogenated block copolymer. This reaction sequence affords a hydrogel .

Alternatively, the protected monohydroxy terminated copolymer may be reacted with functional comonomers, without simultaneously removing the protective group. These copolymers then may be deprotected and then further reacted with the same or different comonomers to form yet other novel copolymers. Thus, for example, a hydroxyterminated copolymer may be hydrogenated, and then reacted with ethylene oxide in the presence of potasεium tert- butoxide to produce a poly(ethylene oxide) -hydrogenated polyεtyrene/polydiene copolymer with one protected hydroxyl group on the polyεtyrene segment . This hydroxyl can then be deprotected and a poly(ethylene oxide) polymer having different chain lengths grown onto both ends of the polystyrene/polydiene εegment . In another possible application, the living copolymer may be reacted with an alkenylarylhalosilane such as styrenyldimethylchloroεilane to yield the correεponding omega- tyrenyl terminated macromonomer according to the teachingε of U.S. Patent No.

5,278,244, which may then be further polymerized by a variety of techniques to yield "comb" polymers which, on deprotection and hydrogenation yield branched polymers with hydroxyfunctionality on the branch-ends. Such multi-functionality can be utilized to graft a water-soluble polymer εuch aε polyethylene oxide onto a hydrophobic polyolefinic core to produce hydrogelε.

In εtill another poεεible application, hydrogenated hydroxyterminated branches of the polymers may be further reacted with acryloyi chloride or methacryloyl chloride, and the resultant acrylate or methacrylate-terminated polymer further polymerized with monomers εelected from the group of alkyl acrylateε, alkyl methacrylateε, and dialkylacrylamideε to produce hydrogelε. Further, acrylate or methacrylate-terminated polymers may be polymerized by free-radical processes.

The following examples further illustrate the invention.

General Procedure

All reagents (monomers, solvent, and additives) were purified as described by Morton and Fetters in "Anionic Polymerization of Vinyl Monomers," Rubb . Chem . Tech . , 48, 3, 1975. High vacuum techniques for the polymerization reactions were also performed as specified by the aforementioned article. PREPARATION OF THE INITIATORS

Example A

Preparation of 3 - (t-Butyldimethylsilyloxy) -1

-Propylli thium Chain Extended wi th 2 Moles of Isoprene A 500 ml, three-necked Morton flask was equipped with a mechanical stirrer, a 125 ml pressure- equalizing addition funnel, and a Claisen adapter fitted with a thermocouple, a reflux condenser, and an argon inlet . This apparatus was dried in an oven overnight at 125°C, aεεembled hot, and allowed to cool to room temperature in a stream of argon. Lithium disperεion waε washed free of mineral oil with hexane (2 X 70 ml) , and pentane (1 X 70 ml) , then dried in a stream of argon. The dry dispersion, 5.20 grams (0.749 mole, 2.80 equivalents) was transferred to the flask with 260 ml cyclohexane. This suspension was stirred at 450 RPMs, and heated to 65°C with a heating mantle. The heat source was removed. 1- (t- Butyldimethylεilyloxy) -3-chloro-propane, 58.82 grams (0.268 mole, 1.00 equivalent) was added dropwise. An exotherm was detected after 31.8% of the feed had been added. A dry ice/hexane cooling bath was applied to maintain the reaction temperature at 60-65°C. The total feed time was one hundred five minutes. An exotherm waε noted until the last drop of feed was added, then the temperature fell off rapidly to room temperature. The reaction mixture was stirred at room temperature for forty five minutes, then heated to 65°C with a heating mantle. The heat source was removed. Isoprene, 36.45 grams (0.535 mole, 2.00 equivalents) was then added dropwise. An exotherm was noted after 24.6% of the feed had been added. Hexane cooling was applied to maintain the reaction temperature at 60- 65°C. The total isoprene feed time was thirty eight minutes. The reaction mixture was allowed to stir at room temperature for one hour, then transferred to a small presεure filter with argon pressure. Very rapid filtration was observed with 2 psi argon. The muds were reεlurried with cyclohexane (2 X 50 ml) . This afforded an orange solution, yield = 530 ml, 425.34 grams. Total base = 17.1 wt . %; Active C-Li = 15.9 wt %; Yield (based on active C-Li) = 80.8%.

Example B

Preparation of 3 - (t -Butyldimethylsilyl thio) -1 -propylli thium Chain Extended wi th 2 Moles of Isoprene

A 500 ml, three-necked Morton flask is equipped with a mechanical stirrer, a 125 ml pressure- equalizing addition funnel, and a Claiεen adapter fitted with a thermocouple, a reflux condenser, and an argon inlet. This apparatus is dried in an oven overnight at 125°C, assembled hot, and allowed to cool to room temperature in a stream of argon. Lithium dispersion is washed free of mineral oil with hexane (2 X 70 ml) , and pentane (1 X 70 ml) , then dried in a stream of argon. The dry disperεion, 5.20 grams (0.749 mole, 2.80 equivalents) iε tranεferred to the flask with 260 ml cyclohexane. This suspension is stirred at 450 RPMs, and heated to 65°C with a heating mantle. The heat source is removed. 1- (t-

Butyldimethylsilylthio) -3-chloro-propane, 60.22 grams (0.268 mole, 1.00 equivalent) is added dropwise. An exotherm is detected after 21.8% of the feed has been added. A dry ice/hexane cooling bath is applied to maintain the reaction temperature at 60-65°C. The total feed time is one hundred minutes. An exotherm is noted until the last drop of feed is added, then the temperature fallε off rapidly to room temperature. The reaction mixture is εtirred at room temperature for forty five minuteε, then heated to 65°C with a heating mantle. The heat εource is removed. Isoprene, 36.45 grams (0.535 mole, 2.00 equivalents) is then added dropwise. An exotherm is noted after 24.6% of the feed has been added. Hexane cooling is applied to maintain the reaction temperature at 60-65°C. The total isoprene feed time is thirty eight minutes. The reaction mixture is allowed to stir at room temperature for one hour, then transferred to a small pressure filter with argon pressure. Very rapid filtration is achieved with 2 psi argon. The muds are reslurried with cyclohexane (2 X 50 ml) . This affords an orange solution; yield = 530 ml, 435.21 grams. Total base = 17.7 wt. %; Active C-Li = 16.9 wt %; Yield (based on active C-Li) = 82.4%.

Example C Preparation of 3 - (N, N-Dimethylamino) -1 -propyl li thium Chain Extended wi th 2 Moles of Isoyrene

A 500 ml, three-necked Morton flask was equipped with a mechanical stirrer, a 125 ml pressure- equalizing addition funnel, and a Claisen adapter fitted with a thermocouple, a reflux condenεer, and an argon inlet. This apparatus was dried in an oven overnight at 125°C, assembled hot, and allowed to cool to room temperature in a stream of argon. Lithium dispersion was washed free of mineral oil with hexane (2 X 70 ml) , and pentane (1 X 70 ml) , then dried in a stream of argon. The dry dispersion, 10.57 grams (1.520 moles) was transferred to the flask with 250 ml cyclohexane. Coarse sand, 45.3 grams, was added to the reaction mixture. This suspenεion was stirred at 600- 675 RPMs, and heated to 37°C with a heating mantle. The heat source was removed. l-Chloro-3- (N,N- dimethylamino)propane, 19.64 grams (0.1615 mole) diεεolved in 120 ml. Cyclohexane was added dropwise. An exotherm (up to 52°C) was detected after 7% of the feed had been added. A dry ice/hexane cooling bath was applied to maintain the reaction temperature at 41- 44°C. The total feed time was thirty-two minutes. An exotherm was noted until the last drop of feed was added, then the temperature waε maintained at 36-40°C for an additional thirty minuteε. The reaction mixture was then transferred to a εintered glass filter while still warm. The filtration was complete in three minutes with three psi argon pressure. This afforded a hazy suεpension. Yield = 400 ml, 298.2 grams. Active C - Li = 0.361 M (0.469 m/kg) at 40°C. Yield (baεed on active C - Li = 87%.

The product cryεtallized from εolution upon εtanding at room temperature. The concentration of the clear supernatant solution was about 0.3 M.

A dry 500 ml round bottom flask was fitted with a magnetic stir bar, and an argon inlet. This apparatus was purged with argon, then 154.77 grams (0.0726 mole) of the suspension prepared above was added to the flask. Isoprene, 9.4 grams (0.138 mole, 1.90 equivalents) was then added all at once. The reaction mixture was then heated to 48-49°C for forty minuteε. Thiε afforded a slightly hazy golden solution, which was partially vacuum-stripped on the rotary evaporator to afford the product solution. Yield = 43.32 grams. Active C - Li = 1.36 M (1.65 m/kg) . Recovered yield (based on active C - Li) = 98.5%.

EXAMPLES OF THE INVENTION - PREPARATION OF POLYMERS

EXAMPLE 1 Preparation of Poly (Styrene-Block-Isoprene) Diblock and Poly (Styrene-Block-Isoprene-Block-Isoprene)

Triblock Covolymers

After thorough evacuation and filling with dry argon, an all-glass, high vacuum reactor was charged with 0.44 mmols of 3-t-butoxy-propyllithium (0.83 mL, 0.53 M in toluene, chain extended with 2 units of isoprene) under a positive argon pressure. After evacuation, 250 mL of purified and dry benzene was distilled directly into the reactor, followed by removal from the vacuum line by heat sealing with a hand torch. Then 3.06 g (29.4 mmol) of purified styrene was added by breaking the breakseal on the respective ampoule. After stirring for 8 hours at 25°C, an aliquot waε removed and terminated by degaεεed methanol. To the remainder of the sample, 5.99 g (87.9 mmol) of purified iεoprene were added via an attached ampoule. After 16 hours of stirring at 25°C, the reaction was divided into three ampoules and one sample was terminated by addition of degassed methanol. The resulting terminated polymers were precipitated into methanol and dried in a vacuum oven. The polystyrene base polymer was analyzed by SEC and exhibited an M_n = 6,900 g/mol and M_w/M_n = 1.08. The block copolymer was analyzed by SEC and by ¹H NMR spectroscopy. The polymer molecular weight by SEC analysiε (polyiεoprene εtandardε) correεponded to M_n = 20,500 g/mol and M_w/M_n = 1.06. An ¹H MNR resonance at δ = 1.17 ppm corresponding to the (CH₃)₃CO- unit was observed. The isoprene microstructure corresponded to 95% 1,4-unitε aε determined by ¹H NMR.

A εample of the living poly(styrene-block- isoprenyl) lithium was coupled with dichlorodimethylsilane (DDS) by εlow addition of a 2% εolution of DDS in benzene. SEC analysis of the resulting ,ω-difunctionalized triblock copolymer indicated that the coupling efficiency was 95%.

EXAMPLE 2

Preparation of Poly (Styrene -Random- I soyr ene) Copolymer

After thorough evacuation and filling with dry argon, an all-glasε, high vacuum reactor was charged with 0.32 mmols of 3-t-butoxy-propyllithium (1.06 mL, 0.3 M in toluene, chain extended with 2 units of isoprene) under a poεitive argon preεεure. After evacuation, 250 mL of purified and dry benzene was distilled directly into the reactor, followed by removal from the vacuum line by heat sealing with a hand torch. Then 3.16 g (30.3 mmol) of purified styrene and 6.50 g (95.4 mmol) of purified isoprene were added via attached ampoules . An ampoule containing 1.27 x IO^"5 mmol of potassium t-amylate ( [Li] / [K] = 25) in benzene was immediately added to promote randomization by breaking the respective breakseal . After 16 hours of stirring at 25°C, the reaction was terminated by addition of degassed methanol . The resulting polymer was precipitated into methanol and dried in a vacuum oven. The polymer was analyzed by SEC and by ¹H NMR spectroscopy. The polymer molecular weight by SEC analysis (polyisoprene standardε) corresponded to M_n = 35,200 g/mol and M_w/M_n = 1.05. An ¹H MNR resonance at δ = 1.17 ppm corresponding to the (CH₃)₃CO- unit was observed. The isoprene microstructure corresponded to 85% 1,4-units as determined by ¹H NMR.

EXAMPLE 3 Preparation of Poly (Styrene-Tapered-Isoprene) Copolymer

After thorough evacuation and filling with dry argon, an all-glasε, high vacuum reactor was charged with 0.681 mmolε of 3-t-butoxy-propyllithium

(2.27 mL, 0.3 M in toluene, chain extended with 2 unitε of iεoprene) under a poεitive argon preεεure. After evacuation, 200 mL of purified and dry benzene was distilled directly into the reactor, followed by removal from the vacuum line by heat εealing with a hand torch. Then 1.02 g (9.79 mmol) of purified styrene and 16.00 g (234.8 mmol) of purified isoprene were added via attached ampoules. The reaction waε frozen at -78°C and then the εide arms with ampoules were removed by heat sealing with a hand torch to minimize the reactor head space. After 8 hours of stirring at 50°C, the reaction was terminated by addition of degassed methanol. The resulting polymer was precipitated into methanol and dried in a vacuum oven. The polymer was analyzed by SEC and by ^XH NMR εpectroεcopy. The polymer molecular weight by SEC analysis (polyisoprene standards) corresponded to M_n = 25,200 g/mol and _w/M_n = 1.04. An ¹H MNR resonance at δ = 1.17 ppm corresponding to the (CH₃)₃CO- unit was observed. The isoprene microstructure corresponded to 87% 1,4-units as determined by ¹H NMR.

EXAMPLE 4 Preparation of Polγ (Styrene -Block -Isoprene) Copolymer

Two ampoules were prepared containing 2.73 g (26.2 mmol) of styrene and 8.18 g (120.1 mmol) isoprene, respectively, and attached to the reactor. Following, 0.525 mmol of initiator (0.53 M in toluene) was added to the reaction flask via syringe, the reactor sealed off, and the system evacuated. After vacuum distill -250 ml of benzene as solvent into the reactor, the system was sealed off from the vacuum line. The styrene monomer was introduced into the flask by the way of a breakseal, where initiation occurred, as evidenced by the development of an orange color. The styrene was allowed to react for 8 hours at 25°C. Following, the isoprene monomer was added, and the reaction mixture aεεumed the characteriεtic pale yellow color. The isoprene block was allowed to propagate for 16 hours at 25°C. A small sample of the solution was terminated for analysiε, while the remainder of the solution was divided among three 100 ml ampoules that were sealed off individually to be used further for coupling reactions.

EXAMPLE 5 Preparation of Poly (Styrene-Random-Isoprene) Copolymer Using a standard high vacuum reaction system,

1.00 g (9.60 mmol) of styrene and 1.50 g (22.0 mmol) of isoprene are added simultaneously to a solution of 0.191 mmol of initiator and 0.880 mmol THF in -150 ml benzene. The reaction solution took on a pale orange color and was stirred at 25°C for 16 hours. The system waε terminated with methanol, precipitated, and analyzed.

EXAMPLE 6 Preparation of Poly (Styrene - Taper -Isoprene) Copolymer In a high vacuum εyεtem, 1.05 g (10.1 mmol) of εtyrene and 13.95 g (204.8 mmol) of iεoprene are added simultaneously to a solution of 0.254 mmol 3- (N,N-dimethylamino) -1-propyllithium in -200 ml benzene. After addition of the monomers, the reaction mixture is frozen, and the reactor arm holding the monomer ampoules is sealed off in order to produce a minimum of headspace within the reactor and maximize the incorporation of the volatile isoprene monomer to assure a styrene block at the termination of the reaction. The reaction proceeds at 50°C for 8 hours. The reaction is then terminated with purified methanol, precipitated, and analyzed.

EXAMPLE 7 Preparation of Poly (Styrene -Random-Butadiene) Copolymer A polystyrene/polyolefin copolymer is produced by reacting styrene (104.16 g, 1 mole) and butadiene (54.10 g, 1 mole) in the preεence of 1 mole % 3-t-butoxy-propyllithium in an appropriate εolvent (100 ml) . The resulting copolymer is quenched with isopropyl alcohol (2 ml) and hydrogenated. The solvent is evaporated under reduced pressure. The residue (1.5 g) is taken up in tert-butylbenzene (25 ml) and Amberlyst^® 15 ion exchange reεin (1.5 g, ground powder, Aldrich) iε added. The protecting group is removed by heating to reflux and monitoring the reaction by then layer chromatography (TLC) until complete. The product solution is filtered to remove the amberlyst resin. The solvent is evaporated under reduced preεεure. The reεulting copolymer is useful as a viscoεity index improving additive for motor oils. EXAMPLE 8 Prepara tion of Pol γ (Al pha -Me thyl s tyr ene -Random - Isoprene) Copol ymer

A polystyrene/polyolefin copolymer is produced by reacting alpha-methylstyrene (118.19 g, 1 mole) and isoprene (68.13 g, 1 mole) in the presence of 1 mole % 3- (t-butyldimethylsilyloxy) -1-propyllithium in an appropriate solvent (100 ml) . The resulting copolymer is coupled with dimethyldichlorosilane (2 ml) and hydrogenated. The solvent is evaporated under reduced presεure. The residue (1.5 g) is taken up in tert-butylbenzene (25 ml) and Amberlyst^® 15 ion exchanged resin (1.5 g, ground powder, Aldrich) is added. The protecting group is removed by heating to reflux and monitoring the reaction by thin layer chromatography (TLC) until complete. The product solution is filtered to remove the amberlyst resin. The solvent is evaporated under reduced pressure. The resulting copolymer iε uεeful aε a viεcosity index improving additive for motor oils.

The foregoing examples are illustrative of the present invention and are not to be construed as limiting thereof. The invention is defined by the following claims, with equivalents of the claims to be included therein.

Claims

THAT WHICH IS CLAIMED IS:

1. A copolymer produced by copolymerizing an alkenylsubεtituted aromatic hydrocarbon and a conjugated diene, εequentially or in admixture, with a protected functional organometaUic initiator of the formula

M-R_n-Z-J-[A(R¹R²R³)]_X (II) wherein:

M is an alkali metal;

R is a saturated or unsaturated hydrocarbyl group derived by incorporation of a compound selected from the group consisting of conjugated diene hydrocarbons, alkenylsubεtituted aromatic hydrocarbonε, and mixtures thereof; n is an integer from 0 to 5; Z is a branched or straight chain hydrocarbon group which contains 3-25 carbon atoms, optionally containing aryl or subεtituted aryl groups;

A is an element selected from Group IVa of the Periodic Table of Elements; J is oxygen, sulfur, or nitrogen;

R¹, R², and R³ are each independently selected from hydrogen, alkyl, εubstituted alkyl groups containing lower alkyl, lower alkylthio, and lower dialkylamino groups, aryl or substituted aryl groupε containing lower alkyl, lower alkylthio, and lower dialkylamino groupε, and cycloalkyl and εubεtituted cycloalkyl containing 5 to 12 carbon atoms; and x is dependent on the valence of J and varies from one when J is oxygen or sulfur to two when J is nitrogen, to form a mono-protected, mono-functionalized living copolymer, followed by quenching or functionalizing the living copolymer with a functionalizing group to terminate and end-cap said living copolymer.

2. The copolymer of Claim 1, wherein said functionalizing compound is selected from the group consisting of ethylene oxide, propylene oxide, εtyrene oxide, oxetane, oxygen, sulfur, carbon dioxide, chlorine, bromine, iodine, chlorotrimethylsilane, εtyrenyldimethyl chlorosilane, 1,3-propane sultone, caprolactam, N-benzylidene trimethylsilylamide, dimethyl formamide, silicon acetals, 1,5- diazabicyclo [3.1.0] hexane, allyl bromide, allyl chloride, methacryloyl chloride, 3- (dimethylamino) - propyl chloride, N- (benzylidene) trimethylsilylamine, epichlorohydrin, epibromohydrin, and epiiodohydrin.

3. A multi-branched or εtar-εhaped copolymer having at leaεt one functional end produced by copolymerizing an alkenylεubεtituted aromatic hydrocarbon and a conjugated diene, εequentially or in admixture, with a protected functional organolithium initiator having the formula:

M-R_n-Z-J-[A(R¹R²R³)]_X (II) wherein:

M is an alkali metal; R is a saturated or unsaturated hydrocarbyl group derived by incorporation of a compound selected from the group consisting of conjugated diene hydrocarbons, alkenylsubεtituted aromatic hydrocarbons, and mixtures thereof; n is an integer from 0 to 5;

Z is a branched or straight chain hydrocarbon group which contains 3-25 carbon atoms, optionally containing aryl or subεtituted aryl groups;

A iε an element εelected from Group IVa of the Periodic Table of Elements;

J is oxygen, sulfur, or nitrogen;

R¹, R², and R³ are each independently selected from hydrogen, alkyl, substituted alkyl groups containing lower alkyl, lower alkylthio, and lower dialkylamino groups, aryl or subεtituted aryl groups containing lower alkyl, lower alkylthio, and lower dialkylamino groups, and cycloalkyl and substituted cycloalkyl containing 5 to 12 carbon atoms; and x is dependent on the valence of J and varies from one when J is oxygen or sulfur to two when J is nitrogen, to form a mono-protected, mono-functionalized living copolymer; and coupling said living copolymer with at least one other living copolymer with a linking agent.

4. The copolymer of Claim 3, wherein said linking agent is selected from the group consisting of halosilaneε, haloεtannaneε, phosphorus halides, isomeric dialkenylaryls, iεomeric divinylaryls, isomeric trivinylaryls, and mixtures thereof.

5. The copolymer of Claim 1 or 3 , wherein said copolymer is produced by polymerizing εaid alkenylεubεtituted aromatic hydrocarbon εequentially with εaid conjugated diene to form a block copolymer.

6. The copolymer of Claim 1 or 3 , wherein said copolymer is produced by polymerizing a mixture of said alkenylsubstituted aromatic hydrocarbon and said conjugated diene in the presence of a polar modifier to form a random copolymer.

7. The copolymer of Claim 1 or 3, wherein said copolymer is produced by polymerizing a mixture of said alkenylsubεtituted aromatic hydrocarbon and εaid conjugated diene to form a tapered copolymer.

8. The copolymer of Claim 1 or 3 , wherein: εaid alkenylsubstituted aromatic hydrocarbon is εelected from the group consisting of styrene, alpha-methylstyrene, vinyltoluene, 2-vinylpyridine, 4- vinylpyridine, 1-vinylnaphthalene, 2-vinylnaphthalene, 1-alpha-methylvinylnaphthalene, 2-alpha- methylvinylnaphthalene, 1, 2-diphenyl-4-methyl-1-hexene, alkyl, cycloalkyl, aryl, alkylaryl and arylalkyl derivatives thereof in which the total number of carbon atoms in the combined hydrocarbon constituentε iε not greater than 18, and mixtureε thereof; and εaid conjugated diene iε selected from the group consisting of 1, 3-butadiene, isoprene, 2,3- dimethyl-1, 3-butadiene, 1, 3-pentadiene, myrcene, 2- methyl-3-ethyl-l, 3-butadiene, 2-methyl-3-ethyl-l, 3- pentadiene, 1, 3-hexadiene, 2-methyl-l, 3-hexadiene, 1,3- heptadiene, 3-methyl-1, 3-heptadiene, 1, 3-octadiene, 3- butyl-1, 3-octadiene, 3 , 4-dimethyl-l, 3-hexadiene, 3-n- propyl-1, 3-pentadiene, 4, 5-diethyl-1, 3-octadiene, 2,4- diethyl-1, 3-butadiene, 2, 3-di-n-propyl-l, 3-butadiene, and 2-methyl-3-isopropyl-1, 3-butadiene.

9. The copolymer of Claim 8, wherein said alkenylsubεtituted aromatic hydrocarbon is εtyrene and wherein said conjugated diene is 1, 3-butadiene or isoprene.

10. The copolymer of Claim 1 or 3, wherein A is carbon or silicon.

11. The copolymer of Claim 1 or 3 , wherein at leaεt a portion of aliphatic unsaturation of said copolymer has been saturated with hydrogen.

12. The copolymer of Claim 11, wherein at least about 90% of aliphatic unsaturation has been εaturated with hydrogen.

13. The copolymer of Claim 11, wherein at leaεt a portion of aliphatic unsaturation of said copolymer has been saturated with hydrogen prior to deprotecting said copolymer.

14. The copolymer of Claim 11, wherein at least a portion of aliphatic unsaturation of said copolymer has been saturated with hydrogen after deprotecting εaid copolymer.

15. The copolymer of Claim 1 or 3 , wherein

[A(R¹R²R³) ] _x haε been removed.

16. The copolymer of Claim 1 or 3 , wherein said organometaUic initiator is selected from the group consiεting of omega- ( ert-alkoxy) -1- alkyllithiumε, omega- ( ert-alkoxy) -1-alkyllithiumε chain extended with conjugated alkadieneε, alkenylεubεtituted aromatic hydrocarbons, and mixtures thereof, omega- ( tert-alkylthio) -1-alkyllithiums, omega- ( ert-alkylthio) -1-alkyllithiums chain extended with conjugated alkadienes, alkenylsubεtituted aromatic hydrocarbonε, and mixtureε thereof, omega- ( ert- butyldimethylεilyloxy) -1-alkyllithiums, omega- (tert- butyldimethylsilylthio) -1-alkyllithiums, omega- (dialkylamino) -1-alkyllithiums, omega- (dialkylamino) -1- alkyllithiums chain-extended with conjugated alkadienes, alkenylsubstituted aromatic hydrocarbons, and mixtures thereof, and omega- (bis- ert- alkylsilylamino) -1-alkyllithiums.

17. The polymer of Claim 16, wherein said organometaUic initiator is selected from the group consisting of 3- (1, 1-dimethylethoxy) -1-propyllithium, 3- ( ert-butyldimethylsilyloxy) -1-propyllithium, 3- (1,1- dimethylethylthio) -1-propyllithium, 3- (dimethylamino) - 1-propyllithium, 3- (di- ert-butyldimethylsilylamino) -1- propyllithium, 3- (1, 1-dimethylethoxy) -1-propyllithium, 3- (1, 1-dimethylethoxy) -2-methyl-l-propyllithium, 3- (1, 1-dimethylethoxy) -2, 2-dimethyl-l-propyllithium, 4- (1, 1-dimethylethoxy) -1-butyllithium, 5- (1, 1- dimethylethoxy) -1-pentyllithium, 6- (1,1- dimethylethoxy) -1-hexyllithium, 8- (1, 1-dimethylethoxy) - 1-octyllithium, 3- (1, 1-dimethylpropoxy) -1- propyllithium, 3- (1, 1-dimethylpropoxy) -2-methyl-l- propyllithium, 3- (1, 1-dimethylpropoxy) -2, 2-dimethyl-l- propyllithium, 4- (1, 1-dimethylpropoxy) -1-butyllithium, 5- (1, 1-dimethylpropoxy) -1-pentyllithium, 6- (1,1- dimethylpropoxy) -1-hexyllithium, 8- (1,1- dimethylpropoxy) -1-octyllithium, 3- (t- butyldimethylεilyloxy) -1-propyllithium, 3- (t- butyldimethylεilyloxy) -2-methyl-l-propyllithium, 3-(t- butyldimethylεilyloxy) -2, 2-dimethyl-1-propyllithium, 4- (t-butyldimethylεilyloxy) -1-butyllithium, 5- (t- butyldimethylsilyloxy) -1-pentyllithium, 6- (t- butyldimethylεilyloxy) -1-hexyllithium, 8- (t- butyldimethylsilyloxy) -1-octyllithium and 3-

(trimethylεilyloxy) -2, 2-dimethyl-1-propyllithium, 3- (dimethylamino) -1-propyllithium, 3- (dimethylamino) -2- methyl-1-propyllithium, 3- (dimethylamino) -2, 2-dimethyl- 1-propyllithium, 4- (dimethylamino) -1-butyllithium, 5- (dimethylamino) -1-pentyllithium, 6- (dimethylamino) -1- hexyllithium, 8- (dimethylamino) -1-propyllithium, 4- (ethoxy) -1-butyllithium, 4- (propyloxy) -1-butyllithium, 4- (1-methylethoxy) -1-butyllithium, 3- (triphenylmethoxy) -2, 2-dimethyl-1-propyllithium, 4- (triphenylmethoxy) -1-butyllithium, 3- [3-

(dimethylamino) -1-propyloxy] -1-propyllithium, 3- [2- (dimethylamino) -1-ethoxy] -1-propyllithium, 3- [2- (diethylamino) -1-ethoxy] -1-propyllithium, 3- [2- (diiεopropyl) amino) -1-ethoxy] -1-propyllithium, 3- [2- (1- piperidino) -1-ethoxy] -1-propyllithium, 3-[2-(l- pyrrolidino) -1-ethoxy] -1-propyllithium, 4- [3- (dimethylamino) -1-propyloxy] -1-butyllithium, 6- [2- (1- piperidino) -1-ethoxy] -1-hexyllithium, 3- [2- (methoxy) -1- ethoxy] -1-propyllithium, 3- [2- (ethoxy) -1-ethoxy] -1- propyllithium, 4- [2- (methoxy) -1-ethoxy] -1-butyllithium, 5- [2- (ethoxy) -1-ethoxy] -1-pentyllithium, 3- [3- (methylthio) -1-propyloxy] -1-propyllithium, 3- [4- (methylthio) -1-butyloxy] -1-propyllithium, 3-

(methylthiomethoxy) -1-propyllithium, 6- [3- (methylthio) -

1-propyloxy] -1-hexyllithium, 3- [4- (methoxy) -benzyloxy] -

1-propyllithium, 3- [4- (1, 1-dimethylethoxy) -benzyloxy] - 1-propyllithium, 3- [2,4- (di ethoxy) -benzyloxy] -1- propyllithium, 8- [4- (methoxy) -benzyloxy] -1- octyllithium, 4- [4- (methylthio) -benzyloxy] -1- butyllithium, 3- [4- (dimethylamino) -benzyloxy] -1- propyllithium, 6- [4- (dimethylamino) -benzyloxy] -1- hexyllithium, 5- (triphenylmethoxy) -1-pentyllithium, 6-

(triphenylmethoxy) -1-hexyllithium, and 8-

(triphenylmethoxy) -1-octyllithium, 3-

(hexamethyleneimino) -1-propyllithium, 4-

(hexamethyleneimino) -1-butyllithium, 5- (hexamethyleneimino) -1-pentyllithium, 6-

(hexamethyleneimino) -1-hexyllithium, 8-

(hexamethyleneimino) -1-octyllithium, 3- (t- butyldimethylεilylthio) -1-propyllithium, 3- (t- butyldimethylεilylthio) -2-methyl-l-propyllithium, 3- (t- butyldimethylεilylthio) -2, 2-dimethyl-l-propyllithium, 4- (t-butyldimethylεilylthio) -1-butyllithium, 6- (t- butyldimethylsilylthio) -1-hexyllithium, 3-

(trimethylεilylthio) -2, 2-dimethyl-1-propyllithium, 3-

(1, 1-dimethylethylthio) -1-propyllithium, 3- (1,1- dimethylethylthio) -2-methyl-l-propyllithium, 3-(l,l- dimethylethylthio) -2,2-dimethyl-1-propyllithium, 4-

(1, 1-dimethylethylthio) -1-butyllithium, 5- (1, 1- dimethylethylthio) -1-pentyllithium, 6- (1, 1- dimethylethylthio) -1-hexyllithium, 8- (1, 1- dimethylethylthio) -1-octyllithium, 3-(l,l- dimethylpropylthio) -1-propyllithium, 3- (1,1- dimethylpropylthio) -2-methyl-l-propyllithium, 3- (1,1- dimethylpropylthio) -2, 2-dimethyl-l-propyllithium, 4-

(1, 1-dimethylpropylthio) -1-butyllithium, 5- (1, 1- dimethylpropylthio) -1-pentyllithium, 6-(l,l- dimethylpropylthio) -1-hexyllithium, and 8-(l,l- dimethylpropylthio) -l-octyllithium, hydrocarbon soluble conjugated alkadiene, alkenylsubstituted aromatic hydrocarbonε, and mixtureε thereof, chain extended oligomeric analogs thereof, and mixtureε thereof.

18. The copolymer of Claim 1 or 3 , wherein at least one functional group is deprotected, and wherein said copolymer further includes a di- or polyfunctional comonomer reacted with εaid at leaεt one deprotected functional group, with the proviεo that when J is reacted with said di- or polyfunctional comonomer, J iε 0 or S.

19. The copolymer of Claim 18, wherein said comonomer is selected from the group consiεting of dieεters, polyesters, diisocyanates, polyisocyanates, diamides, polyamides, cyclic amides, dicarboxylic acids, polycarboxylic acids, diols, polyolε and mixtures thereof.

20. The polymer of Claim 19, wherein said polymer includes at least one hydroxyl functional group, and wherein said at least one hydroxyl functional group iε reacted with diiεocyanate and diol to produce polyurethane blocks .

21. The polymer of Claim 20, wherein said diol includes acid group functionalities, and wherein said acid group functionalities are neutralized with tertiary amineε to provide dispersibility in water.

22. The polymer of Claim 19, wherein said polymer includes at least one hydroxyl functional group, and wherein said at least one hydroxyl functional group is reacted with diacid or anhydride and diamine or lactam to produce polyamide blocks.

23. The polymer of Claim 19, wherein εaid polymer includeε at leaεt one hydroxyl functional group, and wherein εaid at leaεt one hydroxyl functional group iε reacted with diacid or anhydride and diol or polyol to produce polyeεter blockε .

24. The polymer of Claim 23, wherein at least a portion of said diacid or anhydride is subεtituted by an unsaturated acid or anhydride to provide unsaturated polyester blocks capable of croεεlinking with unεaturated monomerε by addition of free radical initiators .

25. The polymer of Claim 19, wherein said polymer includes at least one hydroxyl functional group, and wherein said at least one hydroxyl functional group is reacted with anhydride to form a half-ester with free carboxyl functionality at the terminus thereof.

26. The polymer of Claim 25, wherein said carboxyl functional terminal groupε are further reacted with epoxy reεins and amine curing agents to form epoxy reεin composites.

27. The polymer of Claim 19, wherein said polymer includeε at least one hydroxyl functional group, and wherein said at least one hydroxyl functional group is reacted with methacroyl chloride to provide polymerizable alkenyl groups at the terminus thereof .

28. The polymer of Claim 27, further comprising acrylic monomers polymerized by use of free radical initiators onto said alkenyl terminal groupε.

29. The polymer of Claim 28, wherein said acrylic acid monomers are functional or amide functional acrylic monomers to provide polar hydrophilic polymer segmentε .

30. The polymer of Claim 27, wherein εulfonated styrene and/or 4-vinyl pyridine are polymerized by free radical initiators onto said terminal alkenyl groups to provide functional polymer segments capable of improving dispersability of the polymer.

31. The polymer of Claim 19, wherein said polymer includeε at least one hydroxyl functional group, and wherein said at least one hydroxyl functional group is reacted with sulfonyl chloride in the presence of a tertiary amine catalyst to form εulfonate functional groupε at the terminuε thereof .

32. The polymer of Claim 31, wherein εaid εulfonate functional groupε are reacted with primary amineε or ammonia, under heat and preεεure, to form polymerε with amine functionality at the terminuε thereof.

33. The polymer of Claim 25, wherein εaid carboxyl functional groupε are reacted with an epoxy resin and an excess of amine to completely react all of the epoxy groups, the excess amine is removed by distillation, and the resulting epoxy-amine adduct is reacted with a water soluble organic or inorganic acid to form water soluble quartemary ammonium containing polymers.

34. The copolymer of Claim 3, wherein said copolymer includes at least one functional end and at least one non-functional end prepared by copolymerizing an alkenylsubstituted aromatic hydrocarbon and a conjugated diene, sequentially or in admixture, with said protected functional organolithium initiator of Formula (II) and in addition with a non-functional organometaUic initiator.

35. The copolymer of Claim 3, wherein said copolymer includes at least two functional ends having different functional groups prepared by copolymerizing an alkenylsubstituted aromatic hydrocarbon and a conjugated diene, sequentially or in admixture, with protected functional organolithium initiators of Formula (II) in which J is different.

36. The copolymer of Claim 3, wherein said copolymer includes at least two functional ends having different protecting groups prepared by copolymerizing an alkenylsubεtituted aromatic hydrocarbon and a conjugated diene, sequentially or in admixture, with protected functional organolithium initiators of Formula (II) in which [A(R¹R²R³)]_X is different.

37. A procesε for preparing copolymers, comprising: copolymerizing an alkenylsubεtituted aromatic hydrocarbon and a conjugated diene, sequentially or in admixture, with a protected functional organometaUic initiator of the formula

M-R_n-Z-J-[A(R¹R²R³) ]_x (II) wherein:

M is an alkali metal;

R is a saturated or unsaturated hydrocarbyl group derived by incorporation of a compound selected from the group consisting of conjugated diene hydrocarbons, alkenylsubstituted aromatic hydrocarbons, and mixtures thereof; n is an integer from 0 to 5; Z iε a branched or εtraight chain hydrocarbon group which contains 3-25 carbon atoms, optionally containing aryl or substituted aryl groups;

A is an element selected from Group IVa of the Periodic Table of Elements;

J is oxygen, sulfur, or nitrogen;

R¹, R², and R³ are each independently selected from hydrogen, alkyl, subεtituted alkyl groupε containing lower alkyl, lower alkylthio, and lower dialkylamino groups, aryl or subεtituted aryl groups containing lower alkyl, lower alkylthio, and lower dialkylamino groups, and cycloalkyl and εubstituted cycloalkyl containing 5 to 12 carbon atoms; and x is dependent on the valence of J and varies from one when J is oxygen or sulfur to two when J is nitrogen, to form a mono-protected, mono-functionalized living polymer.

38. The procesε of Claim 37, further compriεing quenching εaid living copolymer after εaid copolymerizing step.

39. The process of Claim 37, further comprising functionalizing said living copolymer with a functionalizing compound capable of terminating and end-capping said living copolymer after said copolymerizing step.

40. The procesε of Claim 37, wherein εaid functionalizing εtep comprises functionalizing said living copolymer with a functionalizing compound selected from the group consisting of ethylene oxide, propylene oxide, styrene oxide, oxetane, oxygen, sulfur, carbon dioxide, chlorine, bromine, iodine, chlorotrimethylsilane, styrenyldimethyl chloroεilane, 1,3-propane εultone, caprolactam, N-benzylidene trimethylεilylamide, dimethyl formamide, εilicon acetalε, 1, 5-diazabicyclo [3.1.0] hexane, allyl bromide, allyl chloride, methacryloyl chloride, 3- (dimethylamino) -propyl chloride, N- (benzylidene) trimethylsilylamine, epichlorohydrin, epibromohydrin, and epiiodohydrin.

41. A process for preparing a multi-branched or star-shaped polymer, comprising: copolymerizing an alkenylsubstituted aromatic hydrocarbon and a conjugated diene, sequentially or in admixture, with a protected functional organometaUic initiator of the formula

M-R_n-Z-J-[A(R^XR²R³)]_X (II) wherein:

M is an alkali metal; R is a saturated or unsaturated hydrocarbyl group derived by incorporation of a compound selected from the group consisting of conjugated diene hydrocarbons, alkenylεubεtituted aromatic hydrocarbons, and mixtureε thereof; n is an integer from 0 to 5;

Z is a branched or εtraight chain hydrocarbon group which contains 3-25 carbon atoms, optionally containing aryl or subεtituted aryl groups;

J is oxygen, sulfur, or nitrogen; A is an element selected from Group IVa of the Periodic Table of Elements;

R¹, R², and R³ are independently selected from hydrogen, alkyl, substituted alkyl groups containing lower alkyl, lower alkylthio, and lower dialkylamino groups, aryl or substituted aryl groups containing lower alkyl, lower alkylthio, and lower dialkylamino groups, and cycloalkyl and substituted cycloalkyl containing 5 to 12 carbon atoms; and x is dependent on the valence of J and varies from one when J iε oxygen or sulfur to two when J is nitrogen, to form a mono-protected, mono-functionalized living polymer; and coupling said living polymer with at least one other living polymer with a linking agent.

42. The procesε of Claim 41, wherein said linking agent is selected from the group consiεting of haloεilanes, halostannes, phosphorus halides, isomeric dialkenylaryls, isomeric divinylaryls, isomeric trivinylaryls, and mixtures thereof.

43. The process of Claim 37 or 41, wherein said copolymerizing step comprises copolymerizing said alkenylsubstituted aromatic hydrocarbon sequentially with said conjugated diene to form a block copolymer.

44. The process of Claim 37 or 41, wherein said copolymerizing step comprises copolymerizing a mixture of said alkenylsubstituted aromatic hydrocarbon and said conjugated diene in the presence of a polar modifier to form a random copolymer.

45. The process of Claim 37 or 41, wherein said copolymerizing step comprises copolymerizing a mixture of said alkenylsubstituted aromatic hydrocarbon and said conjugated diene to form a tapered copolymer.

46. The process of Claim 37 or 41, wherein: said alkenylsubstituted aromatic hydrocarbon is selected from the group consisting of styrene, alpha-methylstyrene, vinyltoluene, 2-vinylpyridine, 4- vinylpyridine, 1-vinylnaphthalene, 2-vinylnaphthalene, 1-alpha-methylvinylnaphthalene, 2-alpha- methylvinylnaphthalene, 1, 2-diphenyl-4-methyl-1-hexene, alkyl, cycloalkyl, aryl, alkylaryl and arylalkyl derivatives thereof in which the total number of carbon atoms in the combined hydrocarbon constituents is not greater than 18, and mixtures thereof; and εaid conjugated diene is selected from the group consiεting of 1, 3-butadiene, isoprene, 2,3- dimethyl-1, 3-butadiene, 1, 3-pentadiene, myrcene, 2- methyl-3-ethyl-l, 3-butadiene, 2-methyl-3-ethyl-1, 3- pentadiene, 1, 3-hexadiene, 2-methyl-l, 3-hexadiene, 1,3- heptadiene, 3-methyl-l, 3-heptadiene, 1, 3-octadiene, 3- butyl-1, 3-octadiene, 3, 4-dimethyl-1, 3-hexadiene, 3-n- propyl-1, 3-pentadiene, 4, 5-diethyl-l, 3-octadiene, 2,4- diethyl-1, 3-butadiene, 2, 3-di-n-propyl-1, 3-butadiene, and 2-methyl-3-iεopropyl-1, 3-butadiene.

47. The process of Claim 46, wherein said alkenylsubεtituted aromatic hydrocarbon is styrene and wherein said conjugated diene is 1, 3-butadiene or isoprene.

48. The procesε of Claim 37 or 41, wherein A iε carbon or εilicon.

49. The proceεε of Claim 37 or 41, further comprising after εaid copolymerizing εtep the step of saturating at least a portion of aliphatic unsaturation of said copolymer with hydrogen.

50. The process of Claim 49, wherein said saturating step compriseε saturating at least about 90% of the aliphatic unsaturation with hydrogen.

51. The procesε of Claim 49, wherein εaid εaturating εtep comprises saturating said copolymer prior to deprotecting said copolymer.

52. The process of Claim 49, further comprising deprotecting said copolymer prior to said saturating step.

53. The process of Claim 37 or 41, further comprising deprotecting εaid copolymer.

54. The process of Claim 37 or 41, wherein said organometaUic initiator is selected from the group consisting of omega- ( ert-alkoxy) -1- alkyllithiumε, omega- (tert-alkoxy) -1-alkyllithiums chain extended with conjugated alkadienes, alkenylεubεtituted aromatic hydrocarbonε, and mixtureε thereof, omega- ( ert-alkylthio) -1-alkyllithiums, omega- ( ert-alkylthio) -1-alkyllithiums chain extended with conjugated alkadienes, alkenylsubεtituted aromatic hydrocarbonε, and mixtureε thereof, omega- ( ert- butyldimethylεilyloxy) -1-alkyllithiums, omega- ( ert- butyldimethylsilylthio) -1-alkyllithiums, omega- (dialkylamino) -1-alkyllithiums, omega- (dialkylamino) -1- alkyllithiumε chain-extended with conjugated alkadienes, alkenylsubstituted aromatic hydrocarbons, and mixtures thereof, and omega- (bis- ert- alkylεilylamino) -1-alkyllithium .

55. The process of Claim 54, wherein said organometaUic initiator is selected from the group consisting of 3- (1, 1-dimethylethoxy) -1-propyllithium, 3- ( ert-butyldimethylsilyloxy) -1-propyllithium, 3- (1,1- dimethylethylthio) -1-propyllithium, 3- (dimethylamino) - 1-propyllithium, 3- (di- ert-butyldimethylsilylamino) -1- propyllithium, 3- (1, 1-dimethylethoxy) -1-propyllithium, 3- (1, 1-dimethylethoxy) -2-methyl-l-propyllithium, 3- (1, 1-dimethylethoxy) -2, 2-dimethyl-l-propyllithium, 4- (1, 1-dimethylethoxy) -1-butyllithium, 5- (1, 1- dimethylethoxy) -1-pentyllithium, 6- (1,1- dimethylethoxy) -1-hexyllithium, 8- (1, 1-dimethylethoxy) - 1-octyllithium, 3- (1, 1-dimethylpropoxy) -1- propyllithium, 3- (1, 1-dimethylpropoxy) -2-methyl-l- propyllithium, 3- (1, 1-dimethylpropoxy) - 2, 2-dimethyl-l- propyllithium, 4- (1, 1-dimethylpropoxy) -1-butyllithium, 5- (1, 1-dimethylpropoxy) -1-pentyllithium, 6- (1,1- dimethylpropoxy) -1-hexyllithium, 8- (1,1- dimethylpropoxy) -1-octyllithium, 3- (t- butyldi ethylsilyloxy) -1-propyllithium, 3- (t- butyldimethylsilyloxy) -2-methyl-l-propyllithium, 3-(t- butyldimethylεilyloxy) -2, 2-dimethyl-l-propyllithium, 4- (t-butyldimethylsilyloxy) -1-butyllithium, 5- (t- butyldimethylεilyloxy) -1-pentyllithium, 6- (t- butyldimethylsilyloxy) -1-hexyllithium, 8- (t- butyldimethylsilyloxy) -1-octyllithium and 3-

(trimethylεilyloxy) -2, 2-dimethyl-l-propyllithium, 3- (dimethylamino) -1-propyllithium, 3- (dimethylamino) -2- methyl-1-propyllithium, 3- (dimethylamino) -2, 2-dimethyl- 1-propyllithium, 4- (dimethylamino) -1-butyllithium, 5- (dimethylamino) -1-pentyllithium, 6- (dimethylamino) -1- hexyllithium, 8- (dimethylamino) -1-propyllithium, 4- (ethoxy) -1-butyllithium, 4- (propyloxy) -1-butyllithium, 4- (1-methylethoxy) -1-butyllithium, 3- (triphenylmethoxy) -2,2-dimethyl-l-propyllithium, 4- (triphenylmethoxy) -1-butyllithium, 3- [3-

(dimethylamino) -1-propyloxy] -1-propyllithium, 3- [2- (dimethylamino) -1-ethoxy] -1-propyllithium, 3- [2- (diethylamino) -1-ethoxy] -1-propyllithium, 3- [2- (diisopropyl) amino) -1-ethoxy] -1-propyllithium, 3- [2- (1- piperidino) -1-ethoxy] -1-propyllithium, 3-[2-(l- pyrrolidino) -1-ethoxy] -1-propyllithium, 4- [3- (dimethylamino) -1-propyloxy] -1-butyllithium, 6- [2- (1- piperidino) -1-ethoxy] -1-hexyllithium, 3- [2- (methoxy) -1- ethoxy] -1-propyllithium, 3- [2- (ethoxy) -1-ethoxy] -1- propyllithium, 4- [2- (methoxy) -1-ethoxy] -1-butyllithium, 5- [2- (ethoxy) -1-ethoxy] -1-pentyllithium, 3- [3- (methylthio) -1-propyloxy] -1-propyllithium, 3- [4- (methylthio) -1-butyloxy] -1-propyllithium, 3- (methylthiomethoxy) -1-propyllithium, 6- [3- (methylthio) - 1-propyloxy] -1-hexyllithium, 3- [4- (methoxy) -benzyloxy] - 1-propyllithium, 3- [4- (1, 1-dimethylethoxy) -benzyloxy] - 1-propyllithium, 3- [2,4- (di ethoxy) -benzyloxy] -1- propyllithium, 8- [4- (methoxy) -benzyloxy] -1- octyllithium, 4- [4- (methylthio) -benzyloxy] -1- butyllithium, 3- [4- (dimethylamino) -benzyloxy] -1- propyllithium, 6- [4- (dimethylamino) -benzyloxy] -1- hexyllithium, 5- (triphenylmethoxy) -1-pentyllithium, 6-

(triphenylmethoxy) -1-hexyllithium, and 8-

(triphenylmethoxy) -1-octyllithium, 3-

(hexamethyleneimino) -1-propyllithium, 4-

(hexamethyleneimino) -1-butyllithium, 5- (hexamethyleneimino) -1-pentyllithium, 6-

(hexamethyleneimino) -1-hexyllithium, 8-

(hexamethyleneimino) -1-octyllithium, 3- (t- butyldimethylsilylthio) -1-propyllithium, 3- (t- butyldimethylεilylthio) -2-methyl-l-propyllithium, 3- (t- butyldimethylsilylthio) -2, 2-dimethyl-1-propyllithium, 4- (t-butyldimethylsilylthio) -1-butyllithium, 6- (t- butyldimethylεilylthio) -1-hexyllithium, 3-

(trimethylsilylthio) -2, 2-dimethyl-1-propyllithium, 3-

(1, 1-dimethylethylthio) -1-propyllithium, 3- (1,1- dimethylethylthio) -2-methyl-l-propyllithium, 3- (1,1- dimethylethylthio) -2, 2-dimethyl-l-propyllithium, 4-

(1, 1-dimethylethylthio) -1-butyllithium, 5- (1, 1- dimethylethylthio) -1-pentyllithium, 6- (1, 1- dimethylethylthio) -1-hexyllithium, 8- (1,1- dimethylethylthio) -1-octyllithium, 3-(l,l- dimethylpropylthio) -1-propyllithium, 3- (1,1- dimethylpropylthio) -2-methyl-l-propyllithium, 3- (1,1- dimethylpropylthio) -2, 2-dimethyl-l-propyllithium, 4-

(1, 1-dimethylpropylthio) -1-butyllithium, 5- (1, 1- dimethylpropylthio) -1-pentyllithium, 6-(l,l- dimethylpropylthio) -1-hexyllithium, and 8-(l,l- dimethylpropylthio) -1-octyllithium, hydrocarbon soluble conjugated alkadiene, alkenylsubεtituted aromatic hydrocarbonε, and mixtureε thereof, chain extended oligomeric analogs thereof, and mixtures thereof.

56. The process of Claim 37 or 41, further comprising copolymerizing said copolymer with at least one di- or polyfunctional comonomer.

57. The procesε of Claim 56, wherein εaid comonomer is selected from the group consisting of diesters, polyesterε, diisocyanates, polyisocyanates, diamides, polyamides, cyclic amides, dicarboxylic acids, polycarboxylic acids, diols, polyols and mixtures thereof .

58. The procesε of Claim 41, wherein εaid polymerizing step comprises polymerizing an alkenylsubεtituted aromatic hydrocarbon and a conjugated diene, sequentially or in admixture, with at least one protected functional organometaUic initiator of Formula (II) and at least one non-functional organometaUic initiator to provide a multi-branched or star-εhaped polymer having at least one functional end and at least one non-functional end.

59. The procesε of Claim 41, wherein εaid polymerizing step comprises polymerizing an alkenylsubstituted aromatic hydrocarbon and a conjugated diene, sequentially or in admixture, with at least two protected functional organometaUic initiators of Formula (II) in which J is different to provide a multi-branched or star-shaped polymer having at least two different functional ends.

60. The process of Claim 41, wherein said polymerizing step comprises polymerizing an alkenylsubεtituted aromatic hydrocarbon and a conjugated diene, sequentially or in admixture, with at least two protected functional organometaUic initiators of Formula (II) in which [A(R¹R²R³) ] _x is different to provide a multi-branched or star-shaped polymer having at least two different protecting groups.

61. A process for modifying the surface adhesion properties of polyolefins, comprising melt mixing the functional polymer of Claim 1 or 3 with a polyolefin in an amount of 1 to 25% by weight baεed on the polyolefin.

62. The proceεε of Claim 61, wherein the polyolefin is selected from the group consisting of low density polyethylene, linear low density polyethylene, high density polyethylene, polypropylene, polyisobutylene, and copolymers and blends thereof.

63. A polymer produced by reacting a living copolymer of Claim 1 with a difunctional linking agent to produce a telechelic, di-protected, di-functional copolymer.

64. The polymer of Claim 63, wherein the difunctional linking agent is selected from the group consiεting of ethylbenzoate, xylene dibromide, and dichlorodimethylsilane.

65. The polymer of Claim 63, wherein the living copolymer before linking is a εequential or tapered diblock copolymer with protected functionality at the initiating chain endε thereof and the polymer after linking iε a triblock copolymer with telechelic protected functionalitieε .

66. The polymer of Claim 63, wherein the living copolymer before linking iε a sequential or tapered diblock copolymer, and the polymer after linking is a telechelic di-protected, di-functional triblock copolymer.

67. The polymer of Claim 66, wherein the di- protected, di-functional triblock copolymer is deprotected.

68. The polymer of Claim 67, wherein the deprotected polymer iε a telechelic polymer having di- hydroxyl functionality.

69. The polymer of Claim 67, wherein εaid deprotected di-functional triblock copolymer is copolymerized with a comonomer or comonomers selected from the group consiεting of diesters, polyesters, diisocyanates, polyisocyanateε, diamides, polyamides, cyclic amides, dicarboxylic acidε, polycarboxylic acids, diols, polyols, and mixtures thereof.

70. A procesε for preparing a telechelic, di-protected, di-functional copolymer, compriεing reacting a living copolymer of Claim 1 with a difunctional linking agent to produce a telechelic, di- protected, di-functional copolymer.

71. The proceεε of Claim 70, wherein the difunctional linking agent iε selected from the group consisting of ethylbenzoate, xylene dibromide, and dichlorodimethylsilane.

72. The proceεε of Claim 70, wherein the living copolymer before linking iε a sequential or tapered diblock copolymer with protected functionality at the initiating chain ends thereof and the polymer after linking is a triblock copolymer with telechelic protected functionalities.

73. The process of Claim 70, wherein the living copolymer before linking is a sequential or tapered diblock copolymer, and the polymer after linking is a telechelic di-protected, di-functional triblock copolymer.

74. The process of Claim 73, further comprising deprotecting the di-protected, di-functional triblock copolymer.

75. The process of Claim 74, wherein the deprotected copolymer is a telechelic di-hydroxyl functional polymer.

76. The polymer of Claim 74, further comprising copolymerizing said deprotected di¬ functional triblock copolymer with a comonomer or comonomers selected from the group consiεting of dieεters, polyesterε, diiεocyanates, polyiεocyanateε, diamideε, polyamideε, cyclic amides, dicarboxylic acids, polycarboxylic acids, diols, polyols, and mixtures thereof.