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WO1997006192A1 - Copolymeres de polystyrene/polydiene fonctionnalises, et procedes pour les preparer - Google Patents

Copolymeres de polystyrene/polydiene fonctionnalises, et procedes pour les preparer Download PDF

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Publication number
WO1997006192A1
WO1997006192A1 PCT/US1996/012519 US9612519W WO9706192A1 WO 1997006192 A1 WO1997006192 A1 WO 1997006192A1 US 9612519 W US9612519 W US 9612519W WO 9706192 A1 WO9706192 A1 WO 9706192A1
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propyllithium
copolymer
polymer
functional
group
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PCT/US1996/012519
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English (en)
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Roderic P. Quirk
Conrad W. Kamienski
Robert J. Letchford
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Fmc Corporation
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Priority to AU66430/96A priority Critical patent/AU6643096A/en
Publication of WO1997006192A1 publication Critical patent/WO1997006192A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
    • C08F297/046—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes polymerising vinyl aromatic monomers and isoprene, optionally with other conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/30—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule
    • C08C19/42—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups
    • C08C19/44—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups of polymers containing metal atoms exclusively at one or both ends of the skeleton
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F236/10—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with vinyl-aromatic monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/04—Reduction, e.g. hydrogenation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
    • C08F2800/10—Copolymer characterised by the proportions of the comonomers expressed as molar percentages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
    • C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages

Definitions

  • 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.
  • 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.
  • olefinic-containing monomers such as styrene and dienes
  • an organo-alkali metal initiator such as styrene and dienes
  • 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.
  • 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 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the molecular architecture of compounds of the present invention can be precisely controlled.
  • 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.
  • 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.
  • 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.
  • 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 group ⁇ ; J is oxygen, sulfur, or nitrogen;
  • X is a protecting group, wherein A is an element selected from Group IVa of the Periodic Table of Elements;
  • R 1 , R 2 , and R 3 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.
  • the protecting group 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) .
  • 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 i ⁇ generally not greater than 18.
  • Examples of these latter compounds include 3- methyl ⁇ tyrene, 3, 5-diethyl ⁇ tyrene, 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.
  • 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,
  • 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.
  • 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.
  • a suitable proton donor such as water, methanol, isopropanol, acetic acid, and the like
  • 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.
  • a difunctional linking agent such as ethylbenzoate, xylene dibromide or dimethyldichlorosilane.
  • 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;
  • the copolymer optionally is hydrogenated, either before after removal of the protecting group.
  • organolithium initiators useful in the present invention include initiators ⁇ elected from the group consi ⁇ ting 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- (bis- tert- alkylsilylamino) -1-alkyllithiums 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 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 contain ⁇ 3-25 carbon atom ⁇ , optionally containing aryl or substituted aryl groups
  • R 1 , R 2 , and R 3 are each independently selected from hydrogen, alkyl, substituted alkyl groups containing lower alkyl, lower alkylthio, and lower dialkylamino group ⁇ , aryl or ⁇ ub ⁇ tituted aryl group ⁇ containing lower alkyl, lower alkylthio, and lower dialkylamino groups, and cycloalkyl and sub ⁇ tituted 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.
  • the ⁇ e initiators can be prepared by reaction of protected organolithium compounds of the following formula: M-Z-J-[A(R 1 R 2 R 3 )] X (III) wherein each of M, Z, J, A, R 1 , R 2 , R 3 , 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 mixture ⁇ thereof, to form an extended hydrocarbon chain between M and Z in Formula (III) , which extended chain i ⁇ denoted as R n in Formula (II) .
  • conjugated alkadienes such as butadiene or isoprene
  • alkenylsubstituted aromatic hydrocarbons such as styrene or alpha-methylstyrene
  • 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 group ⁇ contain 3 to 25 carbon atoms) with an alkali metal, preferably lithium, at a temperature between about 35°C and about
  • a protected monofunctional alkali metal initiator (of Formula III) , which is then optionally reacted with a one or more conjugated diene hydrocarbon ⁇ , one or more alkenyl ⁇ ubstituted aromatic hydrocarbons, or mixture ⁇ of one or more dienes with one or more alkenylsub ⁇ tituted aromatic hydrocarbons, in a predominantly alkane, cycloalkane, or aromatic reaction solvent, which solvent contain ⁇ 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(R 1 R 2 R 3 )] of the formulae above can be any of the elements in Group IVa of the Periodic Table of the Elements, carbon and ⁇ ilicon currently appear the most useful, especially when polymerizing conjugated dienes.
  • Tertiary amino-1-haloalkanes u ⁇ eful in practicing this invention include compounds of the following general structure ⁇ :
  • 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 ⁇ elected from Group IVa of the Periodic Table of the Elements
  • R 1 , R 2 , and R 3 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
  • 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-haloalkane ⁇ who ⁇ e alkyl group ⁇ 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.
  • alkali metal preferably lithium
  • 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 i ⁇ an alkenyl ⁇ ubstituted 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-(
  • halo- or halide group is preferably selected from chlorine and bromine.
  • Omega-hydroxy-protected-1-haloalkane ⁇ useful in producing monofunctional ether initiators useful in practicing this invention have the following general structure:
  • the process reacts selected omega-hydroxy- protected-1-haloalkane ⁇ 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 solvent ⁇ .
  • 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 u ⁇ ed per mole of monomer.
  • the precursor omega-protected-1-haloalkanes (halides) can be prepared from the corresponding haloalcohol by standard literature methods.
  • 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.
  • 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 in ⁇ tance 1-bromo-6-hexane, according to the method of J. Almena, F. Foubelo and M. Yus, Tetrahedron, 51, 1995, 11883.
  • 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, 3-
  • halo- or halide group is preferably selected from chlorine and bromine.
  • Patent 5,362,699 disclo ⁇ e ⁇ a proce ⁇ for the preparation of hydrocarbon ⁇ olution ⁇ of monofunctional ether initiators derived from omega- hydroxy-silyl-protected-1-haloalkane ⁇ of the following general structure:
  • 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 solvent ⁇ .
  • Anionic polymerizations employing the monofunctional siloxy ether initiator ⁇ are conducted in an inert ⁇ olvent, preferably a non-polar ⁇ olvent, 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 ⁇ o that the polymer i ⁇ mono-functionally or di-functionally terminated.
  • the polymer ⁇ may have a molecular weight range of about 1000 to 50,000 but the molecular weight can be higher.
  • Omega-silyl-protected-1-haloalkanes prepared in accordance with thi ⁇ earlier process useful in practicing this invention include, but are not limited to, 3- (t-butyldimethyl ⁇ ilyloxy) -1-propyl halide, 3-(t- butyldimethyl- ⁇ ilyloxy) - 2-methyl-1-propyl halide, 3-(t- butyldi ethyl ⁇ ilyloxy) -2, 2-dimethyl-1-propyl halide, 4- (t-butyldimethylsilyloxy) -1-butyl halide, 5- (t- butyldimethyl- ⁇ ilyloxy) -1-pentyl halide, 6- (t- butyldimethyl ⁇ ilyloxy) -1-hexyl halide, 8- (t- butyldimethyl ⁇ ilyloxy) -1-octyl
  • Monofunctional thioether initiator ⁇ u ⁇ eful in the practice of thi ⁇ invention can be derived from omega-thio-protected-1-haloalkanes of the following general structure:
  • X-Z-S- [A(R 1 R 2 R 3 ) ] 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(R 1 R 2 R 3 )] is a protecting group in which A is an element selected from Group IVa of the Periodic Table of the Element ⁇ ; and R 1 , R 2 , and R 3 are independently defined a ⁇ 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,
  • 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 solvent ⁇ .
  • alkali metal preferably lithium
  • 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 alkenylsub ⁇ tituted aromatic hydrocarbon or a 1,3-diene at a temperature of about -30°C to about 150°C.
  • the polymerization reaction proceed ⁇ from initiation to propagation and i ⁇ finally terminated with appropriate reagent ⁇ 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 i ⁇ u ⁇ ed per mole of monomer.
  • the initiator precur ⁇ or, omega-thio- protected-1-haloalkane ⁇ (halide ⁇ ) can be prepared from the corresponding halothiol by standard literature methods.
  • 3- (1, 1-dimethylethylthio) -1- propylchloride can be synthe ⁇ ized 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.
  • reaction of 1, 1-dimethylethylthiol with l-bromo-3- chloropropane and a ba ⁇ e afford ⁇ 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.
  • 5- (cyclohexylthio) -1-pentylhalide and the like can be prepared by the method of J.
  • Methoxymethylthio compounds such as 6- (methoxymethylthio) -1-hexylchloride, can be prepared by the reaction of the omega-chloro-thiol with bromochloromethane, methanol, and potas ⁇ ium hydroxide, by the method of F. D. Toste and I. W. J. Still,
  • T-Butyldimethylsilyl protected compounds for example 4- (t-butyldimethylsilylthio) -1- butylhalide, can be prepared from t- butyldimethylchloro ⁇ ilane, and the corre ⁇ ponding thiol, according to the method described in U.S. Patent No.
  • Omega-thio-protected 1-haloalkanes prepared in accordance with this earlier proces ⁇ u ⁇ eful in practicing thi ⁇ 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-
  • protected functionalized initiators 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)
  • 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 ⁇ imultaneou ⁇ ly 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 atom ⁇ ⁇ uch 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 monomer sequence distribution can be described schematically by (1) below: -[-A-] n -[-A/B-]-[-B-] m - or - [-A-] perennial-- [-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 ⁇ egment; 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 ⁇ econd block ⁇ egment.
  • A is an aromatic substituted saturated hydrocarbyl group derived by incorporation of an alkenylsub ⁇ tituted aromatic sub ⁇ tituted hydrocarbon; n repre ⁇ ent ⁇ the equivalent ⁇ of A employed primarily in the initial block ⁇ egment; 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.
  • a difunctional linking agent such as ethylbenzoate, xylene dibromide or dimethyldichlorosilane.
  • 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.
  • 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, polye ⁇ ter and polyurethane attached to the ⁇ electively deprotected telechelic functional polydiene/polyarylethylene or polyolefin/polyarylethylene triblocks.
  • 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.
  • 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 group ⁇ 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
  • Tert-butyldimethylsilyl protecting group ⁇ can be removed by treatment of the copolymer with acid, such as hydrochloric acid, acetic acid, para- toluensulfonic acid, or Dowex ® 50W-X8.
  • acid such as hydrochloric acid, acetic acid, para- toluensulfonic acid, or Dowex ® 50W-X8.
  • a source of fluoride ions for instance tetra-n- butylammonium fluoride, potas ⁇ ium 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.
  • 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.
  • 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) .
  • the progress of the deprotection reactions can be monitored by conventional analytical techniques, such as Thin Layer Chromatography (TLC) , Nuclear Magnetic Resonance (NMR) spectro ⁇ copy, or InfraRed (IR) spectroscopy.
  • TLC Thin Layer Chromatography
  • NMR Nuclear Magnetic Resonance
  • IR InfraRed
  • Example ⁇ of method ⁇ to hydrogenate the copolymer ⁇ 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 cataly ⁇ t .
  • a catalyst such as a nickel cataly ⁇ t .
  • the hydrogenation i ⁇ typically performed at temperatures from 25°C to 150°C, with a archetypal hydrogen pre ⁇ sure of 15 p ⁇ ig to 1000 p ⁇ ig.
  • the progress of this hydrogenation can be monitored by InfraRed (IR) spectroscopy or Nuclear Magnetic Resonance (NMR) spectroscopy.
  • IR InfraRed
  • NMR Nuclear Magnetic Resonance
  • 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 ⁇ olvent removal or precipitation of the copolymer.
  • multi- branched or star- ⁇ haped polymer ⁇ which include alkenyl ⁇ ub ⁇ tituted 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 polymer ⁇ 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.
  • 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, re ⁇ ultant polyester and/or polyamide molecules .
  • Novel multi-branched or star-shaped polymer ⁇ 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 ⁇ ame ⁇ ize.
  • linking or coupling agents examples include halosilane ⁇ , ⁇ uch as silicon tetrachloride and methyl trichlorosilane; halostannanes, such as tin tetrachloride; pho ⁇ phorus halides, such as phosphorus trichloride; and isomeric (mixtures of ortho, meta and para) dialkenylaryls and isomeric di- and trivinylaryls, ⁇ uch as 1, 2-divinylbenzene, 1,3- divinylbenzene, 1,4-divinylbenzene, 1,2,4- trivinylbenzene ⁇ , 1, 3-divinylnaphthalene ⁇ , 1,8- divinylnaphthalene, 1, 2-diisopropenylbenzene, 1,3- dii ⁇ opropenylbenzene, 1, 4-dii ⁇ opropenylbenzene, 1,3,5- trivinylnaphthalene, and other ⁇ uitable material ⁇ known in the
  • 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
  • novel multi-branched or star- shaped polymers posses ⁇ ing functional end ⁇ which may be the ⁇ ame or different, and/or both functional and non ⁇ functional end ⁇ , 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.
  • 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 arm ⁇ , using the techniques described above. This includes selective deprotection when di ⁇ imilarly protected functional group ⁇ are pre ⁇ ent, a ⁇ detailed above.
  • Molecular weight ⁇ of the re ⁇ ulting linked or coupled polymer ⁇ can vary depending on the molecular weight of the polymer anion and the number of potential functional linking group ⁇ on a coupling agent.
  • the ⁇ izes 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.
  • 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 hydrolysi ⁇ ) , 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) .
  • a diisocyanate such as methylene 4, 4-diphenyl diisocyanate (2/1 NCO/OH
  • 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.
  • polyethylene including high density polyethylene, low density polyethylene and linear low density polyethylene
  • polypropylene polyisobutylene and copolymers and blends thereof.
  • 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.
  • Protected monohydroxy copolymers alone and in their hydrogenated forms can be u ⁇ ed a ⁇ base materials to lend flexibility and higher impact strength in a number of formulas to produce coatings, sealant ⁇ , binders and block copolymers with polyesters, polyamides and polycarbonates as described in UK Patent Application GB2270317A and in "Polytail" data sheet ⁇ and brochure ⁇ (Mit ⁇ ubi ⁇ hi Ka ⁇ ei America) .
  • 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.
  • hydrogenated hydroxy-terminated copolymers may be reacted with bisphenol A and phosgene in the presence of appropriate catalysts with simultaneou ⁇ deprotection to yield a polycarbonate alternating block copolymer.
  • the re ⁇ ulting product ⁇ are useful as molding resin ⁇ , 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 ⁇ uitable 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.
  • acid functional diols such as dimethylolpropionic acid
  • polyurethane introduces pendant carboxyl groups which can be neutralized with tertiary amines to afford water dispersable polyolefin/polyurethane segmented polymers, useful for water based coating ⁇ .
  • acid functional diols such as dimethylolpropionic acid
  • Thi ⁇ 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.
  • Yet another application includes use as toughening polymers for epoxy compo ⁇ ite ⁇ , 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 polyester ⁇ provides a new polymer toughening system for polyester molding compounds for automotive and other uses.
  • Cathodic electrodepositable coatings may be prepared from epoxy functional polymers described above by reacting with epoxy re ⁇ ins 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 salt ⁇ ( ⁇ ee for reference, U.S. Patent No ⁇ . 3,617,458, 3,619,398, 3,682,814, 3,891,527, 3,947,348, and 4 , 093 , 594) .
  • the above epoxy-amine polymer adduct ⁇ may be converted to quartemary pho ⁇ phonium or ⁇ ulfonium ion containing polymer ⁇ , a ⁇ de ⁇ cribed 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 pre ⁇ ence of a basic reagent.
  • V.I. visco ⁇ ity index
  • carboxyl functional monomers such as acrylic acid and methacrylic acid
  • amine functional monomers such as acrylamide
  • 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) .
  • 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 pos ⁇ ible application ⁇ as compatibilizer ⁇ for polymer blend ⁇ and alloys. In addition to the use of such blends for new applications, much recent interest is generated in the u ⁇ e of compatibilizers to facilitate polymer waste recycling.
  • protecting group ⁇ may be removed, either before or after optional hydrogenation of the aliphatic un ⁇ aturation, then the hydroxy terminated polymer may be reacted with functional comonomers to produce novel copolymers using these and other processes .
  • 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 .
  • 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.
  • a hydroxyterminated copolymer may be hydrogenated, and then reacted with ethylene oxide in the presence of potas ⁇ ium tert- butoxide to produce a poly(ethylene oxide) -hydrogenated poly ⁇ tyrene/polydiene copolymer with one protected hydroxyl group on the poly ⁇ tyrene 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 ⁇ egment .
  • the living copolymer may be reacted with an alkenylarylhalosilane such as styrenyldimethylchloro ⁇ ilane to yield the corre ⁇ ponding omega- tyrenyl terminated macromonomer according to the teaching ⁇ of U.S. Patent No.
  • 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 ⁇ elected from the group of alkyl acrylate ⁇ , alkyl methacrylate ⁇ , and dialkylacrylamide ⁇ to produce hydrogel ⁇ .
  • acrylate or methacrylate-terminated polymers may be polymerized by free-radical processes.
  • Lithium disper ⁇ ion wa ⁇ 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- Butyldimethyl ⁇ ilyloxy) -3-chloro-propane, 58.82 grams (0.268 mole, 1.00 equivalent) was added dropwise.
  • a 500 ml, three-necked Morton flask is equipped with a mechanical stirrer, a 125 ml pressure- equalizing addition funnel, and a Clai ⁇ en 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.
  • 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 fall ⁇ off rapidly to room temperature. The reaction mixture is ⁇ tirred at room temperature for forty five minute ⁇ , then heated to 65°C with a heating mantle. The heat ⁇ ource is removed. Isoprene, 36.45 grams (0.535 mole, 2.00 equivalents) is then added dropwise.
  • 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 conden ⁇ er, 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 product cry ⁇ tallized from ⁇ olution upon ⁇ tanding at room temperature.
  • the concentration of the clear supernatant solution was about 0.3 M.
  • 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 X H NMR ⁇ pectro ⁇ copy.
  • the isoprene microstructure corresponded to 87% 1,4-units as determined by 1 H NMR.
  • 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.
  • the isoprene monomer was added, and the reaction mixture a ⁇ umed the characteri ⁇ tic 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 analysi ⁇ , 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.
  • reaction mixture 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 pre ⁇ ence of 1 mole % 3-t-butoxy-propyllithium in an appropriate ⁇ olvent (100 ml) .
  • the resulting copolymer is quenched with isopropyl alcohol (2 ml) and hydrogenated.
  • the solvent is evaporated under reduced pressure.
  • 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 pres ⁇ ure.

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Abstract

Des copolymères de polystyrène/polydiène fonctionnalisés sont préparés avec un initiateur organométallique dont le groupe fonctionnel est protégé, ayant la formule (II) M-Rn-Z-J-[A(R1R2R3)]x. Dans cette formule, M est un métal alcalin; R est un groupe hydrocarbyle saturé ou non saturé, obtenu en incorporant un composé choisi dans le groupe constitué par les hydrocarbures du type diènes conjugués, les hydrocarbures aromatiques portant un substituant alcényle, et leurs mélanges; n est un nombre entier entre 0 et 5; Z est un groupe hydrocarbure droit ou ramifié contenant 3-25 atomes de carbone, et éventuellement des groupes aryle substitués ou non; A est un atome de carbone ou de silicium; J est l'oxygène, le soufre ou l'azote; R?1, R2 et R3¿ sont choisis chacun indépendamment parmi l'hydrogène, des groupes alkyle, des groupes alkyle substitués contenant un alkyle inférieur, un alkylthio inférieur ou un dialkylamino inférieur, des groupes aryle ou aryle substitués contenant des groupes alkyle inférieur, alkylthio inférieur ou dialkylamino inférieur, et des groupes cycloalkyle substitués ou non, contenant 5 à 12 atomes de carbone; et x dépend de la valence de J et varie entre 1 quand J est l'oxygène ou le soufre et 2 quand J est l'azote. Le copolymère obtenu est un copolymère 'vivant' portant un groupe fonctionnel protégé unique.
PCT/US1996/012519 1995-08-03 1996-07-31 Copolymeres de polystyrene/polydiene fonctionnalises, et procedes pour les preparer WO1997006192A1 (fr)

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998002465A1 (fr) * 1996-07-17 1998-01-22 Schwindeman James A Polymeres heterotelecheliques fonctionnalises proteges et procedes pour les preparer
WO1999025740A1 (fr) * 1997-11-14 1999-05-27 Fmc Corporation Compositions permettant une meilleure fonctionnalisation d'anions terminaux et procedes associes
WO1999060031A1 (fr) * 1998-05-18 1999-11-25 Shell Internationale Research Maatschappij B.V. Procede de fabrication de polymeres anioniques bifonctionnels et polyfonctionnels au moyen d'initiateurs fonctionnels proteges
US6153706A (en) * 1997-07-30 2000-11-28 Fmc Corporation Protected multi-functionalized star polymers and processes for making the same
WO2002008299A1 (fr) * 2000-07-26 2002-01-31 Fmc Corporation Amorceurs fonctionnalises, a chaine etendue, et procedes de preparation et d'utilisatoin associes
WO2002024764A1 (fr) * 2000-09-19 2002-03-28 Fmc Corporation Initiateurs de polymerisation aminofonctionnalises proteges et leurs procedes de production et d'utilisation
WO2002060958A3 (fr) * 2001-02-01 2003-02-20 Fmc Corp Initiateurs fonctionnalisés destinés à la polymérisation anionique, polymères fonctionnalisés protégés, analogues déprotégés de ceux-ci, et procédés de préparation correspondants
US6545103B2 (en) 1997-11-14 2003-04-08 Fmc Corporation Compositions providing improved functionalization of terminal anions and processes for improved functionalization of terminal anions
US6605564B1 (en) 1997-11-14 2003-08-12 Fmc Corporation Compositions providing improved functionalization of terminal anions and processes for improved functionalization of terminal anions
EP1923425A1 (fr) * 2001-05-01 2008-05-21 Kuraray Co., Ltd. Compositions élastomères thermoplastiques
WO2014040640A1 (fr) 2012-09-14 2014-03-20 Styron Europe Gmbh Polymères modifiés par un silane aminé
RU2531821C2 (ru) * 2008-11-11 2014-10-27 Стирон Юроп Гмбх Процесс получения модифицированного интерполимера или модифицированного полимера

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2241239A (en) * 1990-02-08 1991-08-28 Secr Defence Olefinic polymerisation using silylether initiators
WO1995022566A1 (fr) * 1994-02-18 1995-08-24 Fmc Corporation Nouveaux initiateurs fonctionnalises de la polymerisation anionique
US5527753A (en) * 1994-12-13 1996-06-18 Fmc Corporation Functionalized amine initiators for anionic polymerization

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2241239A (en) * 1990-02-08 1991-08-28 Secr Defence Olefinic polymerisation using silylether initiators
WO1995022566A1 (fr) * 1994-02-18 1995-08-24 Fmc Corporation Nouveaux initiateurs fonctionnalises de la polymerisation anionique
US5527753A (en) * 1994-12-13 1996-06-18 Fmc Corporation Functionalized amine initiators for anionic polymerization

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US6107414A (en) * 1996-07-17 2000-08-22 Fmc Corporation Protected functionalized heterotelechelic polymers and processes for preparing the same
US6362284B1 (en) 1996-07-17 2002-03-26 Fmc Corporation Protected functionalized heterotelechelic polymers and processes for preparing the same
WO1998002465A1 (fr) * 1996-07-17 1998-01-22 Schwindeman James A Polymeres heterotelecheliques fonctionnalises proteges et procedes pour les preparer
US6153706A (en) * 1997-07-30 2000-11-28 Fmc Corporation Protected multi-functionalized star polymers and processes for making the same
US6545103B2 (en) 1997-11-14 2003-04-08 Fmc Corporation Compositions providing improved functionalization of terminal anions and processes for improved functionalization of terminal anions
WO1999025740A1 (fr) * 1997-11-14 1999-05-27 Fmc Corporation Compositions permettant une meilleure fonctionnalisation d'anions terminaux et procedes associes
US6858679B2 (en) 1997-11-14 2005-02-22 Fmc Corporation Compositions providing improved functionalization of terminal anions and processes for improved functionalization of terminal anions
US6605564B1 (en) 1997-11-14 2003-08-12 Fmc Corporation Compositions providing improved functionalization of terminal anions and processes for improved functionalization of terminal anions
WO1999060031A1 (fr) * 1998-05-18 1999-11-25 Shell Internationale Research Maatschappij B.V. Procede de fabrication de polymeres anioniques bifonctionnels et polyfonctionnels au moyen d'initiateurs fonctionnels proteges
US6610859B1 (en) 1999-02-24 2003-08-26 Fmc Corporation Protected aminofunctionalized polymerization initiators and methods of making and using same
US6891019B2 (en) 1999-02-24 2005-05-10 Fmc Corporation Protected aminofunctionalized polymerization initiators and methods of making and using same
US6875876B2 (en) 1999-02-24 2005-04-05 Fmc Corporation Protected aminofunctionalized polymerization initiators and methods of making and using same
GB2380484B (en) * 2000-07-26 2004-05-12 Fmc Corp Chain extended functionalized initiators and methods of preparing and using the same
GB2380484A (en) * 2000-07-26 2003-04-09 Fmc Corp Chain extended functionalized initiators and methods of preparing and using the same
WO2002008299A1 (fr) * 2000-07-26 2002-01-31 Fmc Corporation Amorceurs fonctionnalises, a chaine etendue, et procedes de preparation et d'utilisatoin associes
US6770587B1 (en) 2000-07-26 2004-08-03 Fmc Corporation Chain extended functionalized initiators and methods of preparing and using the same
GB2382076B (en) * 2000-09-19 2005-11-30 Fmc Corp Protected aminofuntionalized polymerization initiators and methods of making and using same
WO2002024764A1 (fr) * 2000-09-19 2002-03-28 Fmc Corporation Initiateurs de polymerisation aminofonctionnalises proteges et leurs procedes de production et d'utilisation
GB2382076A (en) * 2000-09-19 2003-05-21 Fmc Corp Protected aminofuntionalized polymerization initiators and methods of making and using same
US6720391B2 (en) 2001-02-01 2004-04-13 Fmc Corporation Functionalized initiators for anionic polymerization, protected functionalized polymers, deprotected analogues thereof, and methods of making the same
GB2389855A (en) * 2001-02-01 2003-12-24 Fmc Corp Functionalized initiators for anionic polymerization,protected funtionalized polymers,deprotected analogues thereof,and method of making the same
WO2002060958A3 (fr) * 2001-02-01 2003-02-20 Fmc Corp Initiateurs fonctionnalisés destinés à la polymérisation anionique, polymères fonctionnalisés protégés, analogues déprotégés de ceux-ci, et procédés de préparation correspondants
GB2389855B (en) * 2001-02-01 2005-09-21 Fmc Corp Functionalized initiators for anionic polymerization,protected funtionalized polymers,deprotected analogues thereof,and method of making the same
EP1923425A1 (fr) * 2001-05-01 2008-05-21 Kuraray Co., Ltd. Compositions élastomères thermoplastiques
RU2531821C2 (ru) * 2008-11-11 2014-10-27 Стирон Юроп Гмбх Процесс получения модифицированного интерполимера или модифицированного полимера
US8952100B2 (en) 2008-11-11 2015-02-10 Styron Europe Gmbh Process to remove silanol from the preparation of a modified polymer
WO2014040640A1 (fr) 2012-09-14 2014-03-20 Styron Europe Gmbh Polymères modifiés par un silane aminé
US9458253B2 (en) 2012-09-14 2016-10-04 Trinseo Europe Gmbh Amino silane-modified polymers

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