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EP1718680A1 - Chaines polymeres comportant des extremites et leurs produits - Google Patents

Chaines polymeres comportant des extremites et leurs produits

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Publication number
EP1718680A1
EP1718680A1 EP05713361A EP05713361A EP1718680A1 EP 1718680 A1 EP1718680 A1 EP 1718680A1 EP 05713361 A EP05713361 A EP 05713361A EP 05713361 A EP05713361 A EP 05713361A EP 1718680 A1 EP1718680 A1 EP 1718680A1
Authority
EP
European Patent Office
Prior art keywords
polymer
copolymer
constitutional units
block
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP05713361A
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German (de)
English (en)
Inventor
Rudolf Faust
Jae Cheol Cho
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University of Massachusetts Lowell
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University of Massachusetts Lowell
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Filing date
Publication date
Priority claimed from US10/776,681 external-priority patent/US7056985B2/en
Application filed by University of Massachusetts Lowell filed Critical University of Massachusetts Lowell
Publication of EP1718680A1 publication Critical patent/EP1718680A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C08F297/026—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 acrylic acid, methacrylic acid or derivatives thereof
    • 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
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/08—Butenes
    • C08F110/10—Isobutene
    • 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
    • C08F295/00—Macromolecular compounds obtained by polymerisation using successively different catalyst types without deactivating the intermediate polymer
    • 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
    • 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
    • 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
    • C08F8/02—Alkylation

Definitions

  • This invention relates to processes for end-capping a cationically polymerized polymer. More particularly this invention relates to processes for end-capping a cationically polymerized polymer with an anionic group, after which the resulting anionically terminated polymer can be used in subsequent anionic reactions, including anionic coupling and polymerization reactions.
  • the present invention also relates to copolymers including a cationically polymerized polymer coupled to an anionically polymerized polymer.
  • Copolymers are an important class of polymers and have numerous commercial applications. For instance, their unique properties, whether in pure form, in blends, in melts, in solutions, and so forth, lead to their use in a wide range of products, for example, compatiblilizers, adhesives and dispersants. Combining various polymerization techniques (e.g., cationic and anionic polymerization techniques in the case of the present invention) may produce new copolymers, each with its own unique properties, which could not otherwise be prepared using a single polymerization method.
  • polyisoolefins are attractive materials because the polymer chain is fully saturated and, consequently, the thermal and oxidative stability of this polymer are excellent.
  • Polyisoolefins are prepared by cationic polymerization. Recently, Muller et al. reported that poly(alkyl methacrylate)-b-polyisobutylene and poly(alkyl mefhacrylate)-/ polyisobutylene-b-poly(alkyl methacrylate) copolymers can be prepared by the combination of cationic and anionic polymerization techniques. See Feldthusen, J.; Ivan, B.; Muller, A. H. E. Macromolecules, 1997, 30, 6989-6993; Feldthusen, J.; Ivan, B.; Muller, A. H. E. Macromolecules 1998, 31, 578-585. In this process, an endfunctionalized polyisobutylene (PIB), specifically 1,1-diphenyl-l-methoxy end ⁇
  • a more recent attempt to combine cationic and anionic polymerization techniques involves the preparation of end-functionalized polymers (e.g., endfunctionalized polyisobutylene) by reacting a carbocationically terminated polymer with a heterocyclic compound (e.g., thiophene) to provide an end-capped polymer (e.g., thiophene end-functionalized polyisobutylene).
  • a heterocyclic compound e.g., thiophene
  • the end-capped polymer is then reacted with an organolithium compound to yield an anionically terminated polymer, which is subsequently reacted with an anionically polymerizable monomer such as tert-butyl methacrylate to produce a copolymer.
  • a method in which a double diphenylethylene compound is reacted with a polymer that contains a carbocationically terminated chain, which chain contains a plurality of constitutional units corresponding to cationically polymerizable monomer species, thereby providing a 1,1 -diphenylene end-functionalized chain.
  • an alkylating agent is reacted with the 1,1 -diphenylene end-functionalized chain, resulting in the formation of an alkylated 1,1 -diphenylene end-functionalized chain.
  • the alkylating agent can be, but is not limited to an alkylaluminum compound or an alkylzinc compound, e.g., dimethyl-zinc.
  • the double diphenylethylene compound can be, but is not limited to l,4-bts(l-phenylefhenyl)benzene.
  • the above method further comprises optionally combining a 1,1-diphenylorganolithium compound with the alkylated 1,1 -diphenylene end-functionalized polymer to remove impurites.
  • the method further comprises reacting an organolithium compound with the alkylated 1,1- diphenylene end-functionalized polymer, resulting in the formation of an anionically terminated polymer, which can be used, for example, in subsequent anionic polymerization and coupling reactions.
  • the organolithium compound is of the formula RLi in which R is a hydrocarbon group containing from 1 to 20 carbon atoms per molecule.
  • the hydrocarbon groups can be alkyl groups, aryl groups, or alky-aryl groups.
  • the organolithium compound can be, but is not limited to, methyllithium, ethyllithium, isopropyllithium, M-butyllithium, sec-butyllithium, tert-butyllithium, tert-octyllithium, phenyllithium, l-naphthyllithium, 7-tolyllithium, cyclohexyllithium, and/or 4- cyclohexylbutyllithium.
  • the 1,1 -diphenylorganolithium compound is of the formula RC(0) 2 Li in which R is a hydrocarbon group containing 1 to 20 carbon atoms per molecule and 0 is an unsubstituted or substituted aryl group.
  • the 1,1- diphenylorganolithium compound can be, but is not limited to, 1,1-diphenylhexyllithium or 1 , 1 -diphenyl-4-methylpentyllithium.
  • the method further includes contacting under reaction conditions the anionically terminated polymer with anionically polymerizable monomer species.
  • the cationically polymerizable monomer species are isoolefin monomer species and the anionically polymerizable monomer species are methacrylate monomer species.
  • the cationically polymerizable monomer species are isoolefin monomer species and the anionically polumerizable monomer species are vinylpyridine monomer species.
  • a novel polymer that comprises a polymer chain, which chain futher comprises the following: (a) a plurality of constitutional units that correspond to cationically polymerizable monomer species and (b) an end-cap comprising a diphenylethylene group.
  • the end-cap comprises a group or a
  • R is a branched or unbranched alkyl group containing from 1 to 20 carbons and R ⁇ is a branched, unbranched, or cyclic alkyl group or an aryl group, containing from 1 to 20 carbons
  • R] is n-pentyl or 2-methyl-butyl. In some embodiments, R is methyl or ethyl. In certain embodiments, the number average molecular weight of said polymer ranges from 5,000 to 500,000. In other embodiments, the chain comprises a plurality of constitutional units that correspond to two or more differing cationically polymerizable monomer species. In some embodiments, the polymer comprises two or more of said polymer chains. In certian embodiments, the constitutional units correspond to isobutylene.
  • a novel copolymer which includes: (a) a first polymer block that comprises a plurality of constitutional units corresponding to cationically polymerizable monomer species, (b) a second polymer block that comprises a plurality of constitutional units corresponding to anionically polymerizable monomer species, and (c) a linking moiety which links the
  • first and second polymer blocks together selected from a group
  • the first polymer block includes a plurality of constitutional units that correspond to two or more differing cationically polymerizable monomer species, e.g., a plurality of constitutional units that correspond to isobutylene.
  • the second polymer block includes a plurality of constitutional units that co ⁇ espond to two or more differing anionically polymerizable monomer species, e.g., a plurality of constitutional units that co ⁇ espond to a methacrylate monomer or a plurality of constitutional units that co ⁇ espond to a vinylpyridine monomer.
  • the polymer includes two or more second polymer blocks and two or more linking moieties.
  • the copolymer is a linear copolymer. In other embodiments, the copolymer is a radial-shaped copolymer.
  • novel copolymers that comprise: (a) a first polymer block that comprises a plurality of constitutional units that correspond to isobutylene; and (b) a second polymer block that comprises a plurality of constitutional units that co ⁇ espond to hydroxyethyl methacrylate.
  • first block is a polyisobutylene block
  • second polymer block is a poly(hydroxyethyl methacrylate) block or is a random polymer block that contains constitutional units co ⁇ esponding to hydroxyethyl methacrylate and to methyl methacrylate.
  • Still other aspects of the present invention relate to novel copolymers that comprise: (a) a first polymer block that comprises a plurality of constitutional units that co ⁇ espond to isobutylene; and (b) a second polymer block that comprises a plurality of constitutional units that correspond to 2-vinylpyridine.
  • the copolymer also comprises (c) a linking moiety linking said first block polymer region with said second block polymer region, said linking moiety selected from a example, a linking
  • the present invention relates to an article of manufacture which includes a copolymer including: (a) a first polymer block that comprises a plurality of constitutional units corresponding to cationically polymerizable monomer species, (b) a second polymer block that comprises a plurality of constitutional units corresponding to anionically polymerizable monomer species, and (c) a linking moiety which links the first and second polymer blocks together selected from a copolymer including: (a) a first polymer block that comprises a plurality of constitutional units corresponding to cationically polymerizable monomer species, (b) a second polymer block that comprises a plurality of constitutional units corresponding to anionically polymerizable monomer species, and (c) a linking moiety which links the first and second polymer blocks together selected from a copolymer including: (a) a first polymer block that comprises a plurality of constitutional units corresponding to cationically polymerizable monomer species, (b) a second polymer block that comprises a
  • R is a branched or unbranched alkyl group, typically containing from 1 to 20 carbons, more typically containing from 1 to 10 carbons, and where R] is a branched, unbranched, or cyclic alkyl group or an aryl group, also typically containing from 1 to 20 carbons, more typically containing from 1 to 10 carbons.
  • the present invention is related to an article of manufacture which includes copolymers including: (a) a first polymer block that comprises a plurality of constitutional units that correspond to isobutylene; and (b) a second polymer block that comprises a plurality of constitutional units that co ⁇ espond to hydroxyethyl methacrylate.
  • Still other aspects of the present invention relate to an article of manufacture which includes copolymers including: (a) a first polymer block that comprises a plurality of constitutional units that co ⁇ espond to isobutylene; and (b) a second polymer block that comprises a plurality of constitutional units that correspond to 2-vinylpyridine.
  • the copolymer also comprises (c) a linking moiety linking said first block polymer region with said second block polymer region, said linking moiety
  • a linking moiety selected from a group and a
  • Ri is a branched, unbranched, or cyclic alkyl group or an aryl group, containing from 1 to 20 carbons.
  • polymers are molecules that contain one or more chains, each containing multiple copies of one or more constitutional units.
  • An example of a common polymer is , where n is an integer, typically an integer of 10 or more, more typically on the order of 10's, 100's, 1000's or even more,
  • Copolymers are polymers that contain at least two dissimilar constitutional units.
  • Methods for making copolymers especially specific living polymerization methods (e.g., anionic and carbocationic living polymerizations) are generally applicable only to a limited number of monomers. The combination of different living polymerization techniques, therefore, should lead to new and unique combinations of blocks in block copolymers.
  • a polymer "block” is defined as a grouping of 10 or more constitutional units, commonly 20 or more, 50 or more, 100 or more, 200 or more, 500 or more, or even 1000 or more units, and can be branched or unbranched.
  • a "chain” is a linear (unbranched) grouping of 10 or more constitutional units (i.e., a linear block).
  • the constitutional units within the blocks and chains are not necessarily identical, but are related to one another by the fact that that they are formed in a common polymerization technique, e.g., a cationic polymerization technique or anionic polymerization technique.
  • copolymers which include (a) one or more blocks which contain a plurality of constitutional units that co ⁇ espond to one or more cationically polymerizable monomer species and (b) one or more blocks which contain a plurality of constitutional units that co ⁇ espond to one or more anionically polymerizable monomer species.
  • these constitutional units occur within the copolymer molecule at a frequency of at least 10 times, and more typically at least 50, 100, 500, 1000 or more times.
  • An advantage of the present invention is that copolymers can be prepared via the combination of living cationic polymerization and living anionic polymerization. Hence, copolymers containing one or more cationically polymerized blocks and one or more anionically polymerized blocks can be formed.
  • the copolymers of the present invention embrace a variety of configurations, including linear, cyclic, and branched configurations.
  • Branched configurations include star-shaped configurations (e.g., radial configurations in which three or more chains emanate from a single region), comb configurations (e.g., graft copolymers having a main chain and a plurality of side chains), and dendritic configurations (e.g. , arborescent or hyperbranched copolymers).
  • the copolymers of the present invention embrace (a) one or more chains containing repeating constitutional units of a single type, (b) one or more chains containing randomly distributed constitutional units of two or more types (e.g., random or statistical copolymers), (c) one or more chains containing two or more types of constitutional units that repeat within an ongoing series (e.g., alternating copolymers), and so forth.
  • olefins including isomonoolefins with 4 to 18 carbon atoms per molecule and multiolefins with 4 to 14 carbon atoms per molecule, for example, isobutylene, 2- methylbutene, isoprene, 3 -methyl- 1-butene, 4-methyl-l-pentene, beta-pinene, and the like
  • vinyl aromatics such as styrene, alpha-methyl styrene, para-chlorostyrene, para- methylstyrene, and the like
  • vinyl ethers such as methyl vinyl ether, isobutyl vinyl ether, butyl vinyl ether, N-vinyl carbazole, and the like.
  • the carbocationically terminated polymer is formed at low temperature (e.g., -80°C) in a reaction mixture that comprises: (a) a solvent system appropriate for cationic polymerization, many of which are well known in the art (for example, a mixture of polar and non-polar solvents, such as a mixture of methyl chloride and hexanes), (b) a monomer (e.g., isobutylene or another cationically polymerizable monomer such as those discussed above), (c) an initiator, for example, tert-ester, tert- ether, tert-hydroxyl or tert-halogen containing compounds, and more typically cumyl esters of hydrocarbon acids such as alkyl cumyl ethers, cumyl halides and cumyl hydroxyl compounds, as well as hindered versions of the same, for instance, tert-butyl dicumyl chloride and tert-butyl dicum
  • Carbocationically terminated star polymers can be formed by selecting initiators having three or more initiation sites such as tricumyl chloride (l,3,5-tris(l-chloroy-l-methylethyl)benzene).
  • an electron pair donor e.g., dimethyl acetamide, dimethyl sulfoxide or dimethyl phthalate
  • a proton-scavenger e.g., 2,6-di-tert-butylpyridine, 4-methyl- 2,6-di-tert-butylpyridine, l,8-bis(dimethylamino)-naphthalene or diisopropylethyl amine
  • 2,6-di-tert-butylpyridine e.g., 2,6-di-tert-butylpyridine, 4-methyl- 2,6-di-tert-butylpyridine, l,8-bis(dimethylamino)-naphthalene or diisoprop
  • a carbocationically terminated polymer is provided in an appropriate solvent system such as those discussed above (e.g. , living cationic PIB provided in a CH 3 Cl/ «-hexane solvent system), a heterocyclic compound like those described above (e.g., thiophene) is added, and allowed to react with the carbocationically terminated polymer under appropriate reaction conditions (e.g., -78°C) to form an end-capped polymer (e.g., PIB-T).
  • an appropriate solvent system such as those discussed above (e.g. , living cationic PIB provided in a CH 3 Cl/ «-hexane solvent system)
  • a heterocyclic compound like those described above e.g., thiophene
  • the amount of proton scavenger is preferably held to a minimum, thereby avoiding reaction of more than one carbocationically terminated polymer with each heterocyclic compound.
  • the molar ratio of proton scavenger to carbocationically terminated polymer (which can be approximated by the initial initiator concentration) is 1:1 or less, for example, 0.75:1 or less, 0.66:1 or less, 0.5:1 or less, 0.25:1 or less, or even 0.1:1 or less.
  • the molar ratio of Lewis acid to carbocationically terminated polymer (or initiator) is typically greater than 10, more typically greater than 20, 30, 40 or more in order to improve reactivity with between the polymer and the heterocyclic compound.
  • these macroinitiators are used to synthesize star polymers (e.g., PLB stars) by reacting the macroinitiators (e.g., PD3-T " ,Li + ) with coupling molecules such as chlorosilanes (which have been used previously to couple living polybutadiene anionic chain ends to form star polymers; see Roovers, J. E. L. and S. Bywater (1972). "Macromolecules 1972. 5, 385).
  • anionically polymerizable monomer species include vinyl aromatic monomers such as styrene, styrene derivatives, alkyl substituted styrene and divinyl benzene, diphenylethylene, conjugated dienes such as isoprene and 1,3-butadiene, N,N- disubstituted acrylamides and methacrylamides such as N,N-dimefhylacrylamide, acrylates, alkyl acrylates and mefhacrylates such as isodecyl methacrylate, glycidyl methacrylate and tert-butyl methacrylate, vinyl unsaturated amides, acrylonitrile, methacrylonitrile, vinyl pyridines, isopropenyl pyridines, other vinyl monomers such as n-alkyl isocyanates, heterocyclic monomers such as ethylene oxide, ⁇ -caprolactone, L,L- lactide, D
  • Substituents for the alkyl groups include hydroxyl, amino and thiol functional groups, among others. In embodiments where monomers are utilized that have functional groups, proper protection of the functional group is commonly needed during the course of anionic polymerization.
  • nonfunctional and protected functional methacrylate monomers include ethyl methacrylate, methyl methacrylate, tert-butyl methacrylate, isodecyl methacrylate, dodecyl methacrylate, stearyl methacrylate, glycidyl methacrylate, 2- [(trimethylsilyl)oxy] ethyl methacrylate, 2-[(tert-butyldimethylsilyl)oxy]ethyl methacrylate, and 2-[(methoxymethyl)oxy]ethyl methacrylate.
  • the anionically polymerizable monomer species is 2-vinylpyridine.
  • the copolymers of the present invention tyically have a molecular weight ranging from 200 to 2,000,000, more typically from 500 to 500,000.
  • the ratio of constitutional units corresponding to the cationically polymerized monomers (e.g., isobutylene) relative to the constitutional units co ⁇ esponding to the anionically polymerized monomers (e.g., methyl methacrylate) in the copolymer usually ranges from 1/99 to 99/1 w/w, e.g., from 30/70 to 95/5 w/w.
  • copolymers which have a narrow molecular weight distribution such that the ratio of weight average molecular weight to number average molecular weight (Mw Mn) (i.e., the polydispersity index) of the polymers ranges from about 1 to 10, or even from about 1 to 2.
  • block copolymers of the formula X(PCA-C-PAN) ⁇ are formed in various embodiments of the invention, where X corresponds to the initiator species, C corresponds to the capping species, PCA is a polymer block comprising a plurality of constitutional units that co ⁇ espond to one or more cationically polymerizable monomer species, for example, a polyolefin block, PAN is a is polymer block comprising a plurality of constitutional units that co ⁇ espond to one or more anionically polymerizable monomer species, for example, a poly(methyl methacrylate) block, and n is a positive whole number.
  • copolymers are made by a process that includes: (a) providing a 1,1 -diphenylene end-functionalized polymer (which polymer contians one or more cationically polymerizable monomer species); and (b) reacting the 1,1 -diphenylene end-functionalized polymer with an organometallic compound to yield an anionically terminated polymer (also referred to herein as a "macrocarbanion", or a "anionic macroinitiator” based on its ability to initiate further reactions such as coupling and polymerization reactions.
  • a 1,1 -diphenylene end-functionalized polymer which polymer contians one or more cationically polymerizable monomer species
  • an organometallic compound also referred to herein as a "macrocarbanion", or a "anionic macroinitiator” based on its ability to initiate further reactions such as coupling and polymerization reactions.
  • Another advantage of the present invention is that end-capped polymers formed of cationically polymerizable monomers can be quantitatively reacted with organolithium compounds to form stable anionic macroinitiators, which are then available for numerous anionic polymerization and coupling reactions.
  • a living macrocarbocation e.g., living cationic polyisobutylene
  • a double diphenylethylene e.g., l,3-bw(l-phenylethenyl)benzene (sometimes referred to as meta- double diphenylethylene) or l,4-bw(l-phenylethenyl)benzene (sometimes refe ⁇ ed to as para-double diphenylethylene)
  • a double diphenylethylene e.g., l,3-bw(l-phenylethenyl)benzene (sometimes referred to as meta- double diphenylethylene) or l,4-bw(l-phenylethenyl)benzene (sometimes refe ⁇ ed to as para-double diphenylethylene)
  • the carbocation is then alkylated with a suitable alkylating agent, e.g., with an organometallic compound such as dimethylzinc, whereupon the resulting macromonomer is readily metallated with a suitable organometallic compound such as an alkyllithium compound, thereby providing a living anionic macroinitiator in near quantitative yield.
  • a suitable alkylating agent e.g., with an organometallic compound such as dimethylzinc
  • an organometallic compound such as an alkyllithium compound
  • a sterically hindered lithium compound e.g., a 1,1- diphenylalkyllithium species, is used in certain embodiments to remove impurities that may be present alongside the 1,1 -diphenylethylene end-functionalized polymer, thereby preventing premature termination of the living macroanion.
  • the end-capped polymer is typically isolated and purified. After isolation and purification, the end-capped polymer is Hthiated with an organolithium compound, thereby yielding an anionically terminated polymer (or macroinitiator).
  • the organolithium compound is typically an alkylhthium compound, for example, methyllithium, ethyllifhium, isopropyllifhium, normal-, secondary- and tertiary-butyllithium, benzyllithium, allyllithium, and so forth.
  • Lithiation can be conducted, for example, at low temperatures (e.g. , -40°C) in a reaction mixture that comprises: (a) a solvent system appropriate for lithiation, many of which are well known in the art (for example, a polar solvent such as THF or a non- polar solvent, such as hexane or toluene in the presence of an electron donor, such as N,N,N'N'-tetramethylethylenedieamine), (b) the end-capped polymer to be hthiated, and (c) the organolithium compound (e.g., an alkylhthium compound such as -BuLi, s-BuLi or tert-BuLi).
  • a solvent system appropriate for lithiation many of which are well known in the art
  • a polar solvent such as THF or a non- polar solvent, such as hexane or toluene in the presence of an electron donor, such as N,N,N'N'-
  • the organolithium compound may be provided in a molar excess relative to the end-capped polymer.
  • the molar ratio of the organolithium compound to the end-capped polymer is beneficially 1.1:1, 1.5:1, 2:1, 4:1, or even greater.
  • Excess organolithium compound can be removed, for example, by increasing the temperature of the same in the presence of a reactive solvent, for example, by increasing the temperature to +30 °C or higher in the presence of THF.
  • anionic macroinitiators formed in accordance with the present invention are used to synthesize star polymers (e.g., polyisobutylene stars), for example, by reacting the macroinitiators with coupling molecules such as unhindered chlorosilanes, e.g., SiCl n R 4 - n , or carbosilanes, such as [Cl ⁇ SiR 3 . n ] 4 - m CR' m , or more highly branched structures, where n and m are integers between 1 and 4, R and R' can independently be either hydrogen or an alkyl group.
  • coupling molecules such as unhindered chlorosilanes, e.g., SiCl n R 4 - n , or carbosilanes, such as [Cl ⁇ SiR 3 . n ] 4 - m CR' m , or more highly branched structures, where n and m are integers between 1 and 4, R
  • Chlorosilanes have been used previously to couple living anionic chain ends to form star polymers in Roovers, J. E. L. and S. Bywater, Macromolecules 1972, 5, 385 and in Application Serial No. 60/480,121 filed June 20, 2003.
  • Other linking agents include aromatic compounds like benzene or naphthalene carrying two or more chloromethyl or bromomethyl or chlorodialkylsilyl groups.
  • linear and star polymers are commonly carried out at a temperature that is higher than that of prior steps (e.g., cationic polymerization, end- capping and lithiation), for example, at room temperature (25°C), or even greater (e.g.,
  • anionic macroinitiators formed in accordance with the present invention are used to efficiently initiate living polymerization of ionically polymerizable monomer species, e.g., acrylate or methacrylate monomers, yielding block copolymers with high blocking efficiency.
  • the "blocking or crossover efficiency" is the percentage of macroanions that actually initiate polymerization (of acrylate or methacrylate monomers in this instance).
  • the resulting block copolymers e.g., diblock polymers, triblock copolymers, radial-shaped block copolymers, etc., will exhibit properties that depend upon the cationically and anionically polymerizable species found within the block copolymer, as well as their absolute and relative amounts.
  • block copolymers are reacted (subsequent to anionic polymerization and before anion quenching) with coupling molecules such as
  • the polymer products of the present invention may be used, for example, as new thermoplastic elastomers, dispersing agents, compatibilizers, emulsifiers, nonionic surfactants or biomaterials.
  • 1,1- diphenylethylene end-functionalized polymers are prepared from a living carbocationic polymer.
  • Carbocationically terminated polymers are commonly formed at low temperature from a reaction mixture that comprises: (a) an initiator, (b) a Lewis acid coinitiator, (c) a cationically polymerizable monomer, (d) an optional proton scavenger and (e) an optional diluent.
  • Suitable initiators include organic ethers, organic esters, and organic halides. Initiators may be monofunctional, difunctional, trifunctional and so forth, thereby producing, for example, diblock copolymers, triblock copolymers, and radial-shaped block copolymers, respectively.
  • tert-alkyl chloride examples include tert-alkyl chloride, cumyl ethers, alkyl cumyl ethers, cumyl halides, cumyl esters, alkyl cumyl esters, cumyl hydroxyl compounds and hindered versions of the same, for instance, 2-chloro-2,4,4- trimethylpentane, cumyl chloride, dicumyl chloride, 5-tert-butyl,l,3-dicumyl chloride ( . e.
  • Lewis acid coinitiators include metal halides and alkyl metal halides such as boron trichloride, titanium tetrachloride and alkyl aluminum halides (e.g., chlorodi ethyl aluminum, dichloroethyl aluminum, chlorodimethyl aluminum, dichloromethyl aluminum).
  • a commonly used coinitiator is titanium tetrachloride.
  • the coinitiator is usually used in concentrations equal to or greater than that of initiator, e.g., 1 to 100 times higher, e.g., 2 to 40 times higher than that of initiator.
  • a proton scavenger typically a Lewis base, typically provided to ensure the virtual absence of protic impurities, such as water, which can lead to polymeric contaminants in the final product.
  • proton scavengers also refe ⁇ ed to as proton traps
  • proton traps include sterically hindered pyridines, for example, substituted or unsubstituted 2,6-di-tert-butylpyridines, such as 2,6-di-tert-butylpyridine and 4-mefhyl- 2,6-di-tert-butylpyridine, as well as 2,6-dimethylpyridine, l,8-bis(dimefhylamino)- naphthalene and diisopropylethyl amine.
  • the proton trap is usually used at the concentration of 1 to 10 times higher than that of protic impurities in the polymerization system.
  • the varoius reactions of the present invention are tyically carried out in the presence of a diluent or a mixture of diluents.
  • typical diluents include (a) halogenated hydrocarbons which contain from 1 to 4 carbon atoms per molecule, such as methyl chloride and methylene dichloride, (b) aliphatic hydrocarbons and cycloaliphatic hydrocarbons which contain from 5 to 8 carbon atoms per molecule, such pentane, hexane, heptane, cyclohexane and methyl cyclohexane, or (c) mixtures thereof.
  • the solvent system contains a mixture of a polar solvent, such as methyl chloride, methylene chloride and the like, and a nonpolar solvent, such as hexane, cyclohexane or methylcyclohexane and the like.
  • a polar solvent such as methyl chloride, methylene chloride and the like
  • a nonpolar solvent such as hexane, cyclohexane or methylcyclohexane and the like.
  • the l,4-bw(l-phenylethenyl)benzene is tyically more beneficial than the l,3-bt.s(l-phenylethenyl)benzene for the functionalization of both living anionic and cationic polymers, because a coupled product is tyically not generated where the l,4-bw(l-phenylefhenyl)benzene is employed.
  • double diphenylethylene is tyically employed at a concentration that is 1 to 10 times higher than that of the initiator, more typically 1 to 6 times higher than that of the initiator.
  • 1,1-diphenylethylene end-functionalized polyisobutylene can be prepared by the reaction of a living cationic polymer such as polyisobutylene with 1 ,3-bis( 1 -phenylethenyl)benzene or 1 ,4-bis( 1 - phenylethenyl)benzene. See Bae, Y. C; Faust, R. Macromolecules 1998, 31(26), 9379-9383.
  • the 1,1- diphenylethylene carbocation is subjected to an alkylation reaction.
  • the alkylation is carried out with an organometallic compound, such as an alkyl aluminum compound and an alkyl zinc compound which typically contains from 1 to 20 carbon atoms, for example, selected from various branched or unbranched alkyl groups.
  • the alkyl aluminum or alkyl zinc compound is typically used at a concentration ranging from 0.1 to 100 times the coinitiator concentration, more typically 0.1 to 10 times the coinitiator concentration.
  • Temperatures for the polymerization of the cationically polymerizable monomer, as well as the subsequent end-functionalization and alkylation of the resulting living polymer, will typically range from 0 °C to -150 °C, more tyipcally from -10 °C to -90 °C.
  • Reaction time for the cationic polymerization and the functionalization and alkylation of of the resulting living cationic polymer will typically range from a few minutes to 24 hours, more typically from 10 minutes to 10 hours.
  • the number average molecular weight of the resulting 1,1-diphenylethylene endfunctionalized polymer will typically range from 1,000 to 1,000,000, more typically
  • a living carbocationically terminated polymer e.g., carbocationically terminated polyisobutylene
  • a coinitiator into a polymerization zone (e.g., a flask), which contains initiator, proton trap, monomer and diluent as discussed above.
  • a polymerization zone e.g., a flask
  • terminated polyisobutylene is reacted with a double diphenylethylene species, in this example l,4-bts(l-phenylethenyl)benzene,
  • cation e.g., , is formed.
  • An alkyl zinc or alkyl aluminum compound e.g., dimethylzinc (CH 3 ) 2 Zn, is then supplied to alkylate the carbenium ion, for example, by dissolving it in a diluent and charging the resulting solution to the polymerization zone.
  • Prechilled alcohol is then charged to the polymerization zone to quench the reaction.
  • functionahzed polymer product e.g., , is then recovered.
  • Organometallic compounds suitable for the metallation of the 1,1- diphenylethylene end-functionalized macromer can be selected, for example, from a wide range of organolithium compounds of the formula RLi in which R is a hydrocarbon group, typically containing from 1 to 20 carbon atoms per molecule, for example, selected from unbranched alkyl groups, branched alkyl groups, cyclic alkyl groups, mono-ring aryl groups and multi-ring aryl groups.
  • organolithium compounds include methyllithium, ethyllithium, isopropyllithium, n- butyllithium, sec-butyllifhium, tert-butyllithium, tert-octyllithium, phenyllithium, 1- naphthyllithium, -tolyllithium, cyclohexyllithium, and 4-cyclohexylbutyllithium.
  • Organolithium compounds are typically used at concentrations that are 1 to 50 times the 1,1-diphenylethylene end-functionalized macromer concentration, more typically 1 to 10 times the macromonomer concentration.
  • Suitable diluents include hydrocarbon solvents, for example, paraffinic, cycloparaffinic, and aromatic hydrocarbon solvents, and polar solvents, for example, ethers such as tetrahydrofuran, dimethylether, diethylether, dioxane, and 1,2- dimefhoxyefhane.
  • Reaction times between the organolithium compound and the 1,1- diphenylethylene end- functional polymer will typically range from a few minutes to 24 hours, more typically from 1 hour to 12 hours. Temperatures for the reaction between the organolithium compound and the 1,1-diphenylethylene end- functional polymer will typically range from 30°C to -100°C, more typically from 30°C to -90°C.
  • a small amount of a sterically hindered lithium compound is charged to the polymerization zone prior to introducing the alkylhthium compound to remove impurities that are frequently present, thereby preventing termination during the reaction of the alkylhthium compound with the 1,1-diphenyethylene end-functionalized polymer. Because the 1,1-diphenylalkyllithium cannot react with 1,1-diphenylethylene end-functionalized polymer due to steric effects, its addition is effective for purposes of removing impurities that are present in the solution.
  • Examples of sterically hindered organolithium compounds include organolithium compounds of the formula RC(0 ⁇ )(0 2 )Li in which R is a hydrocarbon group, typically containing 1 to 20 carbon atoms per molecule, including unbranched alkyl groups, branched alkyl groups, cyclic alkyl groups, mono-ring aryl groups, and multi-ring aryl groups, and and 0 2 can be the same or different and are selected from unsubstituted or substituted, mono- or multi-ring, aryl groups.
  • the sterically hindered organolithium compound is a 1,1-diphenylalkyllithium compound.
  • 1,1-Diphenylalkyllithium may be generated, for example, from the reaction of an alkylhthium compound and 1,1-diphenylethylene at room temperature in the presence of diluent. 1,1 -Diphenylethylene is typically used in concentrations equal to or less than that of the alkylhthium in this reaction.
  • a example of one beneficial 1,1- diphenylalkyllithium compound is 1 1,1-diphenylhexyllithium,
  • the sterically hindered organolithium compound is typically added to a solution containing the 1,1-diphenylethylene end-functional polymer and a diluent or mixture of diluents, for example, at room temperature. Afterwards, the organolithium compound is added to the 1,1-diphenylethylene functional polymer, for instance, under anionic reaction conditions (e.g., at -78°C). After a stable living macroinitiator is formed in this fashion, any unreacted alkylhthium may be destroyed by heating, for example, to 40°C in the presence of a reactive species such as tetrahydrofuran (which can also be used as a diluent).
  • a reactive species such as tetrahydrofuran (which can also be used as a diluent).
  • the resulting anionic macroinitiator is then available for subsequent polymerization or coupling reactions, as desired.
  • an anionically reactive species such as an anionically polymerizable monomer is added under polymerization conditions (e.g., at -78°C) to the macroinitiator.
  • purified alcohol is typically charged to the polymerization zone to quench the reaction.
  • Times for anionic polymerization will typically range from a few minutes to 24 hours, more typically from 5 minutes to 12 hours. Temperatures for anionic polymerization will typically range from 0°C to -100°C, more typically from -10°C to - 90°C.
  • a carbanion e.g., Subsequent exposure of the carbanion to an anionically polymerizable monomer, e.g., a methacrylate monomer such as methyl methacrylate (MMA), results in a copolymer having (a) a cationically polymerized block, for example, a polyisobutylene block, and (b) an anionically polymerized block, for example, a poly(methyl methacrylate) (PMMA)
  • an anionically polymerized block for example, a poly(methyl methacrylate) (PMMA)
  • an exemplary carbanion e.g.,
  • a copolymer having (a) a cationically polymerized block, for example, a polyisobutylene block, and (b) an anionically polymerized block, for example, a
  • PVPy polyvinylpyridine
  • THF was used as an eluent at a flow rate of 1 mL/min.
  • Titanium (IV) chloride TiCl 4 , Aldrich, 99.9% was used as received.
  • 2-Chloro-2,4,4-trimethylpentane was prepared by hydrochlorination of 2,4,4-trimethyl-l-pentene (Fluka, 98 %) with hydrogen chloride gas in dry dichloromethane at 0 °C. Kaszas, G.; Gyor, M.; Kennedy, J. P.; Tud ⁇ s, F. J. Macromol.ScL, Chem 1983, ⁇ 75,1367-1382. The product was dried over CaCl 2 and distilled under reduced pressure before use. 5-tert-butyl-l,3-bts(l-chloro-l- methylethyl)benzene was synthesized following the procedure reported in Gyor, M. Wang., H.
  • Tetrahydrofuran (Merck p. a) was purified first by distillation under nitrogen from CaH and then by refluxing over potassium.
  • n-Butyllithium «-BuLi, 2.5 M in hexane was purchased from Aldrich and its concentration was titrated by a standard method. See, e.g., Reed, P. J.; Urwin, J. R. J. Organometal. Chem. 1972, 39, 1-10.
  • the ⁇ ,A-Bis( ⁇ - phenylefhenyl)benzene is synthesized using known procedures, e.g., those described in U.S. Patent No. 4,182,818 to Tung, L. H. and Lo, G. Y.-S. 1,1 -Diphenylethylene purchased from Aldrich Chemical Company was purified by vacuum distillatin under potassium metal.
  • the preparation of a difunctional macromonomer is carried out at -80 °C under nitrogen atmosphere.
  • To a prechilled 500 mL 3-neck flask equipped with mechanical sti ⁇ er are added sequentially 187 mL of hexane, 111 mL of methyl chloride, 0.086 g of 5-tert- butyl-l,3-bts(l-chloro-l-methylethyl)benzene (3.0 x 10 "4 mol), 0.2 mL of 2,6-di-tert- butylpyridine (9.0 x 10 "4 mol), and 21 mL of isobutylene (0.27 mol).
  • the polymer After the evaporation of solvents, the polymer is dissolved in hexane and inorganics are filtered. The polymer recovered by the precipitation of the polymer solution into methanol. The polymer is then dissolved again in hexane and recovered again by the precipitation of the polymer solution into methanol, followed by drying in a vacuum.
  • 1 ,1 -diphenylhexyllithium in tetrahydrofuran (see above) is added into the reactor dropwise until the color of the polymer solution changes from colorless to yellowish.
  • the amount of 1,1-diphenylhexyllithium used for this purpose is 0.0010 g (4.1 x 10 "6 mol).
  • the polymer solution is subsequently cooled down to -78 °C with vigorous stirring. After 10 minutes at this temperature, 0.0090 g of H-butyllithium (1.4 x 10 "4 mol) in 27.5 mL of hexane is added into the reactor. 12 hours later, the polymer solution is heated up to 40 °C and kept at this temperature for 1 hour.
  • the polymer solution is again cooled to -78 °C. After 10 minutes at this temperature, 0.95 mL of methyl methacrylate (8.9 x 10 "3 mol) is distilled into the reactor. The reactoin is quenched after 5 hours by adding purified degassed methanol to the reactor. The polymer solution is precipiated into methanol to give a white solid polymer. [0083] The blocking efficiency of the obtained block copolymer is measured using GPC and 1H NMR and is calculated to be at leaset 87 %. The product is immersed into hexane for 24 hours to isolate polyisobutylene homopolymer from the block copolymer.
  • the amount of 1,1-diphenylhexyllithium used for this purpose is 0.0010 g (4.1 x 10 "6 mol).
  • the polymer solution is subsequently cooled to -78 °C with vigorous stirring. After 10 minutes at this temperature, 0.0122 g of M-butyllifhium (1.9 x 10 "4 mol) in 40 mL of hexane is added into the reactor. After an additional 12 hours, the polymer solution is heated to 40 °C and kept at this temperature for 1 hour. The polymer solution is then cooled down to -78 °C. After 10 minutes at this temperature, 0.64 mL of methyl methacrylate (6.0 x 10 "3 mol) is distilled into the reactor. 5 hours later, purified methanol is added to reactor to quench the reaction. The polymer solution is poured into methanol to yield a white solid polymer.
  • the blocking efficiency of the obtained block copolymer is measured using GPC and 1H NMR and is calculated to be at least 92 %.
  • 1,1-diphenylhexyllithium in tetrahydrofuran (see above) is then added into reactor dropwise until the color of the polymer solution changes from colorless to yellowish.
  • the amount of 1,1-diphenylhexyllithium used for this purpose is 0.0030 g (1.2 x 10 "5 mol).
  • the polymer solution is cooled down to -78 °C with vigorous stirring. After 10 minutes at this temperature, 0.0160 g of M-butyllithium (2.5 x 10 "4 mol) in 40 mL of hexane is added into the reactor. 2 hours later, the polymer solution is heated to 40 °C and kept at this temperature for 1 hour.
  • the polymer solution is again cooled to -78 °C. After 10 minutes at this temperature, 2 mL of 2- [(trimethylsilyl)oxy] ethyl methacrylate (9.2 x 10 "3 mol) diluted with 2 mL of tetrahydrofuran is added into the reactor. 3 hours later, purified methanol is added to reactor to quench the reaction. The polymer solution is precipitated into methanol to yield a white solid polymer.
  • the blocking efficiency is at least 90 %, as measured using GPC and 1H NMR.
  • the obtained polymer is purified by using hexane to remove polyisobutylene homopolymer. During the recovery step, the trimefhylsilyloxy groups in the block copolymer are completely converted into hydroxyl groups.
  • the block copolymer is treated with benzoic anhydride to protect the hydroxyl groups in the poly(2-hydroxylethyl methacrylate) blocks with a benzoyl group.
  • the polymer solution is cooled down to -78 °C with vigorous stirring. After 10 minutes at this temperature, 0.0961 g of w-butyllithium (1.5 x 10 "3 mol) is added into the reactor. 1 hour later, the polymer solution is heated to 20 °C and kept at this temperature for 1 hour. Then, the polymer solution is again cooled to -78 °C. After 10 minutes at this temperature, 1.5 mL of methyl methacrylate (1.4 x 10 "2 mol) is charged into the reactor. 2 hours later, purified methanol is added to reactor to quench the reaction. The polymer solution is then poured into methanol to yield a white solid polymer.
  • the blocking efficiency is calculated to be 67 % based on GPC and ⁇ NMR results.
  • the blocking efficiency is calculated to be 72 % based on GPC and 1H NMR results.
  • n-butyllithium 2.5 x 10 "4 mol
  • the polymer solution is heated up to 20 °C and kept for 1 hour at this temperature.
  • the polymer solution is again cooled down to -78 °C.
  • 0.4 mL of methyl methacrylate (3.7 x 10 " mol) is charged into the reactor. 2 hours later, purified methanol is added to reactor to quench the reaction. The polymer solution is then poured into methanol to yield a white solid polymer.
  • the blocking efficiency is calculated to be 68 %, based on GPC and 1H NMR results.
  • the amount of 1,1-diphenylhexyllithium used for this purpose is 0.0010 g (4.1 x 10 "6 mol).
  • the polymer solution is subsequently cooled to -78 °C with vigorous stirring. After 10 minutes at this temperature, 0.01 g of M-butyllifhium (1.6 x 10 "4 mol) in 33 mL of hexane is added into the reactor. After an additional 12 hours, the polymer solution is heated to 40 °C and kept at this temperature for 1 hour. The polymer solution is then cooled down to -78 °C. After 10 minutes at this temperature, 1.19 mL 2-vinylpyridine (1.1 x 10 "2 mol) is distilled into the reactor. 40 minutes later, purified methanol is added to reactor to quench the reaction. The polymer solution is poured into methanol to yield a white solid polymer.

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Abstract

Un aspect de la présente invention concerne un procédé consistant à faire réagir un composé diphényléthylène double avec un polymère contenant une chaîne à extrémité carbocationique pour obtenir une chaîne à fonctionnalité d'extrémité 1,1-diphénylène. Ensuite, le procédé consiste à faire réagir un agent d'alkylation avec cette chaîne à fonctionnalité d'extrémité 1,1-diphénylène pour obtenir une chaîne à fonctionnalité d'extrémité 1,1-diphénylène alkylée. Dans certains modes de réalisation, le procédé consiste également (a) à éventuellement combiner un composé de 1,1diphénylorganolithium avec le polymère à fonctionnalité d'extrémité 1,1-diphénylène alkylée, puis (b) à faire réagir un composé d'organolithium avec le polymère à fonctionnalité d'extrémité 1,1-diphénylène alkylée. Cette réaction permet d'obtenir un polymère à extrémité anionique qui peut être utilisé, par exemple, dans des réactions ultérieures de couplage et de polymérisation anionique. Un autre aspect de la présente invention concerne un nouveau polymère comprenant une chaîne polymère qui comporte (a) une pluralité d'unités correspondant à des espèces monomères polymérisables par voie cationique et (b) une extrémité comprenant un groupe (I) ou un groupe (II). Dans ces groupes, R désigne un groupe alkyle ramifié ou non ramifié contenant entre 1 et 20 atomes de carbone et R1 désigne un groupe alkyle ramifié, non ramifié ou cyclique ou un groupe aryle, contenant entre 1 et 20 atomes de carbone. D'autres aspects de la présente invention concernent de nouveaux copolymères comprenant (a) une première séquence comportant une pluralité d'unités correspondant à l'isobutylène et (b) une seconde séquence comportant une pluralité d'unités correspondant au méthacrylate d'hydroxyéthyle. D'autres aspects de la présente invention concernent de nouveaux copolymères comprenant (a) une première séquence comportant une pluralité d'unités correspondant à l'isobutylène et (b) une seconde séquence comportant une pluralité d'unités correspondant au 2-vinylpyridine.
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