EP1919973A1 - Nouveaux procedes de formation de copolymeres comprenant des olefines et des unites hydroxystyrene protegees ou non protegees - Google Patents

Nouveaux procedes de formation de copolymeres comprenant des olefines et des unites hydroxystyrene protegees ou non protegees

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Publication number
EP1919973A1
EP1919973A1 EP06789739A EP06789739A EP1919973A1 EP 1919973 A1 EP1919973 A1 EP 1919973A1 EP 06789739 A EP06789739 A EP 06789739A EP 06789739 A EP06789739 A EP 06789739A EP 1919973 A1 EP1919973 A1 EP 1919973A1
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Prior art keywords
protected
copolymer
hydroxystyrene
monomer species
species
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EP06789739A
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German (de)
English (en)
Inventor
Rudolf Faust
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UMass Lowell
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UMass Lowell
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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

Definitions

  • This invention relates to methods for forming copolymers including an olefin coupled to a polymer comprising protected or unprotected hydroxystyrene units, and the copolymers formed by such methods.
  • Living polymerization i. e. , polymerization proceeding in the practical absence of chain transfer to monomer and irreversible termination
  • is a very useful method for designing polymer structures permitting for example, versatile synthetic routes for the preparation of a wide variety of well-defined polymer structures, such as end-functionalized polymers, star-shaped polymers and/or block copolymers and control of the molecular weight and molecular weight distribution of the polymer, as well as enabling functional groups to be positioned at desired points in the polymer chain. Since Szwarc et al.
  • Living cationic sequential block copolymerization is generally recognized as one of the simplest and most convenient methods to provide well-defined block copolymers with high structural integrity.
  • Linear-, star-, and arborescent-block copolymers with a rubbery polyisobutylene (PIB) center block and glassy end blocks are useful thermoplastic elastomers, exhibiting excellent properties such as thermal and oxidative stability and biocompatibility.
  • PIB rubbery polyisobutylene
  • All of the above thermoplastic elastomers contain a hydrophobic end blocks. Some applications, however, require block copolymers where the end blocks are hydrophilic. The ability to tune the overall hydrophilicity of the block copolymer would provide a wide range of useful products.
  • methods of making block copolymers include: (a) providing a carbocationically terminated polymer comprising one or more olefin blocks; (b) contacting under a first reaction condition the carbocationically terminated polymer with a capping species that does not homopolymerize under the first reaction condition, thereby forming an end- capped carbocationically terminated polymer; (c) altering the first reaction condition to substantially prevent polymerization of protected hydroxystyrene monomer species; and (d) contacting the end-capped carbocationically terminated polymer with protected hydroxystyrene monomer species under a second reaction condition, thereby providing a block copolymer.
  • the first reaction condition includes a Lewis acidity provided by TiCl 4 , and wherein the Lewis acidity is lowered in step (c) by the addition of a titanium tetraalkoxide species, hi one embodiment, the second reaction condition comprises a Lewis acidity provided by SnBr 4 . In another embodiment, the first and second reaction conditions comprise a temperature between -50°C and -90°C.
  • the carbocationically terminated polymer is formed under first reaction conditions from a reaction mixture that includes: (i) a solvent system, (ii) monomer species selected from isomonoolefins containing 4 to 18 carbon atoms per molecule and multiolefins containing 4 to 14 carbon atoms per molecule, (iii) an initiator selected from an organic ether, an organic ester, an organic alcohol, and an organic halide, and (iv) a Lewis acid.
  • the methods can further include hydrolyzing at least a portion of the constitutional units in said block copolymer that correspond to said protected hydroxystyrene monomer species, thereby forming alcohol groups.
  • the present invention provides a method of making a block copolymer that includes: (a) providing a capped carbocationically terminated polymer; (b) neutralizing an initiator associated with the capped polymer; and (c) forming a block copolymer by contacting the capped polymer with a monomer in the presence of a second initiator.
  • the initiator is neutralized by altering the Lewis acidity.
  • the Lewis acidity is altered using a titanium tetraalkoxide species.
  • the initiator is TiCl 4 .
  • the second initiator is SnBr 4 .
  • the monomer can be, but is not limited to protected or unprotected hydroxystyrene.
  • the carbocationically terminated polymer can be, but is not limited to polyisobutylene.
  • the present invention provides copolymers that include: (a) a plurality of constitutional units that correspond to one or more olefin monomer species and (b) a plurality of constitutional units that correspond to one or more protected or unprotected hydroxystyrene monomer species, wherein the copolymer has at least one substantially uniform mechanical property.
  • the olefin monomer species can be, but is not limited to isobutylene, 2-methylbutene, isoprene, 3 -methyl- 1-butene, 4-methyl-l- pentene and beta-pinene.
  • the olefin monomer species includes isobutylene.
  • the protected hydroxystyrene monomer species can be, but is not limited to tert-butyl protected hydroxystyrene, benzyl protected hydroxystyrene, cyclohexyl protected hydroxystyrene, neopentyl protected hydroxystyrene, acetyl protected hydroxystyrene and tert-butyldimethylsilyl protected hydroxystyrene.
  • the substantially uniform property is hardness, recoil, collapse pressure, longitudinal flexibility, crimp profile, tensile strength, flexural strength, impact resistance, elasticity and compressibility.
  • the copolymer is a block copolymer that includes: (a) an olefin block that comprises a plurality of constitutional units corresponding to said one or more olefin monomer species and (b) a styrenic block that comprise a plurality of constitutional units corresponding to said one or more protected or unprotected hydroxystyrene monomer species, wherein the copolymer has substantially uniform mechanical properties.
  • polymer refers to molecules containing one or more chains, each containing multiple copies of one or more constitutional units.
  • 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, in which the constitutional units in the chain correspond to styrene
  • copolymer refers to polymers that contain at least two dissimilar constitutional units. 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, etc., lead to their use in a wide range of products, for example, as compatibilizers, adhesives, dispersants, and so forth. Because each copolymer has its own unique properties, there is continuing demand for novel copolymers, which can be used in products such as those above.
  • a polymer "block” is 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.
  • a block 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.
  • block copolymers e.g., copolymers comprising polyolefin units and protected or unprotected hydroxystyrene units, that have substantially uniform mechanical properties.
  • substantially uniform refers generally, in some embodiments, to a difference of not more than a desired percentage between two areas of a polymer.
  • a polymer with at least one "substantially uniform property” refers to a polymer in which the property, e.g., hardness does not vary more than, e.g., 20%, between two given points.
  • the term "desired percentage” is used to refer to not more than 50%, 40%, 30%, 20%, 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, or 1%. All individual values in between those listed are meant to be encompassed by the present invention.
  • desired percentage refers to 0%.
  • substantially uniform refers to the property being within desired guidelines, regardless of the exact percent variation in value. For example, a specific polymer may be desired that fits into specific hardness ranges, or has a hardness greater than a specific value. In such cases, a substantially uniform hardness would have a value within the desired range. Properties include, but are not limited to, hardness, recoil, collapse pressure, longitudinal flexibility, crimp profile, e.g., low or reduced crimp profile, tensile strength, flexural strength, impact resistance, elasticity and compressibility.
  • synthesis of block copolymers via sequential monomer addition typically relies, for example, on the rational selection of polymerization conditions such as Lewis acid, solvent, additives, temperature, and so forth, as well as on the selection of the appropriate order of monomer addition.
  • rate of crossover to a second monomer i? cr
  • i? p the rate of crossover to a second monomer
  • efficient crossover is achieved when the two sequential monomers have similar reactivities, or when crossover occurs from the more reactive to the less reactive monomer.
  • the present invention provides a process for forming copolymers that includes: (a) providing a carbocationically terminated polymer comprising one or more olefin blocks; (b) contacting under a first reaction condition the carbocationically terminated polymer with a capping species that does not homopolymerize under the first reaction condition, thereby forming an end-capped carbocationically terminated polymer; (c) altering the first reaction condition to substantially prevent polymerization of protected hydroxystyrene monomer species; and (d) contacting the end-capped carbocationically terminated polymer with protected hydroxystyrene monomer species under a second reaction condition, thereby providing a block copolymer.
  • the first reaction condition includes a Lewis acidity provided by TiCl 4 .
  • the Lewis acidity can be lowered in step (c) by the addition of a titanium tetraalkoxide species.
  • the second reaction conditions can include a Lewis acidity provided by SnBr 4 .
  • the block copolymers formed by the methods of the present invention have at least one substantially uniform mechanical property, hi some embodiments, the substantially uniform property is hardness, recoil, collapse pressure, longitudinal flexibility, crimp profile, e.g., low or reduced crimp profile, tensile strength, flexural strength, impact resistance, elasticity and compressibility.
  • Examples of olefin monomer species for use in connection with the present invention include isomonoolefins with 4 to 18 carbon atoms per molecule and multiolefins with 4 to 14 carbon atoms per molecule, for instance, isobutylene, 2- methylbutene, isoprene, 3 -methyl- 1-butene, 4-methyl-l-pentene, beta-pinene, and the like.
  • Examples of hydroxystyrene monomer species include 2-hydroxystyrene, 3- hydroxystyrene, 4-hydroxystyrene, 2,3-dihydroxystryene, 2,4-dihydroxystryene, and 3,4-dihydroxystryene species.
  • Examples of protected hydroxystyrene monomer species include styrene species substituted with one or more functional groups that are stable under cationic polymerization conditions, but which are hydrolysable into hydroxyl groups, for example, under the influence of acids or bases.
  • Protected hydroxystyrene monomer species in accordance with the present invention are generally substituted with either (a) one or more R-O- groups, wherein R is a hydrocarbon group, typically containing from 1 to 12 carbons, including branched alkyl groups, cycloalkyl groups and alkylaryl
  • R 1 , R 2 , R 3 can be the same or different and are hydrocarbon groups, typically containing from 1 to 4 carbons, including unbranched alkyl groups, branched alkyl groups, cycloalkyl groups, and alkylaryl groups.
  • protected hydroxystyrene monomers include tert-bntyl protected hydroxystyrene (Yert-butoxystyrene), benzyl protected hydroxystyrene (benzyloxystyrene), cyclohexyl protected hydroxystyrene (cyclohexoxystyrene), neopentyl protected hydroxystyrene (neopentoxystyrene), acetyl protected hydroxystyrene (acetoxystyrene), tert-butyldimethylsilyl protected hydroxystyrene (tert-butyldimethylsilyloxystyrene) and so forth.
  • the protected hydroxyl groups in the styrene monomer species of the present invention can be substituted at the 2-, 3- or 4- positions, at the 2,3-, 2,4- and 3,4- positions, and so forth. Commonly, the protected hydroxyl groups in the styrene monomer species of the present invention are substituted at the 4- position.
  • the carbocationically terminated olefin blocks are formed at low temperature from a reaction mixture that comprises: (a) an initiator, (b) a Lewis acid coinitiator, (c) an olefin monomer, (c) an optional proton scavenger and (d) an optional solvent system.
  • Polymerization can be conducted, for example, within a temperature range of from about 0 0 C to about -100 0 C, more typically from about -50°C to -90°C. Polymerization times are typically those times that are sufficient to reach 90%, 95%, 99% or even higher conversions of the olefin monomer species to polymer.
  • 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-a ⁇ ky ⁇ chloride examples include tert-a ⁇ ky ⁇ 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-ter?-butyl,l,3-dicumyl chloride (z. e.
  • Lewis acid coinitiators include metal halides and alkyl metal halides such as boron trichloride, titanium tetrachloride and alkyl aluminum halides ⁇ e.g., chlorodiethyl aluminum, dichloroethyl aluminum, chlorodimethyl aluminum, dichloromethyl aluminum).
  • metal halides and alkyl metal halides such as boron trichloride, titanium tetrachloride and alkyl aluminum halides ⁇ e.g., chlorodiethyl aluminum, dichloroethyl aluminum, chlorodimethyl aluminum, dichloromethyl aluminum).
  • One 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, preferably 2 to 40 times higher than that of initiator.
  • a proton scavenger typically a Lewis base, is frequently 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 referred to as proton traps
  • Examples of proton scavengers include sterically hindered pyridines, for example, substituted or unsubstituted 2,6-di-tert-butylpyridines, such as 2,6-di-tert-butylpyridine and 4-methyl- 2,6-di-tert-butylpyridine, as well as 2,6-dimethylpyridine, l,8-bis(dimethylamino)- 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.
  • 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.
  • halogenated hydrocarbons which contain from 1 to 4 carbon atoms per molecule, such as methyl chloride and methylene dichloride
  • 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 capping species that does not homopolymerize under the reaction conditions employed (e.g., the reaction conditions utilized in forming the carbocationically terminated polymer) is contacted with the carbocationically terminated polymer, thereby forming an end-capped carbocationically terminated polymer.
  • capping species examples include diaryl alkenes such as substituted or unsubstituted diphenyl ethylenes, for instance, diphenyl ethylene or ditolyl ethylene. Without wishing to be bound by any particular it is believed that these compounds do not polymerize due to steric hindrance; however, they do form stable carbocations with the carbocationically terminated polyolefin.
  • the diaryl alkylene species is added to the polymerization media in concentrations equal up to about 10 times the concentration of the living chain ends, preferably about 1 to about 5 times the concentration of the living chain ends, even more preferably about 2 times the concentration of the living chain ends.
  • the diaryl alkylene species is allowed to react with the living polymer for a time sufficient to result in practically complete capping.
  • the resulting end-capped carbocationically terminated polymer is then contacted with a compound which alters the Lewis acidity of the solution to substantially prevent polymerization of protected hydroxystyrene monomer species.
  • the Lewis acidity is typically reduced relative to the reaction conditions that existed earlier (e.g., the conditions associated with the olefin polymerization and/or end-capping processes).
  • One suitable method for reducing Lewis acidity is to add a metal alkoxide species, for example, a titanium alkoxide species or similar organotitanium species to TiCl 4 .
  • Typical titanium alkoxide species include Ti(OR) 4 , wherein R is a branched or unbranched alkyl group containing 1 to 4 carbon atoms, for example, Ti[OCH(CH 3 ) 2 ] 4 or Ti[O(CH 2 ) 3 CH 3 ] .
  • the amount added generally depends on the reactivity of the protected hydroxystyrene monomer species.
  • Suitable TiCVTi(OR) 4 ratios substantially prevent polymerization of protected hydroxystyrene monomer species.
  • the TiCl 4 /Ti(OR) 4 ratio is less than about 1.2. Additionally, by tuning the Lewis acidity, e.g., by adding Ti(OR) 4 to reach a desired TiCl 4 ATi(OR) 4 ratio, side reactions are minimized, and polymerization is better controlled, leading to high blocking efficiency.
  • the resulting end-capped carbocationically terminated polymer is then contacted with at least one protected hydroxystyrene monomer species, under conditions of suitable Lewis acidity, to produce block copolymers in accordance with the present invention.
  • Polymerization times are those sufficient to reach the desired conversion of the protected hydroxystyrene monomer species to polymer, which is typically 80%, 90%, 95%, 99% or more.
  • Suitable Lewis acids for the polymerization of the protected hydroxystyrene monomer species include Lewis acids that are weaker than TiCl 4 .
  • Weaker Lewis acids include, but are not limited to SnCl 4 and SnBr 4 . Without wishing to be bound by any particular theory, it is believed that SnBr 4 is well suited for the living polymerization of alkoxystyrenes.
  • the present invention provides a method of making a block copolymer that includes: (a) providing a capped carbocationically terminated polymer; (b) neutralizing an initiator associated with the capped polymer; (c) forming a block copolymer by contacting the capped polymer with a monomer in the presence of a second initiator.
  • the capped carbocationically terminated polymer can be, but is not limited to, a polymer formed from any of the olefin monomer species described herein.
  • the carbocationically terminated polymer can be polyisobutylene.
  • the monomer can be, but is not limited to, any of the hydroxystyrene or protected hydroxystyrene monomer species described herein.
  • the monomer can be protected or unprotected hydroxystyrene.
  • the initiator can be, but is not limited to, any initiator or Lewis acid coinitiator as described herein.
  • the initiator is a Lewis acid initiator, e.g., TiCl 4 .
  • the initiator is neutralized by altering the Lewis acidity.
  • the Lewis acidity can be altered, e.g., but the addition of a titanium tetraalkoxide species as described above.
  • the second initiator can be, but is not limited to, an initiator or Lewis acid coinitiator as described herein, which is not the original initiator.
  • the second initiator can be, but is not limited to, Lewis acids with a weaker Lewis acidity than the original initiator.
  • the second initiator is SnBr 4 .
  • the present invention provides copolymers with properties that can be reliably obtained from batch to batch.
  • At least a portion of the pendant protected hydroxyl groups within the copolymers of the present invention can be hydrolyzed, for example, with a strong acid or base, to form pendant hydroxyl groups. Hydrolysis conditions and reaction times are typically sufficient to achieve 90%, 95%, 99% or even higher conversions of the pendant hydrolysable ether groups to alcohol groups.
  • block copolymers can be formed using the above techniques.
  • block copolymers of the formula X(POL-C-PST) n are formed in various embodiments, where X corresponds to the initiator species, C corresponds to the capping species, POL is an olefin block that contains a plurality of constitutional units corresponding to the one or more olefin monomer species, PST is a styrenic block that contains a plurality of constitutional units corresponding to the one or more protected or unprotected hydroxystyrene monomer species, and n is a positive whole number, e.g., a positive whole number ranging from 1 to 5.
  • the olefin block(s) will contain a plurality of constitutional units that correspond to one or more olefin species, while the styrenic block(s) will contain a plurality of constitutional units that correspond to one or more protected or unprotected hydroxystyrene monomer species.
  • copolymers are • provided which include: (a) a plurality of constitutional units that correspond to one or more olefin monomer species and (b) a plurality of constitutional units that correspond to one or more protected or unprotected hydroxystyrene monomer species. Typically, each of these constitutional units occurs within the copolymer molecule at a frequency of at least 10 times, and more typically at least 50, 100, 500, 1000 or more times.
  • copolymers of the present invention have at least one substantially uniform mechanical property. In some embodiments, the substantially uniform property is hardness, recoil, collapse pressure, longitudinal flexibility, crimp profile, e.g., low or reduced crimp profile, tensile strength, flexural strength, impact resistance, elasticity and compressibility.
  • the copolymers of the present invention embrace a variety of configurations, for example, cyclic, linear 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.
  • the copolymers of the present invention are block copolymers containing (a) one or more olefin blocks, each of which contains a plurality of units corresponding to olefin monomer species, and (b) one or more styrenic blocks, each of which contains a plurality of units that correspond to protected or unprotected hydroxystyrene monomer species. Examples of olefin monomer species and protected and unprotected hydroxystyrene monomer species are discussed above.
  • the number average molecular weight (Mn) of the block copolymers of the present invention typically range, for example, from about 1000 to about 2,000,000, more typically from about 10,000 to about 500,000, even more typically 50,000 to 200,000, with the protected or unprotected hydroxystyrene units typically comprising 10 to 90 mol%, more typically 10 to 50 mol%, even more typically 13 to 28 mol% of the copolymer.
  • polymers 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 1.1 to 1.5, or even from about 1.05 to 1.3.
  • the ratio of constitutional units corresponding to the olefin monomer species relative to the constitutional units corresponding to the protected or unprotected hydroxystyrene monomer species in the copolymer usually ranges from 1/99 to 99/1 w/w, e.g., from 30/70 to 95/5 w/w.
  • the invention relates to an article of manufacture which includes a copolymer, e.g., a block copolymer, of the present invention.
  • copolymers can be produced that are used in a variety of commercial applications.
  • copolymers can be produced that are capable of being hydrolyzed, thereby forming polymers of increased hydrophilicity.
  • the invention is further described with reference to the following non- limiting Examples.
  • Methylcyclohexane (MeChx) (Aldrich, anliydrous grade), titanium(IV) isopropoxide (Aldrich, 99.999 %), titanium (IV) chloride (Aldrich, 99.9%), tetrabutylammonium fluoride (Aldrich, 1.0 M solution in tetrahydrofuran), 2,6-Di-tert- butylpyridine (Aldrich 97%), hydrochloric acid solution (36.5-38.0%, VWR), pyridine (Aldrich, anhydrous grade) and 4-dimethylaminopyridine (Aldrich, 99%) are used as received.
  • TDMSt 4-(te/t-butyldimethylsilyloxy)styrene
  • 2-Chloro-2,4,4-trimethylpentane is prepared by hydrochlorination of 2,4,4-trimethyl-l-pentene (Aldrich, 99%) with hydrogen chloride gas in dry dichloromethane at 0 °C. Kaszas, G.; Gyor, M.; Kennedy, J. P.; T ⁇ d ⁇ s, F. J. Macromol.ScL, Chem 1983, ⁇ I ⁇ °,1367-1382. The product is dried over CaCl 2 and distilled under reduced pressure before use. 5-tert-butyl-l,3- ⁇ z ' 5'(l-chloro-l- methylethyl)benzene is synthesized following the procedure reported in Gyor, M. Wang., H.
  • TMPCl 2-chloro-2,4,4-trimethylpentane
  • Living polyisobutylene (PEB) is first prepared with a molecular weight of -30,000 at -80 0 C in methylcyclohexane (MeChx)/methyl chloride (MeCl) 60/40 v/v solvent mixture.
  • the reagents are applied in the following order: MeChx, MeCl, 2- chloro, 2,4,4-trimethyl ⁇ entane (TMPCl) (1.
  • the reagents are applied in the following order: methylcyclohexane (MeChx, 154.5-mL), methyl chloride (MeCl, 103 mL), 5-tert-butyl- 1,3-dicumyl methyl ether (1.
  • Ti(OiPr) 4 (3.8 mL neat at room temperature) is added to reach a [TiCl 4 ]/[Ti(OiPr) 4 ] ratio of 1.2 and stirred thoroughly for 60 min. Then SnBr 4 (19 ml, 0.072 M in MeChx/MeCl, 60/40 v/v) is added followed by the addition of 4-tert-butoxystyrene (27.3 mL neat at room temperature), which is poured into the polymerization mixture under vigorous stirring. The polymerization is quenched by prechilled methanol after 120 minutes, and the polymer is precipitated into methanol. The polymer is purified by repeated precipitation from THF into methanol.
  • a diblock or triblock copolymer as synthesized above will be dissolved in 50 niL THF and then approximately 2 mL HCl acid (37.0%) will be added. The solution will be refluxed for 3 hours and then cooled down and precipitated into 400 mL water which contains 1 mL ammonia solution (30%). The resulting polymer will be filtered off, washed with water, and dried in vacuum. Substantially complete hydrolysis (absence of a tert-butyl group) is expected.

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Abstract

L’invention concerne de nouveaux procédés de formation de copolymères, y compris de copolymères séquencés, comprenant une ou plusieurs unités d'oléfines, et une ou plusieurs unités hydroxystyrène protégées ou non protégées.
EP06789739A 2005-08-11 2006-08-11 Nouveaux procedes de formation de copolymeres comprenant des olefines et des unites hydroxystyrene protegees ou non protegees Ceased EP1919973A1 (fr)

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PCT/US2006/031613 WO2007022072A1 (fr) 2005-08-11 2006-08-11 Nouveaux procedes de formation de copolymeres comprenant des olefines et des unites hydroxystyrene protegees ou non protegees

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Publication number Priority date Publication date Assignee Title
EP2743618A1 (fr) 2012-12-17 2014-06-18 Electrolux Home Products Corporation N.V. Réfrigérateur pour aliments

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