WO1998002472A1 - Nouveaux copolymeres bisequences constitues de segments polyolefines et de segments polymeres fonctionnels - Google Patents

Nouveaux copolymeres bisequences constitues de segments polyolefines et de segments polymeres fonctionnels Download PDF

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Publication number
WO1998002472A1
WO1998002472A1 PCT/US1997/012196 US9712196W WO9802472A1 WO 1998002472 A1 WO1998002472 A1 WO 1998002472A1 US 9712196 W US9712196 W US 9712196W WO 9802472 A1 WO9802472 A1 WO 9802472A1
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polyolefin
group
polymerization
chain
segment
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PCT/US1997/012196
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Tze-Chiang Chung
Honglan Lu
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The Penn State Research Foundation
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Priority to AU38820/97A priority Critical patent/AU3882097A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • 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
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule

Definitions

  • This invention relates to block copolymer and, more particularly, to diblock copolymers consisting of polyolefin and functional polymer segments which are chemically bonded to each other at their respective chain ends by means of a functional group linkage, such as an ether, ester or amide functional group linkage.
  • a functional group linkage such as an ether, ester or amide functional group linkage.
  • the chemistry that is used to prepare the diblock copolymers is based on the use of a polyolefin that is terminated with a functional group, such as -BR,R 2 , -OH, - NH 2 or a halide.
  • the functional group serves as the initiator for free radical polymerization of free radical polymenzable monomers, such as methyl methacrylate (MMA), ethyl methacrylate (EMA), vinyl acrylate (VA), butyl acrylate (BA) and styrene or as the initiator for ring-opening polymerization of cyclic functional monomers, such as lactones, lactams, cyclic ethers and 2-oxazolines.
  • the invention also relates to a process for preparing such diblock copolymers.
  • the diblock copolymers are useful as interfacial materials for improving the interaction between polyolefins and other materials.
  • polyolefins Although useful in many commercial applications, polyolefins suffer a major deficiency, i.e., poor interaction with other materials.
  • the inert nature of polyolefins significantly limits their end uses, particularly those in which adhesion, dyeability, paintability, printability or compatibility with other functional polymers is paramount.
  • the poor compatibility of polyolefins is evidenced, for example, by a weak adhesion between polyolefins and metal surfaces such that polyolefins have not been used effectively as a protective coating for metals.
  • attempts to blend polyolefins with other polymers have been unsuccessful for much the same reasons, i.e., the incompatibility of the polyolefins and the other polymers.
  • polyolefins have been among the most difficult materials to chemically modify both by functionalization reactions and by graft reactions.
  • the inert nature and crystaUinity of polyolefins usually dictates the need for rather severe reaction conditions to effect any chemical modification. In many cases, the necessary reaction conditions result in serious side reactions, such as degradation in case of polypropylene modification reactions.
  • the only commercially viable processes for preparing linear polyolefins are those which utilize Ziegler-Natta catalysis.
  • Macromolecules, 22, 1313-1319, (1994) disclose that the incompatibility of polymers in a blend can be improved by adding a suitable polyolefin graft copolymer which reduces the domain sizes of the respective polymers in the blend and increases the interaction between domains.
  • Diblock copolymers have also been prepared by processes which involve a transformation reaction.
  • Ziegler-Natta polymerization and U.S. Patent 3,887,650 discloses a transformation form Ziegler-Natta to free radical vinyl polymerization.
  • the preparation of diblock copolymers by means of a coupling reaction is disclosed in Mulhaupt et al, Makromol. Chem., Macromol. Symp. 48/49, 317-332,(1991).
  • the product of such a coupling reaction most likely is an intimate mixture of homopolymers and perhaps some block copolymer. Based on measured lifetimes of the growing chains and efficiency of the coupling reaction, the yields of polyolefin diblock copolymers are well below 20 %.
  • polyolefin segment (polyolefin segment)-f-(functional polymer segment) wherein f is a chemical linkage, such as an ether, ester or amide group linkage.
  • the polyolefin segment is a homo- or co-polymer prepared by transition metal coordination polymerization of at least one C 2 - C , 2 ⁇ -olefin, such as ethylene, 1- propene, 1-butene, 1-pentene, 1-hexene, 1-octene, styrene and mixtures thereof.
  • the molecular weight of the polyolefin segment is above about 2,000 g mole.
  • the molecular weight range of the polyolefin segment is from about 10,000 to about 1,000,000 g/mole, and more preferably from about 10,000 to about 200,000 g/mole.
  • the polyolefin segment may comprise an isotactic, syndiotactic or atactic structure.
  • the functional polymer segment is a polymer which is prepared either by free radical polymerization of a free radical polymerizable monomer, such as methyl methacrylate (MMA), ethyl methacrylate (EMA), vinyl acrylate (VA), butyl acrylate (BA) and styrene, or by ring-opening polymerization of a cyclic functional monomer, such as a lactone, lactam, 2-oxazoline or cyclic ether.
  • a free radical polymerizable monomer such as methyl methacrylate (MMA), ethyl methacrylate (EMA), vinyl acrylate (VA), butyl acrylate (BA) and styrene
  • a cyclic functional monomer such as a lactone, lactam, 2-oxazoline or cyclic ether.
  • the molecular weight of the functional polymer segment is above about 500 g/mole, preferably from about 2,000 to about 1,000,000 g/mole, and more
  • the functional polymer segment may comprise from about 1 to about 95 wt. % of the diblock copolymer. Typically, the functional polymer segment will comprise from about 5 to about 80 wt. % of the diblock copolymer.
  • the preparation of diblock copolymers is based in part on the use of chain-end unsaturated polyolefins which are prepared by transition metal (Ziegler-Natta) catalysts. By using borane chemistry, the chain- end unsaturated polyolefins are effectively functionalized to telechelic polyolefins which have a functional group located at the chain end.
  • Suitable functional groups include, for example, -OH, -NH ⁇ -CHO, a halide, or -BR,R 2 , where R : and R 2 can be the same or different and are H, a halide, a C, to C s alkoxide or a C, to C 20 linear or branched alkyl or cyclic or bicyclic structure.
  • the functional group at the chain end is then used as the catalytic site for either free radical polymerization of a free radical polymerizable monomer, such as methyl methacrylate (MMA), ethyl methacrylate (EMA), vinyl acrylate (VA), butyl acrylate (BA) and styrene, or for ring-opening polymerization and copolymerization of cyclic functional monomers, such as lactones, lactams, 2-oxazolines and cyclic ethers.
  • a free radical polymerizable monomer such as methyl methacrylate (MMA), ethyl methacrylate (EMA), vinyl acrylate (VA), butyl acrylate (BA) and styrene
  • cyclic functional monomers such as lactones, lactams, 2-oxazolines and cyclic ethers.
  • the free radical and ring- opening polymerized polymers are chemically bonded to the chain end of a polyolefin.
  • the desired molecular structure and composition of the diblock copolymer can be obtained.
  • the chain-end functional group is used as the reactive site for transestification reactions.
  • a diblock copolymer structure can also be obtained, e.g. polyolefin-f-polyester, wherein f is a chemical linkage.
  • the transestification reaction may take place simultaneously with a ring opening polymerization of a cyclic ester, thus resulting in the formation of a mixture of copolymers, e.g., a mixture of polyolefin-f-polyester and polyolefin segment -f-functional polymer segment.
  • the polyolefin diblock copolymers of the invention are extremely useful in their own right, i.e., when they are used by themselves.
  • the present diblock copolymers may be used as water-wettable polyolefins, molding compositions, or the like.
  • the present diblock copolymers are particularly useful as interface modifiers, such as compatibilizers in polyolefin blends and composites.
  • the diblock copolymers serve as an emuisifier to alter the morphology of the blends. More particularly, the diblock copolymers reduce the domain sizes for the polymers of the blend and increase the interaction at the interface between the various domains.
  • this invention also provides a method for producing polyolefin/substrate laminate products, such as polypropylene/aluminum and polypropylene/glass, which are characterized by good adhesion at the polyolefin/substrate interface.
  • the polyolefin diblock copolymer locates at the interface and provides the interface adhesion between polyolefin film and substrate.
  • the present invention is based upon a specific class of diblock copolymers which have wide range of properties, including an ability for improving interface interactions between polyolefins and other materials.
  • these diblock copolymers can be formed with high efficiency and desirable molecular microstructures, which include covalent bonds between two polymer segments.
  • the diblock copolymers are soluble in organic solvents and for this reason the diblock polymers are suitable for a variety of applications.
  • compatibilizers it has been found that they can serve as emulsifiers at the interface between two polymer domains so as to greatly change the mo ⁇ hology of these blends.
  • One benefit of this change in mo ⁇ hology is that the macro phase separation between two incompatible polymers is altered and the phase size can be dramatically reduced, there by enabling domain sizes as small as about 10 n to be achieved.
  • the chemistry to prepare the diblock copolymers of the invention is based on the use of intermediate polyolefins (H) and (IH), as shown in following equation, which intermediate polyolefins have been obtained by functionalization of the chain-end unsaturated polyolefin (I) using borane chemistry.
  • F is a polar functional group, such as -OH.-NH ⁇ -halide or -CHO;
  • R and R' can be the same or different and are a proton (H), a halide, or a C j -C 20 alkyl, phenyl or alkyl-substituted phenyl group;
  • R , and R 2 can be the same or different and are a proton (H), or a linear or branched alkyl group, or a cyclic or bicyclic structure.
  • R and R' include , but are not limited to proton, methyl, ethyl propyl, butyl, iso-butyl, hexyl, octyl, decyl, phenyl, p-tolyl and o-tolyl groups.
  • R, and R j include proton, chloro, bromo, iodo, methyl, ethyl, n-butyl, sec-butyl, iso-butyl, iso-amyl, 2, 3-dimethyI-2-butyl, n-pentyl, iso-pentyl, n-hexyl, neopentyl, phenyl, benzyl, cyclopentyl, cyclohexyl, diiospinocampheyl, 9-borodicyclo[3,3,l] nonane, 3, 5 dimethylborinane, boracyclopentane, boracyclohexane and boracycloheptane.
  • the polyolefin segment is a homo- or copolymer prepared by transition metal coordination polymerization of ⁇ -olefins, such as ethylene, 1-propene, 1- butene, 1-pentene, 1-hexene, 1-octene, styrene and their mixtures.
  • the polyolefin segment may have an isotactec, syndiotactic or atactic structure, and the molecular weight thereof is above about 2,000 g/mole, preferably in the range of from 10,000 to about 1,000,000 g/mole. In particularyly preferred embodiments, the molecular weight of the polyolefin segment is in the range from about 10,000 to about 200,000 g/mole.
  • the functional polymer segment, chemically bonded to the polyolefin segment is a polymer which is prepared by either free radical polymerization of a free radical polymerizable monomer, such as methyl methacrylate (MMA), ethyl methacrylate (EMA), vinyl acrylate (VA), butyl acrylate (BA), styrene or acrylonitrile, or by ring-opening polymerization of a cyclic
  • cyclic monomers such as a lactone, lacta , 2-oxazoline, cyclic ether or mixtures thereof.
  • cyclic monomers which are capable of undergoing ring opening polymerization and which may be used to prepare the functional polymer segment include, ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ -valerolactone, glycolide, lactide, e-caprolactone, ⁇ -pyrrolidone, ⁇ -butyrolactam, e-caprolactam, ethylene oxide, propylene oxide, epichlorohydrin, oxetane, tetrahydrofuran and octamethylcyclotetrasiloxane.
  • the molecular weight of functional polymer segment is above about 500 g mole, preferably in the range from about 2,000 to 1,000,000 g/mole, and mostly preferably in the range of from about 10,000 to 200,000 g/mole.
  • the functional polymer segment may comprise from about 1 to about 95 wt. % of the diblock copolymer. However, the functional polymer segment typically comprises form about 5 to about 80 wt. % of the diblock copolymer.
  • ⁇ -proton elimination As is well-known, one of the major termination steps in Ziegler-Natta polymerization of ⁇ -olefins is ⁇ -proton elimination, especially at elevated temperature. This reaction creates a double bond at the end of each polyolefin chain. This phenomena is quite general in all commercial polyolefins, including polyethylene, isotactic polypropylene, poly(l-butene), poly(l-octene) and their copolymers. It also occurs in the cationic polymerization of isobutylene.
  • chain-end unsaturated polyolefin (I) which may include, but which is not limited to, polyethylene, polypropylene, polyisobutylene and poly(ethylene-co-propylene).
  • the post-treatment of the chain-end unsaturated polyolefin (I) involves hydroboration of the terminally unsaturated group and the interconversion of the resulting borane group to a functional group. Hydroboration reagents which may
  • the hydroboration reaction may be performed as described in detail in Chung et al., Macromolecules, 22, 7533-7537, (1994), the disclosure of which is incorporated herein by reference in its entirety.
  • the hydroboration is performed by adding a hydroboration reagent to unsaturated polyolefin and heating the resulting mixture to dissolve the polyolefin and to effect the hydroboration reaction. The heating is performed at about 65 °C for about 3 hours, followed by cooling to precipitate the borated polymer from solution.
  • 9-BBN or dimethylborane is used as the hydroboration reagent.
  • the borane-terminated polyolefin (H) which is formed during the hydroboration reaction is subjected to oxidation by reaction with oxygen in the presence of a free radical polymerizable monomer, such as methyl methacrylate (MMA), ethyl methacrylate (EMA), vinyl acrylate (VA), butyl acrylate (BA) and styrene.
  • a free radical polymerizable monomer such as methyl methacrylate (MMA), ethyl methacrylate (EMA), vinyl acrylate (VA), butyl acrylate (BA) and styrene.
  • the reaction usually takes place by slowly adding oxygen to a polymer solution containing polylefin, monomer and solvent at ambient temperature.
  • oxygen insertion takes place at the B-C bond connecting the polymer chain and the borane group to produce peroxyborane (C-O-O-B).
  • the peroxyborane behaves very differently form regular benzoyl peroxides and consequently decomposes by itself even at ambient temperature.
  • the decomposition reaction follows the homolytic cleavage of peroxide to generate an alkoxy radical (C-O*) and a borinate radical (B-O*) which is relatively stable due to the back-donating of electron density to the empty p-orbital of boron.
  • the alkoxyl radical produced by the homolytic cleavage of peroxyborane, is very reactive and can then be used for the initiation of radical polymerization.
  • the borinate radical may form a weak and reversible bond with the growing chain end during the polymerization reaction. Upon the dissociation of an electron pair in the resting state, the growing chain end can then react with monomers to extend the polymer chain.
  • the radical polymerization can be terminated by precipitating the polymer mixture in methanol (MeOH).
  • MeOH methanol
  • the product isolated by filtration and washed with MeOH, is the subjected to the fractionalization.
  • the resulting polymer is illustrated as product V in the above equation.
  • the borane-terminated polyolefin (II) also can be interconverted to a series of intermediate telechelic polyolefins (HI), which contain a polar functional group, such as -OH, -NH ⁇ -CHO or -I.
  • HI intermediate telechelic polyolefins
  • the interconversion may be accomplished, for example, by following the procedures described in H. C. Brown, Organic Synthesis via Boranes; Wiley-Interscience: NewYork (1975). More specifically, the boran terminal group may be oxidized using NaOH/H j O 2 reagents at about 40°C for about 3 hours to convert the borane group to a hydroxy group.
  • T h e polar functional group in the intermediate polyolefin (IH) is then used as the active site for the ring-opening polymerization of a cyclic functional monomer, such as a lactone, lactam, cyclic ether or 2-oxazoline.
  • the ring opening polymerization may be conducted by contacting the telechelic intermediate polyolefin (HI) with the cyclic monomer neat, or in solution or slurry in an appropriate organic medium, such as toluene.
  • the ring opening polymerization may be conducted at a temperature from about 0 to about 100° C, and for a period of from about 30 minutes to about 12 hours.
  • the ring opening polymerization is conducted at or about room temperature for a period of from about, 1 to about 6
  • the ring-opening polymerized polymer is chemically bonded to the chain end of the polyolefin.
  • a diblock copolymer formed in accordance with the present invention is polypropylene-f-polycaprolactone, the preparation of which is illustrated schematically below:
  • PP represents a polypropylene segment and PCL represents a polycaprolactone segment.
  • the two segments are chemically linked through an ester functional linkage.
  • the hydroxy group in the intermediate functionalized polypropylene is converted to an Al alkoxide group which is then used to initiate the ring opening polymerization of e-caprolactone.
  • the conversion of the hydroxy group to the Al alkoxide group would be accomplished by means of a metallation or graft-from reactions using suspension conditions with PP fine particles slightly swollen in a solvent, such as toluene. Amo ⁇ hous regions should be completely soluble in the toluene, but crystalline domains would be unaffected.
  • polyolefin diblock copolymers of the present invention are useful in their own right, ranging from elastomeric to thermoplastic polymer compositions, and are particularly useful as interface modifiers for improving adhesion of polyolefins to substrates and as compatibilizers in polyolefin blends and composites.
  • one aspect of the invention comprises a method of compatibilizing a mixture containing (a) a polyolefin, prepared by transition metal coordination polymerization of an ⁇ -olefin, such as ethylene, 1-propene, 1-butene, 1-pentene, 1-hexene, 1-octene, styrene and their mixtures, and (b) a functional polymer, such as an acrylic polymer, methacrylic polymer, polyvinyl acetate, polyvinyl chloride, polyacrylionitrile, polyester, polyamide, polyimide, polyether, polycarbonate, polyurethane or cellulose, which is incompatible with polyolefins, which method comprises adding to the mixture a compatibilizing amount, typically from about 0.5 to about 10 % by weight, based on the weight of the compatibilized mixture, of a diblock copolymer as described above.
  • a compatibilizing amount typically from about 0.5 to about 10 % by weight, based on the weight of the compatibilized mixture, of
  • the diblock copolymers of the present invention provide good adhesion between the polyolefin matrix and the fillers or fibers. More specifically, the polar groups in functional polymer segment of the diblock copolymer located at the interface between the polyolefin matrix and the fillers or fibers offer strong interaction to filler or fiber surface whereas the polyolefin segment of the diblock copolymer interacts or co-crystallizes with the polyolefin matrix. The same phenomenon is also observed when polyolefins are coated on an otherwise incompatible substrate.
  • the invention also provides a method for producing polyolefin/substrate laminate products, such as polypropylene/aluminum and polypropylene/glass, wherein the present polyolefin diblock copolymers are applied at the interface to provide adhesion between a polyolefin film or coating and a substrate.
  • polyolefin/substrate laminate products such as polypropylene/aluminum and polypropylene/glass
  • present polyolefin diblock copolymers are applied at the interface to provide adhesion between a polyolefin film or coating and a substrate.
  • the polymer was washed completely with MeOH and dried under vacuum at 50° C for 8 hrs.. About 9.59 g of PP polymer was obtained. Due to high molecular weight polymer, no chain-end unsaturation was detected by IR, 'H NMR.
  • borane terminated PP obtained by Example 8 was placed in a suspension of 50 ml dry, O 2 -free THF in a dry box. The sealed reactor was moved out of the dry box and purged with nitrogen gas. To the polymer slurry, a solution containing 0.4 g of NaOH in 2 ml H 2 O and 0.5 ml MeOH purged by N 2 was added at room temperature, followed by the dropwise addition of 1.6 ml of 30% oxygen-free H z was added dropwise at 0°C. The oxidation was performed at 40° C for 6 hrs. before being terminated by pouring the reaction mass into 100 ml of MeOH.
  • the resulting polymer solid was filtered, and was then refluxed in 100 ml of MeOH for 2 hrs before distilling off 10 ml of MeOH.
  • the resulting hydroxylated PP was then recovered by filtration and was dried in vacuum oven at 50° C for 8 hrs. Chain-end OH groups in the PP were observed by IR, 1H NMR.
  • borane group terminated PP obtained by Example 8 was placed in a suspension of 50 ml dry, O 2 -free THF in a dry box. The sealed reactor was moved out of the dry box and purged with nitrogen gas. Hydroxylamide sulfonic acid (0.5 g) was added to the polymer slurry at room temperature under N 2 purge. The amination reaction was carried out at 50° C for 8 hrs and was then terminated by adding 20 ml of H 2 O. After filtration and several washings with acetone, the polymer powder was dried in vacuum oven at 50° C for 8 hrs. Chain- end NH 2 groups in PP polymer were observed by P, ⁇ NMR.
  • Example 14 Synthesis of PP-b-PCL Diblock Copolymer
  • the hydroxy-terminated PP (0.7 g), obtained from Example 9, was dispersed in a dry, degassed toluene solution in a dry box.
  • the hydroxy-terminated PP was then metal lated with excess n-butyllithium to form the lithium alkoxide.
  • the polymer was stirred for 12 hours before it was isolated by filtration and repeatedly washed and filtered in toluene.
  • the powdery solid was then placed in toluene as a slurry solution and reacted with a 3 molar equivalents of diethylalummum chloride for 12 hours to form PP-aluminum alkoxide (PP- OAlE J.
  • the polymer was isolated by repeated filtration and washing in toluene, followed by filtration and washing in hexane.
  • the cyclic ester caprolactone (Aldrich Chemical) was purified by drying over calcium hydride and distilling under reduced pressure. In the dry box, 5 g of the purified caprolactone was added to a slurry of 0.7 g of PP-OAlEt ⁇ in 20 ml of toluene. The reaction mixture was stirred at room temperature for 3 hours before terminating the reaction by adding 10 ml MeOH. The polymer mixture was isolated by precipitation into acidified MeOH. The polymer was extracted with hot acetone in a Soxhlet apparatus under N 2 for 48 hours to remove any caprolactone homopolymer, which is soluble in acetone.
  • Example 14 A reaction procedure similar to that of Example 14 was used for the synthesis of PP-b-PCL, except that the hydroxy-terminated PP that was used as the starting material was prepared from a higher molecular weight chain end unsaturated PP (obtained from Example 3, rather than from Example 2) than was used in Example 14.
  • 10 g of hydroxy-terminated PP, derived from chain-end unsaturated PP having a Mw of 25,400 g/mole was hydroborated with 9-BBN generally as described in Example 8.
  • the chain end hydroxy polymer was metallated with a 3 molar equivalent of diethylaluminum chloride for 12 hours to form the PP-aluminum alkoxide.
  • the polymer was isolated by repeated filtration and washing in toluene, followed filtration and washing in hexane.
  • the aluminum alkoxide functionalized polymer was then placed in a slurry of 80 g of caprolactone and 80 ml of toluene.
  • the reaction was stirred at room temperature for 18 hours, at which time the reaction was terminated by the addition of MeOH.
  • the polymer was isolated by precipitation into 800 ml of MeOH.
  • Chain end unsaturated PE prepared by Et(Ind) 2 ZrCl 2 MAO catalyst system in Example 6 was subjected to hydroboration and oxidation reactions to form powdered hydroxy group terminated PE.
  • About of 1 g of the hydroxy lated PE powder was suspended in a dry, degassed toluene solution in a dry box and then metallated with excess n- butyllithium to form the PE-lithium alkoxide.
  • the polymer was stirred for 12 hours before it was isolated by filtration and repeadly washed and filtered in toluene followed by the same procedure in hexane.
  • PE-OAlEt-/ PE- aluminum alkoxide
  • the resulting PE-OAIEt ⁇ was isolated by repeated filtration and washing in toluene, followed by filtration and washing in hexane.
  • 15 g of caprolactone was added to a slurry of 1 g of PE-OAlEt, in 15 ml of toluene.
  • the reaction was stirred at room temperature for 18 hours, at which time the reaction was terminated by the addition of MeOH.
  • the resulting diblock PE-b-PCl copolymer was isolated by precipitating into MeOH. The polymer was extracted with hot acetone in a

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Abstract

Copolymères biséquencés comprenant un segment polyoléfine et un segment polymère fonctionnel, de formule structurelle (segment polyoléfine)-f-(segment polymère fonctionnel), dans laquelle f est une liaison chimique, telle qu'une liaison par un groupe éther, ester ou amide. On prépare ces copolymères en mettant en contact une polyoléfine portant un groupe borane terminal avec un monomère pouvant subir une polymérisation à radicaux libres, ou en faisant réagir une polyoléfine fonctionnalisée avec un monomère cyclique pouvant subir une polymérisation à ouverture de cycle, en utilisant le groupe fonctionnel porté par la polyoléfine fonctionnalisée comme initiateur de la polymérisation à ouverture de cycle. Ces copolymères biséquencés, utiles comme matériaux d'interface, améliorent l'interaction entre les polyoléfines et d'autres matériaux.
PCT/US1997/012196 1996-07-15 1997-07-15 Nouveaux copolymeres bisequences constitues de segments polyolefines et de segments polymeres fonctionnels WO1998002472A1 (fr)

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JP2002097237A (ja) * 2000-09-22 2002-04-02 Mitsui Chemicals Inc オレフィン系ブロック共重合体の製造方法
EP1275670A1 (fr) * 2000-01-21 2003-01-15 Mitsui Chemicals, Inc. Copolymeres blocs d'olefine, procedes de fabrication et utilisation
JP2006124723A (ja) * 2006-02-06 2006-05-18 Mitsui Chemicals Inc オレフィン系ブロック共重合体およびその用途
WO2007114134A1 (fr) 2006-03-29 2007-10-11 Mitsui Chemicals, Inc. Composition de resine contenant un polymere sequence d'olefines et son utilisation
US7868097B2 (en) 2005-02-21 2011-01-11 Mitsui Chemicals, Inc. Hybrid polymer and method for production thereof
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