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WO2009038031A1 - Copolymère à blocs et son procédé de fabrication - Google Patents

Copolymère à blocs et son procédé de fabrication Download PDF

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Publication number
WO2009038031A1
WO2009038031A1 PCT/JP2008/066619 JP2008066619W WO2009038031A1 WO 2009038031 A1 WO2009038031 A1 WO 2009038031A1 JP 2008066619 W JP2008066619 W JP 2008066619W WO 2009038031 A1 WO2009038031 A1 WO 2009038031A1
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Prior art keywords
group
methyl
atom
ring
block
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PCT/JP2008/066619
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English (en)
Inventor
Kohtaro Osakada
Daisuke Takeuchi
Sehoon Park
Takeshi Okada
Makoto Uemura
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Sumitomo Chemical Company, Limited
Tokyo Institute Of Technology
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Publication of WO2009038031A1 publication Critical patent/WO2009038031A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/70—Iron group metals, platinum group metals or compounds 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
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/20—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds unconjugated
    • 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
    • C08F293/005—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 using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
    • 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
    • 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
    • C08F297/06—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 coordination type
    • C08F297/08—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 coordination type polymerising mono-olefins

Definitions

  • the present invention relates to a block copolymer whose main chain contains a cyclopentane ring structure, and a process for producing a block copolymer.
  • the block copolymer consists of (i) a polymer block consisting of polymerization units of ethylene, (-CH 2 -CH 2 -) , and (ii) a polymer block consisting of polymerization units of 1, 2-cyclopentylene whose five carbon atoms forming its cyclopentane ring are linked with one or two hydrogen atoms, respectively, both polymer blocks (i) and (ii) being chemically linked with each other.
  • the present invention has an object to provide (i) a block copolymer superior in its heat resistance, whose polymerization units containing a cyclopentane ring structure are derived from a specific diene compound, and have a different chemical structure from that of polymerization units derived from cyclopentene, and (ii) a process producing a block copolymer.
  • the present invention is a block copolymer comprising the following block (bl) and the following block (b2) and/or block (b3) :
  • (bl) a homopolymer block (bl-1) containing one kind of polymerization unit represented by the following formula (1), or a random copolymer block (bl-2) containing two or more kinds of polymerization units represented by the following formula
  • the blocks (b2-l) and (b2-2) having different attributes from those of the blocks (bl-1) and (bl-2), respectively; and/or
  • Y 1 and Y 2 are independently of each another a hydrogen atom, a halogen atom, an alkoxycarbonyl group, an aralkyloxycarbonyl group, an aryloxycarbonyl group, a hydroxyl group, a nitrile group, an aldehyde group, an alkyl group, an aralkyl group, an aryl group, a silyl group, a siloxy group, an alkoxy group, an aralkyloxy group, an aryloxy group, an acyl group, an amino group, a substituted amino group, an amide group, an imide group, a thiol group, an alkylthio group, an aralkylthio group, an arylthio group, an alkylthioxycarbonyl group, or an arylthioxycarbonyl group, and Y 1 and Y 2 may be linked with each other to form a ring; A 1 , A 2 , A 3 ,
  • the present invention is a process for producing the above-mentioned block copolymer, comprising the following steps of, in any order:
  • polymerization unit means a unit of a polymerized monomer, which is also referred to as a "repeating unit”.
  • Examples of the halogen atom of A 1 to A 11 in the formulas (1) and (3) are a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Among them, preferred is a fluorine atom.
  • (1) and (3) are linear alkyl groups such as a methyl group, an ethyl group, and a n-butyl group; branched alkyl groups such as an isopropyl group, an isobutyl group, a tert-butyl group, and a neopentyl group; and cyclic alkyl groups such as a cyclohexyl group and a cyclooctyl group.
  • (1) and (3) are a benzyl group, a phenethyl group, a 2-methylbenzyl group, a 3-methylbenzyl group, a
  • (1) and (3) are a phenyl group, a tolyl group, a 1-biphenyl group, a 2-biphenyl group, a 3-biphenyl group, a 1-naphthyl group, a
  • Examples of the alkoxy group of A 1 to A 11 in the formulas (1) and (3) are linear alkoxy groups such as a methoxy group, an ethoxy group, and a n-butoxy group; branched alkoxy groups such as an isopropoxy group, an isobutoxy group, a tert-butoxy group, and a neopentoxy group; and cyclic alkoxy groups such as a cyclohexyloxy group and a cyclooctyloxy group.
  • Examples of the aralkyloxy group of A 1 to A 11 in the formulas (1) and (3) are a benzyloxy group, a phenethyloxy group, a 2-methylbenzyloxy group, a 3-methylbenzyloxy group, a
  • Examples of the aryloxy group of A 1 to A 11 in the formulas (1) and (3) are a phenoxy group, a 2-methylphenoxy group, a 2-ethylphenoxy group, a 2-n-propylphenoxy group, a 2-isopropylphenoxy group, a 2-n-butylphenoxy group, a 2-isobutylphenoxy group, a 2-tert-butylphenoxy group, a 3-methylphenoxy group, a 3-isopropylphenoxy group, a 3-n-butylphenoxy group, a 3-tert-butylphenoxy group, a 4-methylphenoxy group, a 4-isopropylphenoxy group, a 4-n-butylphenoxy group, a 4-tert-butylphenoxy group, a 2, 3-dimethylphenoxy group, a 2, 4-dimethylphenoxy group, a 2, 5-dimethylphenoxy group, a 2, 6-dimethylphenoxy group, a 3, 5-dimethylphenoxy group,
  • Examples of the substituted amino group of A 1 to A 11 in the formulas (1) and (3) are an N-methylamino group, an N-ethylamino group, an N-n-butylamino group, an N,N-dimethylamino group, an N, N-diethylamino group, an N, N-di-n-butylamino group, an N-isopropylamino group, an N-isobutylamino group, an N-tert-butylamino group, an N-neopentylamino group, an N, N-diisopropylamino group, an N,N-diisobutylamino group, an N,N-di-tert-butylamino group, an N, N-dineopentylamino group, an N-cyclohexylamino group, an N-cyclooctylamino group, an N, N-dicyclohexylamino group,
  • (1) and (3) are an ethanamide group, a n-butanamide group, an
  • N-methylethanamide group an N-ethylethanamide group, an
  • N-n-butylethanamide group an isopropanamide group, an isobutanamide group, a tert-butanamide group, a neopentanamide, an N-isopropylethanamide group, an
  • N-isobutylmethanamide group an N-tert-butylethanamide group, an N-neopentylethanamide group, an
  • N-cyclohexylethanamide group and an N-cyclooctylethanamide group.
  • Examples of the imide group of A 1 to A 11 in the formulas (1) and (3) are a succinimide group, a maleimide group, and a phthalimide group.
  • Examples of the alkylthio group of A 1 to A 11 in the formulas (1) and (3) are linear alkylthio groups such as a methylthio group, an ethylthio group, and a n-butylthio group; branched alkylthio groups such as an isopropylthio group, an isobutylthio group, a tert-butylthio group, and a neopentylthio group; and cyclic alkylthio groups such as a cyclohexylthio group and a cyclooctylthio group.
  • the above-mentioned groups of A 1 to A 11 may have a substituent such as a halogen atom, a hydroxyl group, a thiol group, an amino group, a carboxyl group, a carbamoyl group, a formyl group, a nitro group, a sulfonate group, a silyl group, a siloxy group, and a cyano group.
  • a 1 to A 11 are preferably a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or a methyl group, and further preferably a hydrogen atom.
  • a 3 and A 4 and/or A 5 and A 6 may be linked with each other to form a ring.
  • the ring are aliphatic rings such as a cyclobutane ring, a cyclopentane ring and a cyclohexane ring, and aromatic rings. Those rings may have one or more substituents .
  • halogen atom of Y 1 and Y 2 in the formulas (1) and (3) are a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Among them, preferred is a fluorine atom.
  • alkoxycarbonyl group of Y 1 and Y 2 in the formulas (1) and (3) are linear alkoxycarbonyl groups such as a methoxycarbonyl group, an ethoxycarbonyl group and a n-butoxycarbonyl group; branched alkoxycarbonyl groups such as an isopropoxycarbonyl group, an isobutoxycarbonyl group, a tert-butoxycarbonyl group and a neopentoxycarbonyl group; cyclic alkoxycarbonyl groups such as a cyclohexyloxycarbonyl group and a cyclooctyloxycarbonyl group.
  • Examples of the aralkyloxycarbonyl group of Y 1 and Y 2 in the formulas (1) and (3) are a benzyloxycarbonyl group, a phenethyloxycarbonyl group, a 2-methylbenzyloxycarbonyl group, a 3-methylbenzyloxycarbonyl group, a 4-methylbenzyloxycarbonyl group, a 2, 6-dimethylbenzyloxycarbonyl group, and a 3, 5-dimethylbenzyloxycarbonyl group.
  • Examples of the aryloxycarbonyl group of Y 1 and Y 2 in the formulas (1) and (3) are a phenoxycarbonyl group, a tolyloxycarbonyl group and a mesityloxycarbonyl group.
  • Examples of the alkyl group of Y 1 and Y 2 in the formulas (1) and (3) are linear alkyl groups such as a methyl group, an ethyl group, and a n-butyl group; branched alkyl groups such as an isopropyl group, an isobutyl group, a tert-butyl group, and a neopentyl group; and cyclic alkyl groups such as a cyclohexyl group and a cyclooctyl group.
  • (1) and (3) are a benzyl group, a phenethyl group, a
  • (1) and (3) are a phenyl group, a tolyl group and a mesityl group.
  • (1) and (3) are mono-substituted silyl groups such as a methylsilyl group, an ethylsilyl group, and a phenylsilyl group; di-substituted silyl groups such as a dimethylsilyl group, a diethylsilyl group, and a diphenylsilyl group; and tri-substituted silyl groups such as a trimethylsilyl group, a trimethoxysilyl group, a dimethylmethoxysilyl group, a methyldimethoxysilyl group, a triethylsilyl group, a triethoxysilyl group, a tri-n-propylsilyl group, a triisopropylsilyl group, a tri-n-butylsilyl group, a tri-sec-butylsilyl group, a tert-butyldimethylsilyl group, a triisobut
  • a tri-substituted silyl group preferred is a tri-substituted silyl group, and further preferred is a trimethylsilyl group, a triethylsilyl group, a triphenylsilyl group, a tert-butyldimethylsilyl group, a tert-butyldiphenylsilyl group, a cyclohexyldimethylsilyl group, or a triisopropylsilyl group.
  • (1) and (3) are a trimethylsiloxy group, a trimethoxysiloxy group, a dimethylmethoxysiloxy group, a methyldimethoxysiloxy group, a triethylsiloxy group, a triethoxysiloxy group, a tri-n-propylsiloxy group, a triisopropylsiloxy group, a tri-n-butylsiloxy group, a tri-sec-butylsiloxy group, a tert-butyldimethylsiloxy group, a triisobutylsiloxy group, a tert-butyldiphenylsiloxy group, a cyclohexyldimethylsiloxy group, a tricyclohexylsiloxy group, and a triphenylsiloxy group.
  • a trimethylsiloxy group preferred is a trimethylsiloxy group, a triethylsiloxy group, a triphenylsiloxy group, a tert-butyldimethylsiloxy group, a tert-butyldiphenylsiloxy group, a cyclohexyldimethylsiloxy group, or a triisopropylsiloxy group.
  • Examples of the alkoxy group of Y 1 and Y 2 in the formulas (1) and (3) are linear alkoxy groups such as a methoxy group, an ethoxy group, and a n-butoxy group; branched alkoxy groups such as an isopropoxy group, an isobutoxy group, a tert-butoxy group, and a neopentoxy group; and cyclic alkoxy groups such as a cyclohexyloxy group and a cyclooctyloxy group.
  • Those alkoxy groups may have a substituent such as a halogen atom, an alkoxy group, a nitro group, a sulfonate group, a silyl group, and a cyano group.
  • Examples of the aralkyloxy group of Y 1 and Y 2 in the formulas (1) and (3) are a benzyloxy group, a phenethyloxy group, a 2-methylbenzyloxy group, a 3-methylbenzyloxy group, a 4-methylbenzyloxy group, a 2, 6-dimethylbenzyloxy group, and a 3, 5-dimethylbenzyloxy group.
  • Those aralkyloxy groups may have a substituent such as a halogen atom, an alkoxy group, a nitro group, a sulfonate group, a silyl group, and a cyano group.
  • Examples of the aryloxy group of Y 1 and Y 2 in the formulas (1) and (3) are a phenoxy group, a 2-methylphenoxy group, a 2-ethylphenoxy group, a 2-n-propylphenoxy group, a 2-isopropylphenoxy group, a 2-n-butylphenoxy group, a 2-isobutylphenoxy group, a 2-tert-butylphenoxy group, a 3-methylphenoxy group, a 3-isopropylphenoxy group, a 3-n-butylphenoxy group, a 3-tert-butylphenoxy group, a 4-methylphenoxy group, a 4-isopropylphenoxy group, a 4-n-butylphenoxy group, a 4-tert-butylphenoxy group, a 2, 3-dimethylphenoxy group, a 2, 4-dimethylphenoxy group, a 2, 5-dimethylphenoxy group, a 2, 6-dimethylphenoxy group, a 3, 5-dimethylphenoxy
  • Examples of the acyl group of Y 1 and Y 2 in the formulas (1) and (3) are an acetyl group, a n-propanoyl group, a n-butanoyl group, a n-pentanoyl group, a n-hexanoyl group, a 2-methylpropanoyl group, a pivaloyl group, a 2-methylbutanoyl group, a benzoyl group, a 1-naphthoxyl group, and a 2-naphthoyl group.
  • Examples of the substituted amino group of Y 1 and Y 2 in the formulas (1) and (3) are linear alkylamino groups such as an N-methylamino group, an N-ethylamino group, an N-n-butylamino group, an N, N-dimethylamino group, an N,N-diethylamino group, and an N, N-di-n-butylamino group; branched alkylamino groups such as an N-isopropylamino group, an N-isobutylamino group, an N-tert-butylamino group, an N-neopentylamino group, an N, N-diisopropylamino group, an N,N-diisobutylamino group, an N, N-di-tert-butylamino group, and an N, N-dineopentylamino group; and cyclic alkylamino groups such as an N-cyclohex
  • (1) and (3) are an ethanamide group, a n-butanamide group, an
  • N-isobutylethanamide group, an N-tert-butylethanamide group, and an N-neopentylethanamide group are examples of the imide group of Y 1 and Y 2 in the formulas (1) and (3).
  • the imide group of Y 1 and Y 2 in the formulas (1) and (3) are a maleimide group, a phthalimide group and a succinimide group.
  • alkylthio group of Y 1 and Y 2 in the formulas (1) and (3) are linear alkylthio groups such as a methylthio group, an ethylthio group, and a n-butylthio group; branched alkylthio groups such as an isopropylthio group, an isobutylthio group, a tert-butylthio group, and a neopentylthio group; and cyclic alkylthio groups such as a cyclohexylthio group and a cyclooctylthio group.
  • Examples of the aralkylthio group of Y 1 and Y 2 in the formulas (1) and (3) are a benzylthio group, a 1-naphthylmethylthio group, a 2-naphthylmethylthio group, and a 9-fluorenylmethylthio group.
  • Examples of the arylthio group of Y 1 and Y 2 in the formulas (1) and (3) are a phenylthio group, a 1-naphthyltio group, a 2-naphthylthio group, and a 9-fluorenylthio group.
  • Examples of the alkylthioxycarbonyl group of Y 1 and Y 2 in the formulas (1) and (3) are a methylthioxycarbonyl group, an ethylthioxycarbonyl group, an isopropylthioxycarbonyl group, a tert-butylthioxycarbonyl group, and a cyclohexylthioxycarbonyl group.
  • Y 2 in the formulas (1) and (3) is a phenylthioxycarbonyl group.
  • Y 1 and Y 2 in the formulas (1) and (3) may be linked with each other to form a ring.
  • the ring are hydrocarbon rings such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, a cyclodecane ring, a decahydronaphthalene ring, a norbornane ring, a 1, 2, 3, 4-tetrahydronaphthalene ring, a norbornene ring, an ethylidenenorbornene ring, an indane ring, a fluorene ring, and an acenaphthylene ring; ketone group-carrying rings such as a cyclopropan-1-one ring, a cyclobut
  • N,N-dialkylpropanediamide derivatives such as
  • N, N' -diaralkylpropanediamide derivatives such as N, N' -dibenzyl-2, 2-diallylpropanediamide and
  • N-alkylbarbituric acid derivatives such as N-methyl-5, 5-diallylbarbituric acid
  • N, N' -dialkylbarbiturc acid derivatives such as
  • N-aralkylpyrazolidine-3, 5-dione derivatives such as
  • N, N' -diaralkylpyrazolidine-3, 5-dione derivatives such as
  • N, N' -diarylbarbituric acid derivatives N-aralkylbarbituric acid derivatives
  • N, N' -diaralkylbarbituric acid derivatives N, N' -dialkylpyrazolidine-3, 5-dione derivatives
  • a linear or cyclic olefin having 2 to 20 carbon atoms preferred is a linear or cyclic olefin having 2 to 8 carbon atoms, and particularly preferred is ethylene, propylene, 1-butene, 1-pentene, cyclopentene, 1-hexene, 4-methyl-l-pentene, or 1-octene.
  • olefins may be used in combination with a diene compound.
  • the diene compound are conjugated dienes such as butadiene and isoprene; linear non-conjugated dienes such as 1, 4-pentadiene and 1, 5-hexadiene; and cyclic non-conjugated dienes such as cyclopentadiene, cyclohexadiene, cycloheptadiene, cyclooctadiene, cyclononadiene, ethylidene norbornene, norbornadiene, and dicyclopentadiene .
  • the polymerization unit of an olefin in the present invention has a structure formed by a cleavage-polymerization reaction of a carbon-to-carbon double bond contained in the olefin, and is the same as a polymerization unit contained in an addition polymer of the olefin, such as an ethylene unit (-CH2CH 2 -) contained in polyethylene, which is an addition polymer of ethylene.
  • one or more kinds of polymerization units contained in the block copolymer which are represented by the formula (1), have preferably a trans-form configuration between A 7 and A 8 represented by the following formula (2):
  • a proportion of the polymerization units having the above-mentioned trans-form configuration is measured by a 13 C-NMR spectrum using a solution of the block copolymer of the present invention in chloroform-di.
  • a peak (i) appearing at 45 to 48 ppm in the 13 C-NMR spectrum is assigned to two carbon atoms linking to each of A 7 and A 8 having a trans-form configuration represented by the formula (2), and a peak (ii) appearing at 39 to 42 ppm therein is assigned to two carbon atoms linking each of A 7 and A 8 having a cis-form configuration, provided that a peak assigned to chloroform-di (solvent) appears at 77 ppm. Therefore, the proportion (%) of the polymerization units having the trans-form configuration is obtained from the following formula:
  • the random copolymer block (bl-2) contains two or more kinds of polymerization units represented by the formula (1), and is formed by randomly copolymerizing two or more kinds of diene compounds represented by the formula (3) .
  • a combination of diene compounds for the random copolymer block (bl-2) is preferably a combination of 5,5-diallyl Meldrum's acid with 2, 2-dimethyl-5, 5-diallyl-l, 3-dioxane; a combination of 5,5-diallyl Meldrum's acid with dimethyl 2, 2-diallylmalonate; a combination of 5,5-diallyl Meldrum's acid with 2, 2-diallyl-l, 3-dioxane; a combination of 5,5-diallyl Meldrum's acid with 5, 5-diallylbarbituric acid; a combination of 5,5-diallyl Meldrum's acid with N, N' -dimethyl-4, 4-diallylpyrazolidine-3, 5-dione; a combination of 5,5-diallyl Meldrum's acid with 9, 9-diallylfluorene; a combination of 2, 2-dimethyl-5, 5-diallyl-l, 3-dioxane with dimethyl 2, 2-diallylmalonate;
  • the homopolymer block (b2-l) contains one kind of polymerization unit represented by the formula (1), and has attributes different from those of the above-mentioned homopolymer block (bl-1) .
  • the homopolymer block (b2-l) is formed by homopolymerizing one kind of diene compound represented by the formula (3).
  • the diene compound for the homopolymer block (b2-l) is preferably barbituric acid derivatives, N-alkylbarbituric acid derivatives, N, N' -dialkylbarbiturc acid derivatives, N-arylbarbituric acid derivatives, N, N' -diarylbarbituric acid derivatives, N-aralkylbarbituric acid derivatives,
  • N, N' -diaralkylbarbituric acid derivatives N, N' -dialkylpyrazolidine-3, 5-dione derivatives
  • Examples of the above-mentioned attribute of the homopolymer blocks (bl-1) and (b2-l) are a type of a polymerization unit contained therein (namely, type of a diene compound used for production thereof) , an average molecular weight thereof, a molecular weight distribution thereof, and a proportion of the above-mentioned trans-form configuration contained therein. Namely, the homopolymer blocks (bl-1) and (b2-l) are different from each other in view of one or more of the above-exemplified attributes.
  • the random copolymer block (b2-2) contains two or more kinds of polymerization units represented by the formula (1), and has attributes different from those of the above-mentioned random copolymer block (bl-2).
  • the random copolymer block (b2-2) is formed by randomly copolymerizing two or more kinds of diene compounds represented by the formula (3) .
  • a combination of diene compounds for the random copolymer block (b2-2) is preferably a combination of 5,5-diallyl Meldrum's acid with 2, 2-dimethyl-5, 5-diallyl-l, 3-dioxane; a combination of 5,5-diallyl Meldrum's acid with dimethyl 2, 2-diallylmalonate; a combination of 5,5-diallyl Meldrum's acid with 2, 2-diallyl-l, 3-dioxane; a combination of 5,5-diallyl Meldrum's acid with 5, 5-diallylbarbituric acid; a combination of 5,5-diallyl Meldrum's acid with N, N' -dimethyl-4, 4-diallylpyrazolidine-3, 5-dione; a combination of 5,5-diallyl Meldrum's acid with 9, 9-diallylfluorene;
  • Examples of the above-mentioned attribute of the random copolymer blocks (bl-2) and (b2-2) are a combination of plural kinds of polymerization units contained therein (namely, combination of plural kinds of diene compounds used for production thereof) , an average molecular weight thereof, a molecular weight distribution thereof, and a proportion of the above-mentioned trans-form configuration contained therein. Namely, the random copolymer blocks (bl-2) and (b2-2) are different from each other in view of one or more of the above-mentioned attributes.
  • the homopolymer block (b3-l) contains one kind of polymerization unit of an olefin, and is formed by homopolymerizing one kind of olefin.
  • the olefin for the homopolymer block (b3-l) is preferably ethylene, propylene, 1-butene, 1-pentene, cyclopentene, 1-hexene, 4-methyl-l-pentene, or 1-octene.
  • the random copolymer block (b3-2) contains two or more kinds of polymerization units of an olefin, and is formed by randomly copolymerizing two or more kinds of olefins.
  • a combination of the olefin for the random copolymer block (b3-2) is preferably a combination of ethylene with propylene; a combination of ethylene with 1-butene; a combination of ethylene with 1-pentene; a combination of ethylene with cyclopentene; a combination of ethylene with 1-hexene; a combination of ethylene with 4-methyl-l-pentene; a combination of ethylene with 1-octene; a combination of propylene with 1-butene; a combination of propylene with 1-pentene; a combination of propylene with cyclopentene; a combination of propylene with 1-hexene; a combination of propylene with 4-methyl-l-pentene; a combination of propylene with 1-octene; a
  • Examples of the block copolymer of the present invention are a block copolymer of two kinds of Meldrum' s acid derivatives, a block copolymer of a Meldrum 1 s acid derivative with a barbituric acid derivative, a block copolymer of a Meldrum 1 s acid derivative with a N, N' -dialkylpyrazolidine-3, 5-dione derivative, a block copolymer of a Meldrum' s acid derivative with a fluorene derivative, a block copolymer of a Meldrum 1 s acid derivative with a linear olefin, a block copolymer of a Meldrum' s acid derivative with a cyclic olefin, a block copolymer of two kinds of barbituric acid derivatives, a block copolymer of a barbituric acid derivative with a N, N' -dialkylpyrazolidine-3, 5-dione derivative, a block copolymer of a barbi
  • a block copolymer containing a homopolymer block (bl-1) of 2, 2-diallylindane-l, 3-dione and a homopolymer block (b3-l) of 1-hexene (2) a block copolymer containing a homopolymer block
  • the block copolymer of the present invention is not a polymer blend of the blocks (bl) and (b2) and/or (b3) .
  • the blocks (bl) and (b2) and/or (b3) are covalently bound with each other at one terminal or both terminals of those blocks.
  • the block copolymer of the present invention can be produced using a polymerization catalyst mentioned hereinafter by the below-exemplified process, which comprises the following steps of, in this order:
  • each polymerization reaction in the steps (I) to (III) is similar to a living polymerization reaction, so that each propagating terminal of the homopolymer block (bl-1) and the intermediate polymer block (bl-1) (b2-l) continues to hold a polymerization activity as long as the propagating terminal is not deactivated.
  • a propagating terminal of the target block copolymer (bl-1) (b2-l) (b3-l) formed in the step (III) also continues to hold a polymerization activity without a deactivation treatment, the polymerization activity is destroyed by a treatment such as pouring a polymerization reaction mixture into methanol.
  • polymerization is carried out preferably in the presence of a polymerization catalyst formed by contacting a transition metal compound with an organoaluminum compound and/or boron compound.
  • Polymerization conditions of the steps (I), (II) and (III) can be determined independently from one another, such as a kind of a polymerization catalyst, a concentration of a polymerization catalyst, a concentration of a compound (monomer) polymerized, a polymerization temperature, and a polymerization time.
  • M 1 is an iron atom, a cobalt atom, a nickel atom, a palladium atom or a cupper atom
  • R 3 and R 4 are independently of each other a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, an alkoxy group, an aralkyloxy group or an aryloxy group
  • R 5 , R 6 , R 7 and R 8 are independently of one other a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, an alkoxy group, an aralkyloxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aralkyloxycarbonyl group, an aryloxycarbonyl group, an amino group, a substituted amino group, an amide group or an alkylthio group, and R 7 and R 8 may be linked with each other a
  • M 1 is an iron atom, a cobalt atom, a nickel atom, a palladium atom or a cupper atom
  • R 3 and R 4 are independently of each other a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, an alkoxy group, an aralkyloxy group or an aryloxy group
  • R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 and R 14 are independently of one other a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, an alkoxy group, an aralkyloxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aralkyloxycarbonyl group, an aryloxycarbonyl group, an amino group, a substituted amino group, an amide group or an alkylthio
  • M 1 is an iron atom, a cobalt atom, a nickel atom, a palladium atom or a cupper atom
  • R 3 and R 4 are independently of each other a hydrogen atom, a halogen atom, an alkyl'group, an aralkyl group, an aryl group, an alkoxy group, an aralkyloxy group or an aryloxy group
  • R 15 to R 21 are independently of one other a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, an alkoxy group, an aralkyloxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aralkyloxycarbonyl group, an aryloxycarbonyl group, an amino group, a substituted amino group, an amide group or an alkylthio group, and any two of R 15 to R 21 may be linked with each other to form a ring
  • halogen atom of R 3 to R 21 in the formulas [I], [II] and [III] are a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • Examples of the alkyl group of R 3 to R 21 in the formulas [I], [II] and [III] are linear alkyl groups such as a methyl group, an ethyl group, and a n-butyl group; branched alkyl groups such as an isopropyl group, an isobutyl group, a tert-butyl group, and a neopentyl group; and cyclic alkyl groups such as a cyclohexyl group and a cyclooctyl group.
  • preferred is an alkyl group having 1 to 16 carbon atoms, more preferred is a linear alkyl group having 1 to 8 carbon atoms, and further preferred is a methyl group or an ethyl group.
  • a phenyl group having 6 to 20 carbon atoms preferred is a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 4-isopropylphenyl group, a 4-tert-butylphenyl group, a 2, 6-dimethylphenyl group, a 3, 5-dimethylphenyl group, a 3, 6-dimethylphenyl group, a 2, 6-diisopropylphenyl group, a 2, 6-di-tert-butylphenyl group, a 3, 5-di-tert-butylphenyl group, or a mesityl group, and further preferred is a phenyl group, a 2, 6-dimethylphenyl group, a mesityl group or a 2, 6-diisoprop
  • Examples of the alkoxy group of R 3 to R 21 in the formulas [I], [II] and [III] are linear alkoxy groups such as a methoxy group, an ethoxy group, and a n-butoxy group; branched alkoxy groups such as an isopropoxy group, an isobutoxy group, a tert-butoxy group, and a neopentoxy group; and cyclic alkoxy groups such as a cyclohexyloxy group and a cyclooctyloxy group.
  • preferred is an alkoxy group having 1 to 16 carbon atoms, more preferred is a linear alkoxy group having 1 to 8 carbon atoms, and further preferred is a methoxy group or an ethoxy group.
  • Examples of the aralkyloxy group of R 3 to R 21 in the formulas [I], [II] and [III] are a benzyloxy group, a
  • Examples of the aryloxy group of R 3 to R 21 in the formulas [I], [II] and [III] are a phenoxy group, a 2-methylphenoxy group, a 3-methylphenoxy group, a 4-methylphenoxy group, a 2, 3-dimethylphenoxy group, a 2, 4-dimethylphenoxy group, a 2, 5-dimethylphenoxy group, a 2, 6-dimethylphenoxy group, a 3, 4-dimethylphenoxy group, a 3, 5-dimethylphenoxy group, a 2-tert-butyl-3-methylphenoxy group, a
  • 2-tert-butyl-6-methylphenoxy group a 2, 3, 4-trimethylphenoxy group, a 2, 3, 5-trimethylphenoxy group, a 2, 3, 6-trimethylphenoxy group, a 2, 4 , 5-trimethylphenoxy group, a 2, 4, 6-trimethylphenoxy group, a 2-tert-butyl-3, 4-dimethylphenoxy group, a 2-tert-butyl-3, 5-dimethylphenoxy group, a 2-tert-butyl-3, 6-dimethylphenoxy group, a
  • preferred is an aryloxy group having 6 to 20 carbon atoms.
  • Examples of the acyl group of R 5 to R 21 in the formulas [I], [II] and [III] are an acetyl group, a propanoyl group, a butanoyl group, an isobutanoyl group, a pentanoyl group, an isopentanoyl group, a benzoyl group, and a phenylacetyl group.
  • Examples of the alkoxycarbonyl group of R 5 to R 21 in the formulas [I], [II] and [III] are a methoxycarbonyl group, an ethoxycarbonyl group, a n-propoxycarbonyl group, an isopropoxycarbonyl group, a n-butoxycarbonyl group, an isobutoxycarbonyl group, a tert-butoxycarbonyl group, a n-pentoxycarbonyl group, a neopentoxycarbonyl group, a cyclopentoxycarbonyl group, a n-hexoxycarbonyl group, and a cyclohexoxycarbonyl group.
  • Examples of the aralkyloxycarbonyl group of R 5 to R 21 in the formulas [I], [II] and [III] are a benzyloxycarbonyl group, a phenethyloxycarbonyl group, and a cumyloxycarbonyl group.
  • aryloxycarbonyl group of R 5 to R 21 in the formulas [I], [II] and [III] is a phenoxycarbonyl group.
  • Examples of the substituted amino group of R 5 to R 21 in the formulas [I], [II] and [III] are linear alkylamino groups such as an N-methylamino group, an N-ethylamino group, an
  • N-n-b ⁇ tylamino group an N, N-dimethylamino group, an N, N-dimethylamino group, an N, N-dimethylamino group, an N, N-dimethylamino group, an N, N-dimethylamino group, an N, N-dimethylamino group, an N, N-dimethylamino group, an N, N-dimethylamino group, an
  • N, N-diethylamino group, and an N, N-di-n-butylamino group branched amino groups such as an N,N-diisopropylamino group, an N, N-diisobutylamino group, an N, N-di-tert-butylamino group, and an N, N-dineopentylamino group
  • branched amino groups such as an N,N-diisopropylamino group, an N, N-diisobutylamino group, an N, N-di-tert-butylamino group, and an N, N-dineopentylamino group
  • cyclic alkylamino groups such as an N, N-dicyclohexylamino group and an N, N-dicyclooctylamino group.
  • Examples of the amide group of R 5 to R 21 in the formulas [I], [II] and [III] are an ethanamide group, an N-n-butylethanamide group, an N-methylethanamide group, an N-ethylethanamide group, an N-n-butylhexanamide group, an isopropanamide group, an isobutanamide group, a tert-butanamide group, and a neopentanamide.
  • alkylthio group of R 5 to R 21 in the formulas [I], [II] and [III] are a methylthio group, an ethylthio group, an isopropylthio group, a tert-butylthio group, a benzylthio group, and a 9-fluorenylmethylthio group.
  • the transition metal compound is preferably a compound represented by the formula [II] , from a viewpoint of producing a random copolymer containing polymerization units represented by the formula (2); more preferably a compound represented by the formula [II] wherein R 9 and R 10 are independently of each other an aryl group, and R 11 and R 12 are independently of each other a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an alkoxy group, an aralkyloxy group, an amino group, a substituted amino group or an alkylthio group, from a viewpoint of producing a random copolymer containing a large amount of polymerization units represented by the formula (2); and further preferably a compound represented by the formula [II] wherein R 9 and R 10 are independently of each other an aryl group, and R 11 and R 12 are independently of each other a hydrogen atom, an alkyl group or an aralkyl group.
  • Examples of the ring formed by linking of R 7 with R 8 in the formulas [I] and [II], and examples of the ring formed by linking of any two of R 15 to R 21 with each other in the formula [III] are aliphatic rings and aromatic rings. Those rings may have a substituent such as a halogen atom, an alkoxy group, an aryloxy group, an aralkyloxy group, a nitro group, an amino group, a substituted amino group, an amide group, a sulfonyl group and an alkylthio group.
  • Examples of a divalent group making the above-mentioned aromatic rings formed by linking of R 7 with R 8 , or formed by linking of any two of R 15 to R 21 with each other are a benzene-1, 2-diyl group, a 3-methylbenzene-l, 2-diyl group, a 4-methylbenzene-l, 2-diyl group, a 3-ethylbenzene-l, 2-diyl group, a 4-ethylbenzene-l, 2-diyl group, a 3-n-propylbenzene-l, 2-diyl group, a 4-n-propylbenzene-l, 2-diyl group, a 3-n-butylbenzene-l, 2-diyl group, a 4-n-butylbenzene-l, 2-diyl group, a 3-isopropylbenzene-l, 2-diyl group, a 4-isopropylbenzene-l, 2-
  • Examples of the transition metal compound represented by the formula [I] or [II] , wherein M 1 is a palladium atom, are chloro (methyl) [N, N ' - (ethane-1, 2-diylidene) bis (aniline- /c N) ] palladium, chloro (methyl) [N, N ' - (ethane-1, 2-diylidene) bis (2-methylaniline- K N) ] palladium, chloro (methyl) [N, N ' - (ethane-1, 2-diylidene) bis (2-ethylaniline- /c N) ] palladium, chloro (methyl) [N, N 1 - (ethane-1, 2-diylidene) bis (2-n-propylaniline- K N) ] palladium, chloro (methyl) [N, N ' - (ethane-1, 2-diylidene) bis (2-isopropylaniline- /
  • transition metal compound represented by the formula [I] or [II] wherein M 1 is a nickel atom, an iron atom, a copper atom or a cobalt atom, are compounds named by replacing the term "palladium" contained in the above-exemplified palladium compounds with the term "nickel",
  • transition metal compound represented by the formula [III] wherein M 1 is an iron, are 2, 6-bis- [1- (2, 6-dimethylphenylimino) ethyl] pyridineiron dichloride,
  • transition metal compound represented by the formula [III], wherein M 1 is a nickel atom, a palladium atom, a copper atom, or a cobalt atom are compounds named by replacing the term “iron” contained in the above-exemplified iron compounds with the term “nickel”, “palladium”, “copper” or “cobalt” .
  • the above-mentioned transition metal compounds may be used in combination of two or more thereof.
  • the above-mentioned organoaluminum compound may be a compound known in the art. Examples thereof are the following compounds (Al) to (A3), and a combination of two or more thereof :
  • (A2) a cyclic alumoxane represented by the formula, ⁇ -Al (E 2 )-0- ⁇ e ;
  • (A3) a linear alumoxane represented by the formula, E 3 ⁇ -Al(E 3 )-O- ⁇ f AlE 3 2, wherein E 1 , E 2 and E 3 are independently of one another a hydrocarbyl group, and when plural E 1 S, E 2 S or E 3 S exist, they are the same as, or different from one another;
  • X 2 is a hydrogen atom or a halogen atom, and when plural X 2 S exist, they are the same as, or different from each another;
  • d is a number satisfying 0 ⁇ d ⁇ 3; e is an integer of 2 or more, and preferably an integer of 2 to 40; and f is an integer of 1 or more, and preferably an integer of 1 to 40.
  • the hydrocarbyl group of E 1 , E 2 and E 3 is preferably a hydrocarbyl group having 1 to 8 carbon atoms, and more preferably an alkyl group having 1 to 8 carbon atoms.
  • Examples of the alkyl group of E 1 , E 2 and E 3 are a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a n-pentyl group, and a neopentyl group. Among them, preferred is a methyl group or an isobutyl group.
  • organoaluminum compound (Al) examples include trialkylaluminums such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, and trihexylaluminum; dialkylaluminum chlorides such as dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride and dihexylaluminum chloride; alkylaluminum dichlorides such as methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride and hexylaluminum dichloride; and dialkylaluminum hydrides such as dimethylaluminum hydride, diethylaluminum hydride, dipropylaluminum hydride, diisobutylaluminum;
  • the above-mentioned cyclic alumoxane (A2) and linear alumoxane (A3) can be produced according to various processes. Those processes are not particularly limited, and may be those known in the art. Examples of the process are (i) a process comprising the step of contacting water with a solution of a trialkylaluminum such as trimethylaluminum in a suitable organic solvent such as benzene and an aliphatic hydrocarbon, and (ii) a process comprising the step of contacting a trialkylaluminum such as trimethylaluminum with a crystal water-containing metal salt such as copper sulfate hydrate.
  • the above-mentioned boron compound may be known in the art. Examples thereof are the following compounds (Bl) to (B3) , and a combination of two or more thereof:
  • (B3) a boron compound represented by the formula, (J-H) + (BQ 1 Q 2 Q 3 Q 4 )-; wherein B is a trivalent boron atom; Q 1 , Q 2 , Q 3 and Q 4 are independently of one another a halogen atom, a hydrocarbyl group, a halogenated hydrocarbyl group, a silyl group, a siloxy group, an alkoxy group, an amino group, a substituted amino group, an amide group, or an imide group; G + is an inorganic or organic cation; J is a neutral Lewis base; and (J-H) + is a Broensted acid.
  • Q 1 , Q 2 , Q 3 and Q 4 in the above-mentioned formulas are preferably a halogen atom, a hydrocarbyl group having 1 to 20 carbon atoms, a halogenated hydrocarbyl group having 1 to 20 carbon atoms, a silyl group having 1 to 20 carbon atoms, a siloxy group having 1 to 20 carbon atoms, a C2-2 0 hydrocarbyl group-carrying amino group, a C 2 - 20 hydrocarbyl group-carrying amide group, or a C 2 -2 0 hydrocarbyl group-carrying imide group; more preferably a halogen atom, a hydrocarbyl group having 1 to 20 carbon atoms, or a halogenated hydrocarbyl group having
  • Examples of the above-mentioned boron compound (Bl) are tris (pentafluorophenyl) borane, tris (2,3,5, 6-tetrafluorophenyl) borane, tris (2, 3, 4 , 5-tetrafluorophenyl) borane, tris (3, 4 , 5-trifluorophenyl) borane, tris (2,3, 4-trifluorophenyl) borane, and phenylbis (pentafluorophenyl) borane. Among them, most preferred is tris (pentafluorophenyl) borane .
  • Examples of the inorganic cation of G + in the above-mentioned boron compound (B2) are a ferrocenium cation, an alkyl group-having ferrocenium cation, and a silver cation.
  • An example of the organic cation of G + therein is a triphenylmethyl cation.
  • G + is preferably a carbenium cation, and particularly preferably a triphenylmethyl cation.
  • Examples of (BQ 1 Q 2 Q 3 Q 4 ) " in the above-mentioned boron compound (B2) are tetrakis (pentafluorophenyl) borate, tetrakis (2, 3, 5, 6-tetrafluorophenyl) borate, tetrakis (2, 3, 4, 5-tetrafluorophenyl) borate, tetrakis (3,4, 5-trifluorophenyl) borate, tetrakis (2,3, 4-trifluorophenyl) borate, phenyltris (pentafluorophenyl) borate, and tetrakis (3, 5-bistrifluoromethylphenyl) borate .
  • Examples of the above-mentioned boron compound (B2) are lithium tetrakis (3, 5-bistrifluoromethylphenyl) borate, sodium tetrakis (3, 5-bistrifluoromethylphenyl) borate, potassium tetrakis (3, 5-bistrifluoromethylphenyl) borate, silver tetrakis (pentafluorophenyl) borate, ferrocenium tetrakis (pentafluorophenyl) borate,
  • 1,1' -dimethylferrocenium tetrakis (pentafluorophenyl) borate, tetrabutylphosphponium tetrakis (pentafluorophenyl) borate, tetraphenylphosphponium tetrakis (pentafluorophenyl) borate, tetramethylammonium tetrakis (pentafluorophenyl) borate, trimethylsulphonuim tetrakis (pentafluorophenyl) borate, diphenyliodonium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (pentafluorophenyl) borate, and triphenylcarbenium tetrakis (3, 5-bistrifluoromethylphenyl) borate. Among them, most preferred is triphenylcarbenium tetra
  • Examples of (J-H) + in the above-mentioned boron compound (B3) are a trialkylammonium, an N, N-dialkylanilinium, a dialkylammonium, and a triarylphosphonium.
  • Examples of the (BQ 1 Q 2 Q 3 Q 4 ) " therein are the same as those mentioned above.
  • Examples of the above-mentioned boron compound (B3) are triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (3, 5-bistrifluoromethylphenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethyl-2, 4 , 6-trimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (3, 5-
  • the boron compound is preferably the above-mentioned boron compound (B2) or (B3) , and particularly preferably triphenylcarbenium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, or N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate .
  • the block copolymer of the present invention has a weight-average molecular weight of preferably 1,000 to 10,000,000, more preferably 2,000 to 5,000,000, and most preferably 4,000 to 3,000,000.
  • Each of the blocks (bl), (b2) and (b3) forming the block copolymer of the present invention has a weight-average molecular weight of preferably 95 to 2,000,000, more preferably 1,000 to 1,000,000, and most preferably 2,000 to 500 , 000 .
  • Each of the block copolymer and the blocks (bl), (b2) and (b3) in the present invention has a molecular weight distribution (Mw/Mn) of preferably 1.0 to 50, more preferably 1.0 to 20, and most preferably 1.0 to 10, which is defined as a ratio of a weight-average molecular weight (Mw) to a number-average molecular weight (Mn) .
  • Mw/Mn molecular weight distribution
  • the block copolymer of the present invention preferably has one or more glass transition points, which are preferably -20 0 C or higher, more preferably 20 °C or higher, and most preferably 50°C or higher.
  • the present invention does not have a particular limitation in its method for contacting (i) the diene compound represented by the formula (3), (ii) the olefin, (iii) the transition metal compound, and (iv) the organoaluminum compound and/or boron compound, with one another.
  • the organoaluminum compound is preferably the above-mentioned cyclic alumoxane (A2) , linear alumoxane (A3) , or a combination thereof, from a viewpoint of producing a highly active polymerization catalyst.
  • the organoaluminum compound is preferably the above-mentioned organoaluminum compound (Al) , from the same viewpoint as that mentioned above.
  • the organoaluminum compound is used in amount of generally 0.1 to 10, 000 parts by mol, and preferably 5 to 2, 000 parts by mol, per one part by mol of the transition metal compound.
  • the boron compound is used in amount of generally 0.01 to 100 parts by mol, and preferably 0.5 to 10 parts by mol, per one part by mol of the transition metal compound.
  • Each of the transition metal compound, the organoaluminum compound, and the boron compound may be used as a solution thereof.
  • a solvent for the solution are methylene chloride, chloroform, toluene, pentane, hexane, and heptane. Among them, preferred is methylene chloride, chloroform, or toluene.
  • a solution of the transition metal compound has a concentration of generally 0.01 to 500 ⁇ mol/L, preferably 0.05 to 100 ⁇ mol/L, and more preferably 0.05 to 50 ⁇ mol/L.
  • a solution of the organoaluminum compound has a concentration of generally 0.01 to 10,000 / z mol/L, preferably 0.1 to 5,000 ⁇ mol/L, and more preferably 0.1 to 2,000, in terms of an amount of an aluminum atom contained in the solution.
  • a solution of the boron compound has a concentration of generally 0.01 to 500 //mol/L, preferably 0.05 to 200 ⁇ mol/L, and more preferably 0.05 to 100 /x mol/L.
  • the above-mentioned polymerization catalyst may be combined with a carrier or a support comprising particles of an inorganic or organic compound.
  • the carrier or the support may be known in the art.
  • the inorganic compound are silica gel and alumina
  • an example of the organic compound is a styrene unit-containing polymer.
  • Examples of a polymerization method in the present invention are a gas-phase polymerization method, a bulk polymerization method, and a solution or suspension polymerization method using a suitable polymerization solvent, which are a batch-wise polymerization method or a continuous polymerization method.
  • the polymerization solvent is a solvent non-deactivating a polymerization catalyst.
  • the solvent are a hydrocarbon solvent such as benzene, toluene, pentane, hexane, heptane, and cyclohexane; and a halogenated solvent such as dichloromethane and chloroform.
  • a polymerization temperature in the present invention is generally -100 to 250°C, and preferably -50 to 200°C.
  • a polymerization time is generally one minute to 72 hours.
  • the process of the present invention may use a chain transfer agent such as hydrogen in order to regulate a molecular weight of a random copolymer produced.
  • a chain transfer agent such as hydrogen
  • the present invention is explained with reference to the following Examples, which do not limit the scope of the present invention.
  • Example 1 There were put 6.6 mg (0.01 mmol) of chloro (methyl) [N, N ' - (1, 2-dihydroacenaphthylene-l, 2- diylidene) bis (2, 6-diisopropylaniline- /c N) ] palladium
  • the first reaction mixture was cooled down to -20°C, and 50 mL (0.4 mmol) of 1-hexene (olefin) and 0.25 mL of methylene chloride were added thereto. The mixture was stirred for 36 hours, thereby polymerizing the total amount of 1-hexene, and obtaining a second reaction mixture.
  • the second reaction mixture was poured into methanol, and the precipitated polymer was filtered off and then dried, thereby obtaining a block copolymer comprising a homopolymer block (bl-1) of 2, 2-diallylindane-l, 3-dione containing polymerization units represented by the formula (1), and a homopolymer block (b3-l) of 1-hexene.
  • the block copolymer had a number-average molecular weight (Mn) of 14,300; and a molecular weight distribution (Mw/Mn) of 1.46.
  • the above-mentioned first reaction mixture was poured into methanol, and the precipitated polymer was filtered off and then dried, thereby obtaining a homopolymer of 2, 2-diallylindane-l, 3-dione .
  • the homopolymer had a number-average molecular weight (Mn) of 9,300; and a molecular weight distribution (Mw/Mn) of 1.22.
  • the second reaction mixture was poured into methanol, and the precipitated polymer was filtered off and then dried, thereby obtaining 257 mg of a block copolymer comprising a homopolymer block (bl-1) of 2,2-dimethyl-5-allyl-5- ( (2E) -2-butenyl) -1,3-dioxane containing polymerization units represented by the formula (1) , and a homopolymer block (b2-l) of 2, 2-dimethyl-5, 5-diallyl-l, 3-dioxane containing polymerization units represented by the formula (1) .
  • a block copolymer comprising a homopolymer block (bl-1) of 2,2-dimethyl-5-allyl-5- ( (2E) -2-butenyl) -1,3-dioxane containing polymerization units represented by the formula (1) , and a homopolymer block (b2-l) of 2, 2-dimethyl-5, 5-diallyl-l, 3-dio
  • the block copolymer was soluble in chloroform, methylene chloride or tetrahydrofuran, and was insoluble in hexane or methanol.
  • the block copolymer had a number-average molecular weight (Mn) of 22,800; a molecular weight distribution (Mw/Mn) of 1.28; and a glass transition point of 80°C in a region of -20°C to 180°C. All the polymerization units contained in the block copolymer and represented by the formula (1) had a trans-form configuration represented by the formula (2) .
  • the homopolymer had a number-average molecular weight (Mn) of 12,400; and a molecular weight distribution (Mw/Mn) of 1.13.
  • the above-mentioned glass transition point was measured according to a differential scanning calorimetry (DSC) using an equipment, SSC-5200, manufactured by Seiko Instruments & Electronics Ltd. under the following conditions: heating from 25 °C to 180 °C at a temperature-increasing rate of 10°C /minute, and keeping at 180°C for 5 minutes; then, cooling from 180 °C to -20 °C at a temperature-decreasing rate of 20°C /minute, and keeping at -20°C for 5 minutes; and then, - measuring under heating from -20 0 C to 180 0 C at a temperature-increasing rate of 10°C/minute.
  • DSC differential scanning calorimetry
  • the filtrate was cooled down to -20°C, and 117 mg (0.56 mmol) of 5, 5-diallylbarbituric acid (compound represented by the formula (3) ) was added thereto.
  • the obtained suspension was reacted at -20 °C for 2 days, thereby obtaining a reaction mixture.
  • the reaction mixture was filtered to remove unreacted 5, 5-diallylbarbituric acid, and then, 5 mL of hexane was added to the obtained filtrate, thereby obtaining a solution.
  • the solution was cooled down from -20°C to -40°C over one hour.
  • the solution was allowed to stand at -40°C for four days, thereby obtaining 78 mg (0.046 mmol) of a red solid compound.
  • the red solid compound contained the following tree components (i) to (iii) in the following ratio, those three components being bonded to one another: (i) one molecule of 5, 5-diallylbarbituric acid, (ii) one equivalent of a cationic complex of the transition metal compound, and (iii) one equivalent of an anion of the boron compound.
  • a polymerization proportion (conversion of polymerization) of 5, 5-diallylbarbituric acid was 54%.
  • the obtained reaction mixture (solution) was poured into methanol, and the precipitate was filtered off and then dried under a reduced pressure, thereby obtaining a block copolymer comprising a homopolymer block (bl-1) of 5, 5-diallylbarbituric acid containing polymerization units represented by the formula (1) , and a homopolymer block (b2-l) of 1-hexene.
  • the block copolymer had a number-average molecular weight (Mn) of 8,200; a molecular weight distribution (Mw/Mn) of 1.12; and 1% by mol of polymerization units of 5, 5-diallylbarbituric acid represented by the formula (1), and 99% by mol of polymerization units of 1-hexene, the total of both units being 100% by mol.
  • the above-mentioned amount of polymerization units was measured according to a 1 H-NMR method using an equipment, LA-500, manufactured by JEOL LTD, under the following conditions :
  • the random copolymer of the present invention can be molded according to an extrusion molding method or an injection molding method. Those methods may be known in the art.
  • the extrusion molding method are (1) an inflation molding method comprising the steps of (1-1) extruding a molten resin through a circular die, thereby forming an extruded product,

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Abstract

L'invention porte sur un copolymère à blocs comprenant un bloc (b1) et un bloc (b2) et/ou (b3). Le bloc (b1) contient une unité de polymérisation représentée par la formule définie (1) ; le bloc (b2) contient une unité de polymérisation représentée par celle-ci et présentant des propriétés différentes de celles de (b1) ; et le bloc (b3) contient une unité de polymérisation d'une oléfine, la formule (1) étant issue d'un composé diènique représenté par la formule définie (3) telle que le 2,2-diméthyl-5,5-diallyl-1,3-dioxane. L'invention porte également sur un procédé de fabrication d'un copolymère à blocs comprenant l'étape de fabrication des blocs (b1) et (b2) et/ou (b3).
PCT/JP2008/066619 2007-09-18 2008-09-09 Copolymère à blocs et son procédé de fabrication WO2009038031A1 (fr)

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Citations (2)

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US7956145B2 (en) * 2007-02-28 2011-06-07 Sumitomo Chemical Company, Limited Diene polymer and process for producing the same
US7964691B2 (en) * 2007-02-28 2011-06-21 Sumitomo Chemical Company, Limited Olefin-diene copolymer and process for producing the same
US7943715B2 (en) * 2007-02-28 2011-05-17 Sumitomo Chemical Company, Limited Diene polymer and process for producing the same
US20080221288A1 (en) * 2007-02-28 2008-09-11 Sumitomo Chemical Company, Limited Diene polymer and process for producing the same

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US20050107559A1 (en) * 2003-11-14 2005-05-19 Coates Geoffrey W. Ethylene-C4-C20-alkene copolymers
WO2007023618A1 (fr) * 2005-08-26 2007-03-01 Sumitomo Chemical Company, Limited Homopolymere et copolymere, et leur procede de fabrication

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LI-MING TANG, YI-QUN DUAN, LI PAN, YUE-SHENG LI,: "Copolymerization of ethylene and cyclopentene with bis(beta-enaminoketonato) titanium complexes", JOURNAL OF POLYMER SCIENCE PART A: POLYMER CHEMISTRY, vol. 43, no. 8, 4 March 2005 (2005-03-04), Wiley InterScience, pages 1681 - 1689, XP002506066 *
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