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WO2009038006A1 - Copolymère statistique et son procédé de fabrication - Google Patents

Copolymère statistique et son procédé de fabrication Download PDF

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Publication number
WO2009038006A1
WO2009038006A1 PCT/JP2008/066362 JP2008066362W WO2009038006A1 WO 2009038006 A1 WO2009038006 A1 WO 2009038006A1 JP 2008066362 W JP2008066362 W JP 2008066362W WO 2009038006 A1 WO2009038006 A1 WO 2009038006A1
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group
atom
methyl
ring
palladium
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English (en)
Inventor
Kohtaro Osakada
Daisuke Takeuchi
Sehoon Park
Makoto Uemura
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Sumitomo Chemical Co Ltd
Tokyo Institute of Technology NUC
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Sumitomo Chemical Co Ltd
Tokyo Institute of Technology NUC
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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
    • C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F36/02—Homopolymers and 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
    • C08F36/20—Homopolymers and 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
    • 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

Definitions

  • the present invention relates to a random copolymer comprising polymerization units derived from each of two or more kinds of diene compounds , and a process for producing a random copolymer.
  • the present invention has an object to provide (i) a random copolymer superior in its heat resistance, whose main chain comprises two or more kinds of polymerization units, each of those polymerization units containing a cyclopentane ring structure and being arranged randomly, and (ii) a process producing a random copolymer.
  • the present invention is a random copolymer comprising two or more kinds of polymerization units represented by the following formula ( 1 ) :
  • 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 ,
  • a 6 , A 7 , A 8 , A 9 , A 10 and A 11 are independently of one another 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 amino group, a substituted amino group, an amide group, an imide group or an alkylthio group, and A 3 and A 4 and/or A 5 and A 6 may be linked with each other to form a ring; m is 0 or 1; and n is an integer of 1 to 20.
  • the present invention is a process for producing the above-mentioned random copolymer, comprising the step of copolymerizing two or more kinds of diene compounds represented by the following formula ( 3 ) :
  • 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
  • (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
  • 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,
  • Examples of the amide group of A 1 to A 11 in the formulas (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 aralkyloxycarbony1 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.
  • Examples of the aralkyl group of Y 1 and Y 2 in the formulas (1) and (3) are a benzyl group, a phenethyl group, a 2-methylbenzyl group, a 3-methylbenzyl group, a 4-methylbenzyl group, a 2,6-dimethylbenzyl group, and a 3,5-dimethylbenzyl group.
  • ( 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.
  • Examples of the siloxy group of Y 1 and Y 2 in the formulas (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-dimethyl
  • 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
  • Examples of the amide group of Y 1 and Y 2 in the formulas (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 group, an N-isopropylethanamide group, an N-isobutylethanamide group, an N-tert-butylethanamide group, and an N-neopentylethanamide group.
  • Examples of 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 alkylthioxycarbony1 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 have a substituent independently of each other.
  • substituents are a hydrogen atom, a halogen atom, 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, an amide group, an imide group, a thiol group, an alkylthio group, an aralkylthio group, an arylthio group, an alkylthioxycarbonyl group, and an arylthioxycarbonyl 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
  • N-methylpyrazolidine ring an N-methylmorpholine ring, an N,N' -dimethylpyrazolidine ring, an N-methylimidazolidine ring, an N,N' -dimethylimidazolidine ring, an N-methylpyrrolidine ring, an N-methylpiperidine ring, an N-methylhexahydropyrimidine ring, an
  • N,N' -dimethylhexahydropyrimidine ring an N-methylpiperadine ring, an N,N' -diethylpiperadine ring, an N-ethylpyrazolidine ring, an N,N' -diethylpyrazolidine ring, an N-ethylimidazolidine ring, an N,N' -diethylimidazolidine ring, an N-ethylpyrrolidine ring, an N-ethylpiperidine ring, an N-ethylpiperadine ring, an N-ethylhexahydropyrimidine ring, an N,N' -diethylhexahydropyrimidine ring, an N,N ' -diethylpiperadine ring, an N-phenylpyrazolidine ring, an N,N' -diphenylpyrazolidine ring, an N-phenylimidazolidine ring,
  • N-methylpiperadin-2,5-dione ring an N-methyl-l,2,3,4-tetrahydroquinolin-3-one ring, an N-methyl-1, 2 , 3 , 4-tetrahydroisoquinolin-l-one ring, and an N-methyl-1 , 2 , 3 , 4-tetrahydro-l-isoquinolin-3-one ring; imide group-carrying rings such as a hexahydropyrimidin-2,4,6-trione ring, an N-methylhexahydropyrimidin-2,4,6-trione ring, an N,N' -dimethylhexahydropyrimidin-2 , 4 , 6-trione ring, an N-ethylhexahydropyrimidin-2,4,6-trione ring, an N,N' -diethylhexahydropyrimidin-2, 4, 6-trione ring, an N-phenylhexahydropyrimidin
  • hydrocarbon rings preferred are hydrocarbon rings, ketone group-carrying rings, ether bond-carrying rings, ester bond-carrying rings, amide group-carrying rings, imide group-carrying rings, or urea bond-carrying rings.
  • Compounds represented by the formula ( 3 ) may be known in the art. Examples thereof are Meldrum's acid derivatives such as 5,5-diallyl Meldrum's acid, 5-allyl-5-( (2E)-2-butenyl) Meldrum's acid, 5-allyl-5-( (2E) -2-pentenyl) Meldrum's acid, 5-allyl-5-( (2E) -2-hexenyl) Meldrum's acid, 5-allyl-5-( (2E) -2-heptenyl) Meldrum's acid, 5-allyl-5-((2E)-2-octenyl) Meldrum's acid, 5-allyl-5-( (2E) -2-nonenyl) Meldrum's acid, 5-allyl-5-( (2E) -2-decenyl) Meldrum's acid, 5-allyl-5-( (2E) -2-undecenyl) Meldrum's acid, and 5-allyl-5- ( ( 2E) -2-dodecenyl)
  • N-alkylpropanediamide derivatives such as
  • N-methyl-2-allyl-2-((2E)-2-butenyl )propanediamide N-dialkylpropanediamide derivatives such as
  • N.N' -dialkylpropanediamide derivatives such as
  • N,N,N' -trialkylpropanediamide derivatives such as N,N,N ' -trimethyl-2, 2-diallylpropanediamide and
  • N-aralkypropanediamide derivatives such as N-benzyl-2 , 2-diallylpropanediamide and N-benzyl-2-aryl-2- ( ( 2E) -2-butenyl)propanediamide;
  • N,N' -diaralkylpropanediamide derivatives such as
  • N,N' -dibenzyl-2 2-diallylpropanediamide and N.N' -dibenzyl-2-aryl-2- ( (2E) -2-butenyl )propanediamide; barbituric acid derivatives such as 5, 5-diallylbarbituric acid and 5-ally-5- ( (2E) -2-butenyl)barbiturc acid;
  • N-alkylbarbituric acid derivatives such as
  • N,N' -dialkylbarbiturc acid derivatives such as
  • N,N ' -diethyl-5.5-diallylbarbituric acid N,N'-di-n-propyl-5, 5-diallylbarbituric acid.
  • N,N'-di-n-hexyl-5, 5-diallylbarbituric acid N.N'-dicyclopentyl-5,5-diallylbarbituric acid
  • N,N'-dimethyl-5-ally-5-((2E)-2-butenyl)barbituric acid N,N'-dimethyl-5-ally-5-((2E)-2-pentenyl) barbituric acid
  • N,N'-dimethyl-5-ally-5-( (2E) -2-hexenyl) barbituric acid N,N' -dimethyl-5-ally-5-( (2E) -2-heptenyl) barbituric acid, N,N'-dimethyl-5-ally-5-((2E)-2-octenyl) barbituric acid, N,N'-dimethyl-5-ally-5-( (2E) -2-nonenyl) barbituric acid, N,N' -dimethyl-5-ally-5-( (2E) -2-decenyl) barbituric acid, N,N' -dimethyl-5-ally-5-( (2E) -2-undecenyl) barbituric acid, and N,N' -dimethyl-S-ally-5- ( (2E) -2-dodecenyl) barbituric acid; N-arylbarbituric acid derivatives such as N-phenyl-5, 5-dial
  • N-methyl-4-allyl-4- ( ( 2E ) -2-butenyl )pyrazolidine-3 5-dione; N,N' -dialkylpyrazolidine-3, 5-dione derivatives such as N 1 N 1 -dimethyl-4,4-diallylpyrazolidine-3,5-dione , N,N' -diethyl-4 , 4-diallylpyrazolidine-3 , 5-dione , N,N' -di-n-propyl-4 , 4-diallylpyrazolidine-3 , 5-dione, N,N' -diisopropyl-4 , 4-diallylpyrazolidine-3 , 5-dione, N,N' -di-n-butyl-4, 4-diallylpyrazolidine-3, 5-dione, N,N f -diisobutyl-4 , 4-diallylpyrazolidine-3 , 5-dione, 5-dione, N,N
  • N,N' -di-n-hexyl-4 4-diallylpyrazolidine-3, 5-dione, and N,N' -dicyclohexyl-4 , 4-diallylpyrazolidine-3, 5-dione;
  • N-arylpyrazolidine-3, 5-dione derivatives such as N-phenyl-4 , 4-diallylpyrazolidine-3 , 5-dione, N-phenyl-4-ally-4-((2E)-2-butenyl)pyrazolidine-3,5-dione , N- ( 2-naphthyl) -4 , 4-diallylpyrazolidine-3,5-dione, and N- ( 2-anthracenyl ) -4 , 4-diallypyrazolidine-3 , 5-dione;
  • N,N' -diarylpyrazolidine-3, 5-dione derivatives such as N,N' -diphenyl-4 , 4-diallylpyrazolidine-3, 5-dione, N,N' -diphenyl-4-ally-4-((2E)-2-butenyl )pyrazolidine-3,5- dione , N,N'-diphenyl-4-ally-4-( ( 2E) -2-pentenyl)pyrazolidine-3, 5- dione,
  • N-aralkylpyrazolidine-3,5-dione derivatives such as
  • N,N' -diaralkylpyrazolidine-3, 5-dione derivatives such as
  • 9-allyl-9- ( (2E) -2-tridecenyl) -fluorene particularly preferred are 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 , N,N' -diarylpyrazolidine-3, 5-dione derivatives, or fluorene derivatives .
  • barbituric acid derivatives particularly preferred are barbituric acid derivatives, N-alkylbarbituric acid derivatives, N,N' -dialkylbarbiturc acid derivatives, N-arylbarbituric acid derivatives, N,N'
  • Random copolymer of the present invention are a random copolymer of 5,5-diallyl Meldrum's acid and 2 , 2-dimethyl-5, 5-diallyl-l , 3-dioxane, a random copolymer of 5,5-diallyl Meldrum's acid and dimethyl 2 , 2-diallylmalonate, a random copolymer of 5,5-diallyl Meldrum's acid and 2, 2-diallyl-1, 3-dioxane, a random copolymer of 5,5-diallyl Meldrum's acid and 5, 5-diallylbarbituric acid, a random copolymer of 5,5-diallyl Meldrum' s acid and N,N' -dimethyl-4 , 4-diallylpyrazolidine-3, 5-dione, a random copolymer of 5,5-diallyl Meldrum's acid and 9,9-diallylfluorene, a random copolymer of 2, 2-dimethy1-5, 5-
  • one or more kinds of polymerization units among two or more kinds of polymerizationunits , whicharecontainedin therandomcopolymer of the present invention, and 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 random 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 with 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 with 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 calculated from the following formula:
  • proportion (%) of polymerization units having trans-form configuration area of peak (i) X 100/ [area of peak (i) + area of peak ( ⁇ )].
  • the random copolymer of the present invention may comprise olefin units besides two or more kinds of polymerization units represented by the formula (1).
  • olefin unit means a polymerization unit of an olefin.
  • the olefin unit has a chemical structure formed by a cleavage-polymerization reaction of a carbon-to-carbon double bond contained in an olefin, and is the same as a polymerization unit contained in an addition polymer of an olefin, such as an ethylene unit (-CH 2 CH 2 -) contained in an addition polymer of ethylene, polyethylene.
  • olefin examples include linear olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene and 1-decene; branched olefins such as 3-methyl-l-butene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, and vinylcyclohexane; and cyclic olefins such as cyclopropene , cyclobutene, cyclopentene , cyclohexene, cycloheptene , norbornene, limonene, a -pinene, ⁇ -pinene, camphene, cis-cyclooctene, trans-cyclooctene, cis-cyclononene, trans-cyclononene, cis-cyclodecene, and trans-cyclode
  • an olefin having 2 to 20 carbon atoms preferred is an olefin having 2 to 8 carbon atoms , and particularly preferred is ethylene, propylene, 1-butene, 1-pentene, cyclopentene, 1-hexene, 4-methyl-1-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.
  • conjugated dienes such as butadiene and isoprene
  • linear non-conjugated dienes such as 1, 4-pentadiene and 1 , 5-hexadiene
  • cyclic non-conjugated dienes such as cyclopentadiene.
  • the olefin units are contained in an amount of preferably 0.1 to 99.9% by weight , in order to, for example, improve processability of the random copolymer, the total amount of the olefin units and two or more kinds of polymerization units represented by the formula (1) being 100% by weight.
  • the random copolymer of the present invention can be produced by copolymerization of two or more kinds of diene compounds represented by the formula (3) .
  • the copolymerization 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, namely, is carried out by contacting the polymerization catalyst with two or more kinds of diene compounds represented by the formula ( 3 ) .
  • the transition metal compound may be known in the art .
  • Examples thereof are transition metal compounds containing one or more atoms selected from the group consisting of an iron atom, a cobalt atom, a nickel atom, a palladium atom and a cupper atom; transition metal compounds represented by the following respective formulas [I], [II] and [III]; and a combination of two or more of those transition metal compounds , the formula ⁇ II] being a subordinate position concept of the formula [I]:
  • 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
  • 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
  • M 1 in the formulas [I] and [II] is preferably a nickel atom or a palladium atom.
  • M 1 in the formula [III] is preferably an iron atom or a cobalt atom.
  • alkyl group, aralkyl group, aryl group, alkoxy group, aralkyloxy group and aryloxy group of R 3 and R 4 in the formulas [I] , [II] and [III] may have a substituent such as a halogen atom, an alkoxy group, an aryloxy group, an aralkyloxy group , a nitro group, an amino group, an amide group , an imide group, a sulfonyl group and an alkylthio group.
  • alkyl group, aralkyl group, aryl group, alkoxy group, aralkyloxy group, aryloxy group, acyl group, an alkoxycarbonyl group, an aralkyloxycarbonyl group, an aryloxycarbonyl group, an amino group, a substituted amino group, an amide group and alkylthio group of R 5 to R 21 in the formulas [I], [II] and [III] 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 , an imide group , a sulfonyl group and an alkylthio group .
  • Examples of the 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.
  • alkyl group having 1 to 16 carbon atoms 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.
  • aralkyl group of R 3 to R 21 in the formulas [I], [II] and [III] are a benzyl group, a ( 2-methylphenyl)methyl group, a ( 3-methylphenyl)methyl group, a (4-methylphenyl)methyl group, a (2,3-dimethylphenyl)methyl group , a ( 2 , 4-dimethylphenyl)methyl group , a (2,5-dimethylphenyl)methyl group , a ( 2 , 6-dimethylphenyl)methyl group , a (3,4-dimethylphenyl)methyl group , a (3,5-dimethylphenyl)methyl group , a (2,3,4-trimethylphen
  • Examples of the aryl group of R 3 to R 21 in the formulas [I], [II] and [III] are a 3-methylphenyl group, a 4-isopropylphenyl group, a 4-tert-butylphenyl group, a 2,3-dimethylphenyl group, a 2 , 4-dimethylphenyl group, a 2, 5-dimethylphenyl group, a 3, 4-dimethylphenyl group, a 3, 5-dimethylphenyl group, a 3,6-dimethylphenyl group, a 2, 6-di-tert-butylphenyl group, amesityl group, a phenyl group , a 2-methylphenyl group, a 2-ethylphenyl group, a 2-n-propylphenyl group, a 2-isopropylphenyl group, a 2-n-butylphenyl group, a 2-isobutylphenyl group, a 2-n-he
  • 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-di
  • 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.
  • alkoxy group having 1 to 16 carbon atoms 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 (2-methylphenyl)methoxy group, a ( 3-methylphenyl)methoxy group, a (4-methylphenyl)methoxy group, a
  • (2,3,5,6-tetramethylphenyl)methoxy group a (pentamethylphenyl)methoxy group, an (ethylphenyl)methoxy group, a (n-propylphenyl)methoxy group, an (isopropylphenyl)methoxy group, a (n-butylphenyl)methoxy group, a (sec-butylphenyl)methoxy group, a ( tert-butylphenyl)methoxy group, a (n-hexylphenyl)methoxy group, a (n-octylphenyl)methoxy group, a (n-decylphenyl)methoxy group, a naphthylmethoxy group, and an anthracenylmethoxy group.
  • preferred is an aralkyloxy group having 7 to 20 carbon atoms , and more preferred is a benzyloxy group.
  • 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-4-methylphenoxy group, a 2-tert-butyl-5-methylphenoxy group, a 2-tert-butyl-6-methylphenoxy group, a
  • 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.
  • 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-butylamino 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; and cyclic alkylamino groups such as an N,N-dicyclohexyla
  • 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 aliphatic 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 methylene group, an ethane-l,2-diyl group, a propane-l,3-diyl group, a propane-l,2-diyl group, a butane-l,2-diyl group, a butane-l,3-diyl group, a butane-1 , 4-diyl group, a pentane-1 , 2-diyl group, a pentane-l,3-diyl group, a pentane-1 , 4-diyl group, a pentane-1, 5-diyl group, an ethylene-1, 2-diyl group, a cyclohexane-1, 2-diyl group, a cyclohexane-1 , 3-diyl
  • 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-1, 2-diyl group, a 3-n-propylbenzene-l,2-diyl group, a 4-n-propylbenzene-l, 2-diyl group, a
  • transition metal compound represented by the formula [I] or [II] wherein M 1 is a palladium atom, are chloro(methyl) [N.N 1 - (ethane-1 , 2-diylidene)bis (aniline- /CN) ]palladium, chloro(methyl) [N,N 1 - (ethane-1,2-diylidene)bis (2-methylaniline- /CN) ]palladium, chloro(methyl) [N,N 1 - (ethane-1,2-diylidene)bis (2-ethylaniline- KN) ]palladium, chloro(methyl) [N, N 1 - ( ethane-1 , 2-diylidene)bis (2-n-propylaniline- KN) ]palladium, chloro(methyl) [N,N 1 - (ethane-1, 2-diylidene)bis (2-isopropylaniline- /CN) ]
  • 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 )-O- ⁇ ⁇ ;
  • (A3) a linear alumoxane represented by the formula, E 3 ⁇ -A1(E 3 ) -0- ⁇ f AlE 3 2 , whereinE 1 , E 2 andE 3 are independentlyof one another ahydrocarbyl 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 -5 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.
  • a methyl group or an isobutyl group 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;
  • 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.
  • a trialkylaluminum such as trimethylaluminum
  • 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:
  • (B2) a boron compound represented by the formula, G + (BQ 1 Q 2 Q 3 Q 4 ) " ; and (B3) a boron compound represented by the formula, (J-H) + (BQ 1 Q 2 Q 3 Q 4 ) " ;
  • 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
  • (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 C2-20 hydrocarbyl group-carrying amide group, or a C2-20 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 1 to 20 carbon atoms; further preferably a fluorinated Ci_ 2 o hydrocarbyl group containing one or more fluorine atoms ; and particularly preferably a fluorinated C 6 -2o aryl group
  • 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' -dimethyIferrocenium 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.
  • triphenylcarbenium tetrakis (pentafluorophenyl )borate is triphenylcarbenium tetrakis (pentafluorophenyl )borate .
  • 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-bistrifluoromethylphenyl)borate, diisopropylammonium tetrakis (pentafluorophenyl)borate, dicyclohexylammonium tetrakis (pentafluorophenyl)borate, triphenylphosphonium tetrakis (pentafluorophenyl)borate, tri(methylphenyl) phosphonium tetrakis (pentafluorophenyl)borate, and tri(dimethylphenyl )phosphonium tetrakis (pentafluorophenyl) borate.
  • tri(n-butyl)ammonium tetrakis (pentafluorophenyl)borate, or N,N-dimethylanilinium tetrakis (pentafluorophenyl)borate .
  • 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 random copolymer of the present invention has a weight-average molecular weight (Mw) 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.
  • Mw weight-average molecular weight
  • the random copolymer of the present invention has a molecular weight distribution (Mw/Mn) of preferably 1.0 to 100, more preferably 1.0 to 50, and most preferably 1.0 to 20.
  • the random copolymer of the present invention preferably has a glass-transition point, preferably one or more glass-transition points of -20 "C or higher, more preferably one or more glass-transition points of 20 1 C or higher, and most preferably one or more glass-transition points of 50 1 C or higher.
  • Examples of a method for feeding two or more kinds of diene compounds represented by the formula ( 3 ) to a polymerization system such as a polymerization reactor, in order to produce the random copolymer of the present invention are (1) a method comprising the step of feeding those two or more kinds of diene compounds separately however simultaneously to a polymerization reactor, and (2) a method comprising the step of feeding a mixture of those two or more kinds of diene compounds thereto.
  • the random copolymer of the present invention cannot be produced by a method comprising the steps of (i) feeding a first kind of diene compound to a polymerization reactor, thereby polymerizing the first kind, of diene compound to form a homopolymer thereof, and (ii) feeding a second kind of diene compound thereto, thereby polymerizing the second kind of diene compound completely in the presence of the above-produced homopolymer, which results in a production of a blend of two kinds of homopolymers , because the step (ii) also forms a homopolymer of the second kind of diene compound.
  • 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 a viewpoint of producing a highly active polymerization catalyst .
  • 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 Mmol/L, preferably 0.05 to 100 /imol/L, and more preferably 0.05 to 50 Mraol/L.
  • a solution of the organoaluminum compound has a concentration of generally 0.01 to 10,000 Mmol/L, preferably 0.1 to 5,000 H 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 Umol/L, preferably 0.05 to 200 Umol/L, and more preferably 0.05 to 100 Mmol/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 25OtD, 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.
  • the reaction mixture was poured into methanol, and the precipitated copolymer was filtered off and then dried, thereby obtaining a random copolymer of 2, 2-dimethyl-5, 5-diallyl-l, 3-dioxane with 5,5-diallyl Meldrum's acid.
  • the random copolymer had a number-average molecular weight (Mn) of 3,600; a molecular weight distribution (Mw/Mn) of 1.70; 75% by mol of 2, 2-dimethyl-5, 5-diallyl-l, 3-dioxane units represented by the formula (1), and 25% by mol of 5,5-diallyl Meldrum's acid units represented thereby, the total of both units being 100% by mol; and 87% by mol of a trans-form regarding 2, 2-dimethyl-5, 5-diallyl-l, 3-dioxane units, and 100% by mol of a trans-form regarding 5,5-diallyl Meldrum's acid units, in view of its relative configuration between A 7 and A 8 .
  • Mn number-average molecular weight
  • Mw/Mn molecular weight distribution
  • DG-980-50 degasser
  • PU-980 pump
  • AS-950 auto-sampler
  • CO-966 column oven
  • RI-930 RI detector
  • UV-975 UV detector
  • the above-mentioned amount of the polymerization units represented by the formula ( 1 ) was measured according to a 1 H-NMR method under the following conditions using an equipment , LA-500, manufactured by JEOL LTD:
  • Example 1 was repeated except that (1) 0.156 g (0.7 mmol) of 5,5-diallyl Meldrum's acid was changed to 0.172 g (0.7 mmol) of 9 , 9-diallylfluorene (compound represented by the formula
  • the random copolymer had a number-average molecular weight (Mn) of 8,400; a molecular weight distribution (Mw/Mn) of 1.94; 88% by mol of 2 , 2-dimethyl-5, 5-diallyl-l , 3-dioxane units represented by the formula (1), and 12% by mol of 9 , 9-diallylfluorene units represented thereby, the total of both units being 100% by mol; and a glass-transition point of 63C in a range of 0 to 200 1 C.
  • the above-mentioned glass-transition point was measured according to a differential scanning calorimetry (DSC) using an equipment, SSC-5200, manufactured by Seiko
  • Example 3 Example 1 was repeated except that (1) 0.156 g (0.7 mmol ) of 5,5-diallyl Meldrum's acid was changed to 0.091 g (0.4 mmol) of 2, 2-diallylindan-l, 3-dione (compound represented by the formula (3)). (2) 0.137 g (0.7 mmol) of 2 , 2-dimethyl-5, 5-diallyl-l , 3-dioxane (compound represented by the formula (3)) was changed to 0.079 g (0.4 mmol) thereof, and (3) the agitation temperature was changed from a room temperature to -10 1 C, and (4) the agitation time was changed from 6 hours to 24 hours, thereby obtaining a reaction mixture in a solution state.
  • the reaction mixture was analyzed to show that 2, 2-diallylindan-l, 3-dione was copolymerized in a polymerization rate of 58%, and 2, 2-dimethyl-5 , 5-diallyl-l, 3-dioxane was copolymerized in a polymerization rate of 71%.
  • the random copolymer had a number-average molecular weight (Mn) of 10,000; a molecular weight distribution (Mw/Mn) of 1.21; 48% by mol of 2, 2-diallylindan-l, 3-dione units represented by the formula (1), and 52% by mol of 2, 2-dimethyl-5 , 5-diallyl-l , 3-dioxane units represented thereby, the total of both units being 100% by mol; 100% by mol of a trans-form regarding the 2, 2-diallylindan-l, 3-dione units, and 89% by mol of a trans-form regarding the
  • the random copolymer of the present invention can be molded according to an extrusion molding method or an injection molding method.
  • 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, (1-2) blowing the extruded product into a cylindrical film or sheet , and ( 1-3 ) rewinding the film or sheet , ( 2 ) a T-die molding method comprising the steps of (2-1) extruding a molten resin through a linear die, thereby forming a film or sheet, and (2-2) rewinding the film or sheet, and (3) a calender molding method.

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  • Organic Chemistry (AREA)
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Abstract

L'invention porte sur un copolymère statistique renfermant au moins deux sortes d'unités de polymérisation représentées par la formule définie (1), la formule (1) étant dérivée d'un composé diénique représenté par la formule définie (3), tel que le 2,2-diméthyl-5,5-diallyl-1,3-dioxane ; et sur un procédé de fabrication d'un copolymère statistique comportant l'étape de copolymérisation d'au moins deux sortes des composés diéniques.
PCT/JP2008/066362 2007-09-18 2008-09-04 Copolymère statistique et son procédé de fabrication Ceased WO2009038006A1 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Non-Patent Citations (4)

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Title
FUJITA MASAYUKI ET AL: "SYNTHESIS AND CHARACTERIZATION OF ALTERNATING AND MULTIBLOCK COPOLYMERS FROM ETHYLENE AND CYCLOPENTENE", MACROMOLECULES, ACS, WASHINGTON, DC, US, vol. 35, no. 26, 17 December 2002 (2002-12-17), pages 9640 - 9647, XP008077458, ISSN: 0024-9297 *
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 *
SEHOON PARK, DAISUKE TAKEUCHI, AND KOHTARO OSAKADA: "Pd-complex-promoted cyclopolymerization of functionalized alpha,omega-dienes and copolymerization with ethylene to afford polymers with cyclic repeating units", J. AM. CHEM. SOC., vol. 128, no. 11, 22 February 2006 (2006-02-22), American Chemical Society, pages 3510 - 3511, XP002506067 *
TAKESHI OKADA, SEHOON PARK, DAISUKE TAKEUCHI, KOHTARO OSAKADA,: "Pd-catalyzed polymerization of dienes that involves chain-walking isomerization of the growing polymer end: synthesis of polymers composed of polymethylene and five-membered-ring units", ANGEWANDTE CHEMIE INTERNATIONAL EDITION, vol. 46, no. 32, 12 July 2007 (2007-07-12), WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim, pages 6141 - 6143, XP002506068 *

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