+

WO2009038031A1 - Block copolymer and production process thereof - Google Patents

Block copolymer and production process thereof Download PDF

Info

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
Authority
WO
WIPO (PCT)
Prior art keywords
group
methyl
atom
ring
block
Prior art date
Application number
PCT/JP2008/066619
Other languages
French (fr)
Inventor
Kohtaro Osakada
Daisuke Takeuchi
Sehoon Park
Takeshi Okada
Makoto Uemura
Original Assignee
Sumitomo Chemical Company, Limited
Tokyo Institute Of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sumitomo Chemical Company, Limited, Tokyo Institute Of Technology filed Critical Sumitomo Chemical Company, Limited
Publication of WO2009038031A1 publication Critical patent/WO2009038031A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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,

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

A block copolymer comprising a block (b1) and a block (b2) and/or (b3), wherein (b1) contains a polymerization unit represented by the defined formula (1), (b2) contains a polymerization unit represented thereby, and has attributes different from those of (b1), and (b3) contains a polymerization unit of an olefin, the formula (1) being derived from a diene compound represented by the defined formula (3) such as 2,2-dimethyl-5,5-diallyl-1,3-dioxane; and a process for producing a block copolymer, comprising the step of making the blocks (b1) and (b2) and/or (b3).

Description

DESCRIPTION
BLOCK COPOLYMER AND PRODUCTION PROCESS THEREOF
Technical Field
The present invention relates to a block copolymer whose main chain contains a cyclopentane ring structure, and a process for producing a block copolymer.
Background Art
As a block copolymer whose main chain comprises polymerization units containing a cyclopentane ring structure, Macromolecules Vol. 35, pages 9640-9647 (2002) discloses a block copolymer prepared from ethylene and cyclopentene . The block copolymer consists of (i) a polymer block consisting of polymerization units of ethylene, (-CH2-CH2-) , 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.
Disclosure of Invention
However, there are no block copolymers known in the art 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 .
In view of the above-mentioned circumstances, 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
( 1 ) ; and
(b2) a homopolymer block (b2-l) containing one kind of polymerization unit represented by the following formula (1), or a random copolymer block (b2-2) containing two or more kinds of polymerization units represented by the following formula
(1), the blocks (b2-l) and (b2-2) having different attributes from those of the blocks (bl-1) and (bl-2), respectively; and/or
(b3) a homopolymer block (b3-l) containing one kind of polymerization unit of an olefin, or a random copolymer block
(b3-2) containing two or more kinds of polymerization units of an olefin;
Figure imgf000004_0001
wherein Y1 and Y2 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 Y1 and Y2 may be linked with each other to form a ring; A1, A2, A3, A4, A5, A6, A7, A8, A9, A10 and A11 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 A3 and A4 and/or A5 and A6 may be linked with each other to form a ring; m is 0 or 1; and n is an integer of 1 to 20.
Also, the present invention is a process for producing the above-mentioned block copolymer, comprising the following steps of, in any order:
(I) polymerizing one or more kinds of diene compounds represented by the following formula (3) , thereby forming the above-mentioned homopolymer block (bl-1) or random copolymer block (bl-2); and
(II) polymerizing one or more kinds of diene compounds represented by the following formula (3) , thereby forming the above-mentioned homopolymer block (b2-l) or random copolymer block (b2-2); and/or
(III) polymerizing one or more kinds of olefins, thereby forming the above-mentioned homopolymer block (b3-l) or random copolymer block (b3-2);
Figure imgf000005_0001
wherein all the symbols are the same as those defined in the formula (1); and A8 preferably has a cis-form configuration with - (CH2) n (CA9A10) mH as shown in the formula (3). In the present invention, the above-mentioned term "polymerization unit" means a unit of a polymerized monomer, which is also referred to as a "repeating unit".
Best Mode for Carrying Out the Invention
Examples of the halogen atom of A1 to A11 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.
Examples of the alkyl group of A1 to A11 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 aralky group of A1 to A11 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.
Examples of the aryl group of A1 to A11 in the formulas
(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
2-naphthyl group, a 1-anthracenyl group, a 2-anthracenyl group, and a mesityl group.
Examples of the alkoxy group of A1 to A11 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 A1 to A11 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.
Examples of the aryloxy group of A1 to A11 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, a 2, 6-diisopropylphenoxy group, a 2, 6-di-tert-butylphenoxy group, and a naphthoxy group.
Examples of the substituted amino group of A1 to A11 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, and an N,N-dicyclooctylamino group.
Examples of the amide group of A1 to A11 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 A1 to A11 in the formulas (1) and (3) are a succinimide group, a maleimide group, and a phthalimide group.
Examples of the alkylthio group of A1 to A11 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 A1 to A11 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. Among them, A1 to A11 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.
A3 and A4 and/or A5 and A6 may be linked with each other to form a ring. Examples of 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 .
Examples of the halogen atom of Y1 and Y2 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.
Examples of the alkoxycarbonyl group of Y1 and Y2 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 Y1 and Y2 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 Y1 and Y2 in the formulas (1) and (3) are a phenoxycarbonyl group, a tolyloxycarbonyl group and a mesityloxycarbonyl group. Examples of the alkyl group of Y1 and Y2 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 Y1 and Y2 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.
Examples of the aryl group of Y1 and Y2 in the formulas
(1) and (3) are a phenyl group, a tolyl group and a mesityl group.
Examples of the silyl group of Y1 and Y2 in the formulas
(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 triisobutylsilyl group, a tert-butyldiphenylsilyl group, a cyclohexyldimethylsilyl group, a tricyclohexylsilyl group, and a triphenylsilyl group. Among them, 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 Y1 and Y2 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. Among them, 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 Y1 and Y2 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 Y1 and Y2 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 Y1 and Y2 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, a 2, 6-diisopropylphenoxy group, a 2, 6-di-tert-butylphenoxy group, and a naphthoxy group. Those aryloxy 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 acyl group of Y1 and Y2 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 Y1 and Y2 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-cyclohexylamino group, an N-cyclooctylamino group, an N, N-dicyclohexylamino group, and an NjN-dicyclooctylamino group.
Examples of the amide group of Y1 and Y2 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 Y1 and Y2 in the formulas (1) and (3) are a maleimide group, a phthalimide group and a succinimide group.
Examples of the alkylthio group of Y1 and Y2 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 Y1 and Y2 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 Y1 and Y2 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 Y1 and Y2 in the formulas (1) and (3) are a methylthioxycarbonyl group, an ethylthioxycarbonyl group, an isopropylthioxycarbonyl group, a tert-butylthioxycarbonyl group, and a cyclohexylthioxycarbonyl group.
An examples of the arylthioxycarbonyl group of Y1 and
Y2 in the formulas (1) and (3) is a phenylthioxycarbonyl group.
Y1 and Y2 in the formulas (1) and (3) may have a substituent independently of each other. Examples of the substituent 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.
Y1 and Y2 in the formulas (1) and (3) may be linked with each other to form a ring. Examples of 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 cyclobutan-1-one ring, a cyclopentan-1-one ring, a cyclohexan-1-one ring, a cycloheptan-1-one ring, a cyclooctan-1-one ring, a cyclononan-1-one ring, a cyclodecan-1-one ring, a cyclopropane-1, 2-dione ring, a cyclobutane-1, 3-dione ring, a cyclopentane-1, 3-dione ring, a cyclohexane-1, 3-dione ring, a cycloheptane-1, 3-dione ring, a cyclooctane-1, 3-dione ring, a cyclononane-1, 3-dione ring, a cyclodecane-1, 3-dione ring, an indan-1-one ring, an indan-2-one ring, an indane-1, 3-dione ring, a tetralin-1-one ring, a tetralin-1, 3-dione ring, and a tetralin-1, 4-dione ring; ether bond-carrying rings such as an oxirane ring, an oxetane ring, an oxolane ring, an oxane ring, a 1, 3-dioxetane ring, a 1, 3-dioxolane ring, a 1, 3-dioxane ring, a 1,4-dioxane ring, a 1, 3, 5-trioxane ring, a phthalan ring, a coumaran ring, a chromane ring, an isochromane ring, a xanthene ring, a 1, 3-benzodioxane ring, a 1, 4-benzodioxane ring, and a benzodioxolane ring; amino group or substituted amino group-carrying rings such as a pyrazolidine ring, a morpholine ring, an imidazolidine ring, a pyrrolidine ring, a piperidine ring, a hexahydropyrimidine ring, a piperadine ring, an indoline ring, an indazolin ring, a 1, 2, 3, 4-tetrahydroquinoline ring, a
1, 2, 3, 4-tetrahydroisoquinoline ring, an
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, an N, N' -diphenylimidazolidine ring, an N-phenylpyrrolidine ring, an N-phenylpiperidine ring, an N-phenylhexahydropyrimidine ring, an N, N' -diphenylhexahydropyrimidine ring, an N-phenylpiperadine ring, an N-methylindoline ring, an N-methylindazolin ring, an N, N' -dimethylindazolin ring, an N-methyl-1, 2, 3, 4-tetrahydroquinoline ring, and an N-methyl-1, 2, 3, 4-tetrahydroisoquinoline ring; ester bond-carrying rings such as an a -lactone ring, a β -lactone ring, a γ -lactone ring, a δ -lactone ring, an ε -caprolactone ring, a 1, 3-dioxolan-4-one ring, a 1, 4-dioxan-2-one ring, a 1, 4-dioxane-2, 5-dione ring, a
1, 3-dihydroisobenzofuran-l-one ring, a 2, 3-dihydro-l-benzofuran-2-one ring, a
3, 4-dihydro-2H-l-benzopyran-3-one ring, and a 3, 4-dihydro-lH-2-benzopyran-3-one ring; carbonate bond-carrying rings such as a 1, 3-dioxan-2-one ring and a 1, 3-dioxolan-2-one ring; amide group-carrying rings such as an a -lactam ring, a β -lactam ring, a y -lactam ring, a δ -lactam ring, an e -caprolactam ring, an imidazolidin-4-one ring, a pyrazolidin-3-one ring, a piperadin-2-one ring, a piperadine-2, 5-dione ring, a
1, 2, 3, 4-tetrahydroquinolin-3-one ring, a
1, 2, 3, 4-tetrahydroisoquinolin-l-one ring, a 1, 2, 3, 4-tetrahydro-l-isoquinolin-3-one ring, an N-methyl- a -lactam ring, an N-methyl- j3 -lactam ring, an N-methyl- y -lactam ring, an N-methyl- δ -lactam ring, an N-methyl- ε -caprolactam ring, an N-methylimidazolidin-4-one ring, an N-methylpiperadin-2-one ring, an N-methylpiperadine-2, 5-dione ring, an
N-methyl-1, 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 hexahydropyrimidine-2, 4, 6-trione ring, an
N-methylhexahydropyrimidine-2, 4, 6-trione ring, an N, N' -dimethylhexahydropyrimidine-2, 4 , 6-trione ring, an N-ethylhexahydropyrimidine-2, 4 , 6-trione ring, an N, N' -diethylhexahydropyrimidine-2, 4, 6-trione ring, an N-phenylhexahydropyrimidine-2, 4, 6-trione ring, and an N, N' -diphenylhexahydropyrimidine-2, 4, 6-trione ring; urethane bond-carrying rings such as a 1, 3-oxazolidin-2-one ring; and urea bond-carrying rings such as an imidazolidin-2-one ring and a hexahydropyrimidin-2-one ring. Those rings may have one or more substituents . Among them, 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) Meldrum's acid; malonic diester derivatives such as dimethyl 2, 2-diallylmalonate, diethyl 2, 2-diallylmalonate, di-n-propyl
2, 2-diallylmalonate, diisopropyl 2, 2-diallylmalonate, di-n-butyl 2, 2-diallylmalonate, diisobutyl 2, 2-diallylmalonate, di-tert-butyl 2, 2-diallylmalonate, diethyl 2-allyl-2- ( (2E) -2-butenyl)malonate, diethyl 2-allyl-2- ( (2E) -2-pentenyl) malonate, diethyl
2-allyl-2- ( (2E) -2-hexenyl) malonate, diethyl
2-allyl-2- ( (2E) -2-heptenyl) malonate, diethyl
2-allyl-2- ( (2E) -2-octenyl) malonate, diethyl 2-allyl-2- ( (2E) -2-nonenyl) malonate, diethyl
2-allyl-2- ( (2E) -2-decenyl) malonate, diethyl
2-allyl-2- ( (2E) -2-undecenyl)malonate, and diethyl
2-allyl-2- ( (2E) -2-dodecenyl) malonate; ether bond-containing compounds such as 2, 2-diallyl-l, 3-dioxane, 4 , 4-diallyl-l, 3-dioxane, 5, 5-diallyl-l, 3-dioxane,
2, 2-diallyl-l, 4-dioxane, 2, 2-diallyl-l, 3-dioxolane,
4, 4-diallyl-l, 3-dioxolane,
2, 2-dimethyl-5, 5-diallyl-l, 3-dioxane,
2-allyl-2- ( (2E) -2-butenyl) -1, 3-dioxane, 4-allyl-4- ( (2E) -2-butenyl) -1, 3-dioxane,
5-allyl-5- ( (2E) -2-butenyl) -1, 3-dioxane,
2-allyl-2- ( (2E) -2-butenyl) -1, 4-dioxane,
2-allyl-2- ( (2E) -2-butenyl) -1, 3-dioxolane,
4-allyl-4- ( (2E) -2-butenyl) -1, 3-dioxolane, 2,2-dimethyl-5-allyl-5- ( (2E) -2-butenyl) -1, 3-dioxane,
2-allyl-2- ( (2E) -2-pentenyl) -1, 3-dioxane,
5-allyl-5- ( (2E) -2-pentenyl) -1, 3-dioxane,
2-allyl-2- ( (2E) -2-pentenyl) -1, 4-dioxane,
2-allyl-2- ( (2E) -2-pentenyl) -1, 3-dioxolane, 4-allyl-4- ( (2E) -2-pentenyl) -1, 3-dioxolane,
2, 2-dimethyl-5-allyl-5- ( (2E) -2-pentenyl) -1, 3-dioxane, 2, 2-dimethyl-5-allyl-5- ( (2E) -2-hexenyl) -1, 3-dioxane,
2,2-dimethyl-5-allyl-5- ( (2E) -2-heptenyl) -1, 3-dioxane,
2,2-dimethyl-5-allyl-5- ( (2E) -2-octenyl) -1, 3-dioxane,
2,2-dimethyl-5-allyl-5- ( (2E) -2-nonenyl) -1, 3-dioxane, 2,2-dimethyl-5-allyl-5-( (2E) -2-decenyl) -1, 3-dioxane,
2, 2-dimethyl-5-allyl-5- ( (2E) -2-undecenyl) -1, 3-dioxane,
2, 2-dimethyl-5-allyl-5- ( (2E) -2-dodecenyl) -1, 3-dioxane,
2,2-dimethyl-5-allyl-5- ( (2E) -2-tridecenyl) -1, 3-dioxane,
2, 2-dimethyl-4, 4-diallyl-l, 3-dioxane, 2,2-dimethyl-4, 4-diallyl-l, 3-dioxolane,
2, 2-diethyl-4, 4-diallyl-l, 3-dioxane,
2, 2-diethyl-5,5-diallyl-l, 3-dioxane,
2, 2-diethyl-4, 4-diallyl-l, 3-dioxolane,
2-methyl-4, 4-diallyl-l, 3-dioxane, 2-methyl-5, 5-diallyl-l, 3-dioxane,
2-methyl-4, 4-diallyl-l, 3-dioxolane,
2-ethyl-4 , 4-diallyl-l, 3-dioxane,
2-ethyl-5, 5-diallyl-l, 3-dioxane,
2-ethyl-4, 4-diallyl-l, 3-dioxolane, 2-n-propyl-4, 4-diallyl-l, 3-dioxane,
2-n-propyl-5, 5-diallyl-l, 3-dioxane,
2-n-propyl-4 , 4-diallyl-l, 3-dioxolane,
2-isopropyl-4, 4-diallyl-l, 3-dioxane,
2-isopropyl-5, 5-diallyl-l, 3-dioxane, 2-isopropyl-4, 4-diallyl-l, 3-dioxolane,
2-n-butyl-4, 4-diallyl-l, 3-dioxane, 2-n-butyl-5, 5-diallyl-l, 3-dioxane, and
2-n-butyl-4, 4-diallyl-l, 3-dioxolane; ketone group-containing compounds such as 2, 2-diallylcyclobutane-l, 3-dione, 2, 2-diallylcyclopentane-l, 3-dione, 2, 2-diallylcyclohexane-l, 3-dione, 2, 2-diallylcycloheptane-l, 3-dione, 2, 2-diallylcyclooctane-l, 3-dione, 2, 2-diallylcyclononane-l, 3-dione, 2-allyl-2- ( (2E) -2-butenyl) cyclohexane-1, 3-dione, 2-allyl-2- ( (2E) -2-pentenyl) cyclohexane-1, 3-dione, 2-allyl-2- ( (2E) -2-hexenyl) cyclohexane-1, 3-dione, 2-allyl-2- ( (2E) -2-heptenyl) cyclohexane-1, 3-dione, 2-allyl-2- ( (2E) -2-octenyl) cyclohexane-1, 3-dione, 2-allyl-2- ( (2E) -2-nonenyl) cyclohexane-1, 3-dione, 2-allyl-2- ( (2E) -2-decenyl) cyclohexane-1, 3-dione, 2-allyl-2- ( (2E) -2-undecenyl) cyclohexane-1, 3-dione, 2-allyl-2- ( (2E) -2-dodecenyl) cyclohexane-1, 3-dione, 2-allyl-2- ( (2E) -2-tridecenyl) cyclohexane-1, 3-dione, 2-allyl-2- ( (2E) -2-tetradecenyl) cyclohexane-1, 3-dione, 2-allyl-2- ( (2E) -2-hexadecenyl) cyclohexane-1, 3-dione, 2, 2-diallylindane-l, 3-dione, 2-allyl-2- ( (2E) -2-butenyl) indane-1, 3-dione, 2-allyl-2- ( (2E) -2-pentenyl) indane-1, 3-dione, 2-allyl-2- ( (2E) -2-hexenyl) indane-1, 3-dione, 2-allyl-2- ( (2E) -2-heptenyl) indane-1, 3-dione, 2-allyl-2- ( ( 2E) -2-octenyl ) indane-1 , 3-dione ,
2-allyl-2- ( ( 2E) -2-nonenyl ) indane-1 , 3-dione ,
2-allyl-2- ( ( 2E) -2-decenyl ) indane-1 , 3-dione,
2-allyl-2- (• ( 2E) -2-undecenyl ) indane-1 , 3-dione , 2-allyl-2- ( ( 2E ) -2-dodecenyl ) indane-1 , 3-dione ,
2-allyl-2- ( ( 2E) -2-tridecenyl ) indane-1 , 3-dione,
2-allyl-2- ( (2E) -2-tetradecenyl) indane-1, 3-dione, and
2-allyl-2- ( (2E) -2-hexadecenyl) indane-1, 3-dione; propanediamide derivatives such as 2, 2-diallylpropanediamide and
2-allyl-2- ( (2E) -2-butenyl) propanediamide;
N-alkylpropanediamide derivatives such as
N-methyl-2, 2-diallylpropanediamide,
N-ethyl-2, 2-diallylpropanediamide and N-methyl-2-allyl-2- ( (2E) -2-butenyl) propanediamide;
N,N-dialkylpropanediamide derivatives such as
N, N-dimethyl-2 , 2-diallylpropanediamide and
N,N-dimethyl-2-allyl-2- ( (2E) -2-butenyl) propanediamide;
N, N' -dialkylpropanediamide derivatives such as N, N' -dimethyl-2 , 2-diallylpropanediamide,
N, N' -diethyl-2, 2-diallylpropanediamide,
N, N' -di-n-propyl-2 , 2-diallylpropanediamide,
N, N' -diisopropyl-2 , 2-diallylpropanediamide,
N, N' -di-n-butyl-2, 2-diallylpropanediamide, N, N' -diisobutyl-2, 2-diallylpropanediamide,
N, N' -di-tert-butyl-2, 2-diallylpropanediamide, N, N' -dineopentyl-2, 2-diallylpropanediamide, N, N' -dicyclohexyl-2, 2-diallylpropanediamide, N, N' -di-n-hexyl-2, 2-diallylpropanediamide, N, N' -dicyclopentyl-2 , 2-diallylpropanediamide, N,N'-diethyl-2-allyl-2- ( (2E) -2-butenyl) propanediamide, N, N' -diethyl-2-allyl-2- ( (2E) -2-pentenyl) propanediamide, N,N'-diethyl-2-allyl-2- ( (2E) -2-hexenyl) propanediamide, N, N' -diethyl-2-allyl-2- ( (2E) -2-heptenyl) propanediamide, N, N' -diethyl-2-allyl-2- ( (2E) -2-octenyl) propanediamide, N, N' -diethyl-2-allyl-2- ( (2E) -2-nonenyl) propanediamide, N,N'-diethyl-2-allyl-2- ( (2E) -2-decenyl) propanediamide, N, N' -diethyl-2-allyl-2- ( (2E) -2-undecenyl) propanediamide, and N,N'-diethyl-2-allyl-2- ( (2E) -2-dodecenyl) propanediamide; N, N, N' -trialkylpropanediamide derivatives such as N, N, N' -trimethyl-2 , 2-diallylpropanediamide and
N,N,N'-trimethyl-2-allyl-2- ( (2E) -2-butenyl) propanediamide; N, N, N' ,N' -tetraalkylpropanediamide derivatives such as N, N, N' , N' -tetramethyl-2, 2-diallylpropanediamide and N, N, N' ,N' -tetramethyl-2-allyl-2- ( (2E) -2-butenyl) propanediamide; N-arylpropanediamide derivatives such as N-phenyl-2, 2-diallylpropanediamide and
N-phenyl-2-aryl-2- ( (2E) -2-butenyl) propanediamide; N, N' -diarylpropanediamide derivatives such as N, N' -diphenyl-2, 2-diallylpropanediamide and
N, N' -diphenyl-2-aryl-2- ( (2E) -2-butenyl) propanediamide; 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-ary1-2- ( (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-methyl-5, 5-diallylbarbituric acid,
N-ethyl-5, 5-diallylbarbituric acid, and
N-methyl-5-ally-5- ( (2E) -2-butenyl) barbiturc acid;
N, N' -dialkylbarbiturc acid derivatives such as
N, N' -dimethyl-5, 5-diallylbarbituric acid, N, N' -diethyl-5, 5-diallylbarbituric acid,
N, N' -di-n-propyl-5, 5-diallylbarbituric acid,
N, N' -diisopropyl-5, 5-diallylbarbituric acid,
N, N' -di-n-butyl-5, 5-diallylbarbituric acid,
N, N' -diisobutyl-5, 5-diallylbarbituric acid, N, N' -di-tert-butyl-5, 5-diallylbarbituric acid,
N, N' -dineopentyl-5, 5-diallylbarbituric acid,
N, N' -dicyclohexyl-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-S-ally-δ- ( (2E) -2-decenyl) barbituric acid, N, N' -dimethyl-5-ally-5- ( (2E) -2-undecenyl) barbituric acid, and N,N'-dimethyl-5-ally-5- ( (2E) -2-dodecenyl) barbituric acid; N-arylbarbituric acid derivatives such as N-phenyl-5, 5-diallylbarbituric acid and N-phenyl-5-ally-5- ( (2E) -2-butenyl) barbituric acid; N, N' -diarylbarbituric acid derivatives such as N, N' -diphenyl-5, 5-diallylbarbituric acid and N,N'-diphenyl-5-ally-5- ( (2E) -2-butenyl) barbituric acid; N-aralkylbarbituric acid derivatives such as N-benzyl-5, 5-diallylbarbituric acid and
N-benzyl-5-ally-5- ( (2E) -2-butenyl) barbituric acid; N, N' -diaralkylbarbituric acid derivatives such as N, N' -dibenzyl-5, 5-diallylbarbituric acid and N, N' -dibenzyl-S-ally-5- ( (2E) -2-butenyl) barbituric acid; pyrazolidine-3, 5-dione derivatives such as 4, 4-diallylpyrazolidine-3, 5-dione and
4-allyl-4- ( (2E) -2-butenyl) pyrazolidine-3, 5-dion; N-alkylpyrazolidine-3, 5-dione derivatives such as N-methyl-4, 4-diallylpyrazolidine-3, 5-dione and N-methyl-4-allyl-4- ( (2E) -2-butenyl) pyrazolidine-3, 5-dion;
N, N' -dialkylpyrazolidine-3, 5-dione derivatives such as N, N' -dimethyl-4 , 4-diallylpyrazolidine-3, 5-dion, N, N' -diethyl-4, 4-diallylpyrazolidine-3, 5-dion, N, N' -di-n-propyl-4, 4-diallylpyrazolidine-3, 5-dion, N, N' -diisopropyl-4, 4-diallylpyrazolidine-3, 5-dion, N, N' -di-n-butyl-4, 4-diallylpyrazolidine-3, 5-dion, N, N' -diisobutyl-4, 4-diallylpyrazolidine-3, 5-dion, N, N' -di-tert-butyl-4, 4-diallylpyrazolidine-3, 5-dion, N, N' -dineopentyl-4, 4-diallylpyrazolidine-3, 5-dion, N, N' -dicyclopentyl-4, 4-diallylpyrazolidine-3, 5-dion, N, N' -di-n-hexyl-4, 4-diallylpyrazolidine-3, 5-dion, and N, N' -dicyclohexyl-4, 4-diallylpyrazolidine-3, 5-dion; N-arylpyrazolidine-3, 5-dione derivatives such as N-phenyl-4, 4-diallylpyrazolidine-3, 5-dion, N-phenyl-4-ally-4- ( (2E) -2-butenyl) pyrazolidine-3, 5-dion, N- (2-naphthyl) -4, 4-diallylpyrazolidine-3, 5-dion, and N- (2-anthracenyl) -4, 4-diallypyrazolidine-3, 5-dion; N, N' -diarylpyrazolidine-3, 5-dione derivatives such as N, N' -diphenyl-4, 4-diallylpyrazolidine-3, 5-dion, N, N' -diphenyl-4-ally-4- ( (2E) -2-butenyl) pyrazolidine-3, 5- dion,
N, N' -diphenyl-4-ally-4- ( (2E) -2-pentenyl) pyrazolidine-3, 5- dion,
N, N' -diphenyl-4-ally-4- ( (2E) -2-hexenyl) pyrazolidine-3, 5- dion, N, N' -diphenyl-4-ally-4- ( (2E) -2-heptenyl) pyrazolidine-3, 5- dion, N, N' -diphenyl-4-ally-4- ( (2E) -2-octenyl) pyrazolidine-3, 5- dion,
N, N' -diphenyl-4-ally-4- ( (2E) -2-nonenyl) pyrazolidine-3, 5- dion, N, N' -diphenyl-4-ally-4- ( (2E) -2-decenyl) pyrazolidine-3, 5-dio n,
N, N' -diphenyl-4-ally-4- ( (2E) -2-undecenyl) pyrazolidine-3, 5- dion,
N, N' -diphenyl-4-ally-4- ( (2E) -2-dodecenyl) pyrazolidine-3, 5- dion,
N, N' -bis (2-naphthyl) -4, 4-diallylpyrazolidine-3, 5-dion, and
N, N' -di (2-anthracenyl) -4 , 4-diallylpyrazolidine-3, 5-dion;
N-aralkylpyrazolidine-3, 5-dione derivatives such as
N-benzyl-4, 4-diallylρyrazolidine-3, 5-dion, N-benzyl-4-ally-4- ( (2E) -2-butenyl) pyrazolidine-3, 5-dion, and N- (9-fluorenylmethyl) -4, 4-diallylpyrazolidine-3, 5-dion;
N, N' -diaralkylpyrazolidine-3, 5-dione derivatives such as
N, N' -dibenzyl-4 , 4-diallylpyrazolidine-3, 5-dion,
N, N' -dibenzyl-4-ally-4- ( (2E) -2-butenyl) pyrazolidine-3, 5- dion, and
N, N' -bis (9-fluorenylmethyl) -4, 4-diallylpyrazolidine-3, 5- dion; and fluorene derivatives such as 9, 9-diallylfluorene,
2, 7-di-tert-butyl-9, 9-diallylfluorene,
2, 7-difluoro-9, 9-diallylfluorene, 2, 7-dichloro-9, 9-diallylfluorene,
2, 7-dibromo-9, 9-diallylfluorene, 2, 7-diiodo-9, 9-diallylfluorene,
2-iodo-7-bromo-9, 9-diallylfluorene,
2- (N, N-diphenylamino) -7-bromo-9, 9-diallylfluorene,
3, 6-di-tert-butyl-9, 9-diallylfluorene, 3, 6-difluoro-9, 9-diallylfluorene,
3, 6-dichloro-9, 9-diallylfluorene,
3, 6-dibromo-9, 9-diallylfluorene,
3, 6-diiodo-9, 9-diallylfluorene,
3-iodo-6-bromo-9, 9-diallylfluorene, 3- (N, N-diphenylamino) -6-bromo-9, 9-diallylfluorene,
9-allyl-9- ( (2E) -2-butenyl) -fluorene,
9-allyl-9- ( (2E) -2-pentenyl) -fluorene,
9-allyl-9- ( (2E) -2-hexenyl) -fluorene,
9-allyl-9- ( (2E) -2-octenyl) -fluorene, 9-allyl-9- ( (2E) -2-nonenyl) -fluorene,
9-allyl-9- ( (2E) -2-decenyl) -fluorene,
9-allyl-9- ( (2E) -2-undecenyl) -fluorene,
9-allyl-9- ( (2E) -2-dodecenyl) -fluorene, and
9-allyl-9- ( (2E) -2-tridecenyl) -fluorene. Among them, 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 .
Examples of the olefin in the present invention are 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-1-butene, 2-methyl-l-pentene, 3-methyl-l-pentene, 4-methyl-l-pentene, and vinylcyclohexane; and cyclic olefins such as cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, norbornene, limonene, α -pinene, β -pinene, camphene, cis-cyclooctene, trans-cyclooctene, cis-cyclononene, trans-cyclononene, cis-cyclodecene, and trans-cyclodecene . Among them, preferred is a linear or cyclic olefin having 2 to 20 carbon atoms, further 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.
Those olefins may be used in combination with a diene compound. Examples of 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 (-CH2CH2-) contained in polyethylene, which is an addition polymer of ethylene.
In order to raise the above-mentioned heat resistance of the block copolymer of the present invention, 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 A7 and A8 represented by the following formula (2):
Figure imgf000031_0001
wherein all the symbols are the same as those defined in the formula (1) .
A proportion of the polymerization units having the above-mentioned trans-form configuration is measured by a 13C-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 13C-NMR spectrum is assigned to two carbon atoms linking to each of A7 and A8 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 A7 and A8 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:
proportion (%) of polymerization units having trans-form configuration
= area of peak (i) X 100/ [area of peak (i) + area of peak (U)] .
The homopolymer block (bl-1) contains one kind of polymerization unit represented by the formula (1), and is formed by homopolymerizing one kind of diene compound represented by the formula (3) . The diene compound for the homopolymer block (bl-1) 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, N, N' -diarylpyrazolidine-3, 5-dione derivatives, or fluorene derivatives . 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; a combination of 2, 2-dimethyl-5, 5-diallyl-l, 3-dioxane with
2, 2-diallyl-l, 3-dioxane; a combination of 2, 2-dimethyl-5, 5-diallyl-l, 3-dioxane with
5, 5-diallylbarbituric acid; a combination of 2, 2-dimethyl-5, 5-diallyl-l, 3-dioxane with
N, N' -dimethyl-4 , 4-diallylpyrazolidine-3, 5-dione; a combination of 2, 2-dimethyl-5, 5-diallyl-l, 3-dioxane with 9, 9-diallylfluorene; a combination of dimethyl 2, 2-diallylmalonate with 2, 2-diallyl-l, 3-dioxane; a combination of dimethyl 2, 2-diallylmalonate with 5, 5-diallylbarbituric acid; a combination of dimethyl 2, 2-diallylmalonate with
N, N' -dimethyl-4, 4-diallylpyrazolidine-3, 5-dione; a combination of dimethyl 2, 2-diallylmalonate with 9, 9-diallylfluorene; a combination of 2, 2-diallyl-l, 3-dioxane with 5, 5-diallylbarbituric acid; a combination of 2, 2-diallyl-l, 3-dioxane with N, N' -dimethyl-4, 4-diallylpyrazolidine-3, 5-dione; a combination of 2, 2-diallyl-l, 3-dioxane with 9, 9-diallylfluorene; a combination of 5, 5-diallylbarbituric acid with N, N' -dimethyl-4 , 4-diallylpyrazolidine-3, 5-dione; a combination of 5, 5-diallylbarbituric acid with 9, 9-diallylfluorene; or a combination of N, N' -dimethyl-4, 4-diallylpyrazolidine-3, 5-dione with 9, 9-diallylfluorene.
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,
N, N' -diarylpyrazolidine-3, 5-dione derivatives, or fluorene 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; a combination of 2, 2-dimethyl-5, 5-diallyl-l, 3-dioxane with dimethyl 2, 2-diallylmalonate; a combination of 2, 2-dimethyl-5, 5-diallyl-l, 3-dioxane with
2, 2-diallyl-l, 3-dioxane; a combination of 2, 2-dimethyl-5, 5-diallyl-l, 3-dioxane with
5, 5-diallylbarbituric acid; a combination of 2, 2-dimethyl-5, 5-diallyl-l, 3-dioxane with
N, N' -dimethyl-4, 4-diallylpyrazolidine-3, 5-dione; a combination of 2, 2-dimethyl-5, 5-diallyl-l, 3-dioxane with 9, 9-diallylfluorene; a combination of dimethyl 2, 2-diallylmalonate with 2, 2-diallyl-l, 3-dioxane; a combination of dimethyl 2, 2-diallylmalonate with 5, 5-diallylbarbituric acid; a combination of dimethyl 2, 2-diallylmalonate with N, N' -dimethyl-4, 4-diallylpyrazolidine-3, 5-dione; a combination of dimethyl 2, 2-diallylmalonate with 9, 9-diallylfluorene; a combination of 2, 2-diallyl-l, 3-dioxane with 5, 5-diallylbarbituric acid; a combination of 2, 2-diallyl-l, 3-dioxane with N, N' -dimethyl-4, 4-diallylpyrazolidine-3, 5-dione; a combination of 2, 2-diallyl-l, 3-dioxane with 9, 9-diallylfluorene; a combination of 5, 5-diallylbarbituric acid with N, N' -dimethyl-4, 4-diallylpyrazolidine-3, 5-dione; a combination of 5, 5-diallylbarbituric acid with 9, 9-diallylfluorene; or a combination of N, N' -dimethyl-4, 4-diallylpyrazolidine-3, 5-dione 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 combination of 1-butene with 1-pentene; a combination of 1-butene with cyclopentene; a combination of 1-butene with 1-hexene; a combination of 1-butene with 4-methyl-l-pentene; a combination of 1-butene with 1-octene; a combination of 1-pentene with cyclopentene; a combination of 1-pentene with 1-hexene; a combination of 1-pentene with 4-methyl-l-pentene; a combination of 1-pentene with 1-octene; a combination of cyclopentene with 1-hexene; a combination of cyclopentene with 4-methyl-l-pentene; a combination of cyclopentene with 1-octene; a combination of 1-hexene with 4-methyl-l-pentene; a combination of 1-hexene with 1-octene; or a combination of 4-methyl-l-pentene with 1-octene.
The order of the steps (I) and (II) and/or (III) in the process of the present invention is not limited. Examples of the order thereof are the following:
(1) the steps (I) and (II) are carried out in this order; (2) the steps (I) and (III) are carried out in this order; and
(3) the steps (I) , (II) and (III) are carried out in this order. Among them, preferred is the order (1) or (2) .
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 Meldrum1 s acid derivative with a barbituric acid derivative, a block copolymer of a Meldrum1 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 Meldrum1 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 barbituric acid derivative with a fluorene derivative, a block copolymer of a barbituric acid derivative with a linear olefin, a block copolymer of a barbituric acid derivative with a cyclic olefin, a block copolymer of two kinds of N, N' -dialkylpyrazolidine-3, 5-dione derivatives, a block copolymer of a N, N' -dialkylpyrazolidine-3, 5-dione derivative with a fluorene derivative, a block copolymer of a N, N' -dialkylpyrazolidine-3, 5-dione derivative with a linear olefin, a block copolymer of a N, N' -dialkylpyrazolidine-3, 5-dione derivative with a cyclic olefin, a block copolymer of two kinds of fluorene derivatives, a block copolymer of a fluorene derivative with a linear olefin, and a block copolymer of a fluorene derivative with a cyclic olefin,
Among them, preferred is:
(1) 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
(bl-1) of
2,2-dimethyl-5-allyl-5- ( (2E) -2-butenyl) -1,3-dioxane and a homopolymer block (b2-l) of
2, 2-dimethyl-5, 5-diallyl-l, 3-dioxane; or (3) a block copolymer containing a homopolymer block
(bl-1) of 5, 5-diallylbarbituric acid and a homopolymer block (b3-l) of 1-hexene.
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:
(I) homopolymerizing one kind of diene compound represented by the formula (3), thereby forming a homopolymer block (bl-1);
(II) homopolymerizing another kind of diene compound represented by the formula (3) in the presence of the above-formed homopolymer block (bl-1) , thereby forming an intermediate polymer block (bl-1) (b2-l) , wherein one terminal of the homopolymer block (bl-1) is covalently bound with one terminal of the homopolymer block (b2-l) ; and
(III) homopolymerizing one kind of olefin in the presence of the above-formed intermediate polymer block
(bl-1) (b2-l), thereby forming a target block copolymer (bl-1) (b2-l) (b3-l) , wherein the other terminal of the homopolymer block (b2-l) contained in the intermediate polymer block (bl-1) (b2-l) is covalently bound with one terminal of the homopolymer block (b3-l) .
The reason why the above-mentioned covalent bonds are formed is that 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. Incidentally, since 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.
In the process for producing a block copolymer of the present invention, 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.
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] :
Figure imgf000042_0001
[i: wherein M1 is an iron atom, a cobalt atom, a nickel atom, a palladium atom or a cupper atom; R3 and R4 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; and R5, R6, R7 and R8 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 R7 and R8 may be linked with each other to form a ring;
Figure imgf000043_0001
wherein M1 is an iron atom, a cobalt atom, a nickel atom, a palladium atom or a cupper atom; R3 and R4 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; and R7, R8, R9, R10, R11, R12, R13 and R14 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 R7 and R8 may¬ be linked with each other to form a ring; and
Figure imgf000044_0001
wherein M1 is an iron atom, a cobalt atom, a nickel atom, a palladium atom or a cupper atom; R3 and R4 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; and R15 to R21 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 R15 to R21 may be linked with each other to form a ring. M1 in the formulas [I] and [II] is preferably a nickel atom or a palladium atom.
M1 in the formula [III] is preferably an iron atom or a cobalt atom.
The above defined alkyl group, aralkyl group, aryl group, alkoxy group, aralkyloxy group and aryloxy group of R3 and R4 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.
The above defined 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 R5 to R21 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 R3 to R21 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 R3 to R21 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. Among them, 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.
Examples of the aralkyl group of R3 to R21 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-trimethylphenyl) methyl group, a (2, 3, 5-trimethylphenyl) methyl group, a
(2,3, 6-trimethylphenyl) methyl group, a
(2, 4, 5-trimethylphenyl) methyl group, a
(2,4, 6-trimethylphenyl ) methyl group, a
(3,4, 5-trimethylphenyl) methyl group, a (2,3,4, 5-tetramethylphenyl ) methyl group, a
(2,3,4, 6-tetramethylphenyl) methyl group, a
(2,3,5, 6-tetramethylphenyl) methyl group, a
(pentamethylphenyl) methyl group, an (ethylphenyl) methyl group, a (n-propylphenyl) methyl group, an (isopropylphenyl) methyl group, a (n-butylphenyl) methyl group, a (sec-butylphenyl) methyl group, a (tert-butylphenyl) methyl group, a (n-hexylphenyl) methyl group, a (n-octylphenyl) methyl group, a (n-decylphenyl) methyl group, a naphthylmethyl group, and an anthracenylmethyl group. Among them, preferred is an aralkyl group having 7 to 20 carbon atoms, and more preferred is a benzyl group.
Examples of the aryl group of R3 to R21 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, a mesityl 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-hexylphenyl group, a 4-methylphenyl group, a 2, 6-dimethylphenyl group, a 2, 6-diethylphenyl group, a 2, 6-di-n-propylphenyl group, a 2, 6-diisopropylphenyl group, a 2, 6-di-n-butylphenyl group, a 2, 6-diisobutylphenyl group, a 2, 6-di-n-hexylphenyl group, a 2-methyl-6-ethylphenyl group, a 2-methyl-6-n-propylphenyl group, a 2-methyl-6-isopropylphenyl group, a 2-methyl-6-butylphenyl group, a 2-ethyl-β-n-propylphenyl group, a 2-ethyl-6-isopropylphenyl group, a 2-ethyl-6-n-butylphenyl group, a 2-n-propyl-6-isopropylphenyl group, a 2-n-propyl-6-n-butylphenyl group, a
2-isopropyl-6-n-butylphenyl group, a 2, 4, 6-trimethylphenyl group, a 2, 4-dimethyl-6- (2-methylphenyl) phenyl group, a 2, 4-dimethyl-6- (2-ethylphenyl) phenyl group, a 2, 4-dimethyl-6- (2-n-propylphenyl) phenyl group, a 2, 4-dimethyl-6- (2-isopropylphenyl) phenyl group, a 2, 4-dimethyl-β- (2, 6-dimethylphenyl) phenyl group, a 2, 4-dimethyl-6- (2, 6-diethylphenyl) phenyl group, a 2, 4-dimethyl-6- (2, 6-di-n-propylphenyl) phenyl group, a 2, 4-dimethyl-6- (2, 6-diisopropylphenyl) phenyl αroup. a
2, 4-dimethyl-6- (2-methyl-6-ethylphenyl) phenyl group, a 2, 4-dimethyl-6- (2-methyl-6-n-propylphenyl) phenyl group, a 2, 4-dimethyl-6- (2-methyl-6-isopropylphenyl) phenyl group, a 2, 4-dimethyl-6- (2-ethyl-6-n-propylphenyl) phenyl group, a 2, 4-dimethyl-6- (2-ethyl-6-isopropylphenyl) phenyl group, a 2, 4-dimethyl-6- (1-naphthyl) phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthracenyl group, a 2-anthracenyl group, a 9-anthracenyl group, a 2-methyl-l-naphthyl group, a 3-methyl-l-naphthyl group, a 4-methyl-l-naphthyl group, a 2, 3-dimethyl-l-naphthyl group, a 2, 4-dimethyl-l-naphthyl group, a 2, 5-dimethyl-l-naphthyl group, a 2, 6-dimethyl-l-naphthyl group, a 3, 4-dimethyl-l-naphthyl group, a 3, 5-dimethyl-l-naphthyl group, a 3, 6-dimethyl-l-naphthyl group, a 2-methyl-l-anthracenyl group, a 3-methyl-lO-anthracenyl group, a 4-methyl-lO-anthracenyl group, a 2, 3-dimethyl-lO-anthracenyl group, a
2, 4-dimethyl-lO-anthracenyl group, a
2, 5-dimethyl-lO-anthracenyl group, a
2, 6-dimethyl-lO-anthracenyl group, a 3, 4-dimethyl-10-anthracenyl group, a
3, 5-dimethyl-10-anthracenyl group, a
3, 6-dimethyl-10-anthracenyl group, and a 2-methyl-lO-anthracenyl group. Among them, preferred is an aryl group having 6 to 20 carbon atoms, more 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-diisopropylphenyl group.
Examples of the alkoxy group of R3 to R21 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. Among them, 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 R3 to R21 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-dimethylphenyl ) methoxy group, a
(2,4-dimethylphenyl) methoxy group, a
(2, 5-dimethylphenyl) methoxy group, a
(2, 6-dimethylphenyl) methoxy group, a (3, 4-dimethylphenyl) methoxy group, a
(3, 5-dimethylphenyl) methoxy group, a
(2,3, 4-trimethylphenyl) methoxy group, a
(2,3, 5-trimethylphenyl) methoxy group, a
(2, 3, 6-trimethylphenyl) methoxy group, a (2,4, 5-trimethylphenyl) methoxy group, a
(2,4, 6-trimethylphenyl ) methoxy group, a
(3,4, 5-trimethylphenyl ) methoxy group, a
(2, 3, 4, 5-tetramethylphenyl) methoxy group, a
(2,3,4, 6-tetramethylphenyl ) 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. Among them, preferred is an aralkyloxy group having 7 to 20 carbon atoms, and more preferred is a benzyloxy group. Examples of the aryloxy group of R3 to R21 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 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
2, 6-di-tert-butyl-3-methylphenoxy group, a 2-tert-butyl-4 , 5-dimethylphenoxy group, a
2, 6-di-tert-butyl-4-methylphenoxy group, a 3, 4, 5-trimethylphenoxy group, a 2, 3, 4 , 5-tetramethylphenoxy group, a 2-tert-butyl-3, 4, 5-trimethylphenoxy group, a 2, 3, 4, 6-tetramethylphenoxy group, a 2-tert-butyl-3, 4, 6-trimethylphenoxy group, a 2, 6-di-tert-butyl-3, 4-dimethylphenoxy group, a 2, 3, 5, 6-tetramethylphenoxy group, a
2-tert-butyl-3, 5, 6-trimethylphenoxy group, a 2, 6-di-tert-butyl-3, 5-diitιethylphenoxy group, a pentamethylphenoxy group, an ethylphenoxy group, a n-propylphenoxy group, an isopropylphenoxy group, a n-butylphenoxy group, a sec-butylphenoxy group, a tert-butylphenoxy group, a n-hexylphenoxy group, a n-octylphenoxy group, a n-decylphenoxy group, a naphthoxy group, and an anthracenoxy group. Among them, preferred is an aryloxy group having 6 to 20 carbon atoms.
Examples of the acyl group of R5 to R21 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 R5 to R21 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 R5 to R21 in the formulas [I], [II] and [III] are a benzyloxycarbonyl group, a phenethyloxycarbonyl group, and a cumyloxycarbonyl group.
An example of the aryloxycarbonyl group of R5 to R21 in the formulas [I], [II] and [III] is a phenoxycarbonyl group.
Examples of the substituted amino group of R5 to R21 in the formulas [I], [II] and [III] are linear alkylamino groups such as an N-methylamino group, an N-ethylamino group, an
N-n-bμtylamino 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-dicyclohexylamino group and an N, N-dicyclooctylamino group.
Examples of the amide group of R5 to R21 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. Examples of the alkylthio group of R5 to R21 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 R9 and R10 are independently of each other an aryl group, and R11 and R12 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 R9 and R10 are independently of each other an aryl group, and R11 and R12 are independently of each other a hydrogen atom, an alkyl group or an aralkyl group.
Examples of the ring formed by linking of R7 with R8 in the formulas [I] and [II], and examples of the ring formed by linking of any two of R15 to R21 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 R7 with R8, or formed by linking of any two of R15 to R21 with each other are a methylene group, an ethane-1, 2-diyl group, a propane-1, 3-diyl group, a propane-1, 2-diyl group, a butane-1, 2-diyl group, a butane-1, 3-diyl group, a butane-1, 4-diyl group, a pentane-1, 2-diyl group, a pentane-1, 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 group, a norbornane-1, 2-diyl group, a norborn-5-ene-2, 3-diyl group, a but-l-ene-1, 2-diyl group, a but-l-ene-1, 3-diyl group, a but-l-ene-2, 3-diyl group, a but-2-ene-l, 2-diyl group, a but-2-ene-l, 3-diyl group, a but-2-ene-2, 3-diyl group, a buta-1, 3-diene-l, 2-diyl group, a buta-1, 3-diene-l, 3-diyl group, abuta-1, 3-diene-l, 4-diyl group, a 2, 3-dimethyl-2-butene-2, 3-diyl group, and a 2-pentene-2, 4-diyl group.
Examples of a divalent group making the above-mentioned aromatic rings formed by linking of R7 with R8, or formed by linking of any two of R15 to R21 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-diyl group, a 3-isobutylbenzene-l, 2-diyl group, a 4-isobutylbenzene-l, 2-diyl group, a 3-tert-butylbenzene-l, 2-diyl group, a
4-tert-butylbenzene-l,2-diyl group, a benzene-1, 3-diyl group, a 2-methylbenzene-l, 3-diyl group, a 4-methylbenzene-l, 3-diyl group, a methylenebenzene-1, 2-dily group, a benzene-1, 2-dimethylene group, a benzene-1, 3-dimethylene group, and a naphthalene-1, 8-diyl group.
Examples of the transition metal compound represented by the formula [I] or [II] , wherein M1 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, N1 - (ethane-1, 2-diylidene) bis (2-n-propylaniline- K N) ] palladium, chloro (methyl) [N, N ' - (ethane-1, 2-diylidene) bis (2-isopropylaniline- /c N) ] palladium, chloro (methyl) [N, N '- (ethane-1, 2-diylidene) bis (2-n-butylaniline- K N) ] palladium, chloro (methyl) [N, N ' - (ethane-1, 2-diylidene) bis (2-isobutylaniline- K N) ] palladium, chloro (methyl) [N,N'- (ethane-1, 2-diylidene) bis (2-n-hexylaniline- KN) ] palladium, chloro (methyl) [N, N ' - (ethane-1, 2-diylidene) bis ( 4-methylaniline- K N) ] palladium, chloro (methyl) [N, N ' - (ethane-1, 2-diylidene) bis
(2, 6-dimethylaniline- K N) ] palladium, chloro (methyl) [N, N1 - (ethane-1, 2-diylidene) bis (2, 6-diethylaniline- K N) ]palladium, chloro (methyl) [N, N ' - (ethane-1, 2-diylidene) bis
(2, 6-di-n-propylaniline- K N) ] palladium, chloro (methyl) [N, N ' - (ethane-1, 2-diylidene) bis
(2, 6-diisopropylaniline- K N) ] palladium, chloro (methyl) [N, N '- (ethane-1, 2-diylidene) bis
(2, 6-di-n-butylaniline- /c N) ] palladium, chloro (methyl) [N, N ' - (ethane-1, 2-diylidene) bis
(2, 6-diisobutylaniline- /c N) ] palladium, chloro (methyl) [N, N ' - (ethane-1, 2-diylidene) bis (2, 6-di-n-hexylaniline- /c N) ] palladium, chloro (methyl) [N, N' - (ethane-1, 2-diylidene) bis
(2-methyl-6-ethylaniline- K N) ] palladium, chloro (methyl) [N, N1 - (ethane-1, 2-diylidene) bis
(2-methyl-6-n-propylaniline- /c N) ] palladium, chloro (methyl) [N, N '- (ethane-1, 2-diylidene) bis
(2-methyl-6-isopropylaniline- K N) ] palladium, chloro (methyl) [N, N1 - (ethane-1, 2-diylidene) bis
(2-methyl-6-butylaniline- K N) ] palladium, chloro (methyl) [N, N ' - (ethane-1, 2-diylidene) bis (2-ethyl-6-n-propylaniline- K N) ] palladium, chloro (methyl) [N, N ' - (ethane-1, 2-diylidene) bis (2-ethyl-β-isopropylaniline- K N) ] palladium, chloro (methyl) [N, N ' - (ethane-1, 2-diylidene) bis (2-ethyl-6-n-butylaniline- KN)] palladium, chloro (methyl) [N, N1 - (ethane-1, 2-diylidene) bis (2-n-propyl-β-isopropylaniline- K N) ] palladium, chloro (methyl) [N, N1 - (ethane-1, 2-diylidene) bis (2-n-propyl-6-n-butylaniline- K N) ] palladium, chloro (methyl) [N, N ' - (ethane-1, 2-diylidene) bis (2-isopropyl-6-n-butylaniline- /cN) ] palladium, chloro (methyl) [N, N '- (ethane-1, 2-diylidene) bis (2,4, 6-trimethylaniline- K N) ] palladium, chloro (methyl) [N, N' - (ethane-1, 2-diylidene) bis {2, 4-dimethyl-6- (2-methylphenyl) aniline- K N} ] palladium, chloro (methyl) [N, N ' - (ethane-1, 2-diylidene) bis {2, 4-dimethyl-6- (2-ethylphenyl) aniline- KN}] palladium, chloro (methyl) [N, N1 - (ethane-1, 2-diylidene) bis {2, 4-dimethyl-6- (2-n-propylphenyl) aniline- K N} ] palladium, chloro (methyl) [N, N' - (ethane-1, 2-diylidene) bis { 2, 4-dimethyl-6- (2-isopropylphenyl) aniline- K N} ] palladium, chloro (methyl) [N, N '- (ethane-1, 2-diylidene) bis
{ 2, 4-dimethyl-6- (2, 6-dimethylphenyl) aniline- /c N} ] palladium, chloro (methyl) [N, N1 - (ethane-1, 2-diylidene) bis { 2, 4-dimethyl-6- (2, 6-diethylphenyl) aniline- K N} ] palladium, chloro (methyl) [N, N' - (ethane-1, 2-diylidene) bis {2, 4-dimethy1- 6- (2, 6-di-n-propylphenyl) aniline- K N} ] palladium, chloro (methyl) [N, N ' - (ethane-1, 2-diylidene) bis { 2, 4-dimethyl- 6- (2, 6-diisopropylphenyl) aniline- K N} ] palladium, chloro (methyl) [N, N ' - (ethane-1, 2-diylidene) bis { 2, 4-dimethy1- 6- (2-methyl-6-ethylphenyl) aniline- /c N} ] palladium, chloro (methyl) [N, N ' - (ethane-1, 2-diylidene) bis { 2, 4-dimethyl- 6- (2-methyl-6-n-propylphenyl) aniline- K N} ] palladium, chloro (methyl) [N, N' - (ethane-1, 2-diylidene) bis { 2, 4-dimethyl- 6- (2-methyl-6-isopropylphenyl) aniline- icN)] palladium, chloro (methyl) [N, N ' - (ethane-1, 2-diylidene) bis {2, 4-dimethyl- 6- (2-ethyl-6-n-propylphenyl) aniline- KN}] palladium, chloro (methyl) [N, N '- (ethane-1, 2-diylidene) bis { 2, 4-dimethyl- 6- (2-ethyl-6-isopropylphenyl) aniline- K N} ] palladium, chloro (methyl) [N, N ' - (ethane-1, 2-diylidene) bis { 2, 4-dimethyl-6- (1-naphthyl) aniline- K N} ] palladium, chloro (methyl) [N, N ' - (butane-2, 3-diylidene) bis (aniline- K N) ] palladium, chloro (methyl) [N, N ' - (butane-2, 3-diylidene) bis (2-methylaniline- KN) ] palladium, chloro (methyl) [N, N ' - (butane-2, 3-diylidene) bis (2-ethylaniline- K N) ] palladium, chloro (methyl) [N, N '- (butane-2, 3-diylidene) bis (2-n-propylaniline- /c N) ] palladium, chloro (methyl) [N, N ' - (butane-2, 3-diylidene) bis (2-isopropylaniline- K N) ] palladium, chloro (methyl) [N, N ' - (butane-2, 3-diylidene) bis (2-n-butylaniline- K N) ] palladium, chloro (methyl) [N, N ' - (butane-2, 3-diylidene) bis (2-isobutylaniline- icN) ] palladium, chloro (methyl) [N, N ' - (butane-2, 3-diylidene) bis
(2-n-hexylaniline- /c N) ] palladium, chloro (methyl) [N, N1 - (butane-2, 3-diylidene) bis (4-methylaniline- /c N) ] palladium, chloro (methyl) [N, N ' - (butane-2, 3-diylidene) bis
(2, 6-dimethylaniline- /c N) ] palladium, chloro (methyl) [N, N ' - (butane-2, 3-diylidene) bis
(2, 6-diethylaniline- /c N) ] palladium, chloro (methyl) [N, N '- (butane-2, 3-diylidene) bis
(2, 6-di-n-propylaniline- K N) ] palladium, chloro (methyl) [N, N ' - (butane-2, 3-diylidene) bis
(2, 6-diisopropylaniline- K N) ] palladium, chloro (methyl) [N, N ' - (butane-2, 3-diylidene) bis (2, 6-di-n-butylaniline- K N) ] palladium, chloro (methyl) [N, N1 - (butane-2, 3-diylidene) bis
(2, 6-diisobutylaniline- KN) ] palladium, chloro (methyl) [N, N1 - (butane-2, 3-diylidene) bis
(2, 6-di-n-hexylaniline- K N) ] palladium, chloro (methyl) [N, N '- (butane-2, 3-diylidene) bis
(2-methyl-6-ethylaniline- /cN) ] palladium, chloro (methyl) [N, N ' - (butane-2, 3-diylidene) bis
(2-methyl-6-n-propylaniline- /c N) ] palladium, chloro (methyl) [N, N ' - (butane-2, 3-diylidene) bis (2-methyl-6-isopropylaniline- K N) j palladium, chloro (methyl) [N, N ' - (butane-2, 3-diylidene) bis (2-methyl-β-butylaniline- /c N) ] palladium, chloro (methyl) [N, N ' - (butane-2, 3-diylidene) bis (2-ethyl-6-n-propylaniline- K N) ] palladium, chloro (methyl) [N, N ' - (butane-2, 3-diylidene) bis (2-ethyl-β-isopropylaniline- /c N) ] palladium, chloro (methyl) [N, N ' - (butane-2, 3-diylidene) bis (2-ethyl-6-n-butylaniline- KN) ] palladium, chloro (methyl) [N, N' - (butane-2, 3-diylidene) bis (2-n-propyl-6-isopropylaniline- /cN) ] palladium, chloro (methyl) [N, N '- (butane-2, 3-diylidene) bis (2-n-propyl-6-n-butylaniline- /c N) ] palladium, chloro (methyl) [N, N' - (butane-2, 3-diylidene) bis (2-isopropyl-6-n-butylaniline- K N) ] palladium, chloro (methyl) [N, N ' - (butane-2, 3-diylidene) bis (2,4, 6-trimethylaniline- K N) ] palladium, chloro (methyl) [N, N ' - (butane-2, 3-diylidene) bis
{2, 4-dimethyl-6- (2-methylphenyl) aniline- K N} ] palladium, chloro (methyl) [N, N ' - (butane-2, 3-diylidene) bis
{2, 4-dimethyl-6- (2-ethylphenyl) aniline- /cN} ] palladium, chloro (methyl) [N, N '- (butane-2, 3-diylidene) bis
{2, 4-dimethyl-6- (2-n-propylphenyl) aniline- /cN} ] palladium, chloro (methyl) [N, N1 - (butane-2, 3-diylidene) bis {2, 4-dimethyl-6- (2-isopropylphenyl) aniline- K N} ] palladium, chloro (methyl) [N, N ' - (butane-2, 3-diylidene) bis {2, 4-dimethyl-6- (2, 6-dimethylphenyl) aniline- /c N} ] palladium, chloro (methyl) [N, N ' - (butane-2, 3-diylidene) bis { 2, 4-dimethyl-6- (2, 6-diethylphenyl) aniline- K N} ] palladium, chloro (methyl) [N, N1 - (butane-2, 3-diylidene) bis { 2, 4-dimethyl- 6- (2, 6-di-n-propylphenyl) aniline- K N} ] palladium, chloro (methyl) [N, N' - (butane-2, 3-diylidene) bis { 2, 4-dimethyl- 6- (2, 6-diisopropylphenyl) aniline- /c N} ] palladium, chloro (methyl) [N, N1 - (butane-2, 3-diylidene) bis { 2, 4-dimethyl- 6- (2-methyl-6-ethylphenyl) aniline- /c N} ] palladium, chloro (methyl) [N, N ' - (butane-2, 3-diylidene) bis {2, 4-dimethy1- 6- (2-methyl-6-n-propylphenyl) aniline- /c N} ] palladium, chloro (methyl) [N, N1 - (butane-2, 3-diylidene) bis{ 2, 4-dimethyl- 6- (2-methyl-6-isoproρylphenyl) aniline- K N} ] palladium, chloro (methyl) [N, N1 - (butane-2, 3-diylidene) bis { 2, 4-dimethyl- 6- (2-ethyl-6-n-propylphenyl) aniline- K N} ] palladium, chloro (methyl) [N, N ' - (butane-2, 3-diylidene) bis { 2, 4-dimethy1- 6- (2-ethyl-6-isopropylphenyl) aniline- K N} ] palladium, chloro (methyl) [N, N1 - (butane-2, 3-diylidene) bis {2, 4-dimethyl-6- (1-naphthyl) aniline- /cN} ] palladium, chloro (methyl) [N, N ' - (1, 2-dihydroacenaphthylene-l, 2- diylidene) bis (aniline- K N) ] palladium, chloro (methyl) [N, N '- (1, 2-dihydroacenaphthylene-l, 2- diylidene) bis (2-methylaniline- K N) ] palladium, chloro (methyl) [N, N1 - (1, 2-dihydroacenaphthylene-l, 2- diylidene) bis (2-ethylaniline- /c N) ] palladium, chloro (methyl) [N, N ' - (1, 2-dihydroacenaphthylene-l, 2- diylidene) bis (2-n-propylaniline- /c N) ] palladium, chloro (methyl) [N, N ' - (1, 2-dihydroacenaphthylene-l, 2- diylidene) bis (2-isopropylaniline- K N) ] palladium, chloro (methyl) [N, N1 - (1, 2-dihydroacenaphthylene-l, 2- diylidene) bis (2-n-butylaniline- /c N) ] palladium, chloro (methyl) [N, N' - (1, 2-dihydroacenaphthylene-l, 2- diylidene) bis (2-isobutylaniline- /c N) ] palladium, chloro (methyl) [N, N ' - (1, 2-dihydroacenaphthylene-l, 2- diylidene) bis (2-n-hexylaniline- K N) ] palladium, chloro (methyl) [N, N ' - (1, 2-dihydroacenaphthylene-l, 2- diylidene) bis (4-methylaniline- K N) ] palladium, chloro (methyl) [N, N '- (1, 2-dihydroacenaphthylene-l, 2- diylidene) bis (2, 6-dimethylaniline- K N) ] palladium, chloro (methyl) [N, N' - (1, 2-dihydroacenaphthylene-l, 2- diylidene) bis (2, 6-diethylaniline- K N) ] palladium, chloro (methyl) [N, N ' - ( 1, 2-dihydroacenaphthylene-l, 2- diylidene) bis (2, β-di-n-propylaniline- /cN) ] palladium, chloro (methyl) [N, N1 - (1, 2-dihydroacenaphthylene-l, 2- diylidene) bis (2, 6-diisopropylaniline- K N) ] palladium, chloro (methyl) [N, N1 - (1, 2-dihydroacenaphthylene-l, 2- diylidene) bis (2, 6-di-n-butylaniline- K N) ] palladium, chloro (methyl) [N, N '- (1, 2-dihydroacenaphthylene-l, 2- diylidene) bis (2, 6-diisobutylaniline- /c N) ] palladium, chloro (methyl) [N, N ' - ( 1, 2-dihydroacenaphthylene-l, 2- diylidene) bis (2, 6-di-n-hexylaniline- /c N) ] palladium, chloro (methyl) [N, N1 - (1, 2-dihydroacenaphthylene-l, 2- diylidene) bis (2, 6-dichloroaniline- K N) ] palladium, chloro (methyl) [N, N ' - (1, 2-dihydroacenaphthylene-l, 2- diylidene) bis (2-methyl-6-ethylaniline- /c N) ] palladium, chloro (methyl) [N, N1 - (1, 2-dihydroacenaphthylene-l, 2- diylidene) bis (2-methyl-β-n-propylaniline- K N) ] palladium, chloro (methyl) [N, N ' - (1, 2-dihydroacenaphthylene-l, 2- diylidene) bis (2-methyl-β-isopropylaniline- /cN) ] palladium, chloro (methyl) [N, N1 - (1, 2-dihydroacenaphthylene-l, 2- diylidene) bis (2-methyl-6-butylaniline- K N) ] palladium, chloro (methyl) [N, N ' - (1, 2-dihydroacenaphthylene-l, 2- diylidene) bis (2-ethyl-6-n-propylaniline- K N) ] palladium, chloro (methyl) [N, N1 -( 1, 2-dihydroacenaphthylene-l, 2- diylidene) bis (2-ethyl-6-isopropylaniline- K N) ] palladium, chloro (methyl) [N, N ' - (1, 2-dihydroacenaphthylene-l, 2- diylidene) bis (2-ethyl-6-n-butylaniline- /c N) ] palladium, chloro (methyl) [N, N1 - (1, 2-dihydroacenaphthylene-l, 2- diylidene) bis (2-n-propyl-β-isopropylaniline- K N) ] palladium, chloro (methyl) [N, N ' - (1, 2-dihydroacenaphthylene-l, 2- diylidene) bis (2-n-propyl-6-n-butylaniline- K N) ] palladium, chloro (methyl) [N, N ' - ( 1, 2-dihydroacenaphthylene-l, 2- diylidene) bis (2-isopropyl-6-n-butylaniline- K N) ] palladium, chloro (methyl) [N, N '- (1, 2-dihydroacenaphthylene-l, 2- diylidene) bis (2, 4, 6-trimethylaniline- K N) ] palladium, chloro (methyl) [N, N ' - (1, 2-dihydroacenaphthylene-l, 2- diylidene)bis{2, 4-dimethyl-6- (2-methylphenyl) aniline- KN} ] palladium, chloro (methyl) [N, N '- (1, 2-dihydroacenaphthylene-l, 2- diylidene) bis { 2, 4-dimethyl-6- (2-ethylphenyl) aniline- /cN} ] palladium, chloro (methyl) [N, N1 - (1, 2-dihydroacenaphthylene-l, 2- diylidene)bis{2, 4-dimethyl-6- (2-n-propylphenyl) aniline-
K N} ] palladium, chloro (methyl) [N, N '-( 1, 2-dihydroacenaphthylene-l, 2- diylidene) bis {2, 4-dimethyl-6- (2-isopropylphenyl) aniline-
K N} ] palladium, chloro (methyl) [N, N1 - (1, 2-dihydroacenaphthylene-l, 2- diylidene) bis { 2, 4-dimethyl-6- (2, 6-dimethylphenyl) aniline- K N} ] palladium, chloro (methyl) [N, N1 - (1, 2-dihydroacenaphthylene-l, 2- diylidene) bis {2, 4-dimethyl-6- (2, 6-diethylphenyl) aniline-
/c N} ] palladium, chloro (methyl) [N, N1 - (1, 2-dihydroacenaphthylene-l, 2- diylidene) bis{2, 4-dimethyl-6- (2, 6-di-n-propylphenyl) aniline
- K N} ] palladium, chloro (methyl) [N, N ' - (1, 2-dihydroacenaphthylene-l, 2- diylidene) bis { 2, 4-dimethyl-6- (2, 6-diisopropylphenyl) aniline
- /c N } ] palladium, chloro (methyl) [N, N '- (1, 2-dihydroacenaphthylene-l, 2- diylidene) bis { 2, 4-dimethyl-6- (2-methyl-6-ethylphenyl) aniline- /c N } ] palladium, chloro (methyl) [N, N1 - (1, 2-dihydroacenaphthylene-l, 2- diylidene)bis{2, 4-dimethyl-6- (2-methyl-6-n-propylphenyl) aniline- /c N} ] palladium, chloro (methyl) [N, N ' - (1, 2-dihydroacenaphthylene-l, 2- diylidene) bis {2, 4-dimethyl-6- (2-methyl-6-isopropylphenyl) aniline- K N} ] palladium, chloro (methyl) [N, N ' - (1, 2-dihydroacenaphthylene-l, 2- diylidene) bis{ 2, 4-dimethyl-6- (2-ethyl-6-n-propylphenyl) aniline- /c N} ] palladium, chloro (methyl) [N, N ' - (1, 2-dihydroacenaphthylene-l, 2- diylidene) bis{ 2, 4-dimethyl-6- (2-ethyl-6-isopropylphenyl) aniline- K N} ] palladium, and chloro (methyl) [N, N1 - (1, 2-dihydroacenaphthylene-l, 2- diylidene) bis {2, 4-dimethyl-6- (1-naphthyl) anilinert; N} ] palladium.
Examples of the transition metal compound represented by the formula [I] or [II] , wherein M1 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",
"iron", "copper" or "cobalt".
Examples of the transition metal compound represented by the formula [III] , wherein M1 is an iron, are 2, 6-bis- [1- (2, 6-dimethylphenylimino) ethyl] pyridineiron dichloride,
2,6-bis-[l-(2, 6-diisopropylphenylimino) ethyl] pyridineiron dichloride,
2, 6-bis- [1- (2-tert-butylphenylimino) ethyl] pyridineiron dichloride,
[hydrotris (3, 5-dimethylpyrazolyl) borate] iron chloride, [hydrotris (3, 5-dimethylpyrazolyl) borate] iron bromide, [hydrotris (3, 5-dimethylpyrazolyl) borate] iron iodide, [hydrotris (3, 5-dimethylpyrazolyl) borate] iron methyl, [hydrotris (3, 5-dimethylpyrazolyl) borate] iron ethyl, [hydrotris (3, 5-dimethylpyrazolyl) borate] iron allyl,
[hydrotris (3, 5-dimethylpyrazolyl) borate] iron methallyl, [hydrotris (3, 5-diethylpyrazolyl) borate] iron chloride, [hydrotris (3, 5-diethylpyrazolyl) borate] iron bromide, [hydrotris (3, 5-diethylpyrazolyl) borate] iron iodide, [hydrotris (3, 5-diethylpyrazolyl) borate] iron methyl, [hydrotris (3, 5-diethylpyrazolyl) borate] iron ethyl, [hydrotris (3, 5-diethylpyrazolyl) borate] iron allyl, [hydrotris (3, 5-diethylpyrazolyl) borate] iron methallyl, [hydrotris (3, 5-di-tert-butylpyrazolyl) borate] iron chloride, [hydrotris (3, 5-di-tert-butylpyrazolyl) borate] iron bromide, [hydrotris (3, 5-di-tert-butylpyrazolyl) borate] iron iodide, [hydrotris (3, 5-di-tert-butylpyrazolyl) borate] iron methyl, [hydrotris (3, 5-di-tert-butylpyrazolyl) borate] iron ethyl, [hydrotris (3, 5-di-tert-butylpyrazolyl) borate] iron allyl, and [hydrotris (3, 5-di-tert-butylpyrazolyl) borate] iron methallyl .
Examples of the transition metal compound represented by the formula [III], wherein M1 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 :
(Al) an organoaluminum compound represented by the formula,
Figure imgf000068_0001
(A2) a cyclic alumoxane represented by the formula, {-Al (E2)-0-}e; and
(A3) a linear alumoxane represented by the formula, E3{-Al(E3)-O-}fAlE32, wherein E1, E2 and E3 are independently of one another a hydrocarbyl group, and when plural E1S, E2S or E3S exist, they are the same as, or different from one another; X2 is a hydrogen atom or a halogen atom, and when plural X2S 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 E1, E2 and E3 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 E1, E2 and E3 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.
Examples of the above-mentioned organoaluminum compound (Al) are 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 hydride and dihexylaluminum hydride. Among them, preferred is a trialkylaluminum, and more preferred is triethylaluminum or triisobutylaluminum.
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:
(Bl) a boron compound represented by the formula, BQ1Q2Q3;
(B2) a boron compound represented by the formula, G+(BQ1Q2Q3Q4)"; and
(B3) a boron compound represented by the formula, (J-H) + (BQ1Q2Q3Q4)-; wherein B is a trivalent boron atom; Q1, Q2, Q3 and Q4 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.
Q1, Q2, Q3 and Q4 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 C2-20 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-20 hydrocarbyl group containing one or more fluorine atoms; and particularly preferably a fluorinated C6-20 aryl group containing one or more fluorine atoms.
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. Among them, G+ is preferably a carbenium cation, and particularly preferably a triphenylmethyl cation.
Examples of (BQ1Q2Q3Q4)" 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 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 (BQ1Q2Q3Q4)" 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. Among them, most preferred is 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 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) .
The block copolymer of the present invention preferably has one or more glass transition points, which are preferably -200C 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.
When forming a polymerization catalyst by contacting the transition metal compound with the organoaluminum 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. When forming a polymerization catalyst by contacting the transition metal compound, the organoaluminum compound and the boron compound with one another, 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. Examples of 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 μ mol/L, preferably 0.05 to 100 μ mol/L, and more preferably 0.05 to 50 μ 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 μ 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 μ 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. Examples of the inorganic compound are silica gel and alumina, and 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. Examples of 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. 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
[transition metal compound: prepared according to Recueil des
Travaux Chimiques de Pays-Bas, Vol. 113, page 88 (1994)], 10.6 mg (0.012 mmol) of sodium tetrakis (3, 5-bistrifluoromethylphenyl) borate [boron compound: prepared according to Organometallics, Vol. 11, page
3920 (1992)], and 0.25 mL of methylene chloride, in a Schlenk flask. To the Schlenk flask, 90.5 mg (0.4 mmol) of
2, 2-diallylindane-l, 3-dione (compound represented by the formula (3)) was added. The resultant mixture was allowed to stand at -5°C for 4 days, thereby polymerizing the total amount of 2, 2-diallylindane-l, 3-dione, and obtaining a first reaction mixture.
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. Separately, 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 above-mentioned existence of polymerization units represented by the formula (1) was confirmed by assigning signals in the range of 23 to 50 ppm of a 13C-NMR spectrum obtained by a 13C-NMRmethod to a linear hydrocarbyl structure and a 5-membered hydrocarbyl structure contained in the polymerization unit represented by the formula (1):
- measurement solvent of chloroform-di; - measurement temperature of room temperature;
- sample concentration of 50 mg-sample/0.5 mL-solution; and
- reference material of chloroform-di (77 ppm).
The above-mentioned number-average molecular weight (Mn) and molecular weight distribution (Mw/Mn) were measured according to a gel permeation chromatography (GPC) under the following conditions using an equipment manufactured by JASCO Corporation having a degasser (DG-980-50) , a pump (PU-980) , an auto-sampler (AS-950), a column oven (CO-966) , an RI detector (RI-930) and a UV detector (UV-975) , with a calibration curve prepared using standard polystyrenes:
- two columns, SHODEX-806L, manufactured by Showa Denko K. K. ;
- measurement temperature of 40°C; - solvent of chloroform; and
- sample concentration of 1 mg-sample/mL-solution.
Example 2
There were put 13.2 mg (0.02 mmol) of chloro (methyl) [N, N ' - (1, 2-dihydroacenaphthylene-l, 2- diylidene) bis (2, 6-diisopropylaniline- K N)] palladium (transition metal compound) , and 21.2 mg (0.024 mmol) of sodium tetrakis (3, 5-bistrifluoromethylphenyl) borate (boron compound) in a 25 mL-Schlenk tube. To the Schlenk tube, 1.0 mL of methylene chloride was added. The resultant mixture was stirred for 10 minutes. The obtained mixture was cooled down to -20 0C , and 168.2 mg of 2,2-dimethyl-5-allyl-5- ( (2E) -2-butenyl) -1,3-dioxane (compound represented by the formula (3)) was added thereto. The mixture was stirred at -20°C for 22 hours, thereby obtaining a first reaction mixture.
To the first reaction mixture, 157.0 mg of 2, 2-dimethyl-5, 5-diallyl-l, 3-dioxane (compound represented by the formula (3)) was added. The mixture was cooled down to -30°C, and was stirred at -30°C for 55 hours, thereby 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 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) . 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) .
Separately, 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-dimethyl-5-allyl-5- ( (2E) -2-butenyl) -1, 3-dioxane. 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 -200C to 1800C at a temperature-increasing rate of 10°C/minute.
The above-mentioned proportion of the trans-form was measured according to a 13C-NMR method using an equipment, LA-500, manufactured by JEOL LTD, under the following conditions :
- measurement solvent of chloroform-di;
- measurement temperature of room temperature;
- sample concentration of 50 mg-sample/0.5 mL-solution; and
- reference material of chloroform-di (77 ppm) .
Example 3
There were put 50 mg (0.076 mmol) of chloro (methyl) [N, N ' - ( 1, 2-dihydroacenaphthylene-l, 2- diylidene)bis (2, 6-diisopropylaniline- K N)] palladium (transition metal compound), and 80 mg (0.09 mmol: excess amounts for the transition metal compound) of sodium tetrakis (3, 5-bistrifluoromethylphenyl) borate (boron compound) in a Schlenk tube. To the Schlenk tube, 2.75 mL of methylene chloride was added. The resultant mixture was stirred for 5 minutes at a room temperature. The obtained reaction mixture was filtered to remove insoluble components, thereby obtaining a filtrate, the insoluble components mainly comprising unreacted boron compound and sodium chloride (NaCl) formed by the reaction.
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%.
There were put 17 mg (0.01 mmol) of the red solid compound and 0.5 mL of methylene chloride in a Schlenk tube, thereby preparing a solution. To the solution, 0.08 mL (0.7 mmol) of 1-hexene was added, and the resultant mixture was reacted at -200C for one day and a half, whereby 1-hexene was almost completely reacted. 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 1H-NMR method using an equipment, LA-500, manufactured by JEOL LTD, under the following conditions :
- measurement solvent of chloroform-di; - measurement temperature of room temperature;
- sample concentration of 50 mg-sample/0.5 mL-solution; and
- reference material of chloroform-di (7.26 ppm) .
Industrial Applicability 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. Examples of 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.

Claims

1. 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
( 1 ) ; and
(b2) a homopolymer block (b2-l) containing one kind of polymerization unit represented by the following formula (1), or a random copolymer block (b2-2) containing two or more kinds of polymerization units represented by the following formula (1), the blocks (b2-l) and (b2-2) having different attributes from those of the blocks (bl-1) and (bl-2), respectively; and/or
(b3) a homopolymer block (b3-l) containing one kind of polymerization unit of an olefin, or a random copolymer block (b3-2) containing two or more kinds of polymerization units of an olefin;
Figure imgf000085_0001
wherein Y1 and Y2 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 Y1 and Y2 may be linked with each other to form a ring; A1, A2, A3, A4, A5, A6, A7, A8, A9, A10 and A11 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 A3 and A4 and/or A5 and A6 may be linked with each other to form a ring; m is 0 or 1; and n is an integer of 1 to 20.
2. The block copolymer according to claim 1, wherein one or more kinds of polymerization units contained in the block copolymer have a trans-form configuration between A7 and A8 represented by the following formula (2):
Figure imgf000087_0001
wherein all the symbols are the same as those defined in the formula (1) .
3. A process for producing a block copolymer comprising (i) the following block (bl-1) or (bl-2), and (ii) the following block (b2-l) or (b2-2) and/or block (b3-l) or (b3-2), comprising the following steps of, in any order: (I) polymerizing one or more kinds of diene compounds represented by the following formula (3) , thereby forming a homopolymer block (bl-1) or random copolymer block (bl-2) , the blocks (bl-1) and (bl-2) containing polymerization units represented by the following formula (1); and (II) polymerizing one or more kinds of diene compounds represented by the following formula (3) , thereby forming a homopolymer block (b2-l) or random copolymer block (b2-2), the blocks (b2-l) and (b2-2) containing polymerization units represented by the following formula (1) , and having different attributes from those of the blocks (bl-1) and (bl-2), respectively; and/or
(III) polymerizing one or more kinds of olefins, thereby forming a homopolymer block (b3-l) or random copolymer block (b3-2);
Figure imgf000088_0001
Figure imgf000088_0002
wherein Y1 and Y2 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 Y1 and Y2 may be linked with each other to form a ring; A1, A2, A3, A4, A5, A6, A7, A8, A9, A10 and A11 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 A3 and A4 and/or A5 and A6 may be linked with each other to form a ring; m is 0 or 1; and n is an integer of 1 to 20.
4. The process for producing a block copolymer according to claim 3, wherein one or more kinds of polymerization units among the polymerization units represented by the formula (1) have a trans-form configuration between A7 and A8 represented by the following formula (2):
Figure imgf000089_0001
wherein all the symbols are the same as those defined in the formula ( 1) .
5. The process for producing a block copolymer according to claim 3, wherein the polymerization is carried out in the presence of a polymerization catalyst formed by contacting a transition metal compound with an organic aluminum compound and/or boron compound.
6. The process for producing a block copolymer according to claim 5, wherein the transition metal compound is a compound represented by the following formula [I]:
Figure imgf000090_0001
[I]
wherein M1 is an iron atom, a cobalt atom, a nickel atom, a palladium atom or a cupper atom; R3 and R4 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; and R5, R6, R7 and R8 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 R7 and R8 may be linked with each other to form a ring.
7. The process for producing a block copolymer according to claim 5, wherein the transition metal compound is a compound represented by the following formula [H]:
Figure imgf000091_0001
wherein M1 is an iron atom, a cobalt atom, a nickel atom, a palladium atom or a cupper atom; R3 and R4 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; and R7, R8, R9, R10, R11, R12, R13 and R14 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 R7 and R8 may be linked with each other to form a ring.
8. The process for producing a block copolymer according to claim 5, wherein the transition metal compound is a compound represented by the following formula [III]:
Figure imgf000092_0001
wherein M1 is an iron atom, a cobalt atom, a nickel atom, a palladium atom or a cupper atom; R3 and R4 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; and R15 to R21 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 R15 to R21 may be linked with each other to form a ring.
PCT/JP2008/066619 2007-09-18 2008-09-09 Block copolymer and production process thereof WO2009038031A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2007-240621 2007-09-18
JP2007240621 2007-09-18

Publications (1)

Publication Number Publication Date
WO2009038031A1 true WO2009038031A1 (en) 2009-03-26

Family

ID=40002942

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2008/066619 WO2009038031A1 (en) 2007-09-18 2008-09-09 Block copolymer and production process thereof

Country Status (2)

Country Link
JP (1) JP2009091570A (en)
WO (1) WO2009038031A1 (en)

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 (en) * 2005-08-26 2007-03-01 Sumitomo Chemical Company, Limited Homopolymer and copolymer, and production process thereof

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59155416A (en) * 1983-02-23 1984-09-04 Mitsubishi Petrochem Co Ltd Block copolymer containing unsaturated bond
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
US7956145B2 (en) * 2007-02-28 2011-06-07 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

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 (en) * 2005-08-26 2007-03-01 Sumitomo Chemical Company, Limited Homopolymer and copolymer, and production process thereof

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
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 *

Also Published As

Publication number Publication date
JP2009091570A (en) 2009-04-30

Similar Documents

Publication Publication Date Title
US7964691B2 (en) Olefin-diene copolymer and process for producing the same
JP5268388B2 (en) Diene polymer and process for producing the same
JP5207770B2 (en) Diene polymer and process for producing the same
JP5207771B2 (en) Diene polymer and process for producing the same
JP5336747B2 (en) Diene polymer and process for producing the same
JP5290594B2 (en) Diene polymer and process for producing the same
JP5015036B2 (en) Cyclic olefin-diene copolymer and process for producing the same
US8188202B2 (en) Diene polymer and production process thereof
US8044159B2 (en) Homopolymer and copolymer, and production process thereof
JP5207772B2 (en) Diene polymer and process for producing the same
JP4887962B2 (en) Ring-closing copolymerization with ethylene
JP7277203B2 (en) Method for producing polyolefin copolymer
JP2007084790A (en) Ring-closing polymerization of dienes
WO2009038031A1 (en) Block copolymer and production process thereof
WO2009038006A1 (en) Random copolymer and production process thereof

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 08832583

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 08832583

Country of ref document: EP

Kind code of ref document: A1

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载