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
  • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
  • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
  • C08C19/00—Chemical modification of rubber
  • C08C19/30—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule
  • C08C19/42—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups
  • C08C19/44—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups of polymers containing metal atoms exclusively at one or both ends of the skeleton
• • 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
  • C08F236/04—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 conjugated
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L15/00—Compositions of rubber derivatives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L19/00—Compositions of rubbers not provided for in groups C08L7/00 - C08L17/00
  • C08L19/006—Rubber characterised by functional groups, e.g. telechelic diene polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
  • C08K3/36—Silica
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/54—Silicon-containing compounds
  • C08K5/548—Silicon-containing compounds containing sulfur

Definitions

• the present invention relates to a conjugated diene polymer rubber, and a conjugated diene polymer rubber composition.
• a polymer rubber composition comprising a conjugated diene polymer rubber such as polybutadiene rubber or a butadiene-styrene copolymer rubber and a filler such as carbon black or silica, etc. is used.
• a conjugated diene polymer rubber a rubber composition employing a polymer rubber formed by modifying with a dialkylamino group-containing acrylamide one terminus of a polymer rubber formed by copolymerizing butadiene and styrene using an alkyllithium as a polymerization initiator (see e.g.
• JP-A 1-217047 JP-A denotes a Japanese unexamined patent application publication
• a rubber composition employing a polymer rubber formed by modifying with a dialkylamino group-containing alkoxysilane one terminus of a polymer formed by copolymerizing butadiene and styrene using an alkyllithium as a polymerization initiator (see e.g. JP-A 63-186748 and JP-A 2005-290355), etc. have been proposed as polymer compositions having good fuel economy.
• the rubber composition employing the above-mentioned conventional conjugated diene polymer rubber is not always fully satisfactory in terms of abrasion resistance.
• a first aspect of the present invention relates to a conjugated diene polymer rubber comprising component (A) and component (B) below, component (A) having a content, with the total amount of component (A) and component (B) as 100% by weight, of from 5 to 90% by weight, and component (B) having a content of from 95 to 10% by weight, component (A): a conjugated diene polymer rubber component modified with a carbonyl group- and substituted amino group-containing compound component (B): a conjugated diene polymer rubber component modified with a compound represented by formula (IIa) below,
• R 21 and R 23 denote a hydrocarbyl group
• R 22 denotes a hydrocarbylene group
• A denotes a substituted amino group or an optionally substituted hydrocarbyloxy group
• a second aspect of the present invention relates to a conjugated diene polymer rubber composition
• a conjugated diene polymer rubber composition comprising the conjugated diene polymer rubber and a filler.
• the conjugated diene polymer rubber of the present invention is a diene polymer rubber comprising component (A) and component (B) below, component (A) having a content, with the total amount of component (A) and component (B) as 100% by weight, of from 5 to 90% by weight, and component (B) having a content of from 95 to 10% by weight.
• Component (A) is a conjugated diene polymer rubber component that is modified with a carbonyl group- and substituted amino group-containing compound.
• a conjugated diene polymer rubber component in component (A) contains a conjugated diene based monomer unit (conjugated unit).
• conjugated diene examples include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, and 1,3-hexadiene, and one or more types thereof may be used.
• the conjugated diene is preferably 1,3-butadiene or isoprene.
• the conjugated diene polymer rubber component of component (A) may further comprise, in addition to the conjugated diene-based constituent unit (conjugated diene unit), a constituent unit based on another monomer.
• said other monomer include an aromatic vinyl, a vinylnitrile, and an unsaturated carboxylic acid ester.
• aromatic vinyl include styrene, ⁇ -methylstyrene, vinyltoluene, vinylnaphthalene, divinylbenzene, trivinylbenzene, and divinylnaphthalene.
• Examples of the vinylnitrile include acrylonitrile, and examples of the unsaturated carboxylic acid ester include methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate. Among them, an aromatic vinyl is preferable, and styrene is more preferable.
• the conjugated diene polymer of component (A) preferably contains an aromatic vinyl-based constituent unit (aromatic vinyl unit), and the content of the aromatic vinyl unit, relative to 100% by weight of the total amount of the conjugated diene unit and the aromatic vinyl unit, is preferably at least 10% by weight (the content of the conjugated diene unit being no greater than 90% by weight), and more preferably at least 15% by weight (the content of the conjugated diene unit being no greater than 85% by weight).
• the content of the aromatic vinyl unit is preferably no greater than 50% by weight (the content of the conjugated diene unit being at least 50% by weight), and more preferably no greater than 45% by weight (the content of the conjugated diene unit being at least 55% by weight).
• the conjugated diene polymer rubber component of component (A) preferably contains a constituent unit based on a silicon-containing monomer.
• the silicon-containing monomer is preferably a monomer represented by formula (X) below,
• X 1 , X 2 , and X 3 denote an optionally substituted hydrocarbyl group or a group represented by formula (Xa) below, and at least one of X 1 , X 2 , and X 3 is a group represented by formula (Xa) below,
• R′ and R′′ denote a hydrocarbyl group having 1 to 6 carbon atoms that may contain at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a silicon atom, a silyl group, a substituted silyl group, or a divalent group having 2 to 12 carbon atoms in which R′ and R′′ are bonded to each other, and * denotes a bonding position.
• the hydrocarbyl group denotes a hydrocarbon residue.
• the substituted hydrocarbyl group (the hydrocarbyl group containing a substituent) denotes a group in which at least one hydrogen atom of the hydrocarbon residue is replaced by a substituent.
• the hydrocarbyloxy group denotes a group in which the hydrogen atom of a hydroxy group is replaced by a hydrocarbyl group, and the substituted hydrocarbyloxy group (the hydrocarbyloxy group containing a substituent) denotes a group in which at least one hydrogen atom of a hydrocarbyloxy group is replaced by a substituent.
• the substituted silyl group denotes a group in which at least one hydrogen atom of a silyl group is replaced by a substituent.
• X 1 , X 2 , and X 3 denote an optionally substituted hydrocarbyl group or a group represented by formula (Xa) below, and at least one of X 1 , X 2 , and X 3 is a group represented by formula (Xa) above.
• Examples of the hydrocarbyl groups denoted by X 1 , X 2 , and X 3 include an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, a neopentyl group, an isopentyl group, or an n-hexyl group; a cycloalkyl group such as a cyclohexyl group; an aryl group such as a phenyl group, a methylphenyl group, or an ethylphenyl group; and an aralkyl group such as a benzyl group.
• the hydrocarbyl group is preferably an alkyl group.
• the number of carbon atoms of the hydrocarbyl groups denoted by X 1 , X 2 , and X 3 is preferably from 1 to 4, and more preferably 1 or 2.
• Examples of the substituted hydrocarbyl groups denoted by X 1 , X 2 , and X 3 include an alkoxyalkyl group such as a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, or an ethoxyethyl group.
• the substituted hydrocarbyl group is preferably an alkoxyalkyl group, and more preferably an alkoxyalkyl group having 2 to 4 carbon atoms.
• the number of carbon atoms of the substituted hydrocarbyl groups denoted by X 1 , X 2 , and X 3 is preferably from 1 to 4.
• R′ and R′′ of formula (Xa) are hydrocarbyl groups having 1 to 6 carbon atoms that may contain at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a silicon atom, silyl groups, substituted silyl groups, or divalent groups having 2 to 12 carbon atoms in which R′ and R′′ are bonded to each other.
• Examples of the hydrocarbyl group having 1 to 6 carbon atoms denoted by R′ and R′′ include an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, a neopentyl group, an isopentyl group, or an n-hexyl group; a cycloalkyl group such as a cyclohexyl group; and a phenyl group.
• an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, a neopentyl group,
• alkyl group is preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms, and yet more preferably a methyl group, an ethyl group, an n-propyl group, or an n-butyl group.
• Examples of the nitrogen atom-containing hydrocarbyl group denoted by R′ and R′′ include a dialkylaminoalkyl group such as a dimethylaminomethyl group, a dimethylaminoethyl group, a dimethylaminopropyl group, or a diethylaminoethyl group.
• oxygen atom-containing hydrocarbyl group denoted by R′ and R′′ examples include an alkoxyalkyl group such as a methoxymethyl group, a methoxyethyl group, a methoxypropyl group, an ethoxymethyl group, or an ethoxyethyl group. It is preferably an alkoxyalkyl group, and more preferably an alkoxyalkyl group having 2 to 4 carbon atoms.
• Examples of the silicon atom-containing hydrocarbyl group denoted by R′ and R′′ include a trialkylsilylalkyl group such as a trimethylsilylmethyl group.
• Examples of the substituted silyl group denoted by R′ and R′′ include a trialkylsilyl group such as a trimethylsilyl group, a triethylsilyl group, or a t-butyldimethylsilyl group.
• the substituted silyl group is preferably a trialkylsilyl group, and more preferably a trimethylsilyl group.
• Examples of the divalent group having 2 to 12 carbon atoms in which R′ and R′′ are bonded to each other include an alkylene group such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, or a hexamethylene group; an alkenylene group such as a group represented by —CH ⁇ CH—CH ⁇ CH—; a nitrogen-containing group such as a group represented by —CH 2 CH 2 —NH—CH 2 —, a group represented by —CH ⁇ CH—N ⁇ CH—, a group represented by —CH 2 CH 2 —N ⁇ CH—, a group represented by —CH 2 CH 2 CH 2 —NH—, a group represented by —CH ⁇ CHCH ⁇ N—, or a group represented by —CH 2 CH 2 —NH—CH 2 CH 2 —; and an oxygen-containing group such as a group represented by —CH 2 CH 2 —O—CH 2 CH 2 — or
• R′ and R′′ are preferably alkyl groups, alkoxyalkyl groups, substituted silyl groups or a divalent group in which R′ and R′′ are bonded to each other, and are more preferably alkyl groups.
• acyclic amino group examples include a dialkylamino group such as a dimethylamino group, a diethylamino group, a di(n-propyl)amino group, a di(isopropyl)amino group, a di(n-butyl)amino group, a di(sec-butyl)amino group, a di(tert-butyl)amino group, a di(neopentyl)amino group, or an ethylmethylamino group; a dialkoxyalkylamino group such as a di(methoxyethyl)amino group, a di(ethoxymethyl)amino group, or di(ethoxyethyl)amino group; and a di(trialkylsilyl)amino group such as a di(trimethylsilyl)amino group.
• a dialkylamino group such as a dimethylamin
• Examples of the cyclic amino group include a 1-polymethyleneimino group such as a 1-aziridinyl group, a 1-azetidinyl group, a 1-pyrrolidinyl group, a 1-piperidinyl group, a 1-hexamethyleneimino group, a 1-heptamethyleneimino group, a 1-octamethyleneimino group, a 1-decamethyleneimino group, or a 1-dodecamethyleneimino group.
• a 1-polymethyleneimino group such as a 1-aziridinyl group, a 1-azetidinyl group, a 1-pyrrolidinyl group, a 1-piperidinyl group, a 1-hexamethyleneimino group, a 1-heptamethyleneimino group, a 1-octamethyleneimino group, a 1-decamethyleneimino group, or a 1-dodecamethyleneimino group.
• examples of the cyclic amino group also include a 1-pyrrolyl group, a 1-imidazolidinyl group, a 1-imidazolyl group, a 4,5-dihydro-1-imidazolyl group, a 1-pyrazolidinyl group, a 1-pyrazolyl group, a 1-piperazinyl group, and a morpholino group.
• the group represented by formula (Xa) is preferably an acyclic amino group, and more preferably a dialkyl amino group.
• At least one of X 1 , X 2 , and X 3 of formula (X) is a group represented by formula (Xa). It is preferable that two or more of X 1 , X 2 , and X 3 are a group represented by formula (Xa), and it is more preferable that two of X 1 , X 2 , and X 3 are a group represented by formula (Xa).
• Examples of the (dialkylamino)dialkylvinylsilane include (dimethylamino)dimethylvinylsilane, (ethylmethylamino)dimethylvinylsilane, (diethylamino)dimethylvinylsilane, (ethyl-n-propylamino)dimethylvinylsilane, (ethylisopropylamino)dimethylvinylsilane, di(n-propyl)aminodimethylvinylsilane, (diisopropylamino)dimethylvinylsilane, (n-butyl-n-propylamino)dimethylvinylsilane, di(n-butyl)aminodimethylvinylsilane, (dimethylamino)diethylvinylsilane, di(tert-butyl)aminodimethylvinylsilane, (d
• Examples of the ⁇ di(trialkylsilyl)amino ⁇ dialkylvinylsilane include ⁇ di(trimethylsilyl)amino ⁇ dimethylvinylsilane, ⁇ di(t-butyldimethylsilyl)amino ⁇ dimethylvinylsilane, ⁇ di(trimethylsilyl)amino ⁇ diethylvinylsilane, and ⁇ di(t-butyldimethylsilyl)amino ⁇ diethylvinylsilane.
• Examples of the (dialkylamino)dialkoxyalkylvinylsilane include
• Examples of the bis(dialkylamino)alkylvinylsilane include bis(dimethylamino)methylvinylsilane, bis(ethylmethylamino)methylvinylsilane, bis(diethylamino)methylvinylsilane, bis(ethyl-n-propylamino)methylvinylsilane, bis(ethylisopropylamino)methylvinylsilane, bisdi(n-propyl)aminomethylvinylsilane, bis(diisopropylamino)methylvinylsilane, bis(n-butyl-n-propylamino)methylvinylsilane, bisdi(n-butyl)aminomethylvinylsilane, bis(dimethylamino)ethylvinylsilane, bis(ethylmethylamino)ethylvinylsilane, bis(diethylamin
• Examples of the bis ⁇ di(trialkylsilyl)amino ⁇ alkylvinylsilane include bis ⁇ di(trimethylsilyl)amino ⁇ methylvinylsilane, bis ⁇ di(t-butyldimethylsilyl)amino ⁇ methylvinylsilane, bis ⁇ di(trimethylsilyl)amino ⁇ ethylvinylsilane, and bis ⁇ di(t-butyldimethylsilyl)amino ⁇ ethylvinylsilane.
• Examples of the bis(dialkylamino)alkoxyalkylvinylsilane include
• Examples of the bis(dialkylamino)alkoxyalkylvinylsilane include
• Examples thereof include tri(dimethylamino)vinylsilane, tri(ethylmethylamino)vinylsilane, tri(diethylamino)vinylsilane, tri(ethylpropylamino)vinylsilane, tri(dipropylamino)vinylsilane, and tri(butylpropylamino)vinylsilane.
• examples of compounds in which two of X 1 to X 3 are cyclic amino groups represented by formula (Xa) and one thereof is a hydrocarbyl group or a substituted hydrocarbyl group include bis(1-piperidinyl)methylvinylsilane, bis(hexamethyleneimino)methylvinylsilane, bis(4,5-dihydro-1-imidazolyl)methylvinylsilane, and bis(morpholino)methylvinylsilane.
• the content of the constituent unit based on a silicon-containing monomer (monomer unit based on silicon-containing monomer) in the conjugated diene polymer rubber component of component (A) is preferably not less than 0.001 mmol/g and not more than 0.1 mmol/g per unit weight of component (A). It is more preferably not less than 0.002 mmol/g and not more than 0.07 mmol/g. It is yet more preferably not less than 0.003 mmol/g and not more than 0.05 mmol/g.
• the conjugated diene polymer rubber component of component (A) is modified with a carbonyl group- and substituted amino group-containing compound (hereinafter, also called compound (I)).
• the substituted amino group of compound (I) is a group in which one or more hydrogen atoms on the amino group are replaced by a substituent; examples thereof include a dialkylamino group such as a dimethylamino group, a diethylamino group, a di(n-propyl)amino group, a di(isopropyl)amino group, a di(n-butyl)amino group, a di(sec-butyl)amino group, a di(tert-butyl)amino group, a di(neopentyl)amino group, or an ethylmethylamino group; an aralkylamino group such as a benzylamino group; an arylamino group such as a phenylamino group; a diarylamino group such as a diphenylamino group; an alkylideneamino group such as an ethylideneamino
• Z 1 and Z 2 denote a substituted amino group-containing group, a hydrogen atom, an optionally substituted hydrocarbyl group, or an optionally substituted hydrocarbyloxy group, at least one of Z 1 and Z 2 is a substituted amino group-containing group, or Z 1 and Z 2 are bonded to each other and denote a divalent group in which a substituted amino group-containing ring structure in which Z 1 and Z 2 are bonded is formed by Z 1 , Z 2 , and the carbonyl carbon.
• substituted amino group-containing group a substituted amino group, a hydrocarbyl group containing a substituted amino group as a substituent, and a hydrocarbyloxy group containing a substituted amino group as a substituent can be cited.
• Examples of the substituted amino group include the above-mentioned substituted amino groups. Examples thereof further include an amino group containing a substituted amino group-containing group as a substituent and an amino group containing a hydrocarbyloxy group-containing group as a substituent.
• Examples of the amino group containing a substituted amino group-containing group as a substituent include a (dialkylaminoalkyl)amino group such as a (dimethylaminomethyl)amino group, a (dimethylaminoethyl)amino group, a (dimethylaminopropyl)amino group, a (diethylaminopropyl)amino group, or a (dipropylaminopropyl)amino group; and a bis(dialkylaminoalkyl)amino group such as a bis(dimethylaminoethyl)amino group or a bis(dimethylaminopropyl)amino group.
• a (dialkylaminoalkyl)amino group such as a (dimethylaminomethyl)amino group, a (dimethylaminoethyl)amino group, a (dimethylamino
• Examples of the amino group containing a hydrocarbyloxy group-containing group as a substituent include an (alkoxyalkyl)amino group such as a (methoxymethyl)amino group, a (methoxyethyl)amino group, a (methoxypropyl)amino group, or an (ethoxymethyl)amino group; an (aryloxyalkyl)amino group such as a (phenoxymethyl)amino group or a (phenoxyethyl)amino group; and an (aralkyloxyalkyl)amino group such as a (benzyloxymethyl)amino group or a (benzyloxyethyl)amino group.
• an (alkoxyalkyl)amino group such as a (methoxymethyl)amino group, a (methoxyethyl)amino group, a (methoxypropyl)amino group, or an (ethoxy
• hydrocarbyl group containing a substituted amino group as a substituent a hydrocarbyl group containing a hydrocarbyl-substituted amino group as a substituent can be cited.
• the hydrocarbyl group containing a hydrocarbyl-substituted amino group as a substituent include a dialkylaminoalkyl group such as a dimethylaminomethyl group, a dimethylaminoethyl group, or a dimethylaminopropyl group; and a dialkylaminoaryl group such as a dimethylaminophenyl group or a diethylaminophenyl group.
• hydrocarbyloxy group containing a substituted amino group as a substituent a hydrocarbyloxy group containing a hydrocarbyl-substituted amino group as a substituent can be cited.
• hydrocarbyloxy group containing a hydrocarbyl-substituted amino group as a substituent include a dialkylaminoalkoxy group such as a dimethylaminomethoxy group, a dimethylaminoethoxy group, or a dimethylaminopropoxy group.
• T denotes an oxygen atom or —NR 6 — (R 6 denotes a hydrocarbyl group or a hydrogen atom), R 4 denotes a hydrocarbylene group, R 5 denotes a hydrocarbyl group that may contain a nitrogen atom and/or an oxygen atom (the two R 5 s may be identical to or different from each other), a group having 2 to 20 carbon atoms in which the two R 5 s form a single group and are bonded to the nitrogen atom via a double bond, or a divalent group having 2 to 20 carbon atoms in which the two R 5 s are bonded to each other, and * represents a bonding position.
• a hydrocarbylene group denotes a divalent hydrocarbon residue.
• p denotes 0 or 1.
• T denotes an oxygen atom or —NR 6 —
• R 6 denotes a hydrocarbyl group or a hydrogen atom
• examples of the hydrocarbyl group denoted by R 6 include an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, or a tert-butyl group; an aryl group such as a phenyl group, a methylphenyl group, an ethylphenyl group, or a naphthyl group; and an aralkyl group such as a benzyl group.
• the number of carbon atoms of the hydrocarbyl group denoted by R 6 is preferably from 1 to 10, and more preferably from 1 to 4.
• the hydrocarbyl group denoted by R 6 is preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms, and yet more preferably a methyl group or an ethyl group.
• R 6 is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, yet more preferably a hydrogen atom, a methyl group, or an ethyl group, and yet more preferably a hydrogen atom or a methyl group.
• R 4 in formula (Ib) denotes a hydrocarbylene group
• examples of the hydrocarbylene group include an alkylene group such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, or a hexamethylene group; an arylene group such as a phenylene group, a tolylene group, or a xylylene group; and an aralkylene group.
• the number of carbon atoms of R 4 of formula (Ib) is preferably from 1 to 10, and more preferably from 2 to 4.
• R 5 of formula (Ib) denotes a hydrocarbyl group that may contain a nitrogen atom and/or an oxygen atom (the two R 5 s may be identical to or different from each other), a group having 2 to 20 carbon atoms in which the two R 5 s form a single group and are bonded to the nitrogen atom via a double bond, or a divalent group having 2 to 20 carbon atoms in which the two R 5 s are bonded to each other.
• Examples of the hydrocarbyl group denoted by R 5 include an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, or a tert-butyl group; an aryl group such as a phenyl group, a methylphenyl group, or an ethylphenyl group; and an aralkyl group such as a benzyl group.
• the number of carbon atoms of the hydrocarbyl group denoted by R 5 is preferably from 1 to 10, more preferably from 1 to 6, and yet more preferably from 1 to 4.
• Examples of the nitrogen atom-containing hydrocarbyl group denoted by R 5 include a dialkylaminoalkyl group such as a dimethylaminomethyl group, a dimethylaminoethyl group, a dimethylaminopropyl group, or a diethylaminoethyl group.
• the number of carbon atoms of the nitrogen atom-containing hydrocarbyl group denoted by R 5 is preferably from 3 to 10, more preferably from 3 to 6, and yet more preferably from 3 to 4.
• Examples of the oxygen atom-containing hydrocarbyl group denoted by R 5 include an alkoxyalkyl group such as a methoxymethyl group, a methoxyethyl group, a methoxypropyl group, an ethoxymethyl group, or an ethoxyethyl group; an oxacycloalkyl group such as an oxiranyl group or a tetrahydrofuranyl group; and an oxacycloalkylalkyl group such as a glycidyl group or a tetrahydrofurfuryl group.
• the number of carbon atoms of the oxygen atom-containing hydrocarbyl group denoted by R 5 is preferably from 2 to 10, more preferably from 2 to 6, and yet more preferably from 2 to 4.
• the oxacycloalkyl group denotes a group in which CH 2 on the alicyclic ring of a cycloalkyl group is replaced by an oxygen atom
• the oxacycloalkylalkyl group denotes a group in which a hydrogen atom of an alkyl group is replaced by an oxacycloalkyl group.
• a divalent group that may contain at least one atom selected from the group consisting of a nitrogen atom and an oxygen atom can be cited.
• examples thereof include an ethylidene group, a propylidene group, a butylidene group, a 1-methylethylidene group, a 1-methylpropylidene group, a 1,3-dimethylbutylidene group, a benzylidene group, and a 4-N,N-dimethylaminobenzylidene group.
• the number of carbon atoms of the single group denoted by the two R 5 s in which they bond to the nitrogen atom via a double bond is from 2 to 20, preferably from 2 to 12, and more preferably from 2 to 8.
• Examples of the divalent group having 2 to 20 carbon atoms in which the two R 5 s are bonded to each other include an alkylene group such as an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, or a hexamethylene group; an alkenylene group such as a group represented by —CH ⁇ CH—CH ⁇ CH—; a nitrogen-containing group such as a group represented by —CH 2 CH 2 —NH—CH 2 —, a group represented by —CH ⁇ CH—N ⁇ CH—, a group represented by —CH 2 CH 2 —N ⁇ CH—, a group represented by —CH 2 CH 2 CH 2 —NH—, a group represented by —CH ⁇ CHCH ⁇ N—, or a group represented by —CH 2 CH 2 —NH—CH 2 CH 2 —; and an oxygen-containing group such as a group represented by —CH 2 CH 2 —O—CH 2 CH 2 — or a group represented by —
• hydrocarbyl group examples include an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, or an n-butyl group; a cycloalkyl group such as a cyclohexyl group; an aryl group such as a phenyl group, a methylphenyl group, or an ethylphenyl group; an aralkyl group such as a benzyl group; an alkenyl group such as a vinyl group, a 1-propenyl group, an allyl group, an isopropenyl group, a crotyl group, an isocrotyl group, or a methallyl
• hydrocarbyl group containing a hydrocarbyloxy group as a substituent examples include an alkoxyalkyl group such as a methoxymethyl group, a methoxyethyl group, a methoxypropyl group, or an ethoxymethyl group; an aryloxyalkyl group such as a phenoxymethyl group or a phenoxyethyl group; and an aralkyloxyalkyl group such as a benzyloxymethyl group or a benzyloxyethyl group.
• the optionally substituted hydrocarbyl group is preferably a hydrocarbyl group, and more preferably a hydrocarbyl group having 1 to 4 carbon atoms.
• the hydrocarbyl group is preferably an alkyl group or an alkenyl group.
• hydrocarbyloxy group denoted by Z 1 and Z 2 of formula (Ia)
• a hydrocarbyloxy group and a hydrocarbyloxy group containing a hydrocarbyloxy group as a substituent can be cited.
• hydrocarbyloxy group examples include an alkoxy group such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, or a butoxy group; an aryloxy group such as a phenoxy group, a methylphenoxy group, or an ethylphenoxy group; and an aralkyloxy group such as a benzyloxy group.
• hydrocarbyloxy group containing a hydrocarbyloxy group as a substituent examples include an alkoxyalkoxy group such as a methoxymethoxy group, a methoxyethoxy group, a methoxypropoxy group, or an ethoxymethoxy group; an aryloxyalkoxy group such as a phenoxymethoxy group or a phenoxyethoxy group; and an aralkyloxyalkoxy group such as a benzyloxymethoxy group or a benzyloxyethoxy group.
• alkoxyalkoxy group such as a methoxymethoxy group, a methoxyethoxy group, a methoxypropoxy group, or an ethoxymethoxy group
• an aryloxyalkoxy group such as a phenoxymethoxy group or a phenoxyethoxy group
• an aralkyloxyalkoxy group such as a benzyloxymethoxy group or a
• the optionally substituted hydrocarbyloxy group is preferably a hydrocarbyloxy group, and more preferably a hydrocarbyloxy group having 1 to 4 carbon atoms.
• the hydrocarbyloxy group is preferably an alkoxy group.
• Examples of the divalent group in which Z 1 and Z 2 of formula (Ia) are bonded to each other and a substituted amino group-containing ring structure in which Z 1 and Z 2 are bonded is formed by Z 1 , Z 2 , and the carbonyl carbon include a group represented by —CH 2 CH 2 CH 2 —N(C 6 H 5 )—, a group represented by —CH 2 CH 2 CH 2 CH 2 CH 2 —N(CH 3 )—, a group represented by —N(CH 3 )—CH 2 CH 2 —N(CH 3 )—, a group represented by —CH 2 —N(CH 2 CH 3 )—CH 2 CH 2 CH 2 —, and a group represented by —CH 2 CH 2 C( ⁇ O)—NH—.
• Examples of compounds represented by formula (Ia) include carboxylic acid amide compounds and carboxylic acid ester compounds.
• carboxylic acid amide compound examples include a formamide compound such formamide, N,N-dimethylformamide, or N,N-diethylformamide;
• an acetamide compound such as N,N-dimethylacetamide, N,N-diethylacetamide, aminoacetamide, N,N-dimethyl-N′,N′-dimethylaminoacetamide, N,N-dimethylaminoacetamide, N,N-dimethyl-N′-ethylaminoacetamide, N,N-dimethylaminoacetamide, or N-phenyldiacetamide; a propionamide compound such as propionamide or N,N-dimethylpropionamide; a pyridylamide compound such as 4-pyridylamide or N,N-dimethyl-4-pyridylamide; a benzamide compound such as benzamide, N,N-dimethylbenzamide, N′,N′-(p-dimethylamino)benzamide, N′,N′-(p-diethylamino)benzamide, N,N-dimethyl-N′,N′-(
• carboxylic acid ester compounds examples include
• an N,N-dialkylaminomethyl acetate such as N,N-dimethylaminomethyl acetate or N,N-diethylaminomethyl acetate
• an N,N-dialkylaminoethyl acetate such as N,N-dimethylaminoethyl acetate or N,N-diethylaminoethyl acetate
• an N,N-dialkylaminopropyl acetate such as N,N-dimethylaminopropyl acetate or N,N-diethylaminopropyl acetate
• an N,N-dialkylaminoethylbenzoate such as N,N-dimethylaminoethylbenzoate or N,N-diethylaminoethylbenzoate.
• Examples of the compound include a compound represented by formula (I-1) below and a compound represented by formula (I-2) below, for which p of formula (Ib) is 0,
• R 5 denotes 1 or 2
• R 5 2 N— is a substituent on the benzene ring
• R 5 denotes a hydrocarbyl group that may contain a nitrogen atom and/or an oxygen atom (the two R 5 s may be identical to or different from each other), a group having 2 to 20 carbon atoms in which the two R 5 s form a single group and are bonded to the nitrogen atom via a double bond, or a divalent group having 2 to 20 carbon atoms in which the two R 5 s are bonded to each other
• R 7 denotes a hydrocarbyl group or a hydrogen atom
• R 5 denotes a hydrocarbyl group that may contain a nitrogen atom and/or an oxygen atom (the two R 5 s may be identical to or different from each other), a group having 2 to 20 carbon atoms in which the two R 5 s form a single group and are bonded to the nitrogen atom via a double bond, or a divalent group having 2 to 20 carbon atoms in which the two R 5 s are bonded to each other.
• r of formula (I-1) denotes 1 or 2
• s of formula (I-2) denotes 1 or 2
• t denotes a number from 0 to 2.
• R 5 2 N— of formula (I-1) and formula (I-2) is a substituent on a benzene ring.
• r, s, and t are 2, it means that two R 5 2 N-s are bonded to a benzene ring.
• the definition, examples, and preferred groups for R 5 are the same as the definition, examples, and preferred groups described for R 5 of formula (Ib).
• R 5 2 N— of formula (I-1) and formula (I-2) is preferably a dialkylamino group.
• the alkyl groups of the dialkylamino group are preferably alkyl groups having 1 to 4 carbon atoms.
• R 7 of formula (I-1) denotes a hydrogen atom or a hydrocarbyl group.
• the hydrocarbyl group include an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, or a tert-butyl group; an aryl group such as a phenyl group, a methylphenyl group, or an ethylphenyl group; and an aralkyl group such as a benzyl group.
• Examples of the compound represented by formula (I-1) include a dialkylamino-substituted benzaldehyde compound such as 4-dimethylaminobenzaldehyde, 4-diethylaminobenzaldehyde, or 3,5-bis(dihexylamino)benzaldehyde; a dialkylamino-substituted acetophenone compound such as 4-dimethylaminoacetophenone or 4-diethylaminoacetophenone; a heterocyclic group-substituted acetophenone compound such as 4′-(1-imidazolyl)acetophenone, 4′-(1-pyrazolyl)acetophenone, or, 4-morpholinoacetophenone.
• a dialkylamino-substituted benzaldehyde compound such as 4-dimethylaminobenzaldehyde, 4-diethylaminobenzaldehyde, or 3,5-bis(dihe
• Examples of the compound represented by formula (I-2) include dimethylaminobenzophenone, compound such as 3-dimethylaminobenzophenone, 3-diethylaminobenzophenone, or 4-dimethylaminobenzophenone, 4-diethylaminobenzophenone, or 4,4′-bis(dimethylamino)benzophenone, 4,4′-bis(diethylamino)benzophenone; a heterocyclic group-substituted benzophenone compound such as 4′-(imidazol-1-yl)benzophenone, 4′-(1-pyrazolyl)benzophenone, 4-morpholinobenzophenone.
• dimethylaminobenzophenone compound such as 3-dimethylaminobenzophenone, 3-diethylaminobenzophenone, or 4-dimethylaminobenzophenone, 4-diethylaminobenzophenone, or 4,4′-bis(dimethylamino)benzophenone
• R 5 denotes a hydrocarbyl group that may contain a nitrogen atom and/or an oxygen atom (the two R 5 s may be identical to or different from each other), a group having 2 to 20 carbon atoms in which the two R 5 s form a single group and are bonded to the nitrogen atom via a double bond, or a divalent group having 2 to 20 carbon atoms in which the two R 5 s are bonded to each other, q denotes an integer from 1 to 10, T denotes an oxygen atom or —NR 6 — (R 6 denotes a hydrocarbyl group or a hydrogen atom), and R 8 denotes an optionally substituted hydrocarbyl group or a hydrogen atom.
• R 5 of formula (I-3) are the same as the definition, examples, and preferred groups described for R 5 of formula (Ib).
• R 5 is more preferably a group for which —NR 5 2 is an acyclic amino group, yet more preferably an alkyl group, an oxacycloalkyl group, or an oxacycloalkylalkyl group, and yet more preferably an alkyl group.
• q of formula (I-3) denotes a number from 1 to 10. It is preferably a number from 2 to 4.
• T of formula (I-3) denotes an oxygen atom or —NR 6 — (R 6 denotes a hydrocarbyl group or a hydrogen atom), and the definition, examples, and preferred groups for R 6 are the same as the definition, examples, and preferred groups described for R 6 of formula (Ib).
• R 6 is more preferably a hydrogen atom.
• R 8 of formula (I-3) denotes an optionally substituted hydrocarbyl group or a hydrogen atom.
• the hydrocarbyl group include an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, or a tert-butyl group; an aryl group such as a phenyl group, a methylphenyl group, or an ethylphenyl group; and an aralkyl group such as a benzyl group.
• the hydrocarbyl group is preferably an alkyl group, and more preferably an alkyl group having 1 to 4 carbon atoms.
• Examples of the substituted hydrocarbyl group denoted by R 8 of formula (I-3) include an alkoxyalkyl group such as a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, or an ethoxyethyl group.
• the substituted hydrocarbyl group is preferably an alkoxyalkyl group, and more preferably alkoxyalkyl group having 2 to 4 carbon atoms.
• Examples of the compound represented by formula (I-3) include acrylamide compounds (T: NH, R 8 : H) below.
• Examples of the compound represented by formula (I-3) include methacrylamide compounds (T: NH, R 8 : CH 3 ) below.
• Examples of the compound represented by formula (I-3) include methacrylamide compounds (T: O, R 8 : H) below.
• Examples of the compound represented by formula (I-3) include methacrylamide compounds (T: O, R 8 : CH 3 ) below.
• the compound represented by formula (I-3) is preferably an acrylamide compound (T: NH, R 8 : H) or a methacrylamide compound (T: NH, R 8 : CH 3 ), more preferably an N-(3-dialkylaminopropyl)acrylamide or an N-(3-dialkylaminopropyl)methacrylamide, and yet more preferably N-(3-dimethylaminopropyl)acrylamide, N-(3-diethylaminopropyl)acrylamide, N-(3-dimethylaminopropyl)methacrylamide, or N-(3-diethylaminopropyl)methacrylamide.
• R 9 denotes an optionally substituted hydrocarbyl group
• R 10 , R 11 , and R 12 denote a hydrogen atom or a hydrocarbyl group
• the plurality of R 12 s may be identical to or different from each other.
• R 9 of formula (I-4) denotes an optionally substituted hydrocarbyl group.
• the hydrocarbyl group denoted by R 9 include an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, or a tert-butyl group; an aryl group such as a phenyl group, a methylphenyl group, an ethylphenyl group, or a naphthyl group; and an aralkyl group such as a benzyl group.
• the number of carbon atoms of the hydrocarbyl group is preferably from 1 to 20.
• Examples of the substituted hydrocarbyl group denoted by R 9 of formula (I-4) include a dialkylaminoalkyl group such as a dimethylaminoethyl group or a diethylaminoethyl group; and an alkoxyalkyl group such as a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, or an ethoxyethyl group.
• the number of carbon atoms of the substituted hydrocarbyl group is preferably from 1 to 20.
• R 9 of formula (I-4) is preferably a hydrocarbyl group, and more preferably an alkyl group or an aryl group.
• R 10 and R 11 of formula (I-4) denote a hydrogen atom or a hydrocarbyl group.
• the hydrocarbyl group include an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, or a tert-butyl group; an aryl group such as a phenyl group, a methylphenyl group, an ethylphenyl group, or a naphthyl group; and an aralkyl group such as a benzyl group.
• the number of carbon atoms of the hydrocarbyl group is preferably from 1 to 20.
• R 10 and R 11 of formula (I-4) are preferably hydrogen atoms, alkyl groups, or aryl groups, and more preferably hydrogen atoms.
• g of formula (I-4) denotes a number from 0 to 10. It is preferably a number from 2 to 7.
• R 12 of formula (I-4) denotes a hydrogen atom or a hydrocarbyl group.
• the hydrocarbyl group include an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, or a tert-butyl group.
• R 12 of formula (I-4) is preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom.
• Examples of the compound of formula (I-4) include a ⁇ -propiolactam compound such as N-methyl- ⁇ -propiolactam, N-(tert-butyl)- ⁇ -propiolactam, or N-phenyl- ⁇ -propiolactam;
• a 2-pyrrolidone compound such as 1-methyl-2-pyrrolidone, 1-phenyl-2-pyrrolidone, 1-(p-methylphenyl)-2-pyrrolidone, 1-(p-methoxyphenyl)-2-pyrrolidone, 1-benzyl-2-pyrrolidone, 1-naphthyl-2-pyrrolidone, 1-phenyl-5-methyl-2-pyrrolidone, 1-(tert-butyl)-5-methyl-2-pyrrolidone, or 1-(tert-butyl)-3,3-dimethyl-2-pyrrolidone; a 2-piperidone compound such as 1-(tert-butyl)-2-piperidone, 1-phenyl-2-piperidone, 1-(p-methylphenyl)-2-piperidone, or 1-naphthyl-2-piperidone; an ⁇ -caprolactam compound such as N-methyl- ⁇ -caprolactam, N-ethyl- ⁇ -caprol
• the compound represented by formula (I-4) is preferably a 2-pyrrolidone compound or an ⁇ -caprolactam compound, more preferably a 1-hydrocarbyl-substituted 2-pyrrolidone or an N-hydrocarbyl-substituted ⁇ -caprolactam, and yet more preferably a 1-alkyl-substituted 2-pyrrolidone, a 1-aryl-substituted 2-pyrrolidone, an N-alkyl-substituted ⁇ -caprolactam, or an N-aryl-substituted ⁇ -caprolactam.
• R 13 and R 14 denote an optionally substituted hydrocarbyl group
• R 15 denotes a hydrogen atom or a hydrocarbyl group
• the plurality of R 15 s may be identical to or different from each other.
• R 13 and R 14 of formula (I-5) denote an optionally substituted hydrocarbyl group.
• the hydrocarbyl group denoted by R 13 and R 14 include an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, or a tert-butyl group; an aryl group such as a phenyl group, a methylphenyl group, an ethylphenyl group, or a naphthyl group; and an aralkyl group such as a benzyl group.
• the number of carbon atoms of the hydrocarbyl group is preferably from 1 to 20.
• Examples of the substituted hydrocarbyl group denoted by R 13 and R 14 of formula (I-5) include a dialkylaminoalkyl group such as a dimethylaminoethyl group or a diethylaminoethyl group; and an alkoxyalkyl group such as a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, or an ethoxyethyl group.
• the number of carbon atoms of the substituted hydrocarbyl group is preferably from 1 to 20.
• R 13 and R 14 of formula (I-5) are preferably hydrocarbyl groups, more preferably alkyl groups or aryl groups, and yet more preferably alkyl groups.
• h of formula (I-5) denotes a number from 0 to 10. It is preferably a number from 2 to 7.
• R 15 of formula (I-5) denotes a hydrogen atom or a hydrocarbyl group.
• the hydrocarbyl group include an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, or a tert-butyl group.
• R 15 of formula (I-5) is preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom.
• Examples of the compound represented by formula (I-5) include a 1,3-hydrocarbyl-substituted 2-imidazolidinone such as 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, 1,3-di(n-propyl)-2-imidazolidinone, 1,3-di(tert-butyl)-2-imidazolidinone, or 1,3-diphenyl-2-imidazolidinone.
• a 1,3-hydrocarbyl-substituted 2-imidazolidinone such as 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, 1,3-di(n-propyl)-2-imidazolidinone, 1,3-di(tert-butyl)-2-imidazolidinone, or 1,3-diphenyl-2-imidazolidinone.
• the compound represented by formula (I-5) is preferably a 1,3-substituted 2-imidazolidinone, more preferably a 1,3-hydrocarbyl-substituted 2-imidazolidinone, and yet more preferably a 1,3-dialkyl-2-imidazolidinone.
• the 1,3-dialkyl-2-imidazolidinone is preferably 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, or 1,3-di(n-propyl)-2-imidazolidinone, and more preferably 1,3-dimethyl-2-imidazolidinone.
• Component (B) is a conjugated diene polymer rubber component modified with a compound represented by formula (IIa) below,
• R 21 and R 23 denote a hydrocarbyl group
• R 22 denotes a hydrocarbylene group
• A denotes a substituted amino group or an optionally substituted hydrocarbyloxy group
• a conjugated diene polymer rubber component in component (B) contains a conjugated diene unit.
• the conjugated diene include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, and 1,3-hexadiene, and one or more types thereof may be used.
• the conjugated diene is preferably 1,3-butadiene or isoprene.
• the conjugated diene polymer rubber component of component (B) may further comprise, in addition to the conjugated diene-based constituent unit (conjugated diene unit), a constituent unit based on another monomer.
• said other monomer include an aromatic vinyl, a vinylnitrile, and an unsaturated carboxylic acid ester.
• aromatic vinyl include styrene, a-methylstyrene, vinyltoluene, vinylnaphthalene, divinylbenzene, trivinylbenzene, and divinylnaphthalene.
• Examples of the vinylnitrile include acrylonitrile, and examples of the unsaturated carboxylic acid ester include methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate. Among them, an aromatic vinyl is preferable, and styrene is more preferable.
• the conjugated diene polymer of component (B) preferably contains an aromatic vinyl unit, and the content of the aromatic vinyl unit, relative to 100% by weight of the total amount of the conjugated diene unit and the aromatic vinyl unit, is preferably at least 10% by weight (the content of the conjugated diene unit being no greater than 90% by weight), and more preferably at least 15% by weight (the content of the conjugated diene unit being no greater than 85% by weight). Furthermore, from the viewpoint of fuel economy, the content of the aromatic vinyl unit is preferably no greater than 50% by weight (the content of the conjugated diene unit being at least 50% by weight), and more preferably no greater than 45% by weight (the content of the conjugated diene unit being at least 55% by weight).
• the conjugated diene polymer rubber component of component (B) preferably contains a constituent unit based on a silicon-containing monomer.
• the silicon-containing monomer is preferably a monomer represented by formula (X).
• the monomer represented by formula (X) is as explained for component (A).
• the content of the constituent unit based on a silicon-containing monomer in the conjugated diene polymer rubber component of component (B) is preferably not less than 0.001 mmol/g and not more than 0.1 mmol/g per unit weight of component (B). It is more preferably not less than 0.002 mmol/g and not more than 0.07 mmol/g. It is yet more preferably not less than 0.003 mmol/g and not more than 0.05 mmol/g.
• the conjugated diene polymer rubber component of component (B) is modified with the above-mentioned compound represented by formula (IIa) (hereinafter, also called compound (II)).
• n of formula (IIa) denotes a number from 1 to 3. It is preferably a number from 2 to 3, and more preferably 3.
• n of formula (IIa) denotes a number from 1 to 3. It is preferably a number from 1 to 2, and more preferably 1.
• m+n is a number from 2 to 4, preferably from 3 to 4, and more preferably 4.
• R 21 and R 23 of formula (IIa) denote a hydrocarbyl group.
• the hydrocarbyl group include an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, or a tert-butyl group; an aryl group such as a phenyl group, a methylphenyl group, an ethylphenyl group, or a naphthyl group; and an aralkyl group such as a benzyl group.
• the hydrocarbyl group is preferably an alkyl group.
• the number of carbon atoms of the hydrocarbyl group denoted by R 21 and R 23 is preferably from 1 to 4, more preferably from 1 to 3, and yet more preferably 1 or 2.
• R 22 of formula (IIa) denotes a hydrocarbylene group.
• the hydrocarbylene group include an alkylene group such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, or a hexamethylene group; an arylene group such as a phenylene group, a tolylene group, or a xylylene group; and an aralkylene group.
• the hydrocarbylene group is preferably a straight-chain alkylene group.
• the number of carbon atoms of R 22 of formula (Ib) is preferably from 1 to 10, and more preferably from 2 to 4.
• a of formula (IIa) denotes a substituted amino group or an optionally substituted hydrocarbyloxy group.
• substituted amino group a group represented by formula (IIb) can be cited.
• optionally substituted hydrocarbyloxy group a group represented by formula (IIc), which is described later, can be cited.
• R 24 and R 25 denote a hydrocarbyl group that may contain at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a silicon atom, a substituted silyl group, a group having 2 to 20 carbon atoms in which R 24 and R 25 form a single group and are bonded to the nitrogen atom via a double bond, or a divalent group having 2 to 20 carbon atoms in which R 24 and R 25 are bonded to each other, and * represents a bonding position.
• Examples of the hydrocarbyl group denoted by R 24 and R 25 include an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, a neopentyl group, an isopentyl group, or an n-hexyl group; a cycloalkyl group such as a cyclohexyl group; an aryl group such as a phenyl group, a methylphenyl group, or an ethylphenyl group; and an aralkyl group such as a benzyl group. It is preferably an alkyl group.
• the number of carbon atoms of the hydrocarbyl group denoted by R 24 and R 25 is preferably from 1 to 10, more preferably from 1 to 6, and yet more preferably from 1 to 4.
• Examples of the nitrogen atom-containing hydrocarbyl group denoted by R 24 and R 25 include a dialkylaminoalkyl group such as a dimethylaminomethyl group, a dimethylaminoethyl group, a dimethylaminopropyl group, or a diethylaminoethyl group.
• the number of carbon atoms of the nitrogen atom-containing hydrocarbyl group denoted by R 24 and R 25 is preferably from 3 to 10, more preferably from 3 to 6, and yet more preferably from 3 to 4.
• Examples of the oxygen atom-containing hydrocarbyl group denoted by R 24 and R 25 include an alkoxyalkyl group such as a methoxymethyl group, a methoxyethyl group, a methoxypropyl group, an ethoxymethyl group, or an ethoxyethyl group; an oxacycloalkyl group such as an oxiranyl group or a tetrahydrofuranyl group; and an oxacycloalkylalkyl group such as a glycidyl group or a tetrahydrofurfuryl group. It is preferably an oxacycloalkyl group or an oxacycloalkylalkyl group.
• the number of carbon atoms of the oxygen atom-containing hydrocarbyl group denoted by R 24 and R 25 is preferably from 2 to 10, more preferably from 2 to 6, and yet more preferably from 2 to 4.
• Examples of the silicon atom-containing hydrocarbyl group denoted by R 24 and R 25 include a trialkylsilylalkyl group such as a trimethylsilylmethyl group.
• the number of carbon atoms of the silicon atom-containing hydrocarbyl group denoted by R 24 and R 25 is preferably from 4 to 10, more preferably from 4 to 6, and yet more preferably 4.
• Examples of the substituted silyl group denoted by R 24 and R 25 include a trialkylsilyl group such as a trimethylsilyl group, a triethylsilyl group, or a t-butyldimethylsilyl group; and a trialkoxysilyl group such as a trimethoxysilyl group. It is preferably a trialkylsilyl group.
• the number of carbon atoms of the substituted silyl group denoted by R 24 and R 25 is preferably from 3 to 10, more preferably from 3 to 6, and yet more preferably 3.
• a divalent group that may contain at least one atom selected from the group consisting of a nitrogen atom and an oxygen atom can be cited.
• examples thereof include an ethylidene group, a propylidene group, a butylidene group, a 1-methylethylidene group, a 1-methylpropylidene group, a 1,3-dimethylbutylidene group, a benzylidene group, and a 4-N,N-dimethylaminobenzylidene group.
• the number of carbon atoms of the single group denoted by the two R 24 and R 25 in which they bond to the nitrogen atom via a double bond is from 2 to 20, preferably from 2 to 12, and more preferably from 2 to 8.
• Examples of the divalent group having 2 to 20 carbon atoms in which the R 24 and R 25 are bonded to each other include an alkylene group such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, or a hexamethylene group; an alkenylene group such as a group represented by —CH ⁇ CH—CH ⁇ CH—; a nitrogen-containing group such as a group represented by —CH 2 CH 2 —NH—CH 2 —, a group represented by —CH ⁇ CH—N ⁇ CH—, a group represented by —CH 2 CH 2 —N ⁇ CH—, a group represented by —CH 2 CH 2 CH 2 —NH—, a group represented by —CH ⁇ CHCH ⁇ N—, or a group represented by —CH 2 CH 2 —NH—CH 2 CH 2 —; and an oxygen-containing group such as a group represented by —CH 2 CH 2 —O—CH 2 CH 2 — or
• acyclic amino group examples include a dialkylamino group such as a dimethylamino group, a diethylamino group, a di(n-propyl)amino group, a di(isopropyl)amino group, a di(n-butyl)amino group, a di(sec-butyl)amino group, a di(tert-butyl)amino group, a di(neopentyl)amino group, or an ethylmethylamino group; a di(alkoxyalkyl)amino group such as a di(methoxymethyl)amino group, a di(methoxyethyl)amino group, a di(ethoxymethyl)amino group, or a di(ethoxyethyl)amino group; and a di(trialkylsilyl)amino group such as a di(trimethylsilyl)amin
• di(oxacycloalkyle) amino group such as di(oxiranyl)amino group or a di(tetrahydrofuranyl)amino group
• a di(oxacycloalkylalkyl)amino group such as a di(glycidyl)amino group or a di(tetrahydrofurfuryl)amino group.
• Yet further examples thereof include an ethylideneamino group, a 1-methylpropylideneamino group, a 1,3-dimethylbutylideneamino group, a 1-methylethylideneamino group, and a 4-N,N-dimethylaminobenzylideneamino group.
• Examples of the cyclic amino group include a 1-polymethyleneimino group such as a 1-aziridinyl group, a 1-azetidinyl group, a 1-pyrrolidinyl group, a 1-piperidinyl group, a 1-hexamethyleneimino group, a 1-heptamethyleneimino group, a 1-octamethyleneimino group, a 1-decamethyleneimino group, or a 1-dodecamethyleneimino group.
• a 1-polymethyleneimino group such as a 1-aziridinyl group, a 1-azetidinyl group, a 1-pyrrolidinyl group, a 1-piperidinyl group, a 1-hexamethyleneimino group, a 1-heptamethyleneimino group, a 1-octamethyleneimino group, a 1-decamethyleneimino group, or a 1-dodecamethyleneimino group.
• examples of the cyclic amino group also include a 1-pyrrolyl group, a 1-imidazolidinyl group, a 1-imidazolyl group, a 4,5-dihydro-1-imidazolyl group, a 1-pyrazolidinyl group, a 1-pyrazolyl group, a 1-piperazinyl group, and a morpholino group.
• R 26 denotes a hydrocarbyl group that may contain at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a silicon atom, and * represents a bonding position.
• Examples of the hydrocarbyl group denoted by R 26 include an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, a neopentyl group, an isopentyl group, or an n-hexyl group; a cycloalkyl group such as a cyclohexyl group; an aryl group such as a phenyl group, a methylphenyl group, or an ethylphenyl group; and an aralkyl group such as a benzyl group. It is preferably an alkyl group.
• the number of carbon atoms of the hydrocarbyl group denoted by R 26 is preferably from 1 to 10, more preferably from 1 to 6, and yet more preferably from 1 to 4.
• Examples of the nitrogen atom-containing hydrocarbyl group denoted by R 26 include a dialkylaminoalkyl group such as a dimethylaminomethyl group, a dimethylaminoethyl group, a dimethylaminopropyl group, or a diethylaminoethyl group.
• the number of carbon atoms of the nitrogen atom-containing hydrocarbyl group denoted by R 26 is preferably from 3 to 10, more preferably from 3 to 6, and yet more preferably from 3 to 4.
• Examples of the oxygen atom-containing hydrocarbyl group denoted by R 26 include an alkoxyalkyl group such as a methoxymethyl group, a methoxyethyl group, a methoxypropyl group, an ethoxymethyl group, or an ethoxyethyl group; an oxacycloalkyl group such as an oxiranyl group or a tetrahydrofuranyl group; and an oxacycloalkylalkyl group such as a glycidyl group or a tetrahydrofurfuryl group. It is preferably an alkoxyalkyl group, an oxacycloalkyl group, or an oxacycloalkylalkyl group.
• the number of carbon atoms of the oxygen atom-containing hydrocarbyl group denoted by R 26 is preferably from 2 to 10, more preferably from 2 to 6, and yet more preferably from 2 to 4.
• Examples of the silicon atom-containing hydrocarbyl group denoted by R 26 include a trialkylsilylalkyl group such as a trimethylsilylmethyl group.
• the number of carbon atoms of the silicon atom-containing hydrocarbyl group denoted by R 26 is preferably from 4 to 10, more preferably from 4 to 6, and yet more preferably 4.
• the substituted hydrocarbyl group denoted by R 26 is preferably an alkoxyalkyl group, an oxacycloalkyl group, or an oxacycloalkylalkyl group.
• Examples of the group represented by formula (IIc) include an alkoxy group such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, a sec-butoxy group, or a tert-butoxy group; a phenoxy group; a dialkylaminoalkoxy group such as a dimethylaminomethoxy group, or a diethylaminomethoxy group; and a trialkylsiloxy group such as a trimethylsiloxy group or a t-butyldimethylsiloxy group.
• Examples further include a 1,2-oxiranylalkoxy group such as a 1,2-oxiranylpropoxy group, a 1,2-oxiranylbutoxy group, and a 1,2-oxiranylpentyloxy group.
• the group denoted by A of formula (IIa) is preferably a substituted amino group, more preferably an acyclic amino group, and yet more preferably a dialkylamino group, a di(oxacycloalkyl)amino group, a di(oxacycloalkylalkyl)amino group, or a di(trialkylsilyl)amino group.
• Examples of the compound in which formula (IIb) is a di(oxacycloalkyl) amino group include compounds in which formula (IIa) is a di(oxiranyl)amino group such as
• Examples of the compound in which formula (IIb) is a di(alkylene oxide alkyl)amino group include compounds in which formula (IIb) is a di(glycidyl)amino group such as
• examples of the compound (II) which A of formula (IIa) is a group represented by formula (IIb) include the following compounds in which formula (IIb) is an acyclic amino group such as a 1-piperidinyl group, a 1-hexamethyleneimino group, a 1-imidazolyl group, a 4,5-dihydro-1-imidazolyl group, a 1-piperazinyl group, or a morpholino group.
• Examples of the compound (II) in which A of formula (IIa) is a group represented by formula (IIc) include the following compounds in which R 26 of formula (IIc) is an alkyl group or an oxacycloalkylalkyl group.
• Compound (II) is preferably a [3-(dialkylamino)propyl]trialkoxysilane, and more preferably
• the conjugated diene polymer rubber comprises the above-mentioned component (A) and component (B), component (A) having a content, with the total amount of component (A) and component (B) as 100% by weight, of from 5 to 90% by weight, and component (B) having a content of from 95 to 10% by weight.
• the content of component (A) is preferably not less than 10% by weight (the content of component (B) being not more than 90% by weight), more preferably not less than 15% by weight (the content of component (B) being not more than 85% by weight), and yet more preferably not less than 20% by weight (the content of component (B) being not more than 80% by weight).
• the content of component (A) is preferably not more than 80% by weight (the content of component (B) being not less than 20% by weight), more preferably not more than 70% by weight (the content of component (B) being not less than 30% by weight), and yet more preferably not more than 50% by weight (the content of component (B) being not less than 50% by weight).
• the conjugated diene polymer preferably contains an aromatic vinyl unit in component (A) or/and (B), and the content of the aromatic vinyl unit, relative to 100% by weight of the total amount of the conjugated diene unit and the aromatic vinyl unit, is preferably at least 10% by weight (the content of the conjugated diene unit being no greater than 90% by weight), and more preferably at least 15% by weight (the content of the conjugated diene unit being no greater than 85% by weight).
• the content of the aromatic vinyl unit is preferably no greater than 50% by weight (the content of the conjugated diene unit being at least 50% by weight), and more preferably no greater than 45% by weight (the content of the conjugated diene unit being at least 55% by weight).
• the conjugated diene polymer rubber component preferably contains a constituent unit based on a silicon-containing monomer in component (A) and/or component (B), more preferably contains a constituent unit based on a silicon-containing monomer in component (A), yet more preferably contains a constituent unit based on a silicon-containing monomer in component (A) and component (B).
• the silicon-containing monomer is preferably a monomer represented by formula (X).
• the content of the constituent unit based on a silicon-containing monomer in the conjugated diene polymer rubber is preferably not less than 0.001 mmol/g and not more than 0.1 mmol/g per unit weight of component (B). It is more preferably not less than 0.002 mmol/g and not more than 0.07 mmol/g. It is yet more preferably not less than 0.003 mmol/g and not more than 0.05 mmol/g.
• the vinyl bond content (proportion of conjugated diene-based 1,2-addition constitutional unit) of the conjugated diene polymer of the present invention is preferably no greater than 80% by mol, and more preferably no greater than 70% by mol. Furthermore, from the viewpoint of grip properties, it is preferably at least 10% by mol, more preferably at least 15% by mol, yet more preferably at least 20% by mol, and particularly preferably at least 40% by mol.
• the vinyl bond content may be obtained by IR spectroscopy from the absorption intensity at around 910 cm ⁇ 1 , which is an absorption peak of a vinyl group.
• the Mooney viscosity (ML 1+4 ) of the conjugated diene polymer of the present invention is preferably not less than 10, and more preferably not less than 20. Furthermore, in order to improve processability, it is preferably not more than 200, and more preferably not more than 150.
• the Mooney viscosity (ML 1+4 ) is measured at 100° C. in accordance with JIS K6300 (1994).
• the molecular weight distribution of the conjugated diene polymer rubber is preferably 1 to 5, and more preferably 1 to 2.
• the molecular weight distribution is obtained by measuring number-average molecular weight (Mn) and weight-average molecular weight (Mw) by a gel permeation chromatograph (GPC) method, and dividing Mw by Mn.
• a method for producing the conjugated diene polymer rubber of the present invention a method in which component (A) and component (B) are separately prepared, and component (A) and component (B) are mixed by a known method (a method in which melt mixing is carried out by means of a known kneader such as a roll or a Banbury, a method in which solution mixing is carried out in a hydrocarbon solvent, etc.) can be cited. Furthermore, a production method including step (c-1), step (c-2), and step (c-3) below can also be cited.
• Step (c-1) a step of polymerizing a monomer component including a conjugated diene in a hydrocarbon solvent by an alkali metal catalyst, thus giving a polymer having an alkali metal derived from the catalyst in at least one conjugated diene-based monomer unit-containing polymer chain terminus.
• Step (c-2) a step of reacting the alkali metal-containing polymer terminus of the polymer obtained in step (c-1) with a carbonyl group- and substituted amino group-containing compound (compound (I)), the amount of compound (I) used being not less than 0.05 mol and not more than 0.9 mol per mole of the alkali metal of the alkali metal catalyst used in step (c-1).
• Step (c-3) a step of reacting the alkali metal-containing polymer terminus of the polymer having an alkali metal in at least one polymer terminus with a compound represented by formula (IIa) below (compound (II)) after step (c-2) is completed, the amount of compound (II) used satisfying expression (i) below.
• R 21 and R 23 denote a hydrocarbyl group
• R 22 denotes a hydrocarbylene group
• A denotes a substituted amino group or an optionally substituted hydrocarbyloxy group
• Examples of the alkali metal catalyst that may be used in (c-1) include an alkali metal, an organoalkali metal compound, a complex between an alkali metal and a polar compound, an oligomer having an alkali metal, etc.
• alkali metal examples include lithium, sodium, potassium, rubidium, and cesium.
• organoalkali metal compound examples include ethyllithium, n-propyllithium, iso-propyllithium, n-butyllithium, sec-butyllithium, t-octyllithium, n-decyllithium, phenyllithium, 2-naphthyllithium, 2-butylphenyllithium, 4-phenylbutyllithium, cyclohexyllithium, 4-cyclopentyllithium, dimethylaminopropyllithium, diethylaminopropyllithium, t-butyldimethylsilyloxypropyllithium, N-morpholinopropyllithium, lithium hexamethyleneimide, lithium pyrrolidide, lithium piperidide, lithium heptamethyleneimide, lithium dodecamethyleneimide, 1,4-dilithio-2-butene, sodium naphthalenide, sodium biphenylide, and potassium
• Examples of the complex between an alkali metal and a polar compound include a potassium-tetrahydrofuran complex and a potassium-diethoxyethane complex.
• Examples of the oligomer having an alkali metal include the sodium salt of a-methylstyrene tetramer.
• an organolithium compound or an organosodium compound is preferable, and an organolithium compound or organosodium compound having 2 to 20 carbon atoms is more preferable.
• the hydrocarbon solvent used in step (c-1) is a solvent that does not deactivate the organoalkali metal compound catalyst, and examples thereof include an aliphatic hydrocarbon, an aromatic hydrocarbon, and an alicyclic hydrocarbon.
• the aliphatic hydrocarbon include propane, n-butane, iso-butane, n-pentane, iso-pentane, n-hexane, propene, 1-butene, iso-butene, trans-2-butene, cis-2-butene, 1-pentene, 2-pentene, 1-hexene, and 2-hexene.
• aromatic hydrocarbon examples include benzene, toluene, xylene, and ethylbenzene
• alicyclic hydrocarbon examples include cyclopentane and cyclohexane. They may be used on their own or in a combination of two or more types. Among them, a hydrocarbon having 2 to 12 carbon atoms is preferable.
• step (c-1) monomer containing a conjugated diene are polymerized to produce a conjugated diene polymer having at a polymer chain terminus an alkali metal originating from the above-mentioned alkali metal catalyst.
• the conjugated diene include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, and 1,3-hexadiene, and they may be used on their own or in a combination of two or more types. Among them, from the viewpoint of ready availability, 1,3-butadiene and isoprene are preferable.
• polymerization may be carried out using the conjugated diene and another monomer.
• said other monomer include an aromatic vinyl, a vinylnitrile, and an unsaturated carboxylic acid ester.
• aromatic vinyl include styrene, -methylstyrene, vinyltoluene, vinylnaphthalene, divinylbenzene, trivinylbenzene, and divinylnaphthalene.
• vinylnitrile include acrylonitrile
• specific examples of the unsaturated carboxylic acid ester include methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate.
• an aromatic vinyl is preferable, and styrene is more preferable.
• the amount of aromatic vinyl used is not less than 0% by weight (the amount of conjugated diene used being not more than 100% by weight); in order to improve strength it is preferably not less than 10% by weight (the amount of conjugated diene used being not more than 90% by weight), and more preferably not less than 15% by weight (the amount of conjugated diene used being not more than 85% by weight).
• the amount of aromatic vinyl used is preferably not more than 50% by weight (the amount of conjugated diene used being not less than 50% by weight), and more preferably not more than 45% by weight (the amount of conjugated diene used being not less than 55% by weight).
• step (c-1) in order to improve abrasion resistance and fuel economy of the conjugated diene polymer rubber obtained, it is preferable to use a silicon-containing monomer as one of the monomer components and carry out polymerization of the monomer components including the conjugated diene and the silicon-containing monomer in the hydrocarbon solvent by means of the alkali metal catalyst, thus giving a polymer having a catalyst-derived alkali metal on at least one terminus of a polymer chain containing a conjugated diene-based monomer unit and a constituent unit based on a silicon-containing monomer.
• the silicon-containing monomer is preferably a monomer represented by formula (X) above.
• the amount of silicon-containing monomer used, per g of monomer components used for polymerization is preferably not less than 0.001 m mmol, more preferably not less than 0.002 mmol, and yet more preferably not less than 0.003 mmol.
• the amount used is preferably not more than 0.1 mmol, more preferably not more than 0.07 mmol, and yet more preferably not more than 0.05 mmol.
• the polymerization in step (c-1) may be carried out in the presence of an agent for regulating the vinyl bond content of the conjugated diene unit, an agent for regulating the distribution in the conjugated diene polymer chain of the conjugated diene unit and a constituent unit based on a monomer other than the conjugated diene (hereafter, generally called ‘regulators’), etc.
• agents for regulating the vinyl bond content of the conjugated diene unit an agent for regulating the distribution in the conjugated diene polymer chain of the conjugated diene unit and a constituent unit based on a monomer other than the conjugated diene
• agents include an ether compound, a tertiary amine, and a phosphine compound.
• the ether compound examples include cyclic ethers such as tetrahydrofuran, tetrahydropyran, and 1,4-dioxane; aliphatic monoethers such as diethyl ether and dibutyl ether; aliphatic diethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, and diethylene glycol dibutyl ether; and aromatic ethers such as diphenyl ether and anisole.
• cyclic ethers such as tetrahydrofuran, tetrahydropyran, and 1,4-dioxane
• aliphatic monoethers such as diethyl ether and dibutyl ether
• aliphatic diethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol
• tertiary amine examples include triethylamine, tripropylamine, tributylamine, N,N,N′,N′-tetramethylethylenediamine, N,N-diethylaniline, pyridine, and quinoline.
• phosphine compound examples include trimethylphosphine, triethylphosphine, and triphenylphosphine. They may be used on their own or in a combination of two or more types.
• the polymerization temperature in step A is preferably from 25° C. to 100° C., more preferably from 35° C. to 90° C., and yet more preferably from 50° C. to 80° C.
• the polymerization time is preferably from 10 minutes to 5 hours.
• the amount of compound (I) used in the reaction between the polymer prepared in step (c-1) and compound (I) is preferably from 0.05 to 0.9 mol per mol of the alkali metal of alkali metal catalyst used in step (c-1).
• the amount of the compound (I) is more preferably more than 0.1 mol, yet more preferably more than 0.15 mol, particularly preferably more than 0.2 mol.
• the amount of the compound (I) is more preferably less than 0.8 mol, and yet more preferably less than 0.7 mol, particularly preferably less than 0.5 mol.
• step (c-2) the temperature at which the polymer prepared in step (c-2) and the compound (I) are reacted is preferably from 25° C. to 100° C., more preferably from 35° C. to 90° C., and yet more preferably from 50° C. to 80° C.
• the contact time is preferably 60 sec to 5 hours, and more preferably from 15 min to 1 hour.
• the amount of compound (II) used in the reaction between the polymer having an alkali metal in at least one polymer terminus and compound (II) is preferably an amount that satisfies relationship (i) below. In order to improve abrasion resistance, it is more preferably an amount that satisfies relationship (ii) below, yet more preferably an amount that satisfies relationship (iii) below, and particularly preferably an amount that satisfies relationship (iv) below.
• it is more preferably an amount that satisfies relationship (v) below, yet more preferably an amount that satisfies relationship (vi) below, yet more preferably an amount that satisfies relationship (vii) below, and particularly preferably an amount that satisfies relationship (viii) below.
• the temperature at which the polymer having an alkali metal in at least one polymer terminus and compound (II) are reacted is preferably from 25° C. to 100° C., and more preferably from 35° C. to 90° C. It is yet more preferably from 50° C. to 80° C.
• the reaction time is preferably from 60 seconds to 5 hours, more preferably from 5 minutes to 1 hour, and yet more preferably from 15 minutes to 1 hour.
• a coupling agent may be added to the hydrocarbon solution of the conjugated diene polymer as necessary from initiation of polymerization of monomer by an alkali metal catalyst to termination of polymerization.
• the coupling agent include a compound represented by formula (III) below,
• R 10 denotes an alkyl group, an alkenyl group, a cycloalkenyl group, or an aromatic residue
• M denotes a silicon atom or a tin atom
• L denotes a halogen atom or a hydrocarbyloxy group
• a denotes an integer of 0 to 2.
• the aromatic residue denotes a monovalent group in which a hydrogen bonded to an aromatic ring is removed from an aromatic hydrocarbon.
• Examples of the coupling agent of formula (III) include silicon tetrachloride, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, tin tetrachloride, methyltrichlorotin, dimethyldichlorotin, trimethylchlorotin, tetramethoxysilane, methyltrimethoxysilane, dimethoxydimethylsilane, methyltriethoxysilane, ethyltrimethoxysilane, dimethoxydiethylsilane, diethoxydimethylsilane, tetraethoxysilane, ethyltriethoxysilane, and diethoxydiethylsilane.
• the amount of coupling agent added is preferably not less than 0.03 mol per mol of the alkali metal originating from the alkali metal catalyst, and more preferably not less than 0.05 mol. Furthermore, from the viewpoint of fuel economy, it is preferably not more than 0.4 mol, and more preferably not more than 0.3 mol.
• the conjugated diene polymer rubber may be recovered from the hydrocarbon solution of the conjugated diene polymer rubber by a known recovery method such as, for example, (1) a method in which a coagulant is added to the hydrocarbon solution of the conjugated diene polymer or (2) a method in which steam is added to the hydrocarbon solution of the conjugated diene polymer.
• the conjugated diene polymer thus recovered may be dried by a known dryer such as a band dryer or an extrusion dryer.
• the conjugated diene polymer rubber of the present invention may be used in a conjugated diene polymer rubber composition by combining another polymer component, an additive, etc. therewith.
• Examples of another polymer component include conventional styrene-butadiene copolymer rubber, polybutadiene rubber, butadiene-isoprene copolymer rubber, and butyl rubber. Examples further include natural rubber, an ethylene-propylene copolymer, and an ethylene-octene copolymer. These polymer components may be used in a combination of two or more types.
• the amount of conjugated diene polymer of the present invention is preferably not less than 10 parts by weight, and more preferably not less than 20 parts by weight per 100 parts by weight of the total amount of polymer components combined (including the amount of conjugated diene polymer combined).
• a known additive may be used, and examples thereof include a vulcanizing agent such as sulfur; a vulcanization accelerator such as a thiazole-based vulcanization accelerator, a thiuram-based vulcanization accelerator, a sulfenamide-based vulcanization accelerator, or a guanidine-based vulcanization accelerator; a vulcanization activator such as stearic acid or zinc oxide; an organic peroxide; a filler such as silica, carbon black, calcium carbonate, talc, alumina, clay, aluminum hydroxide, or mica; a silane coupling agent; an extender oil; a processing aid; an antioxidant; and a lubricant.
• a vulcanizing agent such as sulfur
• a vulcanization accelerator such as a thiazole-based vulcanization accelerator, a thiuram-based vulcanization accelerator, a sulfenamide-based vulcanization accelerator, or a guanidine
• silica examples include dry silica (anhydrous silicic acid), wet silica (hydrated silicic acid), colloidal silica, precipitated silica, calcium silicate, and aluminum silicate. One type thereof may be used on its own, or two or more types thereof may be used in combination.
• the BET specific surface area of the silica is preferably from 50 to 250 m 2 /g. The BET specific surface area is measured in accordance with ASTM D1993-03. As a commercial product, product names VN3, AQ, ER, and RS-150 manufactured by Tosoh Silica Corporation, product names Zeosil 1115MP and 1165MP manufactured by Rhodia, etc. may be used.
• Examples of the carbon black include furnace black, acetylene black, thermal black, channel black, and graphite.
• channel carbon black such as EPC, MPC, or CC
• furnace carbon black such as SAF, ISAF, HAF, MAF, FEF, SRF, GPF, APF, FF, CF, SCF, or ECF
• thermal carbon black such as FT or MT
• acetylene carbon black can be cited as examples.
• One type thereof may be used or two or more types thereof may be used in combination.
• the nitrogen adsorption specific surface area (N 2 SA) of the carbon black is preferably from 5 to 200 m 2 /g, and the dibutyl phthalate (DBP) absorption of the carbon black is preferably from 5 to 300 mL/100 g.
• the nitrogen adsorption specific surface area is measured in accordance with ASTM D4820-93, and the DBP absorption is measured in accordance with ASTM D2414-93.
• product names SEAST 6, SEAST 7HM, and SEAST KH manufactured by Tokai Carbon Co., Ltd., product names CK 3 and Special Black 4A manufactured by Degussa, Inc., etc. may be used.
• silane coupling agent examples include vinyltrichlorosilane, vinyltriethoxysilane, vinyltris( ⁇ -methoxyethoxy)silane, ⁇ -(3,4-epoxycyclohexyl)ethyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, N-( ⁇ -aminoethyl)- ⁇ -aminopropyltrimethoxysilane, N-( ⁇ -aminoethyl)- ⁇ -aminopropylmethyldimethoxysilane, N-phenyl- ⁇ -aminopropyltrimethoxysilane, ⁇ -chloropropyltrimethoxysilane, ⁇ -mercaptopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, bis(3-(triethoxysilyl
• the amount of filler combined, relative to 100 parts by weight of the conjugated diene polymer of the present invention combined is preferably from 10 to 150 parts by weight. From the viewpoint of abrasion resistance and strength, the amount combined is more preferably not less than 20 parts by weight, and yet more preferably not less than 30 parts by weight. From the viewpoint of reinforcement being enhanced, it is more preferably not more than 120 parts by weight, and yet more preferably not more than 100 parts by weight.
• silica is preferably not less than 50 parts by weight relative to 100 parts by weight of the total amount of fillers combined, and more preferably not less than 70 parts by weight.
• the extender oil examples include an aromatic mineral oil (viscosity-gravity constant (V.G.C. value) from 0.900 to 1.049), a naphthenic mineral oil (V.G.C. value from 0.850 to 0.899), and a paraffinic mineral oil (V.G.C. value from 0.790 to 0.849).
• the polycyclic aromatic content of the extender oil is preferably less than 3% by weight, and more preferably less than 1% by weight.
• the polycyclic aromatic content is measured in accordance with British Institute of Petroleum method 346/92.
• the aromatic compound content (CA) of the extender oil is preferably not less than 20% by weight. Two or more types of extender oils may be used in combination.
• vulcanization accelerator examples include thiazole-based vulcanization accelerators such as 2-mercaptobenzothiazole, dibenzothiazyl disulfide, and N-cyclohexyl-2-benzothiazylsulfenamide; thiuram-based vulcanization accelerators such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide; sulfenamide-based vulcanization accelerators such as N-cyclohexyl-2-benzothiazolesulfenamide, N-t-butyl-2-benzothiazolesulfenamide, N-oxyethylene-2-benzothiazolesulfenamide, N-oxyethylene-2-benzothiazolesulfenamide, and N,N′-diisopropyl-2-benzothiazolesulfenamide; and guanidine-based vulcanization accelerators such as diphenylguanidine, diorthotolylguanidine and
• a known method such as, for example, a method in which the components are kneaded by means of a known mixer such as a roll or Banbury mixer can be used.
• the kneading temperature is preferably from 50° C. to 200° C. and more preferably from 80° C. to 190° C.
• the kneading time is preferably from 30 sec to 30 min and more preferably from 1 min to 30 min.
• the kneading temperature is preferably not more than 100° C., and more preferably from room temperature to 80° C.
• a composition in which a vulcanizing agent or a vulcanization accelerator is combined is preferably used after carrying out a vulcanization treatment such as press vulcanization.
• the vulcanization temperature is preferably from 120° C. to 200° C., and more preferably from 140° C. to 180° C.
• the conjugated diene polymer rubber composition of the present invention have excellent fuel economy.
• the grip properties are also good.
• the conjugated diene polymer rubber and the conjugated diene polymer rubber composition of the present invention are used for tires, shoe soles, flooring materials, vibration-proofing materials, etc., and are particularly suitably used for tires.
• a conjugated diene polymer rubber that can give a conjugated diene polymer rubber composition having excellent abrasion resistance and a conjugated diene polymer rubber composition containing the conjugated diene polymer rubber and a filler.
• Normal temperature in the Examples means 25° C.
• the Mooney viscosity of a polymer was measured at 100° C. in accordance with JIS K6300 (1994).
• the vinyl bond content of a polymer was determined by IR spectroscopy from the absorption intensity at around 910 cm ⁇ 1 , which is an absorption peak of a vinyl group.
• the styrene unit content of a polymer was determined from refractive index in accordance with JIS K6383 (1995).
• Weight-average molecular weight (Mw) and number-average molecular weight (Mn) were measured under conditions (1) to (8) below by a gel permeation chromatograph (GPC) method, and the molecular weight distribution (Mw/Mn) of a polymer was determined.
• GPC gel permeation chromatograph
• a ring-shaped vulcanized molded body is used as a test piece; the amounts abraded under conditions of a load of 10 pounds and a test piece rotational speed of 300 rpm for from 500 to 1,500 rotations, from 1,500 to 2,500 rotations, and from 2,500 to 3,500 rotations are measured using an Akron abrasion tester (Ueshima Seisakusho Co., Ltd.), and the average value thereof is calculated. The smaller this value, the better the abrasion resistance.
• a strip-shaped test piece having a width of 1 or 2 mm and a length of 40 mm was stamped out from a sheet-shaped vulcanized molding and used for testing.
• the loss tangent (tan ⁇ (70° C.)) at 70° C. of the test piece was measured using a viscoelastometer (Ueshima Seisakusho Co., Ltd.) under conditions of a strain of 1% and a frequency of 10 Hz. The smaller this value, the better the fuel economy.
• a 20 L capacity stainless polymerization reactor was washed, dried, flushed with dry nitrogen, and charged with 10.2 kg of industrial hexane (density 680 kg/m 3 ), 604 g of 1,3-butadiene, 196 g of styrene, 6.1 mL of tetrahydrofuran, and 4.36 mL of ethylene glycol diethyl ether. Subsequently, 14.65 mmol of n-butyllithium was charged as an n-hexane solution, and polymerization was started.
• Copolymerization of 1,3-butadiene and styrene was carried out at a stirring speed of 130 rpm and a polymerization reactor internal temperature of 65° C. for 3 hours while continuously supplying the monomers to the polymerization reactor.
• the amount of 1,3-butadiene supplied was 906 g, and the amount of styrene supplied was 294 g.
• a 20 L capacity stainless polymerization reactor was washed, dried, flushed with dry nitrogen, and charged with 10.2 kg of industrial hexane (density 680 kg/m 3 ), 604 g of 1,3-butadiene, 196 g of styrene, 6.1 mL of tetrahydrofuran, and 4.36 mL of ethylene glycol diethyl ether. Subsequently, 14.99 mmol of n-butyllithium was charged as an n-hexane solution, and polymerization was started.
• Copolymerization of 1,3-butadiene and styrene was carried out at a stirring speed of 130 rpm and a polymerization reactor internal temperature of 65° C. for 3 hours while continuously supplying the monomers to the polymerization reactor.
• the amount of 1,3-butadiene supplied was 906 g, and the amount of styrene supplied was 294 g.
• the rubber composition thus obtained was molded into a sheet using a 6 inch roll, and the sheet was vulcanized by heating at 160° C. for 45 minutes, thus giving a vulcanized sheet.
• the results of evaluation of the physical properties of the vulcanized sheet are given in Table 1.
• Example 1 The procedure of Example 1 was repeated except that a mixed solution was prepared with the amount of solution (A1) as 60 parts by weight and the amount of solution (B1) as 40 parts by weight.
• the results of evaluation of the polymer rubber and the vulcanized sheet are given in Table 1.
• Example 1 The procedure of Example 1 was repeated except that a mixed solution was prepared with the amount of solution (A1) as 70 parts by weight and the amount of solution (B1) as 30 parts by weight.
• the results of evaluation of the polymer rubber and the vulcanized sheet are given in Table 1.
• Example Example 1 2 3 Mooney viscosity — 54 55 56 Vinyl bond content % by mol 58 58 Styrene unit content % by weight 25 25 25 25 Molecular weight — 1.23 1.22 1.18 distribution Abrasion resistance mg/ 290 280 290 Loss 1,000 rotations Fuel economy — 0.158 0.165 0.187 tan ⁇ (70° C. )
• a 30 L capacity stainless polymerization reactor was washed, dried, flushed with dry nitrogen, and charged with 15.3 kg of industrial hexane (density 680 kg/m 3 ), 912 g of 1,3-butadiene, 288 g of styrene, 9.1 mL of tetrahydrofuran, and 6.36 mL of ethylene glycol diethyl ether. Subsequently, 21.25 mmol of n-butyllithium was charged as an n-hexane solution, and polymerization was started.
• Copolymerization of 1,3-butadiene and styrene was carried out at a stirring speed of 130 rpm and a polymerization reactor internal temperature of 65° C. for 3 hours while continuously supplying the monomers to the polymerization reactor.
• the amount of 1,3-butadiene supplied was 1,368 g, and the amount of styrene supplied was 432 g.
• the rubber composition thus obtained was molded into a sheet using a 6 inch roll, and the sheet was vulcanized by heating at 160° C. for 45 minutes, thus giving a vulcanized sheet.
• the results of evaluation of the physical properties of the vulcanized sheet are given in Table 2.
• a 20 L capacity stainless polymerization reactor was washed, dried, flushed with dry nitrogen, and charged with 10.2 kg of industrial hexane (density 680 kg/m 3 ), 547 g of 1,3-butadiene, 173 g of styrene, 6.07 mL of tetrahydrofuran, and 4.12 mL of ethylene glycol diethyl ether. Subsequently, 13.31 mmol of n-butyllithium was charged as an n-hexane solution, and polymerization was started.
• Copolymerization of 1,3-butadiene and styrene was carried out at a stirring speed of 130 rpm and a polymerization reactor internal temperature of 65° C. for 3 hours while continuously supplying the monomers to the polymerization reactor.
• the amount of 1,3-butadiene supplied throughout the polymerization was 821 g, and the amount of styrene supplied was 259 g.
• silica product name: Ultrasil VN3-G, manufactured by Degussa, Inc.
• silane coupling agent product name: Si69, manufactured by Degussa, Inc.
• carbon black product name: Diablack N339, manufactured by Mitsubishi Chemical Corporation
• 47.6 parts by weight of an extender oil product name: X-140, manufactured by Kyodo Sekiyu
• an antioxidant product name: Antigene 3C, manufactured by Sumitomo Chemical Co., Ltd.
• 2 parts by weight of stearic acid 2 parts by weight of zinc oxide
• 1 part by weight of a vulcanizing accelerator product name: Soxinol CZ, manufactured by Sumitomo Chemical Co., Ltd.
• a vulcanizing accelerator product name: Soxinol D, manufactured by Sumitomo Chemical Co., Ltd.
• the rubber composition thus obtained was molded into a sheet using a 6 inch roll, and the sheet was vulcanized by heating at 160° C. for 45 minutes, thus giving a vulcanized sheet.
• the results of evaluation of the physical properties of the vulcanized sheet are given in Table 2.
• a 5 L capacity stainless polymerization reactor was washed, dried, flushed with dry nitrogen, and charged with 2.55 kg of industrial hexane (density 680 kg/m 3 ), 137 g of 1,3-butadiene, 43 g of styrene, 1.52 mL of tetrahydrofuran, and 1.06 mL of ethylene glycol diethyl ether. Subsequently, 3.56 mmol of n-butyllithium was charged as an n-hexane solution, and polymerization was started.
• Copolymerization of 1,3-butadiene and styrene was carried out at a stirring speed of 130 rpm and a polymerization reactor internal temperature of 65° C. for 2.5 hours while continuously supplying the monomers to the polymerization reactor.
• the amount of 1,3-butadiene supplied throughout the polymerization was 205 g, and the amount of styrene supplied was 65 g.
• the rubber composition thus obtained was molded into a sheet using a 6 inch roll, and the sheet was vulcanized by heating at 160° C. for 45 minutes, thus giving a vulcanized sheet.
• the results of evaluation of the physical properties of the vulcanized sheet are given in Table 2.
• a 20 L capacity stainless polymerization reactor was washed, dried, flushed with dry nitrogen, and charged with 10.2 kg of industrial hexane (density 680 kg/m 3 ), 604 g of 1,3-butadiene, 196 g of styrene, 6.1 mL of tetrahydrofuran, and 4.36 mL of ethylene glycol diethyl ether. Subsequently, 8.54 mmol of bis(diethylamino)methylvinylsilane and 14.49 mmol of n-butyllithium were charged as an n-hexane solution, and polymerization was started.
• Copolymerization of 1,3-butadiene and styrene was carried out at a stirring speed of 130 rpm and a polymerization reactor internal temperature of 65° C. for 3 hours while continuously supplying the monomers to the polymerization reactor.
• the amount of 1,3-butadiene supplied was 906 g, and the amount of styrene supplied was 294 g.
• the amount of bis(diethylamino)methylvinylsilane charged per monomer unit weight charged and supplied to the polymerization reactor was 0.0043 mmol.
• a 20 L capacity stainless polymerization reactor was washed, dried, flushed with dry nitrogen, and charged with 10.2 kg of industrial hexane (density 680 kg/m 3 ), 604 g of 1,3-butadiene, 196 g of styrene, 6.1 mL of tetrahydrofuran, and 4.36 mL of ethylene glycol diethyl ether. Subsequently, 8.54 mmol of bis(diethylamino)methylvinylsilane and 14.31 mmol of n-butyllithium were charged as an n-hexane solution, and polymerization was started.
• Copolymerization of 1,3-butadiene and styrene was carried out at a stirring speed of 130 rpm and a polymerization reactor internal temperature of 65° C. for 3 hours while continuously supplying the monomers to the polymerization reactor.
• the amount of 1,3-butadiene supplied was 906 g, and the amount of styrene supplied was 294 g.
• the amount of bis(diethylamino)methylvinylsilane charged per monomer unit weight charged and supplied to the polymerization reactor was 0.0043 mmol.
• the rubber composition thus obtained was molded into a sheet using a 6 inch roll, and the sheet was vulcanized by heating at 160° C. for 45 minutes, thus giving a vulcanized sheet.
• the results of evaluation of the physical properties of the vulcanized sheet are given in Table 3.
• Example 5 The procedure of Example 5 was repeated except that a mixed solution was prepared with the amount of solution (A2) as 25 parts by weight and the amount of solution (B2) as 75 parts by weight.
• the results of evaluation of the polymer rubber and the vulcanized sheet are given in Table 3.
• Example 5 The procedure of Example 5 was repeated except that a mixed solution was prepared with the amount of solution (A2) as 50 parts by weight and the amount of solution (B2) as 50 parts by weight.
• the results of evaluation of the polymer rubber and the vulcanized sheet are given in Table 3.
• Example 5 The procedure of Example 5 was repeated except that a mixed solution was prepared with the amount of solution (A2) as 70 parts by weight and the amount of solution (B2) as 30 parts by weight.
• the results of evaluation of the polymer rubber and the vulcanized sheet are given in Table 3.
• a 20 L capacity stainless polymerization reactor was washed, dried, flushed with dry nitrogen, and charged with 10.2 kg of industrial hexane (density 680 kg/m 3 ), 604 g of 1,3-butadiene, 196 g of styrene, 6.1 mL of tetrahydrofuran, and 4.36 mL of ethylene glycol diethyl ether. Subsequently, 12.2 mmol of bis(diethylamino)methylvinylsilane and 15.72 mmol of n-butyllithium were charged as an n-hexane solution, and polymerization was started.
• Copolymerization of 1,3-butadiene and styrene was carried out at a stirring speed of 130 rpm and a polymerization reactor internal temperature of 65° C. for 3 hours while continuously supplying the monomers to the polymerization reactor.
• the amount of 1,3-butadiene supplied was 906 g, and the amount of styrene supplied was 294 g.
• the amount of bis(diethylamino)methylvinylsilane charged per monomer unit weight charged and supplied to the polymerization reactor was 0.0061 mmol.
• a 20 L capacity stainless polymerization reactor was washed, dried, flushed with dry nitrogen, and charged with 10.2 kg of industrial hexane (density 680 kg/m 3 ), 604 g of 1,3-butadiene, 196 g of styrene, 6.1 mL of tetrahydrofuran, and 4.36 mL of ethylene glycol diethyl ether. Subsequently, 12.2 mmol of bis(diethylamino)methylvinylsilane and 14.84 mmol of n-butyllithium were charged as an n-hexane solution, and polymerization was started.
• Copolymerization of 1,3-butadiene and styrene was carried out at a stirring speed of 130 rpm and a polymerization reactor internal temperature of 65° C. for 3 hours while continuously supplying the monomers to the polymerization reactor.
• the amount of 1,3-butadiene supplied was 906 g, and the amount of styrene supplied was 294 g.
• the amount of bis(diethylamino)methylvinylsilane charged per monomer unit weight charged and supplied to the polymerization reactor was 0.0061 mmol.
• the rubber composition thus obtained was molded into a sheet using a 6 inch roll, and the sheet was vulcanized by heating at 160° C. for 45 minutes, thus giving a vulcanized sheet.
• the results of evaluation of the physical properties of the vulcanized sheet are given in Table 4.
• Example 9 The procedure of Example 9 was repeated except that a mixed solution was prepared with the amount of solution (A3) as 50 parts by weight and the amount of solution (B3) as 50 parts by weight.
• the results of evaluation of the polymer rubber and the vulcanized sheet are given in Table 4.
• Example 9 The procedure of Example 9 was repeated except that a mixed solution was prepared with the amount of solution (A3) as 75 parts by weight and the amount of solution (B3) as 25 parts by weight.
• the results of evaluation of the polymer rubber and the vulcanized sheet are given in Table 4.
• Example Example 9 10 11 Mooney viscosity — 53 48 44 Vinyl bond content % by mol 57 57 57 Styrene unit content % by weight 24 24 25 Molecular weight — 1.21 1.18 1.15 distribution Abrasion resistance mg/ 250 240 240 Loss 1,000 rotations Fuel economy — 0.109 0.104 0.103 tan ⁇ (70° C. )
• a 5 L capacity stainless polymerization reactor was washed, dried, flushed with dry nitrogen, and charged with 2.55 kg of industrial hexane (density 680 kg/m 3 ), 137 g of 1,3-butadiene, 43 g of styrene, 1.52 mL of tetrahydrofuran, and 1.09 mL of ethylene glycol diethyl ether. Subsequently, 1.97 mmol of bis(diethylamino)methylvinylsilane and 3.56 mmol of n-butyllithium were charged as an n-hexane solution, and polymerization was started.
• Copolymerization of 1,3-butadiene and styrene was carried out at a stirring speed of 130 rpm and a polymerization reactor internal temperature of 65° C. for 2.5 hours while continuously supplying the monomers to the polymerization reactor.
• the amount of 1,3-butadiene supplied was 205 g, and the amount of styrene supplied was 65 g.
• the amount of bis(diethylamino)methylvinylsilane charged per monomer unit weight charged and supplied to the polymerization reactor was 0.0044 mmol.
• the rubber composition thus obtained was molded into a sheet using a 6 inch roll, and the sheet was vulcanized by heating at 160° C. for 45 minutes, thus giving a vulcanized sheet.
• the results of evaluation of the physical properties of the vulcanized sheet are given in Table 5.
• a 5 L capacity stainless polymerization reactor was washed, dried, flushed with dry nitrogen, and charged with 2.55 kg of industrial hexane (density 680 kg/m 3 ), 137 g of 1,3-butadiene, 43 g of styrene, 1.52 mL of tetrahydrofuran, and 1.12 mL of ethylene glycol diethyl ether. Subsequently, 1.97 mmol of bis(diethylamino)methylvinylsilane and 3.54 mmol of n-butyllithium were charged as an n-hexane solution, and polymerization was started.
• Copolymerization of 1,3-butadiene and styrene was carried out at a stirring speed of 130 rpm and a polymerization reactor internal temperature of 65° C. for 2.5 hours while continuously supplying the monomers to the polymerization reactor.
• the amount of 1,3-butadiene supplied was 205 g, and the amount of styrene supplied was 65 g.
• the amount of bis(diethylamino)methylvinylsilane charged per monomer unit weight charged and supplied to the polymerization reactor was 0.0044 mmol.
• the rubber composition thus obtained was molded into a sheet using a 6 inch roll, and the sheet was vulcanized by heating at 160° C. for 45 minutes, thus giving a vulcanized sheet.
• the results of evaluation of the physical properties of the vulcanized sheet are given in Table 5.
• a 5 L capacity stainless polymerization reactor was washed, dried, flushed with dry nitrogen, and charged with 2.55 kg of industrial hexane (density 680 kg/m 3 ), 137 g of 1,3-butadiene, 43 g of styrene, 1.52 mL of tetrahydrofuran, and 1.09 mL of ethylene glycol diethyl ether. Subsequently, 1.97 mmol of bis(diethylamino)methylvinylsilane and 3.68 mmol of n-butyllithium were charged as an n-hexane solution, and polymerization was started.
• Copolymerization of 1,3-butadiene and styrene was carried out at a stirring speed of 130 rpm and a polymerization reactor internal temperature of 65° C. for 2.5 hours while continuously supplying the monomers to the polymerization reactor.
• the amount of 1,3-butadiene supplied was 205 g, and the amount of styrene supplied was 65 g.
• the amount of bis(diethylamino)methylvinylsilane charged per monomer unit weight charged and supplied to the polymerization reactor was 0.0044 mmol.
• the rubber composition thus obtained was molded into a sheet using a 6 inch roll, and the sheet was vulcanized by heating at 160° C. for 45 minutes, thus giving a vulcanized sheet.
• the results of evaluation of the physical properties of the vulcanized sheet are given in Table 5.
• Example Example 12 13 14 Mooney viscosity — 62 54 55 Vinyl bond content % by mol 57 58 57 Styrene unit content % by weight 24 24 24 Molecular weight — 1.26 1.19 1.24 distribution Abrasion resistance mg/ 260 240 230 Loss 1,000 rotations Fuel economy — 0.127 0.129 0.126 tan ⁇ (70° C. )

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