WO2012014463A1 - 共役ジエン化合物と非共役オレフィンとの共重合体、ゴム組成物、及びタイヤ - Google Patents
共役ジエン化合物と非共役オレフィンとの共重合体、ゴム組成物、及びタイヤ Download PDFInfo
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- WO2012014463A1 WO2012014463A1 PCT/JP2011/004236 JP2011004236W WO2012014463A1 WO 2012014463 A1 WO2012014463 A1 WO 2012014463A1 JP 2011004236 W JP2011004236 W JP 2011004236W WO 2012014463 A1 WO2012014463 A1 WO 2012014463A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
- C08F236/06—Butadiene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
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- 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
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
Definitions
- the present invention relates to a copolymer of a conjugated diene compound and a nonconjugated olefin, and in particular, the cis 1,4-bond content of the conjugated diene moiety is 50% or more, and the content of the nonconjugated olefin is 20 mol% or more.
- the present invention relates to a conjugated diene compound-nonconjugated olefin copolymer.
- Patent Document 1 discloses a conjugated diene polymerization catalyst containing a group IV transition metal compound of the periodic table having a cyclopentadiene ring structure.
- ethylene is disclosed as a monomer copolymerizable with this conjugated diene.
- ⁇ -olefins such as However, the copolymerization of the conjugated diene compound and the non-conjugated olefin is not specifically described.
- the cis content and the content of the non-conjugated olefin in the copolymer of the conjugated diene and the non-conjugated olefin are 20 mol% or more, and the cis 1,4-bond content of the conjugated diene is 50% or more. There is no description or suggestion on improving the resistance and crack growth resistance.
- Patent Document 2 discloses an olefin polymerization catalyst comprising a transition metal compound such as a titanium compound and a co-catalyst, and a copolymer of an ⁇ -olefin and a conjugated diene compound.
- a transition metal compound such as a titanium compound and a co-catalyst
- a copolymer of an ⁇ -olefin and a conjugated diene compound a copolymer of an ⁇ -olefin and a conjugated diene compound.
- Patent Document 3 discloses a copolymer of ethylene and butadiene synthesized using ethylene and butadiene as starting materials using a special organometallic complex as a catalyst component. It is inserted into the copolymer in the form of -1,2-cyclohexane and has a structure different from that of the copolymer of the present invention. Further, the production and use of the ethylene content, which is a non-conjugated olefin, was specifically supported only in the range of 69.6 to 89.0 mol%. Here, the numerical value of the ethylene content is disclosed from 100 mol%. It was determined by subtracting the molar content of units derived from the butadiene.
- an object of the present invention is to have a cis 1,4 bond in the conjugated diene moiety, the cis 1,4-bond content of the conjugated diene moiety is 50% or more, and the content of non-conjugated olefin is 20 mol% or more.
- Another object of the present invention is to provide a copolymer of a conjugated diene compound and a non-conjugated olefin.
- the present inventors polymerized a conjugated diene compound and a non-conjugated olefin in the presence of a specific catalyst, and the resulting conjugated diene compound-non-conjugated olefin copolymer is:
- the present inventors have found that the cis 1,4-bond content of the conjugated diene moiety is 50% or more and the content of non-conjugated olefin is 20 mol% or more, thereby completing the present invention.
- the copolymer of the conjugated diene compound and the non-conjugated olefin of the present invention has a cis 1,4-bond content of the conjugated diene moiety of 50% or more and a non-conjugated olefin content of 20 mol% or more.
- the cis 1,4-bond content means the proportion of 1,4-cis bonds in the conjugated diene unit in the conjugated diene compound.
- the non-conjugated olefin is an acyclic olefin, more preferably an ⁇ -olefin having 2 to 10 carbon atoms, and still more preferably at least selected from the group consisting of ethylene, propylene and 1-butene. It is a kind.
- the conjugated diene compound has 4 to 8 carbon atoms, more preferably at least one selected from the group consisting of 1,3-butadiene and isoprene, and more preferably The cis 1,4-bond content is 80% or more.
- such a copolymer has a molecular weight distribution (Mw / Mn) of 10 or less.
- the rubber composition containing the copolymer of such a conjugated diene compound and a nonconjugated olefin is preferable.
- the rubber composition contains 5 to 200 parts by mass of a reinforcing filler and 0.1 to 20 parts by mass of a crosslinking agent with respect to 100 parts by mass of the rubber component.
- the crosslinked rubber composition can be obtained by crosslinking the rubber composition.
- a tire can be obtained using the rubber composition or the crosslinked rubber composition.
- the cis 1,4-bond content of the conjugated diene moiety is 50% or more, and the content of the non-conjugated olefin is 20 mol% or more.
- Tg glass transition point
- the cis 1,4-bond content is less than 50%, the elongation crystallinity is low and the glass transition point is high.
- this copolymer is used in a tread rubber, the wear resistance may be reduced.
- the content of the non-conjugated olefin is less than 20 mol%, the static crystallinity is reduced and the mechanical breaking strength may be reduced.
- the present invention is described in detail below.
- the copolymer of the conjugated diene compound and the non-conjugated olefin of the present invention has a cis 1,4-bond content of the conjugated diene moiety of 50% or more and a non-conjugated olefin content of 20 mol% or more.
- the non-conjugated olefin used as the monomer is a non-conjugated olefin other than the conjugated diene compound, and has excellent heat resistance and reduces the proportion of double bonds in the main chain of the copolymer and controls crystallinity. This makes it possible to increase the degree of design freedom as an elastomer.
- the non-conjugated olefin is preferably an acyclic olefin, and the non-conjugated olefin is preferably an ⁇ -olefin having 2 to 10 carbon atoms. Since ⁇ -olefin has a double bond at the ⁇ -position of the olefin, copolymerization with a conjugated diene can be performed efficiently. Accordingly, preferred examples of non-conjugated olefins include ⁇ -olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, and 1-octene. Among these, ethylene, propylene, and 1-butene is preferred. These non-conjugated olefins may be used alone or in combination of two or more.
- the olefin refers to a compound that is an aliphatic unsaturated hydrocarbon and has one or more carbon-carbon double bonds.
- the content of the non-conjugated olefin is 20 mol% or more, and preferably 20 to 50 mol%. If the content of the non-conjugated olefin is within the specified range, the heat resistance can be effectively improved without causing phase separation.
- the conjugated diene compound preferably has 4 to 8 carbon atoms.
- Specific examples of the conjugated diene compound include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, and among these, 1,3-butadiene and isoprene are preferable.
- these conjugated diene compounds may be used independently and may be used in combination of 2 or more type.
- the cis 1,4-bond content of the conjugated diene compound is 50% or more, preferably 80% or more, more preferably 90% or more. By increasing the ratio of the cis 1,4 bond content, the crack resistance can be further improved.
- Such a copolymer does not cause the problem of lowering the molecular weight, and its weight average molecular weight (Mw) is not particularly limited, but from the viewpoint of application to a polymer structure material,
- the weight average molecular weight (Mw) in terms of polystyrene of the coalescence is preferably 10,000 to 1,000,000, and more preferably 50,000 to 600,000. If Mw exceeds 1,000,000, moldability may be deteriorated.
- the molecular weight distribution (Mw / Mn) represented by the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) is preferably 10 or less, and more preferably 6 or less. This is because if the molecular weight distribution exceeds 10, the physical properties are not uniform.
- the average molecular weight and the molecular weight distribution can be determined using polystyrene as a standard substance by gel permeation chromatography (GPC).
- the non-conjugated olefin is not continuously arranged.
- the copolymer of the present invention can polymerize a conjugated diene compound and a non-conjugated olefin in the presence of the polymerization catalyst or polymerization catalyst composition described below.
- a polymerization method any method such as a solution polymerization method, a suspension polymerization method, a liquid phase bulk polymerization method, an emulsion polymerization method, a gas phase polymerization method, and a solid phase polymerization method can be used.
- the solvent used should just be inactive in a polymerization reaction, For example, toluene, cyclohexane, normal hexane, etc. are mentioned.
- the monomer conjugated diene compound and the non-conjugated compound are produced in the same manner as in the production method of a polymer using a normal coordination ion polymerization catalyst.
- Olefin can be copolymerized.
- the polymerization catalyst composition includes the following general formula (I): (wherein M represents a lanthanoid element, scandium or yttrium, Cp R each independently represents an unsubstituted or substituted indenyl group, and R a to R f each independently represents an alkyl having 1 to 3 carbon atoms.
- M represents a lanthanoid element, scandium or yttrium
- Cp R each independently represents an unsubstituted or substituted indenyl group
- X ′ represents a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group.
- a silyl group or a hydrocarbon group having 1 to 20 carbon atoms L represents a neutral Lewis base, and w represents an integer of 0 to 3, and the following general formula (III ):
- M represents a lanthanoid element, scandium or yttrium
- Cp R ′ represents unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl
- X represents a hydrogen atom, a halogen atom, an alkoxide group or a thiolate group.
- a polymerization catalyst composition (hereinafter also referred to as a first polymerization catalyst composition) comprising at least one complex selected from the group consisting of a half metallocene cation complex represented by The product may further contain other components contained in the polymerization catalyst composition containing a normal metallocene complex, such as a promoter.
- the metallocene complex is a complex compound in which one or more cyclopentadienyl or a derivative thereof is bonded to a central metal, and in particular, one cyclopentadienyl or a derivative thereof bonded to the central metal.
- a certain metallocene complex may be called a half metallocene complex.
- the concentration of the complex contained in the first polymerization catalyst composition is preferably in the range of 0.1 to 0.0001 mol / L.
- Cp R in the formula is an unsubstituted indenyl or substituted indenyl.
- Cp R having an indenyl ring as a basic skeleton can be represented by C 9 H 7-X R X or C 9 H 11-X R X.
- X is an integer of 0 to 7 or 0 to 11.
- each R is preferably independently a hydrocarbyl group or a metalloid group.
- the hydrocarbyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 8 carbon atoms.
- hydrocarbyl group examples include a methyl group, an ethyl group, a phenyl group, and a benzyl group.
- metalloid group metalloids include germyl Ge, stannyl Sn, and silyl Si, and the metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group that the metalloid group has is the same as the above hydrocarbyl group. is there.
- Specific examples of the metalloid group include a trimethylsilyl group.
- substituted indenyl examples include 2-phenylindenyl, 2-methylindenyl and the like. Note that the two Cp Rs in the general formulas (I) and (II) may be the same as or different from each other.
- Cp R ′ in the formula is unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl, and among these, unsubstituted or substituted indenyl It is preferable that Cp R ′ having a cyclopentadienyl ring as a basic skeleton is represented by C 5 H 5-X R X. Here, X is an integer of 0 to 5.
- each R is preferably independently a hydrocarbyl group or a metalloid group.
- the hydrocarbyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 8 carbon atoms.
- Specific examples of the hydrocarbyl group include a methyl group, an ethyl group, a phenyl group, and a benzyl group.
- examples of metalloid group metalloids include germyl Ge, stannyl Sn, and silyl Si, and the metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group that the metalloid group has is the same as the above hydrocarbyl group. is there.
- Specific examples of the metalloid group include a trimethylsilyl group.
- Specific examples of Cp R ′ having a cyclopentadienyl ring as a basic skeleton include the following. (In the formula, R represents a hydrogen atom, a methyl group or an ethyl group.)
- Cp R ′ having the indenyl ring as a basic skeleton is defined in the same manner as Cp R in the general formula (I), and preferred examples thereof are also the same.
- Cp R ′ having the fluorenyl ring as a basic skeleton can be represented by C 13 H 9-X R X or C 13 H 17-X R X.
- X is an integer of 0 to 9 or 0 to 17.
- each R is preferably independently a hydrocarbyl group or a metalloid group.
- the hydrocarbyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 8 carbon atoms.
- Specific examples of the hydrocarbyl group include a methyl group, an ethyl group, a phenyl group, and a benzyl group.
- metalloid group metalloids include germyl Ge, stannyl Sn, and silyl Si, and the metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group that the metalloid group has is the same as the above hydrocarbyl group. is there.
- Specific examples of the metalloid group include a trimethylsilyl group.
- the central metal M in the general formulas (I), (II), and (III) is a lanthanoid element, scandium, or yttrium.
- the lanthanoid elements include 15 elements having atomic numbers of 57 to 71, and any of these may be used.
- Preferred examples of the central metal M include samarium Sm, neodymium Nd, praseodymium Pr, gadolinium Gd, cerium Ce, holmium Ho, scandium Sc, and yttrium Y.
- the metallocene complex represented by the general formula (I) includes a silylamide ligand [—N (SiR 3 ) 2 ].
- the R groups contained in the silylamide ligand (R a to R f in the general formula (I)) are each independently an alkyl group having 1 to 3 carbon atoms or a hydrogen atom.
- At least one of R a to R c is a hydrogen atom and at least one of R d to R f is a hydrogen atom. Furthermore, a methyl group is preferable as the alkyl group.
- the metallocene complex represented by the general formula (II) contains a silyl ligand [—SiX ′ 3 ].
- X ′ contained in the silyl ligand [—SiX ′ 3 ] is a group defined in the same manner as X in the general formula (III) described below, and preferred groups are also the same.
- X is a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group, a silyl group, and a hydrocarbon group having 1 to 20 carbon atoms.
- examples of the alkoxide group include aliphatic alkoxy groups such as methoxy group, ethoxy group, propoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group; phenoxy group, 2,6-dioxy -Tert-butylphenoxy group, 2,6-diisopropylphenoxy group, 2,6-dineopentylphenoxy group, 2-tert-butyl-6-isopropylphenoxy group, 2-tert-butyl-6-neopentylphenoxy group, Examples include aryloxide groups such as 2-isopropyl-6-neopentylphenoxy group, and among these, 2,6-di-tert-butylphenoxy group is preferable.
- the thiolate group represented by X includes a thiomethoxy group, a thioethoxy group, a thiopropoxy group, a thio n-butoxy group, a thioisobutoxy group, a thiosec-butoxy group, a thiotert-butoxy group and the like Group thiolate group; thiophenoxy group, 2,6-di-tert-butylthiophenoxy group, 2,6-diisopropylthiophenoxy group, 2,6-dineopentylthiophenoxy group, 2-tert-butyl-6-isopropyl Arylthiolate groups such as thiophenoxy group, 2-tert-butyl-6-thioneopentylphenoxy group, 2-isopropyl-6-thioneopentylphenoxy group, 2,4,6-triisopropylthiophenoxy group, etc. Among these, 2,4,6-triisopropylthiophenoxy group,
- examples of the amide group represented by X include aliphatic amide groups such as dimethylamide group, diethylamide group, diisopropylamide group; phenylamide group, 2,6-di-tert-butylphenylamide group, 2 , 6-diisopropylphenylamide group, 2,6-dineopentylphenylamide group, 2-tert-butyl-6-isopropylphenylamide group, 2-tert-butyl-6-neopentylphenylamide group, 2-isopropyl- Arylamide groups such as 6-neopentylphenylamide group and 2,4,6-tert-butylphenylamide group; bistrialkylsilylamide groups such as bistrimethylsilylamide group. Among them, bistrimethylsilylamide group is preferable.
- examples of the silyl group represented by X include trimethylsilyl group, tris (trimethylsilyl) silyl group, bis (trimethylsilyl) methylsilyl group, trimethylsilyl (dimethyl) silyl group, triisopropylsilyl (bistrimethylsilyl) silyl group, and the like.
- a tris (trimethylsilyl) silyl group is preferable.
- the halogen atom represented by X may be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, but a chlorine atom or a bromine atom is preferred.
- Specific examples of the hydrocarbon group having 1 to 20 carbon atoms represented by X include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.
- Linear or branched aliphatic hydrocarbon groups such as butyl group, neopentyl group, hexyl group, octyl group; aromatic hydrocarbon groups such as phenyl group, tolyl group, naphthyl group; aralkyl groups such as benzyl group, etc.
- Others include hydrocarbon groups containing silicon atoms such as trimethylsilylmethyl group and bistrimethylsilylmethyl group. Among these, methyl group, ethyl group, isobutyl group, trimethylsilylmethyl group and the like are preferable.
- X is preferably a bistrimethylsilylamide group or a hydrocarbon group having 1 to 20 carbon atoms.
- the non-coordinating anion represented by, for example, a tetravalent boron anion.
- tetravalent boron anion include tetraphenyl borate, tetrakis (monofluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis ( Pentafluorophenyl) borate, tetrakis (tetrafluoromethylphenyl) borate, tetra (tolyl) borate, tetra (xylyl) borate, (triphenyl, pentafluorophenyl) borate, [tris (pentafluorophenyl), phenyl] borate, tri Decahydride-7,8-dica
- the metallocene complex represented by the above general formulas (I) and (II) and the half metallocene cation complex represented by the above general formula (III) are further 0 to 3, preferably 0 to 1 neutral.
- examples of the neutral Lewis base L include tetrahydrofuran, diethyl ether, dimethylaniline, trimethylphosphine, lithium chloride, neutral olefins, neutral diolefins, and the like.
- the neutral Lewis bases L may be the same or different.
- metallocene complex represented by the general formula (I) and the formula (II) and the half metallocene cation complex represented by the general formula (III) may exist as a monomer, It may exist as a body or higher multimer.
- the metallocene complex represented by the general formula (I) includes, for example, a lanthanoid trishalide, scandium trishalide, or yttrium trishalide in a solvent, an indenyl salt (for example, potassium salt or lithium salt) and bis (trialkylsilyl). It can be obtained by reacting with an amide salt (for example, potassium salt or lithium salt).
- reaction temperature should just be about room temperature, it can manufacture on mild conditions.
- the reaction time is arbitrary, but is about several hours to several tens of hours.
- the reaction solvent is not particularly limited, but is preferably a solvent that dissolves the raw material and the product. For example, toluene may be used. Below, the reaction example for obtaining the metallocene complex represented by general formula (I) is shown. (In the formula, X ′′ represents a halide.)
- the metallocene complex represented by the general formula (II) includes, for example, a lanthanide trishalide, scandium trishalide, or yttrium trishalide in a solvent, an indenyl salt (for example, potassium salt or lithium salt), and a silyl salt (for example, potassium). Salt or lithium salt).
- reaction temperature should just be about room temperature, it can manufacture on mild conditions.
- the reaction time is arbitrary, but is about several hours to several tens of hours.
- the reaction solvent is not particularly limited, but is preferably a solvent that dissolves the raw material and the product. For example, toluene may be used.
- the reaction example for obtaining the metallocene complex represented by general formula (II) is shown. (In the formula, X ′′ represents a halide.)
- the half metallocene cation complex represented by the general formula (III) can be obtained, for example, by the following reaction.
- M represents a lanthanoid element, scandium or yttrium, and Cp R ′ independently represents unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl.
- X represents a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group, a silyl group, or a hydrocarbon group having 1 to 20 carbon atoms
- L represents a neutral Lewis base
- w represents 0 to 3 Indicates an integer.
- [A] + [B] ⁇ [A] + represents a cation
- [B] ⁇ represents a non-coordinating anion.
- Examples of the cation represented by + include a carbonium cation, an oxonium cation, an amine cation, a phosphonium cation, a cycloheptatrienyl cation, and a ferrocenium cation having a transition metal.
- Examples of the carbonium cation include trisubstituted carbonium cations such as a triphenylcarbonium cation and a tri (substituted phenyl) carbonium cation.
- the tri (substituted phenyl) carbonyl cation is specifically exemplified by tri (methylphenyl). ) Carbonium cation and the like.
- amine cations include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, and tributylammonium cation; N, N-dimethylanilinium cation, N, N-diethylanilinium cation, N, N— N, N-dialkylanilinium cations such as 2,4,6-pentamethylanilinium cation; dialkylammonium cations such as diisopropylammonium cation and dicyclohexylammonium cation.
- trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, and tributylammonium cation
- Examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation.
- triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation.
- N, N-dialkylanilinium cation or carbonium cation is preferable, and N, N-dialkylanilinium cation is particularly preferable.
- the ionic compound represented by the general formula [A] + [B] ⁇ used in the above reaction is a compound selected and combined from the above non-coordinating anions and cations, and is an N, N-dimethylaniline. Preference is given to nium tetrakis (pentafluorophenyl) borate, triphenylcarbonium tetrakis (pentafluorophenyl) borate and the like.
- general formula [A] + [B] - ionic compounds represented by is preferably added from 0.1 to 10 mols per mol of the metallocene complex, more preferably added about 1 molar.
- the half metallocene cation complex represented by the general formula (III) may be provided as it is in the polymerization reaction system, or the compound represented by the general formula (IV) and the general formula used in the reaction [a] + [B] - provides an ionic compound represented separately into the polymerization reaction system, the general formula in the reaction system (III You may form the half metallocene cation complex represented by this.
- the structures of the metallocene complex represented by the general formulas (I) and (II) and the half metallocene cation complex represented by the general formula (III) are preferably determined by X-ray structural analysis.
- the co-catalyst that can be used in the first polymerization catalyst composition can be arbitrarily selected from components used as a co-catalyst for a polymerization catalyst composition containing a normal metallocene complex.
- suitable examples of the cocatalyst include aluminoxanes, organoaluminum compounds, and the above ionic compounds. These promoters may be used alone or in combination of two or more.
- the aluminoxane is preferably an alkylaminoxan, and examples thereof include methylaluminoxane (MAO) and modified methylaluminoxane. Further, as the modified methylaluminoxane, MMAO-3A (manufactured by Tosoh Finechem) and the like are preferable.
- the content of aluminoxane in the first polymerization catalyst composition is such that the element ratio Al / M between the central metal M of the metallocene complex and the aluminum element Al of the aluminoxane is about 10 to 1000, preferably about 100. It is preferable to make it.
- the organoaluminum compound the general formula AlRR′R ′′ (wherein R and R ′ are each independently a C1 to C10 hydrocarbon group or a hydrogen atom, and R ′′ is a C1 to C10).
- An organoaluminum compound represented by (a hydrocarbon group) is preferable.
- the organoaluminum compound include trialkylaluminum, dialkylaluminum chloride, alkylaluminum dichloride, and dialkylaluminum hydride. Among these, trialkylaluminum is preferable.
- the trialkylaluminum include triethylaluminum and triisobutylaluminum.
- the content of the organoaluminum compound in the polymerization catalyst composition is preferably 2 to 50 times mol, more preferably about 10 times mol for the metallocene complex.
- the metallocene complex represented by the general formula (I) and the formula (II) and the half metallocene cation complex represented by the above general formula (III) are each used as an appropriate promoter. By combining them, the amount of cis-1,4 bonds and the molecular weight of the resulting copolymer can be increased.
- (A) component a rare earth element compound or a reaction product of the rare earth element compound and a Lewis base, the rare earth element compound or the reaction product having no bond between the rare earth element and carbon
- B-1 ionic compound composed of non-coordinating anion and cation
- B-2 aluminoxane
- Lewis acid complex compound of metal halide and Lewis base
- active halogen Preferred examples include a polymerization catalyst composition containing at least one selected from the group consisting of at least one halogen compound (B-3) among organic compounds (hereinafter also referred to as a second polymerization catalyst composition).
- the polymerization catalyst composition contains at least one of the ionic compound (B-1) and the halogen compound (B-3), the polymerization catalyst composition further comprises: (C) Component: The following general formula (X): YR 1 a R 2 b R 3 c (X) [Wherein Y is a metal selected from Group 1, Group 2, Group 12 and Group 13 of the Periodic Table, and R 1 and R 2 are the same or different and have 1 to 10 carbon atoms.
- the second polymerization catalyst composition used in the method for producing the copolymer needs to contain the component (A) and the component (B), and the polymerization catalyst composition is the ionic compound (B). -1) and at least one of the above halogen compounds (B-3), (C) Component: The following general formula (X): YR 1 a R 2 b R 3 c (X) [Wherein Y is a metal selected from Group 1, Group 2, Group 12 and Group 13 of the Periodic Table, and R 1 and R 2 are the same or different and have 1 to 10 carbon atoms.
- R 3 is a hydrocarbon group having 1 to 10 carbon atoms, provided that R 3 may be the same as or different from R 1 or R 2, and Y is a periodic table;
- a is 1 and b and c are 0, and when Y is a metal selected from Groups 2 and 12 of the Periodic Table, a and b are 1 and c is 0, and when Y is a metal selected from Group 13 of the Periodic Table, a, b and c are 1]. It is necessary to include.
- the ionic compound (B-1) and the halogen compound (B-3) do not have a carbon atom to be supplied to the component (A), the above (A) as a carbon supply source to the component (A) Component C) is required. Even when the polymerization catalyst composition contains the aluminoxane (B-2), the polymerization catalyst composition can contain the component (C).
- the second polymerization catalyst composition may contain other components, such as a promoter, contained in a normal rare earth element compound-based polymerization catalyst composition.
- the component (A) used in the second polymerization catalyst composition is a rare earth element compound or a reaction product of the rare earth element compound and a Lewis base.
- the reaction of the rare earth element compound and the rare earth element compound with a Lewis base is performed.
- the object does not have a bond between rare earth element and carbon.
- the rare earth element compound and the reactant do not have a rare earth element-carbon bond, the compound is stable and easy to handle.
- the rare earth element compound is a compound containing a lanthanoid element or scandium or yttrium composed of the elements of atomic numbers 57 to 71 in the periodic table.
- the lanthanoid element examples include lanthanium, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium.
- the said (A) component may be used individually by 1 type, and may be used in combination of 2 or more type.
- the rare earth element compound is preferably a divalent or trivalent salt or complex compound of a rare earth metal, and one or more coordinations selected from a hydrogen atom, a halogen atom and an organic compound residue. More preferably, the rare earth element compound contains a child.
- reaction product of the rare earth element compound or the rare earth element compound and a Lewis base is represented by the following general formula (XI) or (XII): M 11 X 11 2 ⁇ L 11 w (XI) M 11 X 11 3 ⁇ L 11 w (XII) [Wherein M 11 represents a lanthanoid element, scandium or yttrium, and X 11 independently represents a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group, a silyl group, an aldehyde residue, a ketone residue. Represents a group, a carboxylic acid residue, a thiocarboxylic acid residue or a phosphorus compound residue, L 11 represents a Lewis base, and w represents 0 to 3.
- the group (ligand) bonded to the rare earth element of the rare earth element compound include a hydrogen atom; a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, a tert- Aliphatic alkoxy groups such as butoxy group; phenoxy group, 2,6-di-tert-butylphenoxy group, 2,6-diisopropylphenoxy group, 2,6-dineopentylphenoxy group, 2-tert-butyl-6- Aromatic alkoxy groups such as isopropylphenoxy group, 2-tert-butyl-6-neopentylphenoxy group, 2-isopropyl-6-neopentylphenoxy group; thiomethoxy group, thioethoxy group, thiopropoxy group, thio n-butoxy group, Fats such as thioisobutoxy group, thiosec-butoxy group
- aldehyde residues such as salicylaldehyde, 2-hydroxy-1-naphthaldehyde, 2-hydroxy-3-naphthaldehyde; 2′-hydroxyacetophenone, 2′-hydroxybutyrophenone, 2′-hydroxypropiophenone, etc.
- examples of the Lewis base that reacts with the rare earth element compound include tetrahydrofuran, diethyl ether, dimethylaniline, trimethylphosphine, lithium chloride, neutral olefins, Diolefins and the like.
- the rare earth element compound reacts with a plurality of Lewis bases (in the formulas (XI) and (XII), when w is 2 or 3), the Lewis base L 11 is the same or different. It may be.
- Component (B) used in the second polymerization catalyst composition is at least one compound selected from the group consisting of ionic compound (B-1), aluminoxane (B-2), and halogen compound (B-3). is there.
- the total content of the component (B) in the second polymerization catalyst composition is preferably 0.1 to 50 times mol of the component (A).
- the ionic compound represented by (B-1) is composed of a non-coordinating anion and a cation, and reacts with the rare earth element compound which is the component (A) or a reaction product thereof with a Lewis base to become cationic.
- Examples thereof include ionic compounds capable of generating a transition metal compound.
- non-coordinating anion for example, tetraphenyl borate, tetrakis (monofluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis ( Pentafluorophenyl) borate, tetrakis (tetrafluoromethylphenyl) borate, tetra (tolyl) borate, tetra (xylyl) borate, (triphenyl, pentafluorophenyl) borate, [tris (pentafluorophenyl), phenyl] borate, tri Decahydride-7,8-dicarbaound decaborate and the like.
- examples of the cation include a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptatrienyl cation, and a ferrocenium cation having a transition metal.
- Specific examples of the carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation and tri (substituted phenyl) carbonium cation, and more specifically, as tri (substituted phenyl) carbonyl cation, Examples include tri (methylphenyl) carbonium cation, tri (dimethylphenyl) carbonium cation, and the like.
- ammonium cations include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, and tributylammonium cation (eg, tri (n-butyl) ammonium cation); N, N-dimethylanilinium N, N-dialkylanilinium cation such as cation, N, N-diethylanilinium cation, N, N-2,4,6-pentamethylanilinium cation; dialkylammonium cation such as diisopropylammonium cation and dicyclohexylammonium cation Is mentioned.
- trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, and tributylammonium cation (eg, tri (n-butyl)
- the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation.
- the ionic compound is preferably a compound selected and combined from the above-mentioned non-coordinating anions and cations, specifically, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbohydrate. Preferred is nitrotetrakis (pentafluorophenyl) borate.
- these ionic compounds can be used individually by 1 type, or 2 or more types can be mixed and used for them.
- the content of the ionic compound in the second polymerization catalyst composition is preferably 0.1 to 10-fold mol, more preferably about 1-fold mol with respect to component (A).
- the aluminoxane represented by the above (B-2) is a compound obtained by bringing an organoaluminum compound and a condensing agent into contact with each other.
- R ′ is a hydrocarbon group having 1 to 10 carbon atoms, and some of the hydrocarbon groups may be substituted with a halogen atom and / or an alkoxy group
- the degree of polymerization of the unit is preferably 5 or more, and more preferably 10 or more.
- R ′ examples include a methyl group, an ethyl group, a propyl group, and an isobutyl group, and among these, a methyl group is preferable.
- organoaluminum compound used as an aluminoxane raw material include trialkylaluminums such as trimethylaluminum, triethylaluminum, and triisobutylaluminum, and mixtures thereof, and trimethylaluminum is particularly preferable.
- an aluminoxane using a mixture of trimethylaluminum and tributylaluminum as a raw material can be preferably used.
- the content of the aluminoxane in the second polymerization catalyst composition is such that the element ratio Al / M of the rare earth element M constituting the component (A) and the aluminum element Al of the aluminoxane is about 10 to 1000. It is preferable to do.
- the halogen compound represented by (B-3) is composed of at least one of a Lewis acid, a complex compound of a metal halide and a Lewis base, and an organic compound containing an active halogen, and is, for example, the component (A).
- a rare earth element compound or a reaction product thereof with a Lewis base By reacting with a rare earth element compound or a reaction product thereof with a Lewis base, a cationic transition metal compound, a halogenated transition metal compound, or a compound in which the transition metal center is deficient in charge can be generated.
- the total content of halogen compounds in the second polymerization catalyst composition is preferably 1 to 5 moles compared to the component (A).
- boron-containing halogen compounds such as B (C 6 F 5 ) 3 and aluminum-containing halogen compounds such as Al (C 6 F 5 ) 3 can be used, as well as III, IV,
- a halogen compound containing an element belonging to the group V, VI or VIII can also be used.
- aluminum halide or organometallic halide is used.
- chlorine or bromine is preferable.
- the Lewis acid examples include methyl aluminum dibromide, methyl aluminum dichloride, ethyl aluminum dibromide, ethyl aluminum dichloride, butyl aluminum dibromide, butyl aluminum dichloride, dimethyl aluminum bromide, dimethyl aluminum chloride, diethyl aluminum bromide, diethyl Aluminum chloride, dibutylaluminum bromide, dibutylaluminum chloride, methylaluminum sesquibromide, methylaluminum sesquichloride, ethylaluminum sesquibromide, ethylaluminum sesquichloride, dibutyltin dichloride, aluminum tribromide, antimony trichloride, antimony pentachloride, phosphorus trichloride , Pentachloride , Tin tetrachloride, titanium tetrachloride, tungsten hexachloride, etc., among which diethylaluminum chloride,
- the metal halide constituting the complex compound of the above metal halide and Lewis base includes beryllium chloride, beryllium bromide, beryllium iodide, magnesium chloride, magnesium bromide, magnesium iodide, calcium chloride, calcium bromide, iodine.
- a phosphorus compound, a carbonyl compound, a nitrogen compound, an ether compound, an alcohol, and the like are preferable.
- tri-2-ethylhexyl phosphate, tricresyl phosphate, acetylacetone, 2-ethylhexanoic acid, versatic acid, 2 -Ethylhexyl alcohol, 1-decanol, lauryl alcohol are preferred.
- the Lewis base is reacted at a ratio of 0.01 to 30 mol, preferably 0.5 to 10 mol, per mol of the metal halide.
- the metal remaining in the polymer can be reduced.
- the organic compound containing the active halogen include benzyl chloride.
- the component (C) used in the second polymerization catalyst composition is represented by the following general formula (X): YR 1 a R 2 b R 3 c (X) [Wherein Y is a metal selected from Group 1, Group 2, Group 12 and Group 13 of the Periodic Table, and R 1 and R 2 are the same or different and have 1 to 10 carbon atoms.
- R 3 is a hydrocarbon group having 1 to 10 carbon atoms, provided that R 3 may be the same as or different from R 1 or R 2, and Y is a periodic table;
- a is 1 and b and c are 0, and when Y is a metal selected from Groups 2 and 12 of the Periodic Table, a and b are 1 and c is 0, and when Y is a metal selected from Group 13 of the Periodic Table, a, b and c are 1].
- organoaluminum compound of the formula (X) examples include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, tripentylaluminum, Trihexyl aluminum, tricyclohexyl aluminum, trioctyl aluminum; diethyl aluminum hydride, di-n-propyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl aluminum hydride, dihexyl aluminum hydride, diisohexyl hydride Aluminum, dioctyl aluminum hydride, diisooctyl aluminum hydride; ethyl aluminum dihydride, n-propyl aluminum Hydride, include isobutyl aluminum dihydride and the like, among these, triethylaluminum, triis
- the organoaluminum compound as component (C) described above can be used alone or in combination of two or more.
- the content of the organoaluminum compound in the second polymerization catalyst composition is preferably 1 to 50 times mol, more preferably about 10 times mol for the component (A).
- the polymerization catalyst is for polymerization of a conjugated diene compound and a non-conjugated olefin, and has the following formula (A): R a MX b QY b (A) [In the formula, each R independently represents unsubstituted or substituted indenyl, the R is coordinated to M, M represents a lanthanoid element, scandium or yttrium, and each X independently represents 1 to 20 represents a hydrocarbon group, X is ⁇ -coordinated to M and Q, Q represents a group 13 element in the periodic table, and Y is independently a hydrocarbon group having 1 to 20 carbon atoms or A hydrogen atom, wherein Y is coordinated to Q and a and b are 2].
- metallocene composite catalyst the following formula (XV): [ Wherein , M 1 represents a lanthanoid element, scandium or yttrium, Cp R independently represents an unsubstituted or substituted indenyl group, and R a and R b each independently represent one having 1 to 20 carbon atoms. R a and R b are ⁇ -coordinated to M 1 and Al, and R c and R d each independently represents a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom.
- the third polymerization catalyst composition includes the metallocene composite catalyst and a boron anion.
- the metallocene composite catalyst includes a lanthanoid element, a rare earth element of scandium or yttrium, and a Group 13 element of the periodic table, and has the following formula (A): R a MX b QY b (A) [In the formula, each R independently represents unsubstituted or substituted indenyl, the R is coordinated to M, M represents a lanthanoid element, scandium or yttrium, and each X independently represents 1 to 20 represents a hydrocarbon group, X is ⁇ -coordinated to M and Q, Q represents a group 13 element in the periodic table, and Y is independently a hydrocarbon group having 1 to 20 carbon atoms or A hydrogen atom, wherein Y is coordinated to Q, and a and b are 2.]
- a copolymer of a conjugated diene compound and
- the metallocene composite catalyst for example, a catalyst previously combined with an aluminum catalyst, the amount of alkylaluminum used at the time of copolymer synthesis can be reduced or eliminated. If a conventional catalyst system is used, it is necessary to use a large amount of alkylaluminum at the time of copolymer synthesis. For example, in the conventional catalyst system, it is necessary to use 10 equivalents or more of alkylaluminum with respect to the metal catalyst. If the metallocene composite catalyst is used, an excellent catalytic action can be obtained by adding about 5 equivalents of alkylaluminum. Is demonstrated.
- the metal M in the formula (A) is a lanthanoid element, scandium or yttrium.
- the lanthanoid elements include 15 elements having atomic numbers of 57 to 71, and any of these may be used.
- Preferred examples of the metal M include samarium Sm, neodymium Nd, praseodymium Pr, gadolinium Gd, cerium Ce, holmium Ho, scandium Sc, and yttrium Y.
- each R is independently an unsubstituted indenyl or a substituted indenyl, and the R is coordinated to the metal M.
- the substituted indenyl group include 1,2,3-trimethylindenyl group, heptamethylindenyl group, 1,2,4,5,6,7-hexamethylindenyl group, and the like. It is done.
- Q represents a group 13 element of the periodic table, and specific examples include boron, aluminum, gallium, indium, thallium and the like.
- X independently represents a hydrocarbon group having 1 to 20 carbon atoms, and X is ⁇ -coordinated to M and Q.
- the hydrocarbon group having 1 to 20 carbon atoms includes methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group.
- the ⁇ coordination is a coordination mode having a crosslinked structure.
- each Y independently represents a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom, and the Y is coordinated to Q.
- the hydrocarbon group having 1 to 20 carbon atoms includes methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group.
- the metal M 1 is a lanthanoid element, scandium or yttrium.
- the lanthanoid elements include 15 elements having atomic numbers of 57 to 71, and any of these may be used.
- Preferable examples of the metal M 1 include samarium Sm, neodymium Nd, praseodymium Pr, gadolinium Gd, cerium Ce, holmium Ho, scandium Sc, and yttrium Y.
- Cp R is unsubstituted indenyl or substituted indenyl.
- Cp R having an indenyl ring as a basic skeleton can be represented by C 9 H 7-X R X or C 9 H 11-X R X.
- X is an integer of 0 to 7 or 0 to 11.
- each R is preferably independently a hydrocarbyl group or a metalloid group.
- the hydrocarbyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 8 carbon atoms.
- hydrocarbyl group examples include a methyl group, an ethyl group, a phenyl group, and a benzyl group.
- metalloid group metalloids include germyl Ge, stannyl Sn, and silyl Si, and the metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group that the metalloid group has is the same as the above hydrocarbyl group. is there.
- Specific examples of the metalloid group include a trimethylsilyl group.
- substituted indenyl examples include 2-phenylindenyl, 2-methylindenyl and the like. Incidentally, the two Cp R in the formula (XV) may each be the same or different from each other.
- R A and R B each independently represent a hydrocarbon group having 1 to 20 carbon atoms, said R A and R are coordinated ⁇ to M 1 ⁇ A l.
- the hydrocarbon group having 1 to 20 carbon atoms includes methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group.
- the ⁇ coordination is a coordination mode having a crosslinked structure.
- R C and R D are each independently a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom.
- the hydrocarbon group having 1 to 20 carbon atoms includes methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group.
- the metallocene composite catalyst is, for example, in a solvent in the following formula (XVI):
- M 2 represents a lanthanoid element, scandium or yttrium
- Cp R each independently represents an unsubstituted or substituted indenyl group
- R E to R J each independently represents a group having 1 to 3 carbon atoms.
- L represents a neutral Lewis base
- w represents an integer of 0 to 3
- a metallocene complex represented by AlR K R L R M It is obtained by reacting with.
- reaction temperature should just be about room temperature, it can manufacture on mild conditions.
- the reaction time is arbitrary, but is about several hours to several tens of hours.
- the reaction solvent is not particularly limited, but is preferably a solvent that dissolves the raw material and the product.
- a solvent that dissolves the raw material and the product For example, toluene or hexane may be used.
- the structure of the metallocene composite catalyst is preferably determined by 1 H-NMR or X-ray structural analysis.
- Cp R is unsubstituted indenyl or substituted indenyl, and has the same meaning as Cp R in the above formula (XV).
- the metal M 2 is a lanthanoid element, scandium or yttrium, and has the same meaning as the metal M 1 in the above formula (XV).
- the metallocene complex represented by the above formula (XVI) contains a silylamide ligand [—N (SiR 3 ) 2 ].
- the R groups (R E to R J groups) contained in the silylamide ligand are each independently an alkyl group having 1 to 3 carbon atoms or a hydrogen atom. Further, it is preferable that at least one of R E to R J is a hydrogen atom. By making at least one of R E to R J a hydrogen atom, the synthesis of the catalyst becomes easy. Furthermore, a methyl group is preferable as the alkyl group.
- the metallocene complex represented by the above formula (XVI) further contains 0 to 3, preferably 0 to 1 neutral Lewis base L.
- the neutral Lewis base L include tetrahydrofuran, diethyl ether, dimethylaniline, trimethylphosphine, lithium chloride, neutral olefins, neutral diolefins, and the like.
- the neutral Lewis bases L may be the same or different.
- metallocene complex represented by the above formula (XVI) may exist as a monomer, or may exist as a dimer or higher multimer.
- the organoaluminum compound used to produce the metallocene composite catalyst is represented by AlR K R L R M , where R K and R L are each independently a monovalent carbon atom having 1 to 20 carbon atoms. hydrogen group or a hydrogen atom, R M is a monovalent hydrocarbon group having 1 to 20 carbon atoms, provided that, R M may be the same or different and the R K or R L.
- Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group , Pentadecyl group, hexadecyl group, heptadecyl group, stearyl group and the like.
- organoaluminum compound examples include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, tripentylaluminum, tri Hexyl aluminum, tricyclohexyl aluminum, trioctyl aluminum; diethyl aluminum hydride, di-n-propyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl aluminum hydride, dihexyl aluminum hydride, diisohexyl aluminum hydride , Dioctylaluminum hydride, diisooctylaluminum hydride; ethylaluminum dihydride, n-propylaluminum Muzi hydride, isobutylaluminum dihydride and the like.
- triethylaluminum, triisobutylaluminum, hydrogenated diethylaluminum, hydrogenated diisobutylaluminum are preferred.
- these organoaluminum compounds can be used individually by 1 type, or 2 or more types can be mixed and used for them.
- the amount of the organoaluminum compound used for the production of the metallocene composite catalyst is preferably 1 to 50 times mol, more preferably about 10 times mol for the metallocene complex.
- the polymerization catalyst composition contains the metallocene composite catalyst and a boron anion, and further contains other components such as a cocatalyst contained in the polymerization catalyst composition containing a normal metallocene catalyst. Etc. are preferably included.
- the metallocene composite catalyst and boron anion are also referred to as a two-component catalyst. According to the third polymerization catalyst composition, since the boron anion is further contained in the same manner as the metallocene composite catalyst, the content of each monomer component in the copolymer can be arbitrarily controlled. It becomes possible.
- boron anion constituting the two-component catalyst in the third polymerization catalyst composition include a tetravalent boron anion.
- tetraphenyl borate tetrakis (monofluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis (pentafluorophenyl) borate, tetrakis (tetrafluoromethyl) Phenyl) borate, tetra (tolyl) borate, tetra (xylyl) borate, (triphenyl, pentafluorophenyl) borate, [tris (pentafluorophenyl), phenyl] borate, tridecahydride-7,8-dicarboundecaborate Among
- the boron anion can be used as an ionic compound combined with a cation.
- the cation include a carbonium cation, an oxonium cation, an amine cation, a phosphonium cation, a cycloheptatrienyl cation, and a ferrocenium cation having a transition metal.
- the carbonium cation include trisubstituted carbonium cations such as a triphenylcarbonium cation and a tri (substituted phenyl) carbonium cation.
- the tri (substituted phenyl) carbonyl cation is specifically exemplified by tri (methylphenyl).
- amine cations include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, and tributylammonium cation; N, N-dimethylanilinium cation, N, N-diethylanilinium cation, N, N— N, N-dialkylanilinium cations such as 2,4,6-pentamethylanilinium cation; dialkylammonium cations such as diisopropylammonium cation and dicyclohexylammonium cation.
- Examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation.
- N, N-dialkylanilinium cation or carbonium cation is preferable, and N, N-dialkylanilinium cation is particularly preferable. Therefore, as the ionic compound, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbonium tetrakis (pentafluorophenyl) borate and the like are preferable.
- the ionic compound composed of a boron anion and a cation is preferably added in an amount of 0.1 to 10 times, more preferably about 1 time, with respect to the metallocene composite catalyst.
- the metallocene composite catalyst In the third polymerization catalyst composition, it is necessary to use the metallocene composite catalyst and the boron anion, but a reaction system for reacting the metallocene catalyst represented by the formula (XVI) with an organoaluminum compound. If a boron anion is present, the metallocene composite catalyst of the above formula (XV) cannot be synthesized. Therefore, for the preparation of the third polymerization catalyst composition, it is necessary to synthesize the metallocene composite catalyst in advance, isolate and purify the metallocene composite catalyst, and then combine with the boron anion.
- aluminoxane can be preferably used.
- the aluminoxane is preferably an alkylaminoxan, and examples thereof include methylaluminoxane (MAO) and modified methylaluminoxane. Further, as the modified methylaluminoxane, MMAO-3A (manufactured by Tosoh Finechem) and the like are preferable. These aluminoxanes may be used alone or in combination of two or more.
- polymerization is carried out in the same manner as in the method for producing a polymer using a normal coordination ion polymerization catalyst, except that the polymerization catalyst or the polymerization catalyst composition is used.
- the components of the polymerization catalyst composition are separately contained in a polymerization reaction system containing a conjugated diene compound as a monomer and a non-conjugated olefin other than the conjugated diene compound.
- the polymerization catalyst composition may be provided in the reaction system, or (2) a polymerization catalyst composition prepared in advance may be provided in the polymerization reaction system.
- (2) includes providing a metallocene complex (active species) activated by a cocatalyst.
- the amount of the metallocene complex contained in the polymerization catalyst composition is preferably in the range of 0.0001 to 0.01-fold mol with respect to the total of the conjugated diene compound and the non-conjugated olefin other than the conjugated diene compound.
- the polymerization may be stopped using a polymerization terminator such as methanol, ethanol, isopropanol or the like.
- the polymerization reaction of the conjugated diene compound and the non-conjugated olefin is preferably performed in an atmosphere of an inert gas, preferably nitrogen gas or argon gas.
- the polymerization temperature of the polymerization reaction is not particularly limited, but is preferably in the range of ⁇ 100 ° C. to 200 ° C., for example, and can be about room temperature. When the polymerization temperature is raised, the cis-1,4 selectivity of the polymerization reaction may be lowered.
- the pressure for the polymerization reaction is preferably in the range of 0.1 to 10.0 MPa in order to sufficiently incorporate the conjugated diene compound and the non-conjugated olefin into the polymerization reaction system.
- reaction time of the polymerization reaction is not particularly limited, and is preferably in the range of, for example, 1 second to 10 days, but may be appropriately selected depending on conditions such as the type of monomer to be polymerized, the type of catalyst, and the polymerization temperature. it can.
- the pressure of the non-conjugated olefin is preferably 0.1 MPa to 10 MPa when the conjugated diene compound is polymerized with a non-conjugated olefin other than the conjugated diene compound.
- the pressure of the non-conjugated olefin is 0.1 MPa or more, the non-conjugated olefin can be efficiently introduced into the reaction mixture.
- the pressure of the non-conjugated olefin is preferably 10 MPa or less.
- the concentration of the conjugated diene compound at the start of polymerization (mol / l) and the concentration of the non-conjugated olefin (Mol / l) means the following formula: Non-conjugated olefin concentration / conjugated diene compound concentration ⁇ 1.0 It is preferable to satisfy the relationship: Non-conjugated olefin concentration / conjugated diene compound concentration ⁇ 1.3 And more preferably the following formula: Non-conjugated olefin concentration / conjugated diene compound concentration ⁇ 1.7 Satisfy the relationship.
- the rubber composition is not particularly limited as long as it contains the copolymer, and can be appropriately selected according to the purpose.
- the rubber component other than the copolymer of the present invention inorganic filler, carbon black, cross-linked It is preferable to contain an agent.
- the rubber component is not particularly limited and may be appropriately selected depending on the intended purpose.
- the copolymer of the present invention natural rubber, various butadiene rubbers, various styrene-butadiene copolymer rubbers, isoprene rubber, Butyl rubber, isobutylene and p-methylstyrene copolymer bromide, halogenated butyl rubber, acrylonitrile butadiene rubber, chloroprene rubber, ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber, styrene-isoprene copolymer Examples include polymer rubber, styrene-isoprene-butadiene copolymer rubber, isoprene-butadiene copolymer rubber, chlorosulfonated polyethylene, acrylic rubber, epichlorohydrin rubber, polysulfide rubber, silicone rubber, fluorine rubber, and
- a reinforcing filler can be blended with the rubber composition as necessary.
- the reinforcing filler include carbon black and inorganic filler, and at least one selected from carbon black and inorganic filler is preferable.
- the inorganic filler is not particularly limited and may be appropriately selected depending on the intended purpose.For example, silica, aluminum hydroxide, clay, alumina, talc, mica, kaolin, glass balloon, glass beads, calcium carbonate, Examples thereof include magnesium carbonate, magnesium hydroxide, calcium carbonate, magnesium oxide, titanium oxide, potassium titanate, and barium sulfate. These may be used individually by 1 type and may use 2 or more types together. In addition, when using an inorganic filler, you may use a silane coupling agent suitably.
- the content of the reinforcing filler is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 5 parts by mass to 200 parts by mass with respect to 100 parts by mass of the rubber component. If the content of the reinforcing filler is less than 5 parts by mass, the effect of adding the reinforcing filler may not be seen so much, and if it exceeds 200 parts by mass, the rubber filler is mixed with the reinforcing filler. There is a tendency that it does not get caught, and the performance as a rubber composition may be reduced.
- the crosslinking agent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a sulfur-based crosslinking agent, an organic peroxide-based crosslinking agent, an inorganic crosslinking agent, a polyamine crosslinking agent, a resin crosslinking agent, and a sulfur compound. Among them, a sulfur-based crosslinking agent is more preferable as a rubber composition for tires.
- the content of the crosslinking agent is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the rubber component.
- the content of the cross-linking agent is less than 0.1 parts by mass, the cross-linking hardly proceeds, and when the content exceeds 20 parts by mass, the cross-linking tends to progress during kneading with a part of the cross-linking agent.
- the physical properties of the sulfide may be impaired.
- vulcanization accelerators can be used in combination.
- vulcanization accelerators include guanidine, aldehyde-amine, aldehyde-ammonia, thiazole, sulfenamide, thiourea, thiuram, Dithiocarbamate and xanthate compounds can be used.
- Known materials such as ultraviolet ray inhibitors, antistatic agents, anti-coloring agents, and other compounding agents can be used depending on the intended use.
- the crosslinked rubber composition is not particularly limited as long as it is obtained by crosslinking the rubber composition of the present invention, and can be appropriately selected according to the purpose.
- the crosslinking conditions are not particularly limited and may be appropriately selected depending on the intended purpose. However, a temperature of 120 ° C. to 200 ° C. and a heating time of 1 minute to 900 minutes are preferable.
- the tire is not particularly limited as long as it uses the rubber composition of the present invention or the crosslinked rubber composition of the present invention, and can be appropriately selected according to the purpose.
- Examples of the application site in the tire of the rubber composition of the present invention or the crosslinked rubber composition of the present invention include, but are not limited to, a tread, a base tread, a sidewall, a side reinforcing rubber, and a bead filler. .
- a method for manufacturing the tire a conventional method can be used. For example, on a tire molding drum, members usually used for manufacturing a tire such as a carcass layer, a belt layer, and a tread layer made of unvulcanized rubber are sequentially laminated, and the drum is removed to obtain a green tire. Next, the desired tire can be manufactured by heat vulcanizing the green tire according to a conventional method.
- the rubber composition of the present invention or the crosslinked rubber composition of the present invention may be used for anti-vibration rubber, seismic isolation rubber, belts (conveyor belts), rubber crawlers, various hoses, Moran and the like. it can.
- the catalyst solution was taken out from the glove box, an amount of 440 ⁇ mol in terms of neodymium was added to the monomer solution, and polymerization was performed at room temperature for 180 minutes. After polymerization, 1 mL of NS-5, 5 mass% isopropanol solution was added to stop the reaction, and the copolymer was separated with a large amount of methanol, followed by vacuum drying at 70 ° C. to obtain copolymer D. The yield of the obtained copolymer D was 35.50 g.
- the weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), cis-1,4 bond content, and ethylene content were measured by the following methods. evaluated.
- the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) in terms of polystyrene of the polymer were determined on the basis of monodisperse polystyrene at ° C.
- Cis-1,4 bond content The microstructure of the butadiene moiety in the copolymer was measured by 1 H-NMR spectrum (1,2-vinyl bond bond content) and 13 C-NMR spectrum (cis-1,4). It was determined from the integral ratio of the bond and the trans-1,4 bond content ratio). The calculated values of cis-1,4 bond content (%) are shown in Table 1.
- (3) Content of ethylene The content (mol%) of the ethylene moiety in the copolymer was determined from the integral ratio of the 1 H-NMR spectrum and the 13 C-NMR spectrum.
- Rubber compounds having the compounding recipe shown in Table 2 were prepared, and vulcanized rubber obtained by vulcanization at 160 ° C. for 20 minutes was subjected to ozone resistance according to the following method. Sex was measured.
- Comparative Example 1 polymerization was carried out in the same manner as in Example 5 except that the ethylene introduction pressure of the copolymer E in Example 5 was 0.1 MPa. Obtained in 50 g.
- Comparative Example 2 dimethylaluminum ( ⁇ -dimethyl) bis (pentamethylcyclopentadienyl) gadolinium [(C 5 Me 5 ) 2 Gd ( ⁇ -Me) 2 AlMe 2 ] of the copolymer of Example 6 is used.
- dimethylaluminum ( ⁇ -dimethyl) bis (bentamtercyclopentadienyl) praseodymium [((C 5 Me 5 ) 2 P ( ⁇ -Me) 2 AlMe 2 ] the same as Example 6 was used.
- copolymer H was obtained in a yield of 9,70 g.
- Ozone resistance was measured according to JIS K6259.
- the strip-shaped test piece was exposed under the conditions of 40 ° C. and ozone concentration of 50 pphm while giving a static elongation of 30%, and the state of the sample (presence of cracks) after 24 hours was visually judged.
- the results are shown in Table 3.
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Abstract
Description
特に、共役ジエンと非共役オレフィンの共重合体を配合ゴムへ適用することで、共重合体中の共役ジエン部分の二重結合が共役ジエン重合体に比べて少なくなるため、耐オゾン性が向上する。また、ゴム組成物を様々な用途(タイヤやベルトコンベア、防振ゴムなど)に適用した時に求められる耐オゾン性以外の要求特性の一つとして、耐亀裂成長性を良好にすることが挙げられる。
ここで、シス1,4-結合含量とは、共役ジエン化合物中の共役ジエン単位における1,4-シス結合の割合を意味する。
好ましくは、このような共重合体は分子量分布(Mw/Mn)が10以下である。
また好ましくは、ゴム組成物は、ゴム成分100質量部に対し、補強性充填剤5質量部~200質量部と、架橋剤0.1質量部~20質量部とを含む。
好ましくは、架橋ゴム組成物は、前記ゴム組成物を架橋して得ることができる。
そしてまた好ましくは、前記ゴム組成物、又は、前記架橋ゴム組成物を用いてタイヤをえることはできる。
非共役オレフィンの含有量が20mol%未満では、静的な結晶性が少なくなり、機械的な破断強度が低減するおそれがある。
本発明の共役ジエン化合物と非共役オレフィンとの共重合体は、共役ジエン部分のシス1,4-結合含量が50%以上であるとともに、非共役オレフィンの含有量が20mol%以上であることを特徴とする。
ここで、平均分子量及び分子量分布は、ゲルパーミエーションクロマトグラフィー(GPC)によりポリスチレンを標準物質として求めることができる。
本発明の共重合体は、下記に示す重合触媒または重合触媒組成物の存在下、共役ジエン化合物と非共役オレフィンとを重合させることができる。なお、重合方法としては、溶液重合法、懸濁重合法、液相塊状重合法、乳化重合法、気相重合法、固相重合法等の任意の方法を用いることができる。また、重合反応に溶媒を用いる場合、用いられる溶媒は重合反応において不活性であればよく、例えば、トルエン、シクロヘキサン、ノルマルヘキサン等が挙げられる。
上記重合触媒組成物としては、下記一般式(I):
また、上記重合触媒組成物としては、
(A)成分:希土類元素化合物又は該希土類元素化合物とルイス塩基との反応物であって、希土類元素と炭素との結合を有さない該希土類元素化合物又は反応物と、
(B)成分:非配位性アニオンとカチオンとからなるイオン性化合物(B-1)、アルミノキサン(B-2)、並びにルイス酸、金属ハロゲン化物とルイス塩基との錯化合物及び活性ハロゲンを含む有機化合物のうち少なくとも一種のハロゲン化合物(B-3)よりなる群から選択される少なくとも一種とを含む重合触媒組成物(以下、第二重合触媒組成物ともいう)を好適に挙げることができ、
該第二重合触媒組成物が、イオン性化合物(B-1)及びハロゲン化合物(B-3)の少なくとも一種を含む場合、該重合触媒組成物は、更に、
(C)成分:下記一般式(X):
YR1 aR2 bR3 c ・・・ (X)
[式中、Yは、周期律表第1族、第2族、第12族及び第13族から選択される金属であり、R1及びR2は、同一又は異なり、炭素数1~10の炭化水素基又は水素原子で、R3は炭素数1~10の炭化水素基であり、但し、R3は上記R1又はR2と同一又は異なっていてもよく、また、Yが周期律表第1族から選択される金属である場合には、aは1で且つb及びcは0であり、Yが周期律表第2族及び第12族から選択される金属である場合には、a及びbは1で且つcは0であり、Yが周期律表第13族から選択される金属である場合には、a,b及びcは1である]で表される有機金属化合物を含むことを特徴とする。
(C)成分:下記一般式(X):
YR1 aR2 bR3 c ・・・ (X)
[式中、Yは、周期律表第1族、第2族、第12族及び第13族から選択される金属であり、R1及びR2は、同一又は異なり、炭素数1~10の炭化水素基又は水素原子で、R3は炭素数1~10の炭化水素基であり、但し、R3は上記R1又はR2と同一又は異なっていてもよく、また、Yが周期律表第1族から選択される金属である場合には、aは1で且つb及びcは0であり、Yが周期律表第2族及び第12族から選択される金属である場合には、a及びbは1で且つcは0であり、Yが周期律表第13族から選択される金属である場合には、a,b及びcは1である]で表される有機金属化合物を含むことを要する。上記イオン性化合物(B-1)及び上記ハロゲン化合物(B-3)は、(A)成分へ供給するための炭素原子が存在しないため、該(A)成分への炭素供給源として、上記(C)成分が必要となる。なお、上記重合触媒組成物が上記アルミノキサン(B-2)を含む場合であっても、該重合触媒組成物は、上記(C)成分を含むことができる。また、上記第二重合触媒組成物は、通常の希土類元素化合物系の重合触媒組成物に含有される他の成分、例えば助触媒等を含んでいてもよい。
M11X11 2・L11w ・・・ (XI)
M11X11 3・L11w ・・・ (XII)
[式中、M11は、ランタノイド元素、スカンジウム又はイットリウムを示し、X11は、それぞれ独立して、水素原子、ハロゲン原子、アルコキシド基、チオラート基、アミド基、シリル基、アルデヒド残基、ケトン残基、カルボン酸残基、チオカルボン酸残基又はリン化合物残基を示し、L11は、ルイス塩基を示し、wは、0~3を示す]で表されることができる。
上記活性ハロゲンを含む有機化合物としては、ベンジルクロライド等が挙げられる。
YR1 aR2 bR3 c ・・・ (X)
[式中、Yは、周期律表第1族、第2族、第12族及び第13族から選択される金属であり、R1及びR2は、同一又は異なり、炭素数1~10の炭化水素基又は水素原子で、R3は炭素数1~10の炭化水素基であり、但し、R3は上記R1又はR2と同一又は異なっていてもよく、また、Yが周期律表第1族から選択される金属である場合には、aは1で且つb及びcは0であり、Yが周期律表第2族及び第12族から選択される金属である場合には、a及びbは1で且つcは0であり、Yが周期律表第13族から選択される金属である場合には、a,b及びcは1である]で表される有機金属化合物であり、下記一般式(Xa):
AlR1R2R3 ・・・ (Xa)
[式中、R1及びR2は、同一又は異なり、炭素数1~10の炭化水素基又は水素原子で、R3は炭素数1~10の炭化水素基であり、但し、R3は上記R1又はR2と同一又は異なっていてもよい]で表される有機アルミニウム化合物であることが好ましい。式(X)の有機アルミニウム化合物としては、トリメチルアルミニウム、トリエチルアルミニウム、トリ-n-プロピルアルミニウム、トリイソプロピルアルミニウム、トリ-n-ブチルアルミニウム、トリイソブチルアルミニウム、トリ-t-ブチルアルミニウム、トリペンチルアルミニウム、トリヘキシルアルミニウム、トリシクロヘキシルアルミニウム、トリオクチルアルミニウム;水素化ジエチルアルミニウム、水素化ジ-n-プロピルアルミニウム、水素化ジ-n-ブチルアルミニウム、水素化ジイソブチルアルミニウム、水素化ジヘキシルアルミニウム、水素化ジイソヘキシルアルミニウム、水素化ジオクチルアルミニウム、水素化ジイソオクチルアルミニウム;エチルアルミニウムジハイドライド、n-プロピルアルミニウムジハイドライド、イソブチルアルミニウムジハイドライド等が挙げられ、これらの中でも、トリエチルアルミニウム、トリイソブチルアルミニウム、水素化ジエチルアルミニウム、水素化ジイソブチルアルミニウムが好ましい。以上に述べた(C)成分としての有機アルミニウム化合物は、1種単独で使用することも、2種以上を混合して用いることもできる。なお、上記第二重合触媒組成物における有機アルミニウム化合物の含有量は、(A)成分に対して1~50倍モルであることが好ましく、約10倍モルであることが更に好ましい。
上記重合触媒としては、共役ジエン化合物と非共役オレフィンとの重合用であり、下記式(A):
RaMXbQYb ・・・ (A)
[式中、Rはそれぞれ独立して無置換もしくは置換インデニルを示し、該RはMに配位しており、Mはランタノイド元素、スカンジウム又はイットリウムを示し、Xはそれぞれ独立して炭素数1~20の炭化水素基を示し、該XはM及びQにμ配位しており、Qは周期律表第13族元素を示し、Yはそれぞれ独立して炭素数1~20の炭化水素基又は水素原子を示し、該YはQに配位しており、a及びbは2である]で表されるメタロセン系複合触媒が挙げられる。
以下に、上記メタロセン系複合触媒を詳細に説明する。上記メタロセン系複合触媒は、ランタノイド元素、スカンジウム又はイットリウムの希土類元素と周期律表第13族元素とを有し、下記式(A):
RaMXbQYb ・・・ (A)
[式中、Rはそれぞれ独立して無置換もしくは置換インデニルを示し、該RはMに配位しており、Mはランタノイド元素、スカンジウム又はイットリウムを示し、Xはそれぞれ独立して炭素数1~20の炭化水素基を示し、該XはM及びQにμ配位しており、Qは周期律表第13族元素を示し、Yはそれぞれ独立して炭素数1~20の炭化水素基又は水素原子を示し、該YはQに配位しており、a及びbは2である]で表されることを特徴とする。上記メタロセン系重合触媒を用いることで、共役ジエン化合物と非共役オレフィンとの共重合体を製造することができる。また、上記メタロセン系複合触媒、例えば予めアルミニウム触媒と複合させてなる触媒を用いることで、共重合体合成時に使用されるアルキルアルミニウムの量を低減したり、無くしたりすることが可能となる。なお、従来の触媒系を用いると、共重合体合成時に大量のアルキルアルミニウムを用いる必要がある。例えば、従来の触媒系では、金属触媒に対して10当量以上のアルキルアルミニウムを用いる必要があるところ、上記メタロセン系複合触媒であれば、5当量程度のアルキルアルミニウムを加えることで、優れた触媒作用が発揮される。
また、上記重合触媒組成物は、上記メタロセン系複合触媒と、ホウ素アニオンとを含むことを特徴とし、更に、通常のメタロセン系触媒を含む重合触媒組成物に含有される他の成分、例えば助触媒等を含むことが好ましい。なお、上記メタロセン系複合触媒とホウ素アニオンとを合わせて2成分触媒ともいう。上記第三重合触媒組成物によれば、上記メタロセン系複合触媒と同様に、更にホウ素アニオンを含有するため、各単量体成分の共重合体中での含有量を任意に制御することが可能となる。
非共役オレフィンの濃度/共役ジエン化合物の濃度 ≧ 1.0
の関係を満たすことが好ましく、更に好ましくは下記式:
非共役オレフィンの濃度/共役ジエン化合物の濃度 ≧ 1.3
の関係を満たし、一層好ましくは下記式:
非共役オレフィンの濃度/共役ジエン化合物の濃度 ≧ 1.7
の関係を満たす。非共役オレフィンの濃度/共役ジエン化合物の濃度の値を1以上とすることで、反応混合物中に非共役オレフィンを効率的に導入することができる。
ゴム組成物としては、前記共重合体を含む限り、特に制限はなく、目的に応じて適宜選択することができるが、本発明の共重合体以外のゴム成分、無機充填剤、カーボンブラック、架橋剤などを含むことが好ましい。
前記共重合体のゴム成分中の含有量としては、特に制限はなく、目的に応じて適宜選択することができるが、3質量%以上が好ましい。
前記共重合体のゴム成分中の含有量が、3質量%未満であると、本発明の特徴が小さかったり、またはその特徴を発揮しなかったりすることがある。
前記ゴム成分としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、本発明の共重合体、天然ゴム、各種ブタジエンゴム、各種スチレン-ブタジエン共重合体ゴム、イソプレンゴム、ブチルゴム、イソブチレンとp-メチルスチレンの共重合体の臭化物、ハロゲン化ブチルゴム、アクリロニトリロブタジエンゴム、クロロプレンゴム、エチレン-プロピレン共重合体ゴム、エチレン-プロピレン-ジエン共重合体ゴム、スチレン-イソプレン共重合体ゴム、スチレン-イソプレン-ブタジエン共重合体ゴム、イソプレン-ブタジエン共重合体ゴム、クロロスルホン化ポリエチレン、アクリルゴム、エピクロルヒドリンゴム、多硫化ゴム、シリコーンゴム、フッ素ゴム、ウレタンゴムなどが挙げられる。これらは、1種単独で使用してもよいし、2種以上を併用してもよい。
<無機充填剤>
前記無機充填剤としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、シリカ、水酸化アルミニウム、クレー、アルミナ、タルク、マイカ、カオリン、ガラスバルーン、ガラスビーズ、炭酸カルシウム、炭酸マグネシウム、水酸化マグネシウム、炭酸カルシウム、酸化マグネシウム、酸化チタン、チタン酸カリウム、硫酸バリウムなどが挙げられる。これらは、1種単独で使用してもよいし、2種以上を併用してもよい。
なお、無機充填剤を用いる時は適宜シランカップリング剤を使用してもよい。
前記補強性充填剤の含有量が、5質量部未満であると、補強性充填剤を入れる効果があまりみられないことがあり、200質量部を超えると前記ゴム成分に補強性充填剤が混ざり込まなくなる傾向があり、ゴム組成物としての性能を低下させることがある。
前記架橋剤としては、特に制限はなく、目的に応じて適宜選択することができ、例えば硫黄系架橋剤、有機過酸化物系架橋剤、無機架橋剤、ポリアミン架橋剤、樹脂架橋剤、硫黄化合物系架橋剤、オキシム-ニトロソアミン系架橋剤硫黄などが挙げられるが、中でもタイヤ用ゴム組成物としては硫黄系架橋剤がより好ましい。
前記架橋剤の含有量が0.1質量部未満では、架橋がほとんど進行しなかったり、20質量部を超えると一部の架橋剤により混練り中に架橋が進んでしまう傾向があったり、加硫物の物性が損なわれたりすることがある。
その他に加硫促進剤を併用することも可能であり、加硫促進剤としては、グアジニン系、アルデヒド-アミン系、アルデヒド-アンモニア系、チアゾール系、スルフェンアミド系、チオ尿素系、チウラム系、ジチオカルバメート系、ザンテート系等の化合物が使用できる。
また必要に応じて、補強剤、軟化剤、充填剤、加硫助剤、着色剤、難燃剤、滑剤、発泡剤、可塑剤、加工助剤、酸化防止剤、老化防止剤、スコーチ防止剤、紫外線防止剤、帯電防止剤、着色防止剤、その他の配合剤など公知のものをその使用目的に応じて使用することができる。
架橋ゴム組成物は、本発明のゴム組成物を架橋して得られたものである限り、特に制限はなく、目的に応じて適宜選択することができる。
前記架橋の条件としては、特に制限はなく、目的に応じて適宜選択することができるが、温度120℃~200℃、加温時間1分間~900分間が好ましい。
タイヤは、本発明のゴム組成物、又は、本発明の架橋ゴム組成物を用いたものである限り、特に制限はなく、目的に応じて適宜選択することができる。
本発明のゴム組成物、又は、本発明の架橋ゴム組成物のタイヤにおける適用部位としては、例えば、トレッド、ベーストレッド、サイドウォール、サイド補強ゴム及びビードフィラーなどが挙げられるが、これに限定されない。
前記タイヤを製造する方法としては、慣用の方法を用いることができる。例えば、タイヤ成形用ドラム上に未加硫ゴムからなるカーカス層、ベルト層、トレッド層等の通常タイヤ製造に用いられる部材を順次貼り重ね、ドラムを抜き去ってグリーンタイヤとする。次いで、このグリーンタイヤを常法に従って加熱加硫することにより、所望のタイヤを製造することができる。
タイヤ用途以外にも、防振ゴム、免震ゴム、ベルト(コンベアベルト)、ゴムクローラ、各種ホース、モランなどに本発明のゴム組成物、又は、本発明の架橋ゴム組成物を使用することができる。
十分に乾燥した200mL耐圧ガラス反応器に、1,3-ブタジエン3.38g(0.063mol)を含むトルエン溶液20mLを添加した後、エチレンを2.45g(0.088mol)導入した。一方、窒素雰囲気下のグローブボックス中で、ガラス製容器にビス(2-フェニルインデニル)ガドリニウムビス(ジメチルシリルアミド)[(2-PhC9H6)2GdN(SiHMe2)2]5.5μmol、ジメチルアニリニウムテトラキス(ペンタフルオロフェニル)ボレート(Me2NHPhB(C6F5)4)11.0μmol、及びトリイソブチルアルミニウム0.41mmolを仕込み、トルエン10mLに溶解させて触媒溶液とした。その後、グローブボックスから触媒溶液を取り出し、ガドリニウム換算で17.5μmolとなる量をモノマー溶液へ添加し、室温で240分間重合を行った。重合後、2,2’-メチレン-ビス(4-エチル-6-t-ブチルフェノール)(NS-5)5質量%のイソプロパノール溶液1mLを加えて反応を停止させ、さらに大量のメタノールで共重合体を分離し、70℃で真空乾燥し共重合体Aを得た。得られた共重合体Aの収量は4.15gであった。
十分に乾燥した400mL耐圧ガラス反応器に、1,3-ブタジエン18.20g(0.34mol)を含むトルエン溶液300mLを添加した後、エチレンを0.8MPaで導入した。一方、窒素雰囲気下のグローブボックス中で、ガラス製容器にトリスビストリメチルシリルアミドガドリニウム〔Gd[N(SiMe3)2]3〕34.0μmol、ジメチルアニリニウムテトラキス(ペンタフルオロフェビル)ボレート(Me2NHPhB(C6F5)4)41.0μmol、及びトリイソブチルアルミニウム1.19mmolを仕込み、トルエン8mLに溶解させて触媒溶液とした。その後、グローブボックスから触媒溶液を取り出し、ガドリニウム換算で33.7μmolとなる量をモノマー溶液へ添加し、室温で180分間重合を行った。重合後、2、2’-メチレン-ビス(4-エチル-6-t-ブチルフェノール)(NS-5)5質量%のイソブロパノール溶液1mLを加えて反応を停止させ、さらに大量のメタノールで共重合体を分離し、70℃で真空乾燥し共重合体Bを得た。得られた共重合体Bの収量は29.50gであった。
1,3-ブタジエン4.55g(0.084mol)を用いること以外は共重合体Bの製造方法と同様の方法で重合を行ったところ収量22.50gで共重合体Cを得た。
十分に乾燥した400mL耐圧ガラス反応器に、1,3-ブタジエン23.78g(0.44mol)を含むトルエン溶液300mLを添加した後、エチレンを0.8MPaで導入した。一方、窒素雰囲気下の中で、ガラス製容器にトリスビストリメチルシリルアミドネオジウム[Nd〔N(SiMe)2〕3]を500μmol、Me2NHPhB(C6F5)4600μmol、及びジイソブチルアルミニウムハイドライド10.0mmolを仕込み、トルエン25mLに溶解させて触媒溶液とした。その後、グローブボックスから触媒溶液を取り出し、ネオジウム換算で440μmolとなる量をモノマー溶液へ添加し、室温で180分間重合を行った。重合後、NS-5、5質量%のイソプロパノール溶液1mLを加えて反応を停止させ、さらに大量のメタノールで共重合体を分離し、70℃で真空乾燥し共重合体Dを得た。得られた共重合体Dの収量は35.50gであった。
Nd[N(SiMe3)2]3の代わりに、トリスビスジメチルシリルアミドスカンジウム[Sc〔N(SiHMe2)2]3・(thf)2〕を用いること以外は、共重合体Dの製造方法と同様の方法で重合を行ったところ、収量37.40gで共重合体Eを得た。
十分に乾燥した400mL耐圧ガラス反応器に、1,3-ブタジエン1.57g(0.029mol)を含むトルエン溶液110mLを添加した後、エチレンを0.8MPaで導入した。一方、窒素雰囲気下のグローブボックス中で、ガラス製容器にジメチルアルミニウム(μ-ジメチル)ビス(ペンタメチルシクロペンタジエニル)ガドリニウム[(C5Me5)2Gd(μ-Me)2AlMe2]30.0μmol、トリフェニルカルボニウムテトラキス(ペンタフルオロフェニル)ボレート(Ph3CB(C6F5)4)30.0μmo1、及びトリイソブチルアルミニウム0.60mmolを仕込み、トルエン8mLに溶解させて触媒溶液とした。その後、グローブボックスから触媒溶液を取り出し、ガドリニウム換算で29.0μmolとなる量をモノマー溶液へ添加し、室温で20分間重合を行った。その後、新たに1,3-ブタジエン3.13g(0.058mol)を含むトルエン溶液20mLを添加した後、さらに30分間重合を行う操作を2回繰り返した。重合後、2,2’-メチレン-ビス(4-エチル-6-t-ブチルフェノール)(NS-5)5質量%のイソプロパノール溶液1mLを加えて反応を停止させ、さらに大量のメタノールで共重合体を分離し、70℃で真空乾燥し共重合体Fを得た。得られた共重合体Fの収量は10.00gであった。
ゲルパーミエーションクロマトグラフィー[GPC:東ソー製HLC-8121GPC/HT、カラム:東ソー製GMHHR-H(S)HT×2本、検出器:示差屈折率計(RI)]を用いて、測定温度140℃で単分散ポリスチレンを基準として、重合体のポリスチレン換算の重量平均分子量(Mw)及び分子量分布(Mw/Mn)を求めた。
(2)シス-1,4結合含量
共重合体中のブタジエン部分のミクロ構造を、1H-NMRスペクトル(1,2-ビニル結合の結合含量)及び13C-NMRスペクトル(シス-1,4結合とトランス-1,4結合の含有量比)の積分比より求めた。シス-1,4結合含量(%)の計算値を表1に示す。
(3)エチレンの含有率
共重合体中のエチレン部分の含有率(mol%)を1H-NMRスペクトル及び13C-NMRスペクトルの積分比より求めた。
比較例2では、実施例6の共重合体のジメチルアルミニウム(μ-ジメチル)ビス(ペンタメチルシクロペンタジエニル)ガドリニウム[(C5Me5)2Gd(μ-Me)2AlMe2]を用いる代わりに、ジメチルアルミニウム(μ-ジメチル)ビス(ベンタメテルシクロペンタジエニル)プラセオジウム[((C5Me5)2P(μ-Me)2AlMe2]を用いること以外は、実施例6と同様方法で重合を行ったところ、共重合体Hを収量9,70gで得た。
※2:N-シクロヘキシル-2-ベンゾチアゾリルスルフェンアミド、大内新興化学(株)製、ノクセラーCZ-G
※3:ジベンゾチアジルジスルフィド、大内新興化学(株)製、ノクセラーDM-P
JIS K6259に従って、耐オゾン性を測定した。短冊状試験片を30%の静的伸張を与えながら、40℃、オゾン濃度50pphm条件で暴露し、24時間後の試料の状況(亀裂の有無)を目視で判断した。結果を表3に示す。
実施例1、4、6及び比較例2については、JIS3号試験片中心部に0.5mmの亀裂を入れ、室温で0%~100%の歪みで繰り返し疲労を与え、サンプルが切断するまでの回数を測定した。測定結果は、比較例2を100としてそれぞれを指数表示した。指数値が大きい程、耐亀裂成長性が良好であることを示す。
なお、表3中の>200は、比較例1に対し2倍の回数の繰り返し疲労を与えても、サンプルの切断が起こらなかったことを示す。
Claims (12)
- 共役ジエン化合物と、共役ジエン以外の非共役オレフィンの共重合体において、
共役ジエン部分のシス1,4-結合含量が50%以上であるとともに、非共役オレフィンの含有量が20mol%以上であることを特徴とする共役ジエン化合物と非共役オレフィンとの共重合体。 - 前記非共役オレフィンが、非環状オレフィンである請求項1に記載の共役ジエン化合物と非共役オレフィンとの共重合体。
- 前記非共役オレフィンは、炭素数が2~10のαオレフィンである請求項1または2に記載の共役ジエン化合物と非共役オレフィンとの共重合体。
- 前記非共役オレフィンが、エチレン、プロピレン及び1-ブテンよりなる群から選択される少なくとも一種である請求項1~3のいずれかに記載の共役ジエン化合物と非共役オレフィンとの共重合体。
- 前記共役ジエン化合物は、炭素数が4~8である請求項1~4のいずれかに記載の共役ジエン化合物と非共役オレフィンとの共重合体。
- 前記共役ジエン化合物が、1,3-ブタジエン及びイソプレンよりなる群から選択される少なくとも一種である請求項1~5のいずれかに記載の共役ジエン化合物と非共役オレフィンとの共重合体。
- 共役ジエン化合物のシス1,4-結合含量が80%以上である請求項1~6のいずれかに記載の共役ジエン化合物と非共役オレフィンとの共重合体。
- 分子量分布(Mw/Mn)が10以下である請求項1~7のいずれかに記載の共役ジエン化合物と非共役オレフィンとの共重合体。
- 請求項1に記載の共役ジエン化合物と非共役オレフィンとの共重合体を含むゴム組成物。
- ゴム成分100質量部に対し、補強性充填剤5質量部~200質量部と、架橋剤0.1質量部~20質量部とを含む請求項9に記載のゴム組成物。
- 請求項9に記載のゴム組成物を架橋して得られた架橋ゴム組成物。
- 請求項9に記載のゴム組成物、又は、請求項11に記載の架橋ゴム組成物を用いたタイヤ。
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CN103154058B (zh) | 2015-12-16 |
US8962743B2 (en) | 2015-02-24 |
CN103154058A (zh) | 2013-06-12 |
US20130210994A1 (en) | 2013-08-15 |
JP5918134B2 (ja) | 2016-05-18 |
EP2599805B1 (en) | 2016-01-13 |
EP2599805A4 (en) | 2014-08-06 |
EP2599805A1 (en) | 2013-06-05 |
JPWO2012014463A1 (ja) | 2013-09-12 |
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