WO2013132849A1 - ゴム組成物、及び、前記ゴム組成物を有するタイヤ - Google Patents
ゴム組成物、及び、前記ゴム組成物を有するタイヤ Download PDFInfo
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- WO2013132849A1 WO2013132849A1 PCT/JP2013/001416 JP2013001416W WO2013132849A1 WO 2013132849 A1 WO2013132849 A1 WO 2013132849A1 JP 2013001416 W JP2013001416 W JP 2013001416W WO 2013132849 A1 WO2013132849 A1 WO 2013132849A1
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- polymer
- cation
- polymerization
- rubber composition
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- 0 C*C1CCCC1 Chemical compound C*C1CCCC1 0.000 description 1
- GDOPTJXRTPNYNR-UHFFFAOYSA-N CC1CCCC1 Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
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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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- 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
- B60C1/0016—Compositions of the tread
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F36/08—Isoprene
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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
- C08K3/02—Elements
- C08K3/04—Carbon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
Definitions
- the present invention relates to a rubber composition and a tire having the rubber composition, and in particular, a rubber composition capable of obtaining a crosslinked rubber composition having improved durability (destructive properties and wear resistance), and
- the present invention relates to a tire having the rubber composition.
- an object of the present invention is to provide a rubber composition capable of obtaining a crosslinked rubber composition having improved durability (destructive resistance and wear resistance), and a tire having the rubber composition. .
- the present inventors considered that the durability of the crosslinked rubber composition obtained from the conventional synthetic polyisoprene was not sufficient because the gel having a high molecular weight was included in the conventional synthetic polyisoprene. .
- the inventors of the present invention have a rubber composition containing a rubber component, and the rubber component is a synthetic polyisoprene or an isoprene copolymer, and includes at least a polymer having a gel fraction of 20% or less.
- the present inventors have found that a crosslinked rubber composition having improved durability (breaking resistance and wear resistance) than conventional synthetic rubbers can be obtained, and the present invention has been completed.
- studies have been made to reduce the gel amount of synthetic polyisoprene (see, for example, US Pat. No. 5,987,076), rubber compositions containing synthetic polyisoprene having a reduced gel amount have not yet been studied. There is no current situation.
- the rubber composition contains a rubber component, and the rubber component is a synthetic polyisoprene or isoprene copolymer, and at least a polymer having a gel fraction of 20% or less. It is characterized by including.
- the rubber composition contains a rubber component, and when the rubber component is at least a polymer having a gel fraction of 20% or less, which is a synthetic polyisoprene or isoprene copolymer, the elongation crystallinity increases.
- a crosslinked rubber composition having improved durability (destructive properties and wear resistance) can be obtained.
- the phrase “including at least a polymer” means including at least one of the synthetic polyisoprene and the isoprene copolymer.
- “synthetic polyisoprene” means a homopolymer of isoprene polymerized (synthesized) using isoprene as a monomer.
- “isoprene copolymer” means a copolymer (copolymer) of isoprene and a compound other than isoprene polymerized (synthesized) using isoprene and a compound other than isoprene as a monomer (monomer). Means. Both “synthetic polyisoprene” and “isoprene copolymer” include those obtained by modifying a part of the polymer polymer chain.
- the refractive index (RI) Ss (unit: msec) was measured, the horizontal axis represents the polymer concentration (unit: mg / g) in the THF (tetrahydrofuran) solution, and the vertical axis represents the differential refractive index (RI) Ss (unit: msec) means a value that can be obtained using a calibration curve created.
- a THF solution of a polymer for which a gel fraction is to be obtained is passed through the filter, and the differential refractive index (RI) Sx (unit: msec) is measured.
- Gel fraction (%) ⁇ (Ss ⁇ Sx) / Ss ⁇ ⁇ 100 (X)
- the total amount of the polymer in the rubber component is preferably 15% by mass to 100% by mass.
- the total blending amount of the polymer in the rubber component is 15% by mass to 100% by mass, the characteristics of the polymer can be sufficiently exhibited.
- the 3,4-vinyl bond content of the isoprene-derived portion of the polymer is preferably 5% or less.
- the amount of 3,4-vinyl bonds in the isoprene-derived portion of the polymer is 5% or less, the orientational crystallinity of the polymer is increased, so that the stretched crystallinity can be improved.
- the “3,4-vinyl bond amount” means the ratio of the 3,4-vinyl structure to the entire isoprene portion of the polymer. The same applies to “cis-1,4 bond amount”, “trans-1,4 bond amount”, and “1,2-vinyl bond amount” in this specification.
- the amount of catalyst residue in the polymer is preferably 300 ppm or less.
- the residual amount of the catalyst in the polymer is 300 ppm or less, a network structure can be more reliably formed during vulcanization of the rubber composition.
- the rubber composition of the present invention preferably has a number average molecular weight (Mn) of 1.5 million or more as measured by gel permeation chromatography (GPC) of the polymer.
- Mn number average molecular weight measured by gel permeation chromatography
- GPC gel permeation chromatography
- the rubber composition of the present invention preferably has a nitrogen content in the polymer of less than 0.02% by mass.
- the nitrogen content in the polymer is less than 0.02% by mass, gel formation can be more reliably suppressed.
- the rubber composition of the present invention further contains a filler, and the blending amount of the filler is preferably 10 to 75 parts by mass with respect to 100 parts by mass of the rubber component.
- the blending amount of the filler is 10 parts by mass to 75 parts by mass with respect to 100 parts by mass of the rubber component, the effect of adding the filler is obtained, and the filler is reliably mixed with the rubber component. Can be included. If the blending amount of the filler is more than 75 parts by mass with respect to 100 parts by mass of the rubber component, workability may be deteriorated.
- the crosslinked rubber composition is obtained by crosslinking the rubber composition of the present invention.
- the durability (destructive property and abrasion resistance) of the crosslinked rubber composition can be improved.
- the tire of the present invention is characterized by having the rubber composition of the present invention.
- the durability (destruction resistance and wear resistance) of the tire can be improved.
- the tire of the present invention includes a tread member having the rubber composition of the present invention.
- durability destructive resistance and wear resistance
- a rubber composition capable of obtaining a crosslinked rubber composition having improved durability (destructive properties and abrasion resistance), and a tire having the rubber composition.
- the rubber composition of the present invention includes at least a rubber component, and further includes a filler, a crosslinking agent, and other components as necessary.
- the rubber component includes at least a polymer, and further includes other rubber components as necessary.
- the polymer is a synthetic polyisoprene or isoprene copolymer.
- the gel fraction in the polymer is 20% or less, a crosslinked rubber composition having improved durability (breakage resistance and wear resistance) can be obtained.
- the polymer having a gel fraction of 20% or less in the polymer is obtained at a low temperature ( ⁇ 50 ° C. to 100 ° C.) using, for example, the first, second, or third polymerization catalyst composition described later. Thus, it can be obtained by polymerization for a predetermined time (30 minutes to 2 days).
- the amount of the catalyst residue in the polymer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 300 ppm (weight ratio) or less, more preferably 200 ppm or less, and even more preferably 100 ppm or less.
- the amount of the catalyst residue in the polymer is 300 ppm or less, the formation of a network structure is prevented during vulcanization of the rubber composition containing the polymer, and elongation crystallinity and durability are reduced. It is possible to prevent the decrease.
- the amount of the catalyst residue in the polymer is within the more preferable range, it is advantageous in that an effective cross-linking network is formed.
- the amount of the catalyst residue can be measured, for example, by elemental analysis of residual metals (for example, aluminum and gadolinium) in the polymer using elemental analysis. The catalyst will be described in detail when the method for producing the polymer is described.
- the number average molecular weight (Mn) of the polymer is not particularly limited and may be appropriately selected depending on the purpose. It is preferably 1.5 million or more, more preferably 1.5 million to 2 million, and preferably 1.5 million to 1.8 million. Particularly preferred. When the number average molecular weight (Mn) is 1,500,000 or more, a crosslinked rubber composition having sufficiently improved durability (destructive properties and wear resistance) can be obtained. On the other hand, when the number average molecular weight (Mn) is within the more preferable range or the particularly preferable range, it is advantageous in terms of both durability and workability.
- the number average molecular weight (Mn) is determined as a polystyrene-converted average molecular weight using polystyrene as a standard substance by gel permeation chromatography (GPC) at a measurement temperature of 140 ° C.
- the polymer having a number average molecular weight (Mn) of 1.5 million or more is obtained at a low temperature ( ⁇ 50 ° C. to 100 ° C.) using, for example, a first, second, or third polymerization catalyst composition described later. Can be obtained by polymerization for a predetermined time (30 minutes to 2 days).
- the molecular weight distribution (Mw / Mn) represented by the ratio between the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polymer is not particularly limited and may be appropriately selected according to the purpose. 4.0 or less is preferable and 3.0 or less is more preferable. When the molecular weight distribution (Mw / Mn) is 4.0 or less, physical properties can be made uniform. On the other hand, when it is in the more preferable range, it is advantageous in terms of low heat generation.
- the molecular weight distribution is a weight average molecular weight (Mw) and a number average molecular weight as a polystyrene-converted average molecular weight using polystyrene as a standard substance by gel permeation chromatography (GPC) at a measurement temperature of 140 ° C. (Mn) is calculated and calculated from the calculated weight average molecular weight (Mw) and number average molecular weight (Mn).
- nitrogen content in the said polymer there is no restriction
- the nitrogen content can be measured by, for example, elemental analysis.
- ⁇ Synthetic polyisoprene >>> -Cis-1,4 binding amount-
- the amount of cis-1,4 bonds in the synthetic polyisoprene is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 90% or more, more preferably 95% or more, and particularly preferably 98% or more. preferable. When the cis-1,4 bond amount is 90% or more, sufficient elongation crystallinity can be expressed. On the other hand, when the amount of cis-1,4 bond is within the more preferable range or the particularly preferable range, it is advantageous in terms of improvement in durability due to elongation crystallinity.
- the amount of trans-1,4 bonds in the synthetic polyisoprene is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10% or less, more preferably 5% or less. When the amount of the trans-1,4 bond is 10% or less, sufficient elongation crystallinity can be expressed. On the other hand, when the amount of the trans-1,4 bond is within the more preferable range, it is advantageous in terms of improvement in durability due to elongation crystallinity.
- the 3,4-vinyl bond amount of the synthetic polyisoprene is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 5% or less, more preferably 2% or less. When the amount of 3,4-vinyl bond is 5% or less, sufficient elongation crystallinity can be expressed. On the other hand, when the 3,4-vinyl bond amount is within the more preferable range, it is advantageous in terms of improvement in durability due to elongation crystallinity.
- the synthetic polyisoprene can be produced by polymerizing isoprene as a monomer in the presence of a polymerization catalyst composition.
- the production method of the synthetic polyisoprene includes at least a polymerization step, and further includes a coupling step, a washing step, and other steps that are appropriately selected as necessary.
- the polymerization step is a step of polymerizing an isoprene monomer.
- a monomer is prepared in the same manner as in the method for producing a polymer using a normal coordination ion polymerization catalyst, except that the first, second, or third polymerization catalyst composition described later is used.
- Certain isoprene can be polymerized.
- the polymerization catalyst composition used will be described in detail later.
- the 1st, 2nd, or 3rd polymerization catalyst composition mentioned later can be used.
- 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, mixtures thereof etc. are mentioned.
- the polymerization step includes, for example, (1) separately providing the components of the polymerization catalyst composition in a polymerization reaction system containing isoprene as a monomer,
- the polymerization catalyst composition may be used, 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 polymerization may be stopped using a polymerization terminator such as methanol, ethanol, isopropanol or the like.
- the isoprene polymerization reaction 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 so that isoprene is sufficiently taken into the polymerization reaction system.
- the reaction time of the above polymerization reaction is not particularly limited and is preferably in the range of, for example, 1 second to 10 days, but can be appropriately selected depending on conditions such as the type of catalyst and polymerization temperature.
- 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.
- L represents a neutral Lewis base
- w represents an integer of 0 to 3
- 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.
- L represents a neutral Lewis base
- w represents an integer of 0 to 3
- [B] ⁇ represents non-coordinating.
- the first polymerization catalyst composition 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 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.
- 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) contains 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. Further, it is preferable that at least one of R a to R f is a hydrogen atom. By making at least one of R a to R f a hydrogen atom, the synthesis of the catalyst is facilitated, and the bulk height around silicon is reduced, so that non-conjugated olefin is easily introduced.
- 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- Arylamido groups such as 6-neopentylphenylamide group and 2,4,6-tri-tert-butylphenylamide group; bistrialkylsilylamide groups such as bistrimethylsilylamide group, among them bistrimethylsilylamide Groups are preferred.
- 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.
- the metallocene complex represented by the general formula (II) includes, for example, a lanthanoid trishalide, a scandium trishalide, or a 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.
- 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 [A] + 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. As the tri (substituted phenyl) carbonyl cation, specifically, 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 for 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. Further, the ionic compound represented by the general formula [A] + [B]-is preferably added in an amount of 0.1 to 10 times, more preferably about 1 time, with respect to the metallocene complex.
- 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.
- a half metallocene cation complex represented by the formula (III) can also be formed.
- 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.
- alkylaminoxan is preferable, 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 1 to 50 times mol, and more preferably about 10 times mol to 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 polymer can be increased.
- the second polymerization catalyst composition (hereinafter also referred to as second polymerization catalyst composition) will be described.
- Preferred examples include a polymerization catalyst composition (hereinafter also referred to as a second polymerization catalyst composition) containing at least one selected from the group consisting of at least one halogen compound (B-3) among organic compounds.
- 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 are hydrocarbons having 1 to 10 carbon atoms. R 3 is a group or a hydrogen atom, and R 3 is a hydrocarbon group having 1 to 10 carbon atoms, provided that R 3 may be the same as or different from the above R 1 or R 2, and Y is 1 in the periodic table.
- Y is a metal selected from Group 1, Group 2, Group 12 and Group 13 of the Periodic Table
- R 1 and R 2 are the same or different and are hydrocarbons having 1 to 10 carbon atoms.
- R 3 is a group or a hydrogen atom
- R 3 is a hydrocarbon
- a is 1, and b and c are 0, and when Y is the metal selected from groups 2 and 12 of the periodic table, a and In the case where b is 1 and c is 0, and Y is a metal selected from Group 13 of the Periodic Table, a, b, and c are 1].
- the second polymerization catalyst composition used in the production method needs to contain the component (A) and the component (B).
- the polymerization catalyst composition contains the ionic compound (B-1) and the ionic compound (B-1).
- (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 or a hydrogen atom, and 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.
- 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 concentration of the component (A) contained in the second polymerization catalyst composition is preferably in the range of 0.1 to 0.0001 mol / l.
- 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. 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- Isopropylphenoxy group, 2-tert-butyl-6-neopentylphenoxy group, 2-isopropyl-6-neopentylphenoxy group; thiomethoxy group, thioethoxy group, thiopropoxy group, thio n-butoxy group, thioisobutoxy group, thio an aliphatic thiolate group such as a sec-
- 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. Among these, a methyl group is preferable.
- the organoaluminum compound used as the raw material for the aluminoxane include trialkylaluminums such as trimethylaluminum, triethylaluminum, and triisobutylaluminum, and mixtures thereof. 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.
- 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 reaction product with the Lewis base is used, the metal remaining in the polymer can be reduced.
- organic compound containing the active halogen examples 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 or a hydrogen atom, and 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.
- organoaluminum compound of the general formula (X) examples include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, and tripentylaluminum.
- Trihexylaluminum tricyclohexylaluminum, trioctylaluminum
- diethylaluminum hydride di-n-propylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride, dihexylaluminum hydride, diisohydride hydride
- ethyl aluminum dihydride, n-propyl aluminum Muzi hydride isobutylaluminum dihydride and the like.
- 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 third polymerization catalyst composition (hereinafter also referred to as a third polymerization catalyst composition) contains the following metallocene composite catalyst and a boron anion, and further comprises a normal metallocene catalyst. It is preferable that other components contained in the polymerization catalyst composition to be contained, such as a promoter, are 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 polymer can be arbitrarily controlled. It becomes.
- the metallocene catalyst 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 in a preferred example of the metallocene composite catalyst, the following formula (XV): [ Wherein , M 1 represents a lanthanoid element, scandium or yttrium, Cp R independently represents unsubstituted or substituted indenyl, and R A and R B each independently represent 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 represent a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom.
- Metallocene composite catalysts represented by A polymer can be produced by using the metallocene polymerization catalyst.
- the amount of alkylaluminum used during the synthesis of the polymer can be reduced or eliminated.
- a conventional catalyst system it is necessary to use a large amount of alkylaluminum at the time of polymer synthesis.
- 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.
- Preferred 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 B is 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 independently represents unsubstituted or substituted indenyl
- R E to R J each independently represents 1 to 3 carbon atoms.
- L is a neutral Lewis base
- w is, the metallocene complex represented by an integer of 0-3)
- an organoaluminum compound 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, at least one of R E to R J is preferably a hydrogen atom. By making at least one of R E to R J a hydrogen atom, the catalyst can be easily synthesized. 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.
- R M represents a hydrogen group or a hydrogen atom and is a monovalent hydrocarbon group having 1 to 20 carbon atoms, provided that R M may be the same as or different from R K or R L described above.
- 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.
- boron anion constituting the two-component catalyst in the third polymerization catalyst composition include a tetravalent boron anion.
- tetraphenylborate 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.
- the coupling step is a step in which at least a part (for example, terminals) of the polymer chains of the synthetic polyisoprene obtained in the polymerization step are coupled to each other.
- a coupling reaction reaction for modifying the terminal of the polymer chain
- the coupling agent used in the coupling reaction is not particularly limited and may be appropriately selected depending on the intended purpose.
- tin such as bis (-1-octadecyl maleate) dioctyl tin (IV)
- isocyanate compounds such as 4,4′-diphenylmethane diisocyanate
- alkoxysilane compounds such as glycidylpropyltrimethoxysilane, and the like.
- bis (-1-octadecyl maleate) dioctyltin (IV) is preferable from the viewpoint of reaction efficiency and low gel formation.
- by performing a coupling reaction it is possible to achieve a high molecular weight by bonding polymer chains together, and also to prevent degradation other than hydrolysis and to reduce the number average molecular weight (Mn). Can be suppressed.
- the reaction temperature in the coupling reaction is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10 ° C to 100 ° C, more preferably 20 ° C to 80 ° C.
- the reaction temperature is 10 ° C. or higher, the reaction rate can be prevented from significantly decreasing, and when the reaction temperature is 100 ° C. or lower, the gelation of the polymer can be prevented.
- reaction time in the said coupling reaction there is no restriction
- the reaction time is 10 minutes or longer, the reaction can be sufficiently performed, and when it is 1 hour or shorter, the polymer can be prevented from gelling.
- the washing step is a step of washing the polyisoprene obtained in the polymerization step.
- the objective it can select suitably, For example, methanol, ethanol, isopropanol, etc. are mentioned.
- Isoprene copolymer >> -Compounds other than isoprene-
- the compound other than the isoprene to be copolymerized with isoprene is not particularly limited and may be appropriately selected depending on the intended purpose.
- 1,3-butadiene and styrene are preferable from the viewpoint of easy molecular weight control.
- the amount of cis-1,4 bonds in the isoprene-derived portion in the isoprene copolymer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 90% or more, more preferably 95% or more, 98% or more is particularly preferable. When the cis-1,4 bond amount is 90% or more, sufficient stretched crystallinity can be expressed. On the other hand, when the amount of cis-1,4 bonds is within the more preferable range or the particularly preferable range, it is advantageous in terms of improvement in durability due to stretched crystallinity.
- the cis-1,4 bond amount (trans 1,4 bond amount and 3,4-vinyl bond amount to be described later) is the amount in the isoprene-derived portion, and is based on the entire isoprene copolymer. It is not a percentage.
- the amount of trans-1,4 bond in the isoprene copolymer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10% or less, and more preferably 5% or less. When the amount of the trans-1,4 bond is 10% or less, sufficient stretched crystallinity can be expressed. On the other hand, when the amount of the trans-1,4 bond is within the more preferable range, it is advantageous in terms of improvement in durability due to stretched crystallinity.
- the amount of 3,4-vinyl bond in the isoprene-derived portion of the isoprene copolymer is not particularly limited and can be appropriately selected according to the purpose, but is preferably 5% or less, more preferably 2% or less. preferable.
- the 3,4-vinyl bond amount is 5% or less, sufficient stretched crystallinity can be expressed.
- the 3,4-vinyl bond amount is within the more preferable range, it is advantageous in terms of improvement in durability due to stretched crystallinity.
- the isoprene copolymer having an isoprene-derived portion having a 3,4-vinyl bond content of 5% or less can be obtained at a low temperature (for example, using the above-mentioned first, second, or third polymerization catalyst composition).
- the polymerization can be carried out at a temperature of ⁇ 100 ° C. for a predetermined time (30 minutes to 2 days).
- isoprene-derived part in the isoprene copolymer- There is no restriction
- the block copolymer has a structure of (AB) x , A- (BA) x, and B- (AB) x (where A is a block portion composed of monomer units of isoprene). And B is a block part composed of monomer units of compounds other than isoprene, and x is an integer of 1 or more.
- a block copolymer having a plurality of (AB) or (BA) structures is referred to as a multi-block copolymer.
- the structure of the random copolymer is a structure in which monomer units of isoprene and monomer units of compounds other than isoprene are randomly arranged.
- the taper copolymer is a copolymer in which a random copolymer and a block copolymer are mixed, from a block portion consisting of a monomer unit of isoprene and a monomer unit of a compound other than isoprene.
- a block portion comprising at least one block portion (also referred to as a block structure) and a random portion (called a random structure) in which monomer units of compounds other than isoprene and isoprene are randomly arranged. It is a polymer.
- the structure of the taper copolymer indicates that the composition of the isoprene component and the compound component other than isoprene is distributed continuously or discontinuously.
- the alternating copolymer has a structure in which isoprene and a compound other than isoprene are alternately arranged (when the monomer unit of isoprene is A and the monomer unit of a compound other than isoprene is B, -ABABABAB- A molecular chain structure).
- the isoprene copolymer can polymerize isoprene and a compound other than isoprene as a monomer in the presence of the polymerization catalyst composition.
- the production method of the isoprene copolymer of the present invention includes at least a polymerization step, and further includes a coupling step, a washing step, and other steps that are appropriately selected as necessary.
- the polymerization step is a step of copolymerizing isoprene as a monomer and a compound other than isoprene.
- a monomer is produced in the same manner as in the method for producing a polymer using a normal coordination ion polymerization catalyst, except that the first, second or third polymerization catalyst composition is used. Isoprene and a compound other than isoprene can be copolymerized.
- the polymerization catalyst composition used is as described above.
- the first, second, or third polymerization catalyst composition described above can be used.
- 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, mixtures thereof etc. are mentioned.
- the polymerization step provides, for example, (1) a component of the polymerization catalyst composition separately in a polymerization reaction system containing isoprene and a compound other than isoprene as a monomer, A polymerization catalyst composition may be used in the reaction system, or (2) a polymerization catalyst composition prepared in advance may be provided in the polymerization reaction system. Moreover, (2) includes providing a metallocene complex (active species) activated by a cocatalyst.
- the polymerization may be stopped using a polymerization terminator such as methanol, ethanol, isopropanol or the like.
- the polymerization reaction of isoprene and a compound other than isoprene 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 of the polymerization reaction is preferably in the range of 0.1 to 10.0 MPa in order to sufficiently incorporate isoprene and a compound other than isoprene 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 coupling step is a step in which at least a part (for example, terminals) of the polymer chains of the isoprene copolymer obtained in the polymerization step are subjected to a coupling reaction.
- a coupling reaction reaction for modifying the terminal of the polymer chain
- the coupling agent used in the coupling reaction is not particularly limited and may be appropriately selected depending on the intended purpose.
- tin such as bis (-1-octadecyl maleate) dioctyl tin (IV)
- isocyanate compounds such as 4,4′-diphenylmethane diisocyanate
- alkoxysilane compounds such as glycidylpropyltrimethoxysilane, and the like.
- bis (-1-octadecyl maleate) dioctyltin (IV) is preferable from the viewpoint of reaction efficiency and low gel formation.
- Mn number average molecular weight
- the reaction temperature in the coupling reaction is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10 ° C to 100 ° C, more preferably 20 ° C to 80 ° C.
- the reaction temperature is 10 ° C. or higher, the reaction rate can be prevented from significantly decreasing, and when the reaction temperature is 100 ° C. or lower, the gelation of the polymer can be prevented.
- reaction time in the said coupling reaction there is no restriction
- the reaction time is 10 minutes or longer, the reaction can be sufficiently performed, and when it is 1 hour or shorter, the polymer can be prevented from gelling.
- the washing step is a step of washing the isoprene copolymer obtained in the polymerization step.
- the objective it can select suitably, For example, methanol, ethanol, isopropanol, etc. are mentioned.
- the synthetic polyisoprene and the isoprene copolymer are as described above.
- the total blending amount (content) of the polymer (the synthetic polyisoprene, the isoprene copolymer, or the synthetic polyisoprene and the isoprene copolymer) in the rubber component is not particularly limited. Although it can be appropriately selected according to the above, it is preferably 15% by mass to 100% by mass.
- the characteristic of the said polymer can fully be exhibited as the total compounding quantity of the said polymer in the said rubber component is 15 mass% or more.
- the other rubber is not particularly limited and may be appropriately selected depending on the intended purpose.
- BR butadiene rubber
- SBR styrene butadiene rubber
- NBR acrylonitrile-butadiene rubber
- EPM ethylene-Propylene rubber
- EPDM ethylene-propylene-nonconjugated diene rubber
- silicone rubber fluorine rubber, urethane rubber, and the like.
- ⁇ Filler> There is no restriction
- the blending amount (content) of the filler is not particularly limited and may be appropriately selected depending on the intended purpose. It is preferably 10 parts by weight to 75 parts by weight, and 20 parts by weight with respect to 100 parts by weight of the rubber component. Part to 75 parts by weight is more preferable, and 30 parts to 60 parts by weight is particularly preferable.
- the blending amount of the filler is 10 parts by mass or more, the effect of adding the filler is seen, and when it is 75 parts by mass or less, the rubber component can be mixed with the filler, and as a rubber composition Performance can be improved.
- the blending amount of the filler is within the more preferable range or the particularly preferable range, it is advantageous in terms of a balance between workability and low loss / durability.
- the nitrogen adsorption specific surface area of the carbon black is not particularly limited and may be appropriately selected depending on the intended purpose, but is 20 m 2 / g to 150 m 2 / g is preferable, and 35 m 2 / g to 145 m 2 / g is more preferable.
- the nitrogen adsorption specific surface area (N 2 SA) of the carbon black is 20 m 2 / g or more, the durability of the obtained rubber can be prevented from deteriorating and sufficient crack growth resistance can be obtained. If it is 100 m 2 / g or less, the low-loss property can be improved and the workability can be improved.
- the content of carbon black with respect to 100 parts by mass of the rubber component is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10 parts by mass to 100 parts by mass, and 10 parts by mass to 70 parts by mass. More preferred is 20 to 60 parts by mass.
- the content of the carbon black is 10 parts by mass or more, it is possible to prevent deterioration of the fracture resistance due to insufficient reinforcement, and when it is 100 parts by mass or less, workability and low loss property Can be prevented from deteriorating.
- the content of the carbon black is within the more preferable range or the particularly preferable range, it is advantageous in terms of balance of performances.
- the inorganic filler is not particularly limited and may be appropriately selected depending on the intended purpose.
- 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.
- silane coupling agent suitably.
- ⁇ Crosslinking agent> there is no restriction
- 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 0.1 parts by mass or more, the cross-linking can be advanced, and is 20 parts by mass or less to prevent the cross-linking from proceeding during kneading with some cross-linking agents. Or the physical properties of the vulcanizate can be prevented from being 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 agents such as a colorant, an anti-coloring agent, and other compounding agents can be used depending on the purpose of 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 of the present invention is not particularly limited as long as it has the crosslinked rubber composition of the present invention, and can be appropriately selected according to the purpose.
- the application site in the tire of the crosslinked rubber composition of the present invention is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include treads, base treads, sidewalls, side reinforcing rubbers, and bead fillers. It is done. Among these, it is advantageous in terms of durability that the application site is a tread.
- a method for manufacturing the tire a conventional method can be used.
- members used in normal tire production such as a carcass layer, a belt layer, and a tread layer made of unvulcanized rubber and / or cord are sequentially laminated on a tire molding drum, and the drum is removed to obtain a green tire.
- a desired tire for example, a pneumatic tire
- a desired tire can be manufactured by heating and vulcanizing the green tire according to a conventional method.
- the crosslinked rubber composition of the present invention can be used for vibration-proof rubber, seismic isolation rubber, belt (conveyor belt), rubber crawler, various hoses and the like.
- the concentration of neodymium in the catalyst solution thus obtained was 0.010 M (mol / L).
- ⁇ Preparation of polymer D> A glass bottle with a rubber stopper having a volume of about 1 L was dried and purged with nitrogen, and a dry-purified cyclohexane solution of butadiene and a dry cyclohexane were respectively added, and 400 g of a 12.5% isoprene cyclohexane solution was charged. Next, 1.24 mL (0.015 mmol in terms of neodymium) of the prepared catalyst solution was added, and polymerization was performed in a 25 ° C. water bath for 3.0 hours.
- polymers A to D and polyisoprene rubber (trade name: IR2200, manufactured by JSR Corporation) prepared as described above, microstructure (cis-1,4 bond amount), number average molecular weight (Mn), molecular weight distribution (Mw / Mn) was measured and evaluated by the following method. The results are shown in Table 1. Further, the gel fractions of the polymers A to D and polyisoprene rubber (trade name: IR2200, manufactured by JSR Corporation) prepared as described above were measured and evaluated by the following methods. The results are shown in Table 1.
- Fracture resistance A tensile test was performed at room temperature in accordance with JIS K 6301-1995, the tensile strength (Tb) of the vulcanized rubber composition was measured, and the index when the tensile strength of Comparative Example 1 was taken as 100 was shown in Table 3. Shown in The larger the index value, the better the fracture resistance.
- Abrasion resistance The amount of wear was measured at a slip rate of 60% at room temperature using a Lambourn type wear tester, and displayed as an index with the reciprocal of Comparative Example 1 being 100. The higher the value, the better the wear resistance.
- the rubber composition contains a synthetic polyisoprene having a gel fraction of 20% or less, thereby obtaining a crosslinked rubber composition having improved durability (destructive properties and wear resistance). it can.
- the polymer of the present invention and the rubber composition containing the polymer can be suitably used for, for example, a tire member (particularly, a tread member of a tire).
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Abstract
Description
そこで、従来より、耐久性を向上させるために、合成ポリイソプレンの高シス化による伸長結晶性の改良が行われてきた(例えば、特許文献1及び2参照)。
しかしながら、従来の合成ポリイソプレンを用いて得られた架橋ゴム組成物の耐久性が十分でないという問題がある。
本発明者らは、ゴム組成物が、ゴム成分を含み、前記ゴム成分が、合成ポリイソプレン又はイソプレン共重合体であって、ゲル分率が20%以下である重合体を少なくとも含むことにより、従来の合成ゴムよりも耐久性(耐破壊特性及び耐摩耗性)が向上した架橋ゴム組成物を得ることができることを見出し、本発明を完成させるに至った。
なお、合成ポリイソプレンのゲル量を低減させる検討がなされているが(例えば、米国特許第5919876号明細書参照)、ゲル量が低減した合成ポリイソプレンを含むゴム組成物については、未だ検討されていないのが現状である。
前記ゴム組成物は、ゴム成分を含み、前記ゴム成分が、合成ポリイソプレン又はイソプレン共重合体であって、ゲル分率が20%以下である重合体を少なくとも含むと、伸長結晶性が増加し、耐久性(耐破壊特性及び耐摩耗性)が向上した架橋ゴム組成物を得ることができる。
なお、「重合体を少なくとも含む」とは、前記合成ポリイソプレン及び前記イソプレン共重合体の少なくともいずれかを含むことを意味する。
ゲル分率(%)={(Ss-Sx)/Ss}×100・・・(X)
前記ゴム成分中における前記重合体の合計配合量が15質量%~100質量%であると、重合体の特性を十分に発揮することができる。
前記重合体のイソプレン由来部分の3,4-ビニル結合量が5%以下であると、重合体の配向性が増すことで伸長結晶性を向上することができる。
本明細書における、「シス-1,4結合量」、「トランス-1,4結合量」、「1,2-ビニル結合量」についても、同様である。
前記重合体中における触媒の残渣量が300ppm以下であると、ゴム組成物の加硫時に網目構造をより確実に形成することができる。
前記重合体のゲルパーミエーションクロマトグラフィー(GPC)測定による数平均分子量(Mn)が150万以上であると、ゴム組成物に混合したときに、十分な伸長結晶性を発現でき、耐久性(耐破壊特性及び耐摩耗性)がより向上した架橋ゴム組成物を得ることができる。
前記重合体中における窒素含有量が0.02質量%未満であると、ゲルの生成をより確実に抑制することができる。
前記充填剤の配合量が前記ゴム成分100質量部に対して10質量部~75質量部であると、前記充填剤を入れる効果が得られ、且つ、前記ゴム成分に前記充填剤を確実に混ぜ込むことができる。
前記充填剤の配合量が前記ゴム成分100質量部に対して75質量部超であると、作業性が悪化することがある。
前記架橋ゴム組成物が、前記ゴム組成物を架橋して得られたものであると、架橋ゴム組成物の耐久性(耐破壊特性及び耐摩耗性)を向上させることができる。
前記タイヤが、前記ゴム組成物を有するものであると、タイヤの耐久性(耐破壊特性及び耐摩耗性)を向上させることができる。
前記タイヤが、前記ゴム組成物を有するトレッド部材を備えるものであると、トレッド部材の耐久性(耐破壊特性及び耐摩耗性)を向上させることができる。
本発明のゴム組成物は、少なくとも、ゴム成分を含み、さらに必要に応じて、充填剤、架橋剤、その他の成分を含む。
前記ゴム成分は、少なくとも、重合体を含み、さらに必要に応じて、その他のゴム成分を含む。
前記重合体は、合成ポリイソプレン又はイソプレン共重合体である。
前記重合体中におけるゲル分率が20%以下であると、耐久性(耐破壊特性及び耐摩耗性)が向上した架橋ゴム組成物を得ることができる。
なお、重合体中におけるゲル分率が20%以下の重合体は、例えば、後述する第一、第二、若しくは、第三の重合触媒組成物を用いて、低温(-50℃~100℃)で、所定時間(30分間~2日間)重合することによって、得ることができる。
前記重合体中における触媒の残渣量が300ppm以下であると、前記重合体が含まれるゴム組成物の加硫時に網目構造の形成が阻害されるのを防止すると共に、伸長結晶性及び耐久性が低下するのを防止することができる。
前記重合体中における触媒の残渣量が、前記より好ましい範囲内であると、有効な架橋網目を形成する点で有利である。
前記触媒の残渣量は、例えば、元素分析を用いて重合体中の残存金属(例えば、アルミニウム、ガドリニウム)を元素分析することにより測定することができる。
前記触媒については、前記重合体の製造方法を説明する際に、詳述する。
ここで、前記数平均分子量(Mn)は、測定温度を140℃とし、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たポリスチレン換算平均分子量として求める。
なお、数平均分子量(Mn)が150万以上の重合体は、例えば、後述する第一、第二、若しくは、第三の重合触媒組成物を用いて、低温(-50℃~100℃)で、所定時間(30分間~2日間)重合することによって、得ることができる。
前記重合体中における窒素含有量が0.02質量%未満であれば、前記重合体中における蛋白質由来の窒素含有量も0.02質量%未満となるので、蛋白質に起因するゲルの発生を抑制することができ、もってゲル分率を低減することができる。
なお、前記窒素含有量は、例えば、元素分析することにより測定することができる。
-シス-1,4結合量-
前記合成ポリイソプレンのシス-1,4結合量としては、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、90%以上が好ましく、95%以上がより好ましく、98%以上が特に好ましい。
前記シス-1,4結合量が、90%以上であると、十分な伸長結晶性を発現することができる。
一方、前記シス-1,4結合量が、前記より好ましい範囲内、又は、前記特に好ましい範囲内であると、伸長結晶性による耐久性の向上の点で有利である。
前記合成ポリイソプレンのトランス-1,4結合量としては、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、10%以下が好ましく、5%以下がより好ましい。
前記トランス-1,4結合量が、10%以下であると、十分な伸長結晶性を発現できる。
一方、前記トランス-1,4結合量が、前記より好ましい範囲内であると、伸長結晶性による耐久性の向上の点で有利である。
前記合成ポリイソプレンの3,4-ビニル結合量としては、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、5%以下が好ましく、2%以下がより好ましい。
前記3,4-ビニル結合量が、5%以下であると、十分な伸長結晶性を発現できる。
一方、前記3,4-ビニル結合量が、前記より好ましい範囲内であると、伸長結晶性による耐久性の向上の点で有利である。
次に、前記合成ポリイソプレンを製造することができる製造方法を詳細に説明する。但し、以下に詳述する製造方法は、あくまで例示に過ぎない。前記合成ポリイソプレンは、重合触媒組成物の存在下、単量体としてのイソプレンを重合させることにより製造することができる。
前記重合工程は、イソプレン単量体を重合する工程である。
前記重合工程においては、後述する第一、第二、若しくは第三の重合触媒組成物を用いること以外は、通常の配位イオン重合触媒による重合体の製造方法と同様にして、単量体であるイソプレンを重合させることができる。本発明において、使用される重合触媒組成物については、後に詳述する。
前記重合工程における触媒としては、後述する第一、第二、若しくは第三の重合触媒組成物を用いることができる。
前記第一の重合触媒組成物(以下、第一重合触媒組成物ともいう)としては、下記一般式(I):
(式中、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、CpR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、Ra~Rfは、それぞれ独立して炭素数1~3のアルキル基又は水素原子を示し、Lは、中性ルイス塩基を示し、wは、0~3の整数を示す)で表されるメタロセン錯体、及び下記一般式(II):
(式中、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、CpR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、X'は、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、シリル基又は炭素数1~20の炭化水素基を示し、Lは、中性ルイス塩基を示し、wは、0~3の整数を示す)で表されるメタロセン錯体、並びに下記一般式(III):
(式中、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、CpR’’は、無置換もしくは置換シクロペンタジエニル、インデニル又はフルオレニルを示し、Xは、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、シリル基又は炭素数1~20の炭化水素基を示し、Lは、中性ルイス塩基を示し、wは、0~3の整数を示し、[B]-は、非配位性アニオンを示す)で表されるハーフメタロセンカチオン錯体からる群より選択される少なくとも1種類の錯体を含む重合触媒組成物が挙げられる。
なお、重合反応系において、第一重合触媒組成物に含まれる錯体の濃度は0.1~0.0001mol/Lの範囲であることが好ましい。
(式中、X''はハライドを示す。)
上記一般式(II)で表されるメタロセン錯体は、例えば、溶媒中でランタノイドトリスハライド、スカンジウムトリスハライド又はイットリウムトリスハライドを、インデニルの塩(例えばカリウム塩やリチウム塩)及びシリルの塩(例えばカリウム塩やリチウム塩)と反応させることで得ることができる。なお、反応温度は室温程度にすればよいので、温和な条件で製造することができる。また、反応時間は任意であるが、数時間~数十時間程度である。反応溶媒は特に限定されないが、原料及び生成物を溶解する溶媒であることが好ましく、例えばトルエンを用いればよい。以下に、一般式(II)で表されるメタロセン錯体を得るための反応例を示す。
次に、前記第二の重合触媒組成物(以下、第二重合触媒組成物ともいう)について説明する。
また、前記第二の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る。
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。
(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。
なお、重合反応系において、第二重合触媒組成物に含まれる(A)成分の濃度は0.1~0.0001mol/lの範囲であることが好ましい。
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。
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。一般式(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。
また、前記第三の重合触媒組成物(以下、第三重合触媒組成物ともいう)は、下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。前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。
前記メタロセン系触媒は、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。
[式中、M1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、CpR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、RA及びRBは、それぞれ独立して炭素数1~20の炭化水素基を示し、該RA及びRBは、M1及びAlにμ配位しており、RC及びRD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す]で表されるメタロセン系複合触媒が挙げられる。
上記メタロセン系重合触媒を用いることで、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、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、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。
(式中、M2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、CpR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、RE~RJは、それぞれ独立して炭素数1~3のアルキル基又は水素原子を示し、Lは、中性ルイス塩基を示し、wは、0~3の整数を示す)で表されるメタロセン錯体を、AlRKRLRMで表される有機アルミニウム化合物と反応させることで得られる。なお、反応温度は室温程度にすればよいので、温和な条件で製造することができる。また、反応時間は任意であるが、数時間~数十時間程度である。反応溶媒は特に限定されないが、原料及び生成物を溶解する溶媒であることが好ましく、例えばトルエンやヘキサンを用いればよい。なお、上記メタロセン系複合触媒の構造は、1H-NMRやX線構造解析により決定することが好ましい。
前記カップリング工程は、前記重合工程において得られた合成ポリイソプレンの高分子鎖の少なくとも一部(例えば、末端)の重合体同士をカップリング反応させる工程である。
前記カップリング工程において、重合反応が100%に達した際にカップリング反応(高分子鎖の末端を変性する反応)を行うことが好ましい。
前記カップリング反応に用いるカップリング剤としては、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、(i)ビス(マレイン酸-1-オクタデシル)ジオクチルスズ(IV)等のスズ含有化合物、(ii)4,4’-ジフェニルメタンジイソシアネート等のイソシアネート化合物、(iii)グリシジルプロピルトリメトキシシラン等のアルコキシシラン化合物、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。
これらの中でも、ビス(マレイン酸-1-オクタデシル)ジオクチルスズ(IV)が、反応効率と低ゲル生成の点で、好ましい。
なお、カップリング反応を行うことにより、高分子鎖同士を結合させて高分子量化を図ることができ、また、加水分解以外の分解を阻害して、数平均分子量(Mn)が低下するのを抑制することができる。
前記反応温度が、10℃以上であると、反応速度が著しく低下するのを防止することができ、100℃以下であると、ポリマーがゲル化するのを防止することができる。
前記反応時間が、10分間以上であると、反応を十分に行うことができ、1時間以下であると、ポリマーがゲル化するのを防止することができる。
前記洗浄工程は、前記重合工程において得られたポリイソプレンを洗浄する工程である。なお、洗浄に用いる媒体としては、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、メタノール、エタノール、イソプロパノール、などが挙げられる。
-イソプレン以外の化合物-
イソプレンと共重合させる前記イソプレン以外の化合物としては、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、1,3-ブタジエン、1,3-ペンタジエン、2,3-ジメチルブタジエン等の共役ジエン化合物;スチレン等の芳香族ビニル化合物;エチレン、プロピレン、1-ブテン、1-ペンテン、1-ヘキセン、1-ヘプテン、1-オクテン等の非共役オレフィン化合物;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。
これらの中でも、1,3-ブタジエン、スチレンが、分子量制御の容易性の点で、好ましい。
前記イソプレン共重合体におけるイソプレン由来部分のシス-1,4結合量としては、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、90%以上が好ましく、95%以上がより好ましく、98%以上が特に好ましい。
前記シス-1,4結合量が、90%以上であると、十分な伸張結晶性を発現することができる。
一方、前記シス-1,4結合量が、前記より好ましい範囲内、又は、前記特に好ましい範囲内であると、伸張結晶性による耐久性の向上の点で有利である。
なお、前記シス-1,4結合量(後述するトランス-1,4結合量、3,4-ビニル結合量も同様)は、前記イソプレン由来部分中の量であって、イソプレン共重合体全体に対する割合ではない。
前記イソプレン共重合体のトランス-1,4結合量としては、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、10%以下が好ましく、5%以下がより好ましい。
前記トランス-1,4結合量が、10%以下であると、十分な伸張結晶性を発現することができる。
一方、前記トランス-1,4結合量が、前記より好ましい範囲内であると、伸張結晶性による耐久性の向上の点で有利である。
前記イソプレン共重合体におけるイソプレン由来部分のイソプレンの3,4-ビニル結合量としては、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、5%以下が好ましく、2%以下がより好ましい。
前記3,4-ビニル結合量が、5%以下であると、十分な伸張結晶性を発現することができる。
一方、前記3,4-ビニル結合量が、前記より好ましい範囲内であると、伸張結晶性による耐久性の向上の点で有利である。
なお、前記3,4-ビニル結合量が5%以下のイソプレン由来部分を有するイソプレン共重合体は、例えば、前述した第一、第二、若しくは第三の重合触媒組成物を用いて、低温(-100℃)で、重合を所定時間(30分間~2日間)行うことによって、得ることができる。
前記イソプレン共重合体におけるイソプレン由来部分の含有量としては、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、5mol%~95mol%が好ましい。
前記イソプレン共重合体におけるイソプレン由来部分の含有量が、5mol%以上であると、イソプレンの特性を十分に発揮できるので好ましく、95mol%以下であると、イソプレン以外の共重合成分の特性を十分に発揮できるので好ましい。
前記連鎖構造としては、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、ブロック共重合体、ランダム共重合体、テーパー共重合体、交互共重合体などが挙げられる。
前記ブロック共重合体の構造は、(A-B)x、A-(B-A)x及びB-(A-B)x(ここで、Aは、イソプレンの単量体単位からなるブロック部分であり、Bは、イソプレン以外の化合物の単量体単位からなるブロック部分であり、xは1以上の整数である)のいずれかである。なお、(A-B)又は(B-A)の構造を複数備えるブロック共重合体をマルチブロック共重合体と称する。
前記ランダム共重合体の構造は、イソプレンの単量体単位とイソプレン以外の化合物の単量体単位とがランダムに配列する構造である。
前記テーパー共重合体とは、ランダム共重合体とブロック共重合体とが混在してなる共重合体であり、イソプレンの単量体単位からなるブロック部分及びイソプレン以外の化合物の単量体単位からなるブロック部分のうち少なくとも一方のブロック部分(ブロック構造ともいう)と、イソプレン及びイソプレン以外の化合物の単量体単位が不規則に配列してなるランダム部分(ランダム構造という)とから構成される共重合体である。
前記テーパー共重合体の構造は、イソプレン成分とイソプレン以外の化合物成分との組成が連続的又は不連続的に分布があることを示す。
前記交互共重合体は、イソプレンとイソプレン以外の化合物とが交互に配列する構造(イソプレンの単量体単位をAと、イソプレン以外の化合物の単量体単位をBとした場合の、-ABABABAB-の分子鎖構造)を有する重合体である。
次に、前記イソプレン共重合体を製造することができる製造方法を詳細に説明する。但し、以下に詳述する製造方法は、あくまで例示に過ぎない。前記イソプレン共重合体は、重合触媒組成物の存在下、単量体としての、イソプレンとイソプレン以外の化合物とを重合させることができる。
前記重合工程は、単量体としてのイソプレン及びイソプレン以外の化合物を共重合する工程である。
前記重合工程においては、前述の、第一、第二、若しくは第三重合触媒組成物を用いること以外は、通常の配位イオン重合触媒による重合体の製造方法と同様にして、単量体であるイソプレンとイソプレン以外の化合物とを共重合させることができる。本発明において、使用される重合触媒組成物については、前述した通りである。
前記重合工程における触媒としては、前述した第一、第二、若しくは、第三の重合触媒組成物を用いることができる。
前記カップリング工程は、前記重合工程において得られたイソプレン共重合体の高分子鎖の少なくとも一部(例えば、末端)の重合体同士をカップリング反応させる工程である。
前記カップリング工程において、重合反応が100%に達した際にカップリング反応(高分子鎖の末端を変性する反応)を行うことが好ましい。
これらの中でも、ビス(マレイン酸-1-オクタデシル)ジオクチルスズ(IV)が、反応効率と低ゲル生成の点で、好ましい。
なお、カップリング反応を行うことにより、高分子鎖同士を結合させて高分子量化を図ることができ、また、加水分解以外の分解を阻害して、数平均分子量(Mn)が低下するのを抑制することができる。
前記反応温度が、10℃以上であると、反応速度が著しく低下するのを防止することができ、100℃以下であると、ポリマーがゲル化するのを防止することができる。
前記反応時間が、10分間以上であると、反応を十分行うことができ、1時間以下であると、ポリマーがゲル化するのを防止することができる。
前記洗浄工程は、前記重合工程において得られたイソプレン共重合体を洗浄する工程である。なお、洗浄に用いる媒体としては、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、メタノール、エタノール、イソプロパノール、などが挙げられる。
前記ゴム成分中における前記重合体(前記合成ポリイソプレン、前記イソプレン共重合体、又は、前記合成ポリイソプレン及び前記イソプレン共重合体)の合計配合量(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、15質量%~100質量%が好ましい。
前記ゴム成分中における前記重合体の合計配合量が、15質量%以上であると、前記重合体の特性を十分に発揮することができる。
前記その他のゴムとしては、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、ブタジエンゴム(BR)、スチレンブタジエンゴム(SBR)、アクリロニトリル-ブタジエンゴム(NBR)、クロロプレンゴム、エチレン-プロピレンゴム(EPM)、エチレン-プロピレン-非共役ジエンゴム(EPDM)、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。
前記充填剤としては、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、カーボンブラック、無機充填剤、などを挙げることができ、カーボンブラック及び無機充填剤から選択される少なくとも一種が好ましい。ここで、前記ゴム組成物には、カーボンブラックが含まれることがより好ましい。なお、前記充填剤は、補強性などを向上させるためにゴム組成物に配合するものである。
前記充填剤の配合量が、10質量部以上であると、充填剤を入れる効果がみられ、75質量部以下であると、前記ゴム成分に充填剤を混ぜ込むことができ、ゴム組成物としての性能を向上させることができる。
一方、前記充填剤の配合量が、前記より好ましい範囲、又は、前記特に好ましい範囲内であると、加工性と低ロス性・耐久性のバランスの点で有利である。
前記カーボンブラックとしては、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、FEF、GPF、SRF、HAF、N339、IISAF、ISAF、SAF、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。
前記カーボンブラックの窒素吸着比表面積(N2SA、JIS K 6217-2:2001に準拠して測定する)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、20m2/g~150m2/gが好ましく、35m2/g~145m2/gがより好ましい。
前記カーボンブラックの窒素吸着比表面積(N2SA)が20m2/g以上であると、得られたゴムの耐久性が悪化するのを防止して、十分な耐亀裂成長性を得ることができ、100m2/g以下であると、低ロス性を向上し、また、作業性を向上することができる。
前記ゴム成分100質量部に対するカーボンブラックの含有量としては、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、10質量部~100質量部が好ましく、10質量部~70質量部がより好ましく、20質量部~60質量部が特に好ましい。
前記カーボンブラックの含有量が、10質量部以上であると、補強性が不十分で耐破壊性が悪化するのを防止することができ、100質量部以下であると、加工性および低ロス性が悪化するのを防止することができる。
一方、前記カーボンブラックの含有量が、前記より好ましい範囲内、又は、前記特に好ましい範囲内であると、各性能のバランスの点で有利である。
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、これらの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質量部以上であると、架橋を進行させることができ、20質量部以下であって、一部の架橋剤により混練り中に架橋が進むのを防止したり、加硫物の物性が損なわれるのを防止することができる。
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、軟化剤、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。
前記架橋ゴム組成物は、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。
本発明のタイヤは、本発明の架橋ゴム組成物を有するものである限り、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。
本発明の架橋ゴム組成物のタイヤにおける適用部位としては、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、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。
これらの中でも、前記適用部位をトレッドとすることが、耐久性の点で有利である。
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及び/又はコード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(例えば、空気入りタイヤ)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、各種ホースなどに本発明の架橋ゴム組成物を使用することができる。
窒素雰囲気下のグローブボックス中で1L耐圧ガラス反応器に、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[(Cp*)2Gd(μ-Me)2AlMe2](Cp*:ペンタメチルシクロペンタジエニル配位子)を150μmol、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)150μmol、及びトリイソブチルアルミニウム21.0mmolを仕込み、トルエン250gに溶解させて触媒溶液とした。30分後グローブボックスから反応器を取り出し、イソプレン50.0gを添加し-40℃で60時間重合を行った。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重合体を分離し、70℃で真空乾燥し重合体Aを得た。得られた重合体Aの収量は43.1gであった。
窒素雰囲気下のグローブボックス中で1L耐圧ガラス反応器に、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]36.2μmol、トリイソブチルアルミニウム3.22mmol、トルエン5.0gを仕込んだのち30分間熟成を行った。その後、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)を6.2μmol、及びシクロヘキサン472.0gを仕込みさらに30分間熟成を行った。その後、グローブボックスから反応器を取り出し、イソプレン120.0gを添加し、室温で12時間重合を行った。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重合体を分離し、70℃で真空乾燥し重合体Bを得た。得られた重合体Bの収量は103.0gであった。
窒素雰囲気下のグローブボックス中で1L耐圧ガラス反応器に、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]34.65μmol、ジイソブチルアルミニウムハイドライド0.70mmol、トルエン5.0gを仕込んだのち30分間熟成を行った。その後、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)を4.65μmol、及びシクロヘキサン378.0gを仕込みさらに30分間熟成を行った。その後、グローブボックスから反応器を取り出し、イソプレン127.5gを添加し、室温で3時間重合を行った。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重合体を分離し、70℃で真空乾燥し重合体Cを得た。得られた重合体Cの収量は99.0gであった。
<触媒の調製>
乾燥・窒素置換された、ゴム詮付容積100mLのガラスびんに、以下の順番に、ブタジエンのシクロヘキサン溶液(15.2重量%)7.11g、ネオジムネオデカノエートのシクロヘキサン溶液(0.56M)0.59mL、メチルアルミノキサンMAO(東ソ-アクゾ製PMAO)のトルエン溶液(アルミニウム濃度として3.23M)10.32mL、水素化ジイソブチルアルミ(関東化学製)のヘキサン溶液(0.90M)7.77mLを投入し、室温で2分間熟成した後、塩素化ジエチルアルミ(関東化学製)のヘキサン溶液(0.95M)1.57mLを加え室温で、時折攪拌しながら15分間熟成した。こうして得られた触媒溶液中のネオジムの濃度は、0.010M(mol/L)であった。
<重合体Dの調製>
約1L容積のゴム栓付きガラスびんを乾燥・窒素置換し、乾燥精製されたブタジエンのシクロヘキサン溶液および乾燥シクロヘキサンを各々投入し、イソプレン12.5%のシクロヘキサン溶液が400g投入された状態とした。次に、前記調製した触媒溶液1.24mL(ネオジム換算0.015mmol)を投入し、25℃水浴中で3.0時間重合を行った。その後、ネオジム対比15等量のジオクチルスズオクタノマレートを25℃にて1時間反応させ、老化防止剤2,2’-メチレン-ビス(4-エチル-6-t-ブチルフェノール)(NS-5)のイソプロパノール5%溶液2mLを加えて反応の停止を行い、さらに微量のNS-5を含むイソプロパノール中で再沈殿した後、ドラムにて乾燥することでほぼ100%の収率で重合体Dを得た。
さらに、上記のようにして調製した重合体A~D及びポリイソプレンゴム(商品名:IR2200、JSR株式会社製)のゲル分率を下記の方法で測定・評価した。結果を表1に示す。
(1)ミクロ構造(シス-1,4結合量)
1H-NMRおよび13C-NMRにより得られたピーク[1H-NMR:δ4.6-4.8(3,4-ビニルユニットの=CH2)、5.0-5.2(1,4-ユニットの-CH=)、13C-NMR:[δ23.4(1,4-シスユニット)、15.9(1,4-トランスユニット)、18.6(3,4-ユニット)]の積分比からそれぞれ算出した。また、数平均分子量(Mn)、分子量分布(Mw/Mn)は、GPCによりポリスチレンを標準物質として用い求めた。
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-8020]により検出器として屈折計を用いて測定し、単分散ポリスチレンを標準としたポリスチレン換算で示した。なお、カラムはGMHXL[東ソー製]で、溶離液はテトラヒドロフラン、測定温度は40℃である。
サンプルポリマー12mgを5ccのテトラヒドロフランが入ったサンプル瓶に入れ、一晩放置した。PTFE0.45μmのフィルターに通し、GPCを測定した。GPC測定の結果得られたRIのサンプル面積(mV)を用いたサンプル重量で割り、割合を算出した。
触媒残渣量(残存金属量)については、元素分析を行うことにより測定した。
表2に示す配合処方のゴム配合物を調製し、加硫して得た加硫ゴムに対し、下記の方法に従って、(1)耐破壊性、(2)耐摩耗性、を測定した。測定結果を表3に示す。
JIS K 6301-1995に準拠して室温で引張試験を行い、加硫したゴム組成物の引張り強さ(Tb)を測定し、比較例1の引張り強さを100とした場合の指数を表3に示す。指数値が大きい程、耐破壊性が良好であることを示す。
(2)耐摩耗性(指数)
ランボーン型摩耗試験機を用い、室温におけるスリップ率60%で摩耗量を測定し、比較例1の逆数を100とする指数で表示した。数値が大きいほど耐摩耗性が良好である。
*1:重合体A~D及びポリイソプレンゴム(商品名:IR2200、JSR株式会社製)
*2:RSS #3
*3:シースト6(東海カーボン株式会社製)
*4:マイクロクリスタリンワックス:オゾエース0280(日本精蝋製)
*5:N-(1,3-ジメチルブチル)-N’-p-フェニレンジアミン、大内新興化学(株)製、ノックラック6C
*6:大内新興化学工業株式会社製のノクセラーNS(N-tert-ブチル-2-ベンゾチアジルスルフェンアミド)
Claims (8)
- ゴム成分を含み、
前記ゴム成分が、合成ポリイソプレン又はイソプレン共重合体であって、ゲル分率が20%以下である重合体を少なくとも含むことを特徴とするゴム組成物。 - 前記ゴム成分中における前記重合体の合計配合量が、15質量%~100質量%であることを特徴とする請求項1に記載のゴム組成物。
- 前記重合体中における触媒の残渣量が、300ppm以下であることを特徴とする請求項1又は2に記載のゴム組成物。
- 前記重合体のゲルパーミエーションクロマトグラフィー(GPC)測定による数平均分子量(Mn)が150万以上であることを特徴とする請求項1から3のいずれかに記載のゴム組成物。
- 前記重合体中における窒素含有量が、0.02質量%未満であることを特徴とする請求項1から4のいずれかに記載のゴム組成物。
- 充填剤をさらに含み、
前記充填剤の配合量が、前記ゴム成分100質量部に対して10質量部~75質量部であることを特徴とする請求項1から5のいずれかに記載のゴム組成物。 - 請求項6に記載のゴム組成物を有することを特徴とするタイヤ。
- 請求項6に記載のゴム組成物を有するトレッド部材を備えることを特徴とするタイヤ。
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US14/383,363 A-371-Of-International US20150080525A1 (en) | 2012-03-07 | 2013-03-06 | Rubber composition and tire containing rubber composition |
US15/832,869 Division US10087312B2 (en) | 2012-03-07 | 2017-12-06 | Rubber composition and tire containing rubber composition |
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EP (1) | EP2824118B1 (ja) |
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Cited By (2)
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WO2016139996A1 (ja) * | 2015-03-04 | 2016-09-09 | Jsr株式会社 | 共重合体、重合体組成物及び架橋重合体 |
US20180291127A1 (en) * | 2015-04-30 | 2018-10-11 | Bridgestone Corporation | Method for producing polyisoprene |
Families Citing this family (5)
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JP5899011B2 (ja) * | 2012-03-07 | 2016-04-06 | 株式会社ブリヂストン | 重合体、前記重合体を含むゴム組成物、及び、前記ゴム組成物を有するタイヤ |
JP6353710B2 (ja) * | 2014-06-16 | 2018-07-04 | 株式会社ブリヂストン | 分岐イソプレン重合体の製造方法 |
US20190161571A1 (en) * | 2016-05-24 | 2019-05-30 | Bridgestone Corporation | Terminal-modified conjugated diene polymer, rubber composition, rubber product and method for manufacturing terminal-modified conjugated diene polymer |
WO2020208901A1 (ja) * | 2019-04-12 | 2020-10-15 | 株式会社ブリヂストン | ポリイソプレン、ゴム組成物及びタイヤ |
JP7398266B2 (ja) | 2019-12-19 | 2023-12-14 | 株式会社ブリヂストン | ランフラットタイヤ用ゴム組成物及びその製造方法、並びにランフラットタイヤ |
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-
2012
- 2012-03-07 JP JP2012050995A patent/JP5941302B2/ja active Active
-
2013
- 2013-03-06 US US14/383,363 patent/US20150080525A1/en not_active Abandoned
- 2013-03-06 EP EP13757224.4A patent/EP2824118B1/en active Active
- 2013-03-06 RU RU2014140303/04A patent/RU2578566C1/ru active
- 2013-03-06 CN CN201380012801.3A patent/CN104159930B/zh active Active
- 2013-03-06 WO PCT/JP2013/001416 patent/WO2013132849A1/ja active Application Filing
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2017
- 2017-12-06 US US15/832,869 patent/US10087312B2/en active Active
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WO2016139996A1 (ja) * | 2015-03-04 | 2016-09-09 | Jsr株式会社 | 共重合体、重合体組成物及び架橋重合体 |
JPWO2016139996A1 (ja) * | 2015-03-04 | 2017-12-14 | Jsr株式会社 | 共重合体、重合体組成物及び架橋重合体 |
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US20180291127A1 (en) * | 2015-04-30 | 2018-10-11 | Bridgestone Corporation | Method for producing polyisoprene |
Also Published As
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US10087312B2 (en) | 2018-10-02 |
JP2013185058A (ja) | 2013-09-19 |
CN104159930B (zh) | 2016-12-07 |
RU2578566C1 (ru) | 2016-03-27 |
JP5941302B2 (ja) | 2016-06-29 |
US20150080525A1 (en) | 2015-03-19 |
EP2824118A1 (en) | 2015-01-14 |
CN104159930A (zh) | 2014-11-19 |
EP2824118A4 (en) | 2015-10-21 |
US20180094124A1 (en) | 2018-04-05 |
EP2824118B1 (en) | 2017-12-13 |
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