Classifications

• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
  • C08C19/00—Chemical modification of rubber
  • C08C19/26—Incorporating metal atoms into the molecule
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
  • C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
  • C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
  • C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
  • C08K3/013—Fillers, pigments or reinforcing additives
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L15/00—Compositions of rubber derivatives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers

Definitions

• the present invention relates to a rubber composition for tires and a tire.
• a known method for improving abrasion resistance is to increase the amount of filler mixed in, but increasing the amount of filler mixed in causes the filler to become less dispersed, resulting in poorer fuel economy. It also causes the problem of increased unvulcanized viscosity of the rubber composition, resulting in poor processability. Thus, it is generally difficult to achieve a good balance between fuel economy, abrasion resistance, and processability.
• Patent Documents 1 and 2 disclose rubber compounds for passenger car tires and rubber compounds for heavy-duty truck and bus tires that contain specific long-chain branched cyclopentene ring-opening rubber (LCB-CPR), and these rubber compounds are said to be effective in reducing tire rolling resistance, improving wet skid resistance, and improving abrasion resistance.
• LLB-CPR long-chain branched cyclopentene ring-opening rubber
• Patent Documents 1 and 2 the inventors' investigations revealed that even with the techniques described in Patent Documents 1 and 2, it is difficult to achieve a good balance between the processability of the rubber composition and the fuel economy and wear resistance of a tire to which the rubber composition is applied, and that there is still room for improvement.
• an object of the present invention is to solve the above-mentioned problems of the conventional technology and to provide a rubber composition for tires that can achieve a good balance between processability and the fuel efficiency and wear resistance of the tire when applied to the tire.
• Another object of the present invention is to provide a tire that achieves a good balance between fuel economy, wear resistance, and productivity.
• a rubber composition comprising a rubber component and a filler,
• the rubber component is a compound represented by the following general formula (1): [wherein R 1 to R 4 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a substituent containing a halogen atom, a silicon atom, an oxygen atom, or a nitrogen atom, R 2 and R 3 may be bonded to each other to form a ring, and m is an integer of 0 to 2.], and a modified polymer.
• a tire comprising the rubber composition for tires described in any one of [1] to [12].
• a rubber composition for tires which is capable of achieving a good balance between processability and the fuel efficiency and wear resistance of the tire when used in the tire.
• a tire can be provided that achieves a good balance between fuel economy, wear resistance, and productivity.
• the compounds described herein may be derived in whole or in part from fossil sources, from biological sources such as plant sources, from recycled sources such as used tires, or from a mixture of two or more of fossil, biological and/or renewable sources.
• the rubber composition for a tire of the present embodiment includes a rubber component and a filler.
• the rubber component is a cyclic alkylene group having cyclopentene and a cyclic alkylene group represented by the following general formula (1): [wherein R 1 to R 4 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a substituent containing a halogen atom, a silicon atom, an oxygen atom, or a nitrogen atom, R 2 and R 3 may be bonded to each other to form a ring, and m is an integer of 0 to 2.], and a modified polymer (also simply referred to as a modified polymer).
• the copolymer of cyclopentene and a norbornene-based compound is characterized in that it has crosslinking points and in that polymer chains are entangled with each other.
• a reinforcing layer consisting of the filler and the rubber component is formed around the filler, and this reinforcing layer contributes to improving the reinforcing properties of the rubber composition, thereby improving the abrasion resistance, etc.
• the rubber component contains the copolymer of cyclopentene and a norbornene-based compound, and therefore the reinforcing layer formed around the filler is specifically increased due to the entanglement of the polymer chains described above, thereby making it possible to sufficiently improve the abrasion resistance.
• the rubber component contains a modified polymer, which has high affinity with the filler and can improve the dispersibility of the filler, thereby improving the fuel economy, abrasion resistance, and processability of the rubber composition. Therefore, the rubber composition for tires of the present embodiment can achieve a good balance between processability and fuel efficiency and abrasion resistance of the tire when used in a tire.
• the rubber composition for a tire of the present embodiment contains a rubber component, and the rubber component provides rubber elasticity to the composition.
• the rubber component of the rubber composition for a tire of the present embodiment contains a copolymer of cyclopentene and a norbornene-based compound represented by the above general formula (1), a modified polymer, and may further contain other rubbers.
• copolymer of cyclopentene and norbornene compounds contains a structural unit derived from cyclopentene and a structural unit derived from a norbornene-based compound represented by the above general formula (1).
• the copolymer of cyclopentene and a norbornene-based compound is a ring-opened copolymer, and in particular, a cyclopentene ring-opened copolymer.
• R 1 to R 4 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a substituent containing a halogen atom, a silicon atom, an oxygen atom, or a nitrogen atom
• R 2 and R 3 may be bonded to each other to form a ring
• m is an integer of 0 to 2.
• examples of the hydrocarbon group having 1 to 20 carbon atoms include alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a neopentyl group, a hexyl group, and an octyl group; alkenyl groups such as a vinyl group, an allyl group, a 2-pentenyl group, a 3-pentenyl group, and a 4-methyl-3-pentenyl group; aryl groups such as a phenyl group, a tolyl group, a 2,6-dimethylphenyl group, a 2,6-diisopropylphenyl group, and a naphthyl group; and aralkyl groups such as a benzyl group and a phenethyl
• Examples of the norbornene-based compounds represented by the above general formula (1) include 2-norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-decyl-2-norbornene, 5-cyclohexyl-2-norbornene, 5-cyclopentyl-2-norbornene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, 5-propenyl-2-norbornene, 5-cyclohexenyl-2-norbornene, 5-cyclopentenyl-2-norbornene, 5-phenyl-2-norbornene, tetracyclo[9.2.1.0 2,10 .
• bicyclo[2.2.1]hept-2 - enes such as tetracyclo[10.2.1.0 2,11 . 0 4,9 ]pentadeca-4,6,8,13-tetraene (also referred to as "1,4-methano-1,4,4a,9,9a,10-hexahydroanthracene"), dicyclopentadiene, methyldicyclopentadiene, and dihydrodicyclopentadiene (also referred to as "tricyclo[5.2.1.0 2,6 ]dec-8-ene”); Tetracyclo[6.2.1.1 3,6 .
• Bicyclo[2.2.1]hept-2-enes having an alkoxycarbonyl group such as methyl 5-norbornene-2-carboxylate, ethyl 5-norbornene-2-carboxylate, methyl 2-methyl-5-norbornene-2-carboxylate, and ethyl 2-methyl-5-norbornene-2-carboxylate; Tetracyclo[6.2.1.1 3,6 . 0 2,7 ]dodec-4-enes having an alkoxycarbonyl group, such as methyl tetracyclo[6.2.1.1 3,6 .
• dodec-4-enes having a hydroxycarbonyl group or an acid anhydride group Bicyclo[2.2.1]hept-2-enes having a hydroxyl group, such as 5-hydroxy-2-norbornene, 5-hydroxymethyl-2-norbornene, 5,6-di(hydroxymethyl)-2-norbornene, 5,5-di(hydroxymethyl)-2-norbornene, 5-(2-hydroxyethoxycarbonyl)-2-norbornene, and 5-methyl-5-(2-hydroxyethoxycarbonyl)-2-norbornene; Tetracyclo[6.2.1.1 3,6 .
• dodec-4-enes having a carbonyloxy group such as 9-tetracyclo[6.2.1.1 3,6 . 0 2,7 ] dodec-4-enyl acetate, 9-tetracyclo[6.2.1.1 3,6 . 0 2,7 ] dodec-4-enyl acrylate, and 9-tetracyclo[6.2.1.1 3,6 .
• Bicyclo[2.2.1]hept-2-enes having a functional group containing a silicon atom such as 5-trimethoxysilyl-2-norbornene and 5-triethoxysilyl-2-norbornene
• Examples of the norbornene-based compound include tetracyclo[6.2.1.1 3,6 . 0 2,7 ]dodec-4-enes having a functional group containing a silicon atom, such as 4-trimethoxysilyltetracyclo[6.2.1.1 3,6 . 0 2,7 ]dodec-9-ene and 4-triethoxysilyltetracyclo[6.2.1.1 3,6 . 0 2,7 ]dodec-9-ene.
• the norbornene-based compound may be used alone or in combination of two or more.
• the norbornene-based compound represented by the above general formula (1) is preferably one in which m is 0 or 1, and more preferably one in which m is 0.
• R 1 to R 4 may be the same or different.
• R 1 to R 4 in the above general formula (1) are a hydrogen atom, a chain hydrocarbon group having 1 to 20 carbon atoms, or a substituent containing a halogen atom, a silicon atom, an oxygen atom, or a nitrogen atom.
• R 1 to R 4 are not particularly limited as long as they are groups that are not bonded to each other and do not form a ring, and may be the same or different, and R 1 to R 4 are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
• m is 0 or 1
• R 1 to R 4 in the above general formula (1) are a hydrogen atom, a chain hydrocarbon group having 1 to 20 carbon atoms, or a substituent containing a halogen atom, a silicon atom, an oxygen atom, or a nitrogen atom
• unsubstituted or hydrocarbon-substituted bicyclo[2.2.1]hept-2-enes are preferred, and among these, 2-norbornene is particularly preferred.
• a compound in which R 2 and R 3 are bonded to each other to form a ring is also preferred.
• specific examples of the ring structure formed by R 2 and R 3 being bonded to each other include a cyclopentane ring, a cyclopentene ring, a cyclohexane ring, a cyclohexene ring, a benzene ring, etc., which may form a polycyclic structure, and may further have a substituent.
• a cyclopentane ring, a cyclopentene ring, and a benzene ring are preferred, and in particular, a compound having a cyclopentene ring alone, or a compound having a polycyclic structure of a cyclopentane ring and a benzene ring is preferred.
• R 1 and R 4 other than R 2 and R 3 forming a ring structure may be the same or different, and are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. In this case, it is preferable that m is 0.
• the copolymer of cyclopentene and a norbornene-based compound preferably has a content of cyclopentene-derived structural units of 20 to 75 mass%, more preferably 25 to 70 mass%, even more preferably 30 to 65 mass%, and particularly preferably 35 to 60 mass%, based on all repeating structural units of the copolymer.
• the copolymer of cyclopentene and a norbornene-based compound preferably contains structural units derived from a norbornene-based compound represented by the above general formula (1) in a proportion of 10 to 80 mass %, more preferably 20 to 70 mass %, even more preferably 25 to 65 mass %, and particularly preferably 40 to 65 mass %, based on all repeating structural units of the copolymer.
• the norbornene-based compound represented by the above general formula (1) is preferably 2-norbornene and/or dicyclopentadiene. Since 2-norbornene and dicyclopentadiene are easily available, a copolymer of cyclopentene and 2-norbornene and/or dicyclopentadiene is also easily available. Therefore, a rubber composition for tires containing a copolymer of cyclopentene and 2-norbornene and/or dicyclopentadiene is advantageous in terms of cost.
• the copolymer of cyclopentene and a norbornene-based compound preferably contains 10 to 60 mass% of structural units derived from 2-norbornene relative to the total repeating structural units of the copolymer, and more preferably 20 to 60 mass%.
• the copolymer of cyclopentene and a norbornene-based compound preferably has a content of dicyclopentadiene-derived structural units of 10 to 60 mass%, and more preferably 20 to 50 mass%, relative to the total repeating structural units of the copolymer.
• a terpolymer of cyclopentene (CP), 2-norbornene (NB), and dicyclopentadiene (DCPD) may be used as the copolymer of cyclopentene and a norbornene-based compound.
• the terpolymer of cyclopentene, 2-norbornene, and dicyclopentadiene is highly effective in improving the fuel economy of the rubber composition.
• the copolymer of cyclopentene and a norbornene compound may be a copolymer of cyclopentene and a norbornene compound represented by the general formula (1) with other monomers copolymerizable therewith.
• examples of such other monomers include cyclic monoolefins such as cyclopropene, cyclobutene, methylcyclopentene, cyclohexene, methylcyclohexene, cycloheptene, and cyclooctene; cyclic diolefins such as cyclohexadiene, methylcyclohexadiene, cyclooctadiene, and methylcyclooctadiene; and polycyclic cycloolefins having aromatic rings such as phenylcyclooctene, 5-phenyl-1,5-cyclooctadiene, and phenylcyclopentene.
• the content of structural units derived from other monomers in the copolymer of cyclopentene and a norbornene compound is preferably 40% by mass or less, more preferably 30% by mass or less, based on the total repeating structural units of the copolymer. It is particularly preferable that the copolymer does not substantially contain structural units derived from other monomers.
• the copolymer of cyclopentene and norbornene-based compound preferably has a weight average molecular weight (Mw) of 200,000 to 1,000,000, more preferably 200,000 to 800,000, even more preferably 200,000 to 700,000, and particularly preferably 200,000 to 600,000.
• Mw weight average molecular weight
• a copolymer having a weight average molecular weight (Mw) in the range of 200,000 to 1,000,000 is easy to manufacture and has good processability (workability).
• the weight average molecular weight (Mw) of the copolymer in the range of 200,000 to 1,000,000, the fuel economy and wear resistance of a rubber composition containing the copolymer can be further improved.
• the copolymer of cyclopentene and a norbornene-based compound preferably has a ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw/Mn, also referred to as "molecular weight distribution") of 1.0 to 5.0, more preferably 1.5 to 2.9, even more preferably 1.5 to 2.5, and particularly preferably 1.5 to 2.3.
• Mw/Mn weight average molecular weight
• Mw/Mn number average molecular weight distribution
• the copolymer of cyclopentene and a norbornene-based compound preferably has a cis/trans ratio of 0/100 to 60/40, more preferably 5/95 to 55/45, even more preferably 10/90 to 50/50, and particularly preferably 15/85 to 39/61.
• the cis/trans ratio is the ratio of the cis structure and the trans structure of the double bond present in the repeating units constituting the copolymer of cyclopentene and a norbornene-based compound (cis/trans ratio).
• the copolymer of cyclopentene and a norbornene-based compound preferably has a glass transition temperature (Tg) of -80°C to 10°C, more preferably -75°C to 0°C, and even more preferably -70°C to -10°C.
• Tg glass transition temperature
• the glass transition temperature of the copolymer can be controlled, for example, by adjusting the type and amount of the norbornene-based compound used.
• the copolymer of cyclopentene and a norbornene compound may have a modified group at the polymer chain end.
• a modified end group By having such a modified end group, the affinity for silica and the like can be further increased, and the dispersibility of silica and the like in the rubber composition can be increased, and as a result, the processability (workability), fuel efficiency, and wear resistance of the rubber composition can be further improved.
• the modified group to be introduced into the polymer chain end of the copolymer is not particularly limited, but is preferably a modified group containing an atom selected from the group consisting of an atom of Group 15 of the periodic table, an atom of Group 16 of the periodic table, and a silicon atom.
• a modified group containing an atom selected from the group consisting of a nitrogen atom, an oxygen atom, a phosphorus atom, a sulfur atom, and a silicon atom is more preferable, and among these, a modified group containing an atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a silicon atom is even more preferable.
• Examples of the modified group containing a nitrogen atom include an amino group, a pyridyl group, an imino group, an amide group, a nitro group, a urethane bond group, or a hydrocarbon group containing any of these groups.
• Examples of the modified group containing an oxygen atom include a hydroxyl group, a carboxylic acid group, an ether group, an ester group, a carbonyl group, an aldehyde group, an epoxy group, or a hydrocarbon group containing any of these groups.
• Examples of the modified group containing a silicon atom include an alkylsilyl group, an oxysilyl group, or a hydrocarbon group containing any of these groups.
• modified group containing a phosphorus atom examples include a phosphate group, a phosphino group, or a hydrocarbon group containing any of these groups.
• modified group containing a sulfur atom examples include a sulfonyl group, a thiol group, a thioether group, or a hydrocarbon group containing any of these groups.
• the modified group may also be a modified group containing a plurality of the above groups.
• amino groups, pyridyl groups, imino groups, amide groups, hydroxyl groups, carboxylic acid groups, aldehyde groups, epoxy groups, oxysilyl groups, and hydrocarbon groups containing any of these groups are preferred, and from the viewpoint of affinity for silica, etc., oxysilyl groups are particularly preferred.
• the oxysilyl group refers to a group having a silicon-oxygen bond.
• the oxysilyl group includes an alkoxysilyl group, an aryloxysilyl group, an acyloxy group, an alkylsiloxysilyl group, and an arylsiloxysilyl group.
• an alkoxysilyl group, an aryloxysilyl group, or a hydroxysilyl group obtained by hydrolysis of an acyloxy group can be mentioned.
• an alkoxysilyl group is preferred from the viewpoint of affinity with silica.
• the alkoxysilyl group is a group in which one or more alkoxy groups are bonded to a silicon atom, and specific examples thereof include a trimethoxysilyl group, a dimethoxymethylsilyl group, a methoxydimethylsilyl group, a methoxydichlorosilyl group, a triethoxysilyl group, a diethoxymethylsilyl group, an ethoxydimethylsilyl group, a dimethoxyethoxysilyl group, a methoxydiethoxysilyl group, and a tripropoxysilyl group.
• the introduction ratio of the modified group at the polymer chain end of the copolymer of cyclopentene and norbornene-based compound is not particularly limited, but is preferably 10% or more, more preferably 20% or more, even more preferably 30% or more, and particularly preferably 40% or more, as a percentage value of the number of copolymer chain ends into which the modified group is introduced/the total number of copolymer chain ends.
• the method for measuring the introduction ratio of the modified group at the polymer chain end is not particularly limited, but for example, in the case of introducing an oxysilyl group as the terminal modified group, it can be determined from the peak area ratio corresponding to the oxysilyl group determined by 1 H-NMR spectrum measurement and the number average molecular weight (Mn) determined by gel permeation chromatography (GPC).
• the copolymer of cyclopentene and a norbornene compound preferably has a Mooney viscosity (ML 1+4 , 100° C.) of 20-150, more preferably 22-120, and particularly preferably 25-90.
• the method for producing the copolymer of cyclopentene and a norbornene-based compound is not particularly limited, but an example thereof is a method in which cyclopentene and a norbornene-based compound represented by the above general formula (1) are copolymerized in the presence of a ring-opening polymerization catalyst.
• the ring-opening polymerization catalyst is not particularly limited as long as it can ring-open copolymerize cyclopentene with the norbornene-based compound represented by the above general formula (1), but ruthenium carbene complexes and halogen-containing Group 6 transition metal compounds of the periodic table (hereinafter also referred to as "Group 6 transition metal compounds of the periodic table"). These ring-opening polymerization catalysts may be used alone or in combination of two or more.
• the ruthenium carbene complexes include bis(tricyclohexylphosphine)benzylidene ruthenium dichloride, bis(triphenylphosphine)-3,3-diphenylpropenylidene ruthenium dichloride, bis(tricyclohexylphosphine)t-butylvinylidene ruthenium dichloride, dichloro-(3-phenyl-1H-inden-1-ylidene)bis(tricyclohexylphosphine)ruthenium, bis(1,3-diisopropylimidazolin-2-ylidene)benzylidene ruthenium dichloride, bis(1,3-dicyclohexylimidazolin-2-ylidene)benzylidene ruthenium dichloride, and bis(1,3-dicyclohexylimidazolin-2-ylidene)benzylidene ruthenium dichloride
• Examples include (1,3-dimesitylimidazolin-2-ylidene)benzylidene ruthenium dichloride, (1,3-dimesitylimidazolin-2-ylidene)(tricyclohexylphosphine)benzylidene ruthenium dichloride, (1,3-dimesitylimidazolin-2-ylidene)(tricyclohexylphosphine)benzylidene ruthenium dichloride, bis(tricyclohexylphosphine)ethoxymethylidene ruthenium dichloride, (1,3-dimesitylimidazolin-2-ylidene)(tricyclohexylphosphine)ethoxymethylidene ruthenium dichloride, etc.
• the periodic table Group 6 transition metal compound is a compound having a periodic table Group 6 transition metal atom (long period periodic table, the same applies below), specifically, a compound having a chromium atom, a molybdenum atom, or a tungsten atom, with a compound having a molybdenum atom or a compound having a tungsten atom being preferred, and a compound having a tungsten atom being more preferred from the viewpoint of high solubility in cyclopentene.
• the periodic table Group 6 transition metal compound examples include molybdenum compounds such as molybdenum pentachloride, molybdenum oxotetrachloride, and molybdenum (phenylimido) tetrachloride; tungsten compounds such as tungsten hexachloride, tungsten oxotetrachloride, tungsten (phenylimido) tetrachloride, monocatecholate tungsten tetrachloride, bis(3,5-ditertiarybutyl)catecholate tungsten dichloride, and bis(2-chloroetherate) tetrachloride; and the like.
• molybdenum compounds such as molybdenum pentachloride, molybdenum oxotetrachloride, and molybdenum (phenylimido) tetrachloride
• tungsten compounds such as tungsten hexachloride,
• the amount of the ring-opening polymerization catalyst used is, in terms of the molar ratio of (ring-opening polymerization catalyst:monomer used in copolymerization), usually in the range of 1:500 to 1:2,000,000, preferably 1:700 to 1:1,500,000, and more preferably 1:1,000 to 1:1,000,000.
• the amount of the periodic table Group 6 transition metal compound used is, in terms of the molar ratio of "Group 6 transition metal atom in the ring-opening polymerization catalyst:monomer used in ring-opening polymerization", preferably in the range of 1:100 to 1:200,000, more preferably 1:200 to 1:150,000, and even more preferably 1:500 to 1:100,000.
• the above-mentioned Group 6 transition metal compound of the periodic table is used as the ring-opening polymerization catalyst, it is preferable to use it in combination with an organoaluminum compound represented by the following general formula (2):
• the organoaluminum compound acts as a ring-opening polymerization catalyst together with the above-mentioned Group 6 transition metal compound.
• R 5 and R6 are each independently a hydrocarbon group having 1 to 20 carbon atoms, and preferably a hydrocarbon group having 1 to 10 carbon atoms. Also, x satisfies 0 ⁇ x ⁇ 3.
• examples of R5 and R6 include alkyl groups such as a methyl group, an ethyl group, an isopropyl group, an n-propyl group, an isobutyl group, an n-butyl group, a t-butyl group, an n-hexyl group, a cyclohexyl group, an n-octyl group, and an n-decyl group; and aryl groups such as a phenyl group, a 4-methylphenyl group, a 2,6-dimethylphenyl group, a 2,6-diisopropylphenyl group, and a naphthyl group.
• x is 0 ⁇ x ⁇ 3. That is, in general formula (2), the composition ratio of R5 to OR6 can be any value within the ranges of 0 ⁇ 3-x ⁇ 3 and 0 ⁇ x ⁇ 3, respectively, but from the viewpoint of increasing the polymerization activity, it is preferable that x is 0.5 ⁇ x ⁇ 1.5.
• the organoaluminum compound represented by the above general formula (2) can be synthesized, for example, by reacting trialkylaluminum with an alcohol, as shown in the following general formula (3).
• x in the above general formula (2) can be arbitrarily controlled by specifying the reaction ratio of the corresponding trialkylaluminum and alcohol, as shown in the above general formula (3).
• the amount of the organoaluminum compound used varies depending on the type of organoaluminum compound used, but is preferably 0.1 to 100 times by mole, more preferably 0.2 to 50 times by mole, and even more preferably 0.5 to 20 times by mole, based on the Group 6 transition metal atoms constituting the Group 6 transition metal compound. If the amount of the organoaluminum compound used is too small, the polymerization activity may be insufficient, and if it is too large, side reactions tend to occur more easily during ring-opening polymerization.
• the polymerization reaction may be carried out without a solvent or in a solution.
• the solvent used is not particularly limited as long as it is inert in the polymerization reaction and can dissolve the cyclopentene used in the copolymerization, the norbornene compound represented by the above general formula (1), the polymerization catalyst, etc., but it is preferable to use a hydrocarbon solvent or a halogen-based solvent.
• hydrocarbon solvent examples include aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; aliphatic hydrocarbons such as hexane, n-heptane, and n-octane; alicyclic hydrocarbons such as cyclohexane, cyclopentane, and methylcyclohexane; and the like.
• halogen-based solvent include haloalkanes such as dichloromethane and chloroform; aromatic halogens such as chlorobenzene and dichlorobenzene; and the like. These solvents may be used alone or in combination of two or more.
• an olefin compound or a diolefin compound may be added to the polymerization reaction system as a molecular weight regulator, if necessary, in order to adjust the molecular weight of the resulting copolymer.
• the olefin compound is not particularly limited as long as it is an organic compound having an ethylenically unsaturated bond, and examples thereof include ⁇ -olefins such as 1-butene, 1-pentene, 1-hexene, 1-octene, etc.; styrenes such as styrene and vinyl toluene; halogen-containing vinyl compounds such as allyl chloride; alkenyl alcohols such as allyl alcohol and 5-hexenol; silicon-containing vinyl compounds such as allyltrimethoxysilane, allyltriethoxysilane, allyltrichlorosilane, and styryltrimethoxysilane; disubstituted olefins such as 2-butene and 3-hexene; etc.
• ⁇ -olefins such as 1-butene, 1-pentene, 1-hexene, 1-octene, etc.
• styrenes
• diolefin compound examples include non-conjugated diolefins such as 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,6-heptadiene, 2-methyl-1,4-pentadiene, and 2,5-dimethyl-1,5-hexadiene.
• the amount of the olefin compound and diolefin compound used as the molecular weight regulator may be appropriately selected depending on the molecular weight of the copolymer to be produced, but is usually in the range of 1/100 to 1/100,000, preferably 1/200 to 1/50,000, more preferably 1/500 to 1/10,000 in terms of molar ratio to the monomer used in the copolymerization.
• the copolymer of cyclopentene and norbornene-based compounds is to have a modifying group at the polymer chain end
• a modifying group-containing olefinically unsaturated hydrocarbon compound as a molecular weight regulator instead of the above-mentioned olefin compound or diolefin compound.
• the modifying group can be suitably introduced at the polymer chain end of the copolymer obtained by copolymerization.
• the modifying group-containing olefinically unsaturated hydrocarbon compound is not particularly limited as long as it has a modifying group and one olefinic carbon-carbon double bond that has metathesis reactivity.
• an oxysilyl group-containing olefinically unsaturated hydrocarbon may be present in the polymerization reaction system.
• Examples of the oxysilyl group-containing olefinic unsaturated hydrocarbons include alkoxysilane compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allylmethoxydimethylsilane, allyltriethoxysilane, allylethoxydimethylsilane, styryltrimethoxysilane, styryltriethoxysilane, styrylethyltriethoxysilane, allyltriethoxysilylmethylether, and allyltriethoxysilylmethylethylamine, which introduce a modifying group only at one end (single end) of the polymer chain of the copolymer; vinyltriphenoxysilane, allyltriphenoxysilane, and a aryloxysilane compounds such as allylphenoxydimethylsilane; acyloxysilane compounds such as vinyl
• examples of compounds for introducing modifying groups into both ends (both ends) of the polymer chain of the copolymer include alkoxysilane compounds such as bis(trimethoxysilyl)ethylene, bis(triethoxysilyl)ethylene, 2-butene-1,4-di(trimethoxysilane), 2-butene-1,4-di(triethoxysilane), and 1,4-di(trimethoxysilylmethoxy)-2-butene; aryloxysilane compounds such as 2-butene-1,4-di(triphenoxysilane); Examples include acyloxysilane compounds such as 1,4-di(triacetoxysilane); alkylsiloxysilane compounds such as 2-butene-1,4-di[tris(trimethylsiloxy)silane]; arylsiloxysilane compounds such as 2-butene-1,4-di[tris(triphenylsiloxy)silane]
• the modifying group-containing olefinically unsaturated hydrocarbon compound acts as a molecular weight regulator in addition to introducing a modifying group to the polymer chain end of the copolymer, so the amount of the modifying group-containing olefinically unsaturated hydrocarbon compound used may be appropriately selected depending on the molecular weight of the copolymer to be produced, but is usually in the range of 1/100 to 1/100,000, preferably 1/200 to 1/50,000, and more preferably 1/500 to 1/10,000 in molar ratio to the monomers used in the copolymerization.
• the polymerization reaction temperature is not particularly limited, but is preferably -100°C or higher, more preferably -50°C or higher, even more preferably 0°C or higher, and particularly preferably 20°C or higher.
• the upper limit of the polymerization reaction temperature is not particularly limited, but is preferably less than 120°C, more preferably less than 100°C, even more preferably less than 90°C, and particularly preferably less than 80°C.
• the polymerization reaction time is not particularly limited, but is preferably 1 minute to 72 hours, and more preferably 10 minutes to 20 hours.
• an anti-aging agent such as a phenol-based stabilizer, a phosphorus-based stabilizer, or a sulfur-based stabilizer may be added to the copolymer obtained by the polymerization reaction.
• the amount of the anti-aging agent to be added may be determined appropriately depending on the type of the anti-aging agent.
• an extender oil may be blended into the copolymer.
• a known recovery method may be used to recover the copolymer from the polymerization solution. For example, a method may be used in which the solvent is separated by steam stripping, the solid is filtered off, and then the solid is dried to obtain a solid copolymer.
• the content of the copolymer of cyclopentene and norbornene-based compounds is preferably 20 to 90 parts by mass, and more preferably 30 to 85 parts by mass, per 100 parts by mass of the rubber component.
• the content of the copolymer of cyclopentene and norbornene-based compounds is in the range of 20 to 90 parts by mass per 100 parts by mass of the rubber component, the balance of fuel economy, abrasion resistance, and processability of the rubber composition is further improved.
• the rubber component contains a modified polymer, which has high affinity with a filler and can improve the dispersibility of the filler, thereby improving the fuel economy, abrasion resistance, and processability of the rubber composition.
• the "modified polymer” excludes the above-mentioned copolymer of cyclopentene and a norbornene-based compound represented by the above-mentioned general formula (1). That is, the rubber component of the rubber composition for tires of this embodiment contains the above-mentioned copolymer of cyclopentene and a norbornene-based compound and a modified polymer other than the copolymer.
• modified functional group in the modified polymer examples include a nitrogen-containing functional group, a silicon-containing functional group, a tin-containing functional group, an oxygen-containing functional group, and the like. Among these, a nitrogen-containing functional group is preferred.
• the modified polymer has a nitrogen-containing functional group, the affinity with the filler is further increased and the dispersibility of the filler can be further improved, so that the fuel economy, abrasion resistance, and processability of the rubber composition can be further improved.
• the functional group containing a nitrogen atom is preferably selected from the following:
• the functional group is selected from the group consisting of a primary amino group, a primary amino group protected with a hydrolyzable protecting group, an onium salt residue of a primary amine, an isocyanate group, a thioisocyanate group, an imine group, an imine residue, an amide group, a secondary amino group protected with a hydrolyzable protecting group, a cyclic secondary amino group, an onium salt residue of a cyclic secondary amine, a non-cyclic secondary amino group, an onium salt residue of a non-cyclic secondary amine, an isocyanuric acid triester residue, a cyclic tertiary amino group, a non-cyclic tertiary amino group, a nitrile group, a pyridine residue, an onium salt residue of a cyclic tertiary amine, and an onium salt residue of a non-cyclic terti
• the modified polymer may be a polymer obtained by using a conjugated diene compound, or a conjugated diene compound and an aromatic vinyl compound as a monomer, and modifying the molecular terminals and/or main chain of a polymer or copolymer of the conjugated diene compound, or a copolymer of a conjugated diene compound and an aromatic vinyl compound, with a modifying agent; or a polymer obtained by using a conjugated diene compound, or a conjugated diene compound and an aromatic vinyl compound as a monomer, and polymerizing or copolymerizing these monomers with a polymerization initiator having a modifying functional group.
• examples of conjugated diene compounds include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 2-phenyl-1,3-butadiene, 1,3-hexadiene, etc.
• examples of aromatic vinyl compounds include styrene, ⁇ -methylstyrene, 1-vinylnaphthalene, 3-vinyltoluene, ethylvinylbenzene, divinylbenzene, 4-cyclohexylstyrene, 2,4,6-trimethylstyrene, etc.
• the modified polymers include modified synthetic isoprene rubber (IR), modified butadiene rubber (BR), modified styrene-butadiene rubber (SBR), modified styrene-isoprene rubber (SIR), etc., among which modified butadiene rubber (BR) and modified styrene-butadiene rubber (SBR) are preferred, and modified butadiene rubber (BR) is particularly preferred.
• Modified butadiene rubber (BR) has a low glass transition temperature (Tg), and by combining it with the above-mentioned copolymer of cyclopentene and norbornene-based compounds, it is possible to further improve the fuel efficiency and wear resistance of the rubber composition.
• modified styrene-butadiene rubber (SBR) has a high glass transition temperature (Tg), is excellent in processability, and also has the effect of suppressing uneven wear of the rubber composition.
• the modifying agent is preferably a hydrocarbyloxysilane compound, and the hydrocarbyloxysilane compound is preferably a compound represented by the following general formula (i).
• R 11 and R 12 each independently represent a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, a is an integer of 0 to 2, and when there are multiple OR 12 , each OR 12 may be the same or different, and no active proton is contained in the molecule.
• hydrocarbyloxysilane compound an aminoalkoxysilane compound represented by the following general formula (ii) is also preferred.
• a 1 is at least one functional group selected from a saturated cyclic tertiary amine compound residue, an unsaturated cyclic tertiary amine compound residue, a ketimine residue, a nitrile group, a (thio)isocyanate group, an isocyanuric acid trihydrocarbyl ester group, a nitrile group, a pyridine group, a (thio)ketone group, an amide group, and a primary or secondary amino group having a hydrolyzable group.
• a 1 When n4 is 2 or more, A 1 may be the same or different, and A 1 may be a divalent group that bonds with Si to form a cyclic structure.
• R 21 is a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and when n1 is 2 or more, R 21 may be the same or different.
• R 22 is a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, either of which may contain a nitrogen atom and/or a silicon atom.
• R 22 When n2 is 2 or greater, R 22 may be the same or different from each other, or may be joined together to form a ring.
• R 23 represents a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, or a halogen atom, and when n3 is 2 or greater, may be the same or different.
• R 24 is a divalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and when n4 is 2 or greater, R 24 may be the same or different.
• the hydrolyzable group in the hydrolyzable group-containing primary or secondary amino group a trimethylsilyl group or a tert-butyldimethylsilyl group is preferred, and a trimethylsilyl group is particularly preferred.
• aminoalkoxysilane compound represented by the above general formula (ii) is preferably an aminoalkoxysilane compound represented by the following general formula (iii).
• p1+p2+p3 2 (wherein p2 is an integer of 1 or 2, and p1 and p3 are integers of 0 or 1).
• A2 is NRa (Ra is a monovalent hydrocarbon group, a hydrolyzable group, or a nitrogen-containing organic group).
• R 25 is a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms.
• R 26 is a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, or a nitrogen-containing organic group, any of which may contain a nitrogen atom and/or a silicon atom.
• R 26 may be the same or different from each other, or may be joined together to form a ring.
• R 27 is a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, or a halogen atom.
• R 28 is a divalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms.
• a trimethylsilyl group or a tert-butyldimethylsilyl group is preferred, and a trimethylsilyl group is particularly preferred.
• aminoalkoxysilane compound represented by the above general formula (ii) is also preferably an aminoalkoxysilane compound represented by the following general formula (iv) or (v).
• R 31 is a divalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms.
• R 32 and R 33 each independently represent a hydrolyzable group, a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms.
• R 34 is a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and when q1 is 2, may be the same or different.
• R 35 is a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and when q2 is 2 or greater, R 35 may be the same or different.
• aminoalkoxysilane compound represented by general formula (iv) is N,N-bis(trimethylsilyl)-3-[diethoxy(methyl)silyl]propylamine (also referred to as "N,N-bis(trimethylsilyl)aminopropylmethyldiethoxysilane").
• R 36 is a divalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms.
• R 37 is a dimethylaminomethyl group, a dimethylaminoethyl group, a diethylaminomethyl group, a diethylaminoethyl group, a methylsilyl(methyl)aminomethyl group, a methylsilyl(methyl)aminoethyl group, a methylsilyl(ethyl)aminomethyl group, a methylsilyl(ethyl)aminoethyl group, a dimethylsilylaminomethyl group, a dimethylsilylaminoethyl group, a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and when r1 is 2 or more, they may be the same or different.
• R 38 is a hydrocarbyloxy group having 1 to 20 carbon atoms, a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and when r2 is 2, they may be the same or different.
• a specific example of the aminoalkoxysilane compound represented by the general formula (v) is N-(1,3-dimethylbutylidene)-3-triethoxysilyl-1-propaneamine.
• aminoalkoxysilane compound represented by the above general formula (ii) is also preferably an aminoalkoxysilane compound represented by the following general formula (vi) or (vii).
• R 40 represents a trimethylsilyl group, a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms.
• R 41 is a hydrocarbyloxy group having 1 to 20 carbon atoms, a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms.
• R 42 is a divalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms.
• TMS represents a trimethylsilyl group (hereinafter the same).
• R 43 and R 44 each independently represent a divalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms.
• R 45 is a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and each R 45 may be the same or different.
• aminoalkoxysilane compound represented by the above general formula (ii) is also preferably an aminoalkoxysilane compound represented by the following general formula (viii) or the following general formula (ix).
• s1+s2 is 3 (wherein s1 is an integer of 0 to 2, and s2 is an integer of 1 to 3).
• R 46 is a divalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms.
• R 47 and R 48 are each independently a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms. Multiple R 47s or R 48s may be the same or different.
• X is a halogen atom.
• R 49 is a divalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms.
• R 50 and R 51 are each independently a hydrolyzable group, a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, or R 50 and R 51 combine together to form a divalent organic group.
• R 52 and R 53 each independently represent a halogen atom, a hydrocarbyloxy group, a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms.
• R 50 and R 51 are preferably a hydrolyzable group, and the hydrolyzable group is preferably a trimethylsilyl group or a tert-butyldimethylsilyl group, and particularly preferably a trimethylsilyl group.
• aminoalkoxysilane compound represented by the above general formula (ii) is also preferably an aminoalkoxysilane compound represented by the following general formula (x), the following general formula (xi), the following general formula (xii), or the following general formula (xiii).
• R 54 to R 92 in general formulas (x) to (xiii) may be the same or different and are a monovalent or divalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a monovalent or divalent aromatic hydrocarbon group having 6 to 18 carbon atoms.
• ⁇ and ⁇ are integers of 0 to 5.
• N1,N1,N7,N7-tetramethyl-4-((trimethoxysilyl)methyl)heptane-1,7-diamine 2-((hexyl-dimethoxysilyl)methyl)-N1,N1,N3,N3-2-pentamethylpropane-1,3-diamine, N1-(3-(dimethylamino)propyl)-N3,N3-dimethyl-N1-(3-(trimethoxysilyl)propyl)propane-1,3-diamine, and 4-(3-(dimethylamino)propyl)-N1,N1,N7,N7-tetramethyl-4-((trimethoxysilyl)methyl)heptane-1,7-diamine are particularly preferred.
• hydrocarbyloxysilane compound a compound represented by the following general formula (xiv) is also preferred.
• A3 is a monovalent group having at least one functional group selected from (thio)epoxy, (thio)isocyanate, (thio)ketone, (thio)aldehyde, imine, amide, isocyanuric acid trihydrocarbyl ester, (thio)carboxylate, (thio)carboxylic acid metal salt, carboxylic acid anhydride, carboxylic acid halide, and carbonic acid dihydrocarbyl ester.
• (thio)epoxy refers to epoxy and thioepoxy
• (thio)isocyanate refers to isocyanate and thioisocyanate
• (thio)ketone refers to ketone and thioketone
• (thio)aldehyde refers to aldehyde and thioaldehyde
• (thio)carboxylate refers to carboxylate and thiocarboxylate
• (thio)carboxylic acid metal salt refers to carboxylate and thiocarboxylate.
• R 101 is a single bond or a divalent inert hydrocarbon group, and the divalent inert hydrocarbon group preferably has 1 to 20 carbon atoms.
• R 102 and R 103 each independently represent a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, n is an integer from 0 to 2, and when there is a plurality of R 102 , the plurality of R 102 may be the same or different, and when there is a plurality of OR 103 , the plurality of OR 103 may be the same or different.
• the molecule of the hydrocarbyloxysilane compound represented by general formula (xiv) does not contain an active proton or an onium salt.
• the imine includes ketimine, aldimine, and amidine
• the (thio)carboxylic acid ester includes unsaturated carboxylic acid ester such as acrylate and methacrylate.
• examples of the metal in the metal salt of the (thio)carboxylic acid include alkali metals, alkaline earth metals, Al, Sn, and Zn.
• Preferred examples of the divalent inactive hydrocarbon group of R 101 include alkylene groups having 1 to 20 carbon atoms. The alkylene group may be linear, branched, or cyclic, with linear alkylene groups being particularly preferred.
• linear alkylene groups include methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, decamethylene, and dodecamethylene.
• R 102 and R 103 include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, and an aralkyl group having 7 to 18 carbon atoms.
• the alkyl group and the alkenyl group may be linear, branched, or cyclic, and examples thereof 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, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, a cyclopentyl group, a cyclohexyl group, a vinyl group, a propenyl group, an allyl group, a hexenyl group, an octenyl group, a cyclopentenyl group, and a cyclohexenyl group.
• the aryl group may have a substituent such as a lower alkyl group on the aromatic ring, and examples thereof include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.
• the aralkyl group may have a substituent such as a lower alkyl group on the aromatic ring, examples of which include a benzyl group, a phenethyl group, and a naphthylmethyl group.
• n is an integer of 0 to 2, preferably 0, and it is necessary that the molecule does not contain active protons or onium salts.
• hydrocarbyloxysilane compound represented by the above general formula (xiv) examples include (thio)epoxy group-containing hydrocarbyloxysilane compounds, such as 2-glycidoxyethyltrimethoxysilane, 2-glycidoxyethyltriethoxysilane, (2-glycidoxyethyl)methyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane (hereinafter also referred to as "GPMOS”), 3-glycidoxypropyltriethoxysilane, (3-glycidoxypropyl)methyldimethoxysilane, 2-(3,4-epoxy Preferred examples of the silane derivatives include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl
• triethoxysilyl compounds include N-(1-methylpropylidene)-3-(triethoxysilyl)-1-propanamine and trimethoxysilyl compounds, methyldiethoxysilyl compounds, ethyldiethoxysilyl compounds, methyldimethoxysilyl compounds, ethyldimethoxysilyl compounds, and the like corresponding to these triethoxysilyl compounds.
• N-(1-methylpropylidene)-3-(triethoxysilyl)-1-propanamine and N-(1,3-dimethylbutylidene)-3-(triethoxysilyl)-1-propanamine are particularly preferred.
• the modifying agent is preferably a coupling agent represented by the following general formula (xv).
• R 111 , R 112 and R 113 each independently represent a single bond or an alkylene group having 1 to 20 carbon atoms.
• R 114 , R 115 , R 116 , R 117 and R 119 each independently represent an alkyl group having 1 to 20 carbon atoms.
• R 118 and R 121 each independently represent an alkylene group having 1 to 20 carbon atoms.
• R 120 represents an alkyl group or a trialkylsilyl group having 1 to 20 carbon atoms.
• m represents an integer of 1 to 3; p represents 1 or 2.
• R 111 to R 121 , m and p are each independent, and i, j and k each independently represent an integer of 0 to 6, with the proviso that (i+j+k) is an integer of 3 to 10.
• A4 represents a hydrocarbon group having 1 to 20 carbon atoms, or an organic group having at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, a silicon atom, a sulfur atom and a phosphorus atom and having no active hydrogen.
• the hydrocarbon group represented by A4 includes saturated, unsaturated, aliphatic and aromatic hydrocarbon groups.
• organic group not having active hydrogen examples include organic groups not having a functional group having active hydrogen, such as a hydroxyl group (-OH), a secondary amino group (>NH), a primary amino group (-NH 2 ) or a sulfhydryl group (-SH).
• the coupling agent represented by the general formula (xv) is preferably at least one selected from the group consisting of tetrakis[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]-1,3-propanediamine, tetrakis(3-trimethoxysilylpropyl)-1,3-propanediamine, and tetrakis(3-trimethoxysilylpropyl)-1,3-bisaminomethylcyclohexane.
• the modifying agent is preferably a coupling agent represented by the following general formula (xvi). (R 126 ) b ZX c ... (xvi)
• Z is tin or silicon
• X is chlorine or bromine.
• R 126 is selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms, where specific examples of R 126 include a methyl group, an ethyl group, an n-butyl group, a neophyl group, a cyclohexyl group, an n-octyl group, and a 2-ethylhexyl group.
• tin tetrachloride As the coupling agent represented by the above general formula (xvi), tin tetrachloride, (R 126 )SnCl 3 , (R 126 ) 2 SnCl 2 , (R 126 ) 3 SnCl, silicon tetrachloride, etc. are preferred, and among these, tin tetrachloride is particularly preferred.
• the polymerization initiator having the modified functional group is preferably a lithium amide compound.
• the lithium amide compound include lithium hexamethyleneimide, lithium pyrrolidide, lithium piperidide, lithium heptamethyleneimide, lithium dodecamethyleneimide, lithium dimethylamide, lithium diethylamide, lithium dibutylamide, lithium dipropylamide, lithium diheptylamide, lithium dihexylamide, lithium dioctylamide, lithium di-2-ethylhexylamide, lithium didecylamide, lithium N-methylpiperazide, lithium ethylpropylamide, lithium ethylbutylamide, lithium ethylbenzylamide, and lithium methylphenethylamide.
• the lithium amide compound may also be a compound represented by the formula: Li-AM [wherein AM is represented by the following formula (xvii): (wherein R 131 and R 132 each independently represent an alkyl group, a cycloalkyl group, or an aralkyl group having 1 to 12 carbon atoms), or a substituted amino group represented by the following formula (xviii): (wherein R 133 represents an alkylene group, a substituted alkylene group, an oxyalkylene group or an N-alkylamino-alkylene group having 3 to 16 methylene groups).
• R 131 and R 132 are an alkyl group, a cycloalkyl group, or an aralkyl group having 1 to 12 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a butyl group, an octyl group, a cyclohexyl group, a 3-phenyl-1-propyl group, and an isobutyl group.
• R 131 and R 132 may be the same or different.
• R 133 is an alkylene group, a substituted alkylene group, an oxyalkylene group, or an N-alkylamino-alkylene group having 3 to 16 methylene groups.
• the substituted alkylene group includes mono- to octa-substituted alkylene groups, and the substituents include linear or branched alkyl groups, cycloalkyl groups, bicycloalkyl groups, aryl groups, and aralkyl groups having 1 to 12 carbon atoms.
• R 133 examples include a trimethylene group, a tetramethylene group, a hexamethylene group, an oxydiethylene group, an N-alkylazadiethylene group, a dodecamethylene group, and a hexadecamethylene group.
• the lithium amide compound may be prepared in advance from a secondary amine and a lithium compound and then used in the polymerization reaction, or may be generated in the polymerization system.
• the secondary amine include dimethylamine, diethylamine, dibutylamine, dioctylamine, dicyclohexylamine, diisobutylamine, and the like, as well as azacycloheptane (also called “hexamethyleneimine (HMI)”), 2-(2-ethylhexyl)pyrrolidine, 3-(2-propyl)pyrrolidine, 3,5-bis(2-ethylhexyl)piperidine, 4-phenylpiperidine, 7-decyl-1-azacyclotridecane, 3,3-dimethyl-1-azacyclotetradecane, 4-dodecyl-1-azacyclooctane, 4-(2-phenylbutyl)-1-azacyclooctane, 3-ethyl-5-cycl
• examples of the lithium compound that can be used include hydrocarbyl lithium such as ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, tert-octyl lithium, n-decyl lithium, phenyl lithium, 2-naphthyl lithium, 2-butyl-phenyl lithium, 4-phenyl-butyl lithium, cyclohexyl lithium, cyclopentyl lithium, and a reaction product of diisopropenylbenzene with butyl lithium.
• hydrocarbyl lithium such as ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, tert-octyl lithium, n-decyl lithium, phenyl lithium, 2-naphthyl lithium, 2-butyl-phenyl lithium, 4-phenyl-butyl lithium, cyclo
• anionic polymerization using the above-mentioned polymerization initiator having a modifying functional group or the above-mentioned lithium compound i.e., a polymerization initiator not having a modifying functional group
• the reaction mechanism of the polymerization is not limited thereto, and for example, coordination polymerization may be used.
• coordination polymerization it is preferable to use a rare earth metal compound as the polymerization initiator, and it is more preferable to use the following components (a), (b) and (c) in combination.
• the component (a) used in the coordination polymerization is selected from rare earth metal compounds, complex compounds of rare earth metal compounds and Lewis bases, etc.
• the rare earth metal compounds include carboxylates, alkoxides, ⁇ -diketone complexes, phosphates, and phosphites of rare earth elements
• the Lewis bases include acetylacetone, tetrahydrofuran, pyridine, N,N-dimethylformamide, thiophene, diphenyl ether, triethylamine, organic phosphorus compounds, monohydric or dihydric alcohols, etc.
• rare earth elements of the rare earth metal compounds lanthanum, neodymium, praseodymium, samarium, and gadolinium are preferred, and among these, neodymium is particularly preferred.
• component (a) include neodymium versatate, neodymium tri-2-ethylhexanoate, a complex compound thereof with acetylacetone, neodymium trineodecanoate, a complex compound thereof with acetylacetone, neodymium tri-n-butoxide, and the like.
• the component (b) used in the coordination polymerization is selected from organoaluminum compounds.
• organoaluminum compounds include trihydrocarbylaluminum compounds, hydrocarbylaluminum hydrides, and hydrocarbylaluminoxane compounds having a hydrocarbon group with 1 to 30 carbon atoms.
• specific examples of the organoaluminum compounds include trialkylaluminum, dialkylaluminum hydrides, alkylaluminum dihydrides, and alkylaluminoxanes. It is preferable to use aluminoxane in combination with another organoaluminum compound as the component (b).
• the component (c) used in the coordination polymerization is selected from compounds having a hydrolyzable halogen or complexes of these with a Lewis base; organic halides having a tertiary alkyl halide, benzyl halide, or allyl halide; ionic compounds consisting of a non-coordinating anion and a counter cation; etc.
• component (c) examples include alkylaluminum dichloride, dialkylaluminum chloride, silicon tetrachloride, tin tetrachloride, complexes of zinc chloride with a Lewis base such as alcohol, complexes of magnesium chloride with a Lewis base such as alcohol, benzyl chloride, t-butyl chloride, benzyl bromide, t-butyl bromide, triphenylcarbonium tetrakis(pentafluorophenyl)borate, etc.
• the modified polymer may be reacted with a modifying agent such as a hydrocarbyloxysilane compound, and then with at least one selected from the group consisting of a condensation promoter containing a metal element, an inorganic acid, and a metal halide.
• a modifying agent such as a hydrocarbyloxysilane compound
• at least one selected from the group consisting of a condensation promoter containing a metal element, an inorganic acid, and a metal halide By reacting with the condensation promoter containing a metal element, or at least one selected from the group consisting of an inorganic acid and a metal halide, a modified polymer having a high Mooney viscosity and excellent shape stability can be produced.
• condensation promoter containing the metal element it is preferable to use a metal compound containing at least one metal selected from the metals contained in Groups 2 to 15 of the periodic table.
• Specific metal elements include titanium, zirconium, aluminum, bismuth, tin, etc.
• an alkoxide, carboxylate, or acetylacetonate complex salt of the above-mentioned metal is preferable.
• the condensation accelerator is preferably tetrakis(2-ethyl-1,3-hexanediolato)titanium, tetrakis(2-ethylhexyloxy)titanium (hereinafter also referred to as "tetra 2-ethylhexyl titanate” or "EHOTi”), tetra(octanediolate)titanium, tris(2-ethylhexanoate)bismuth, tetra n-propoxyzirconium, tetra n-butoxyzirconium, bis(2-ethylhexanoate)zirconium oxide, bis(oleate)zirconium oxide, tri-i-propoxyaluminum, tri-sec-butoxyaluminum, tris(2-ethylhexanoate)aluminum, tris(stearate)aluminum, zirconium tetrakis(ace
• examples of the inorganic acid include hydrochloric acid, sulfuric acid, and phosphoric acid.
• a metal halide containing at least one of the metals included in Groups 2 to 15 of the periodic table can be suitably used, and it is more preferable to use a halide containing at least one metal atom selected from the group consisting of silicon, tin, aluminum, zinc, titanium, and zirconium.
• the metal halide trimethylsilyl chloride, dimethyldichlorosilane, methyltrichlorosilane, silicon tetrachloride, methyldichlorosilane, tin tetrachloride, diethylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, zinc chloride, titanium tetrachloride, titanocene dichloride, zirconium tetrachloride, zirconoc
• the modified polymer may be stabilized by reacting it with a modifying agent such as a hydrocarbyloxysilane compound and then reacting it with a partial carboxylic acid ester of a polyhydric alcohol.
• a modifying agent such as a hydrocarbyloxysilane compound
• a partial carboxylic acid ester of a polyhydric alcohol means an ester of a polyhydric alcohol and a carboxylic acid, which has one or more hydroxyl groups.
• an ester of a sugar or modified sugar having 4 or more carbon atoms and a fatty acid is preferably used.
• this ester include (1) a fatty acid partial ester of a polyhydric alcohol, in particular a partial ester (which may be a monoester, diester, or triester) of a saturated higher fatty acid or an unsaturated higher fatty acid having 10 to 20 carbon atoms and a polyhydric alcohol, and (2) an ester compound in which 1 to 3 partial esters of a polycarboxylic acid and a higher alcohol are bonded to a polyhydric alcohol.
• the polyhydric alcohol used as a raw material for the partial ester is preferably a saccharide having 5 or 6 carbon atoms and at least three hydroxyl groups (which may or may not be hydrogenated), glycol, polyhydroxy compound, etc.
• the raw material fatty acid is preferably a saturated or unsaturated fatty acid having 10 to 20 carbon atoms, such as stearic acid, lauric acid, or palmitic acid.
• fatty acid partial esters of the polyhydric alcohols sorbitan fatty acid esters are preferred, and specific examples thereof include sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan tristearate, sorbitan monooleate, and sorbitan trioleate.
• the content of the modified polymer is preferably 5 to 90 parts by mass, more preferably 10 to 80 parts by mass, and even more preferably 15 to 70 parts by mass, per 100 parts by mass of the rubber component.
• the content of the modified polymer is 5 to 90 parts by mass or more per 100 parts by mass of the rubber component, the balance of fuel economy, abrasion resistance, and processability of the rubber composition is further improved.
• the rubber component may further contain other rubbers.
• other rubbers include natural rubber (NR), unmodified synthetic isoprene rubber (IR), butadiene rubber (BR), styrene-butadiene rubber (SBR), chloroprene rubber (CR), butyl rubber (IIR), halogenated butyl rubber, ethylene-propylene rubber (EPR, EPDM), fluororubber, silicone rubber, urethane rubber, etc.
• the content of these other rubbers is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 10 parts by mass or less, per 100 parts by mass of the rubber component.
• the rubber composition for tires of the present embodiment contains a filler.
• the filler include carbon black, silica, clay, talc, calcium carbonate, aluminum hydroxide, etc., and among these, carbon black is preferable.
• the content of the filler is preferably in the range of 5 to 80 parts by mass per 100 parts by mass of the rubber component.
• the content of the filler is 5 parts by mass or more per 100 parts by mass of the rubber component, the abrasion resistance of the rubber composition is further improved, and when the content is 80 parts by mass or less, the fuel economy and processability of the rubber composition are further improved.
• the content of the filler is more preferably 10 parts by mass or more, and even more preferably 20 parts by mass or more per 100 parts by mass of the rubber component, and from the viewpoint of fuel economy and processability, it is more preferably 70 parts by mass or less, and even more preferably 60 parts by mass or less.
• the filler preferably contains carbon black, which has a large effect of reinforcing the rubber composition and improving the abrasion resistance of the rubber composition, and therefore a rubber composition for tires containing carbon black as a filler has further improved abrasion resistance.
• the carbon black content is preferably in the range of 5 to 80 parts by mass per 100 parts by mass of the rubber component.
• the carbon black content is more preferably 10 parts by mass or more, and even more preferably 20 parts by mass or more per 100 parts by mass of the rubber component, and from the viewpoint of fuel economy and processability, it is more preferably 70 parts by mass or less, and even more preferably 60 parts by mass or less.
• the proportion of carbon black in the filler is preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and may be 100% by mass.
• the rubber composition for tires of this embodiment may contain various components commonly used in the rubber industry, such as silane coupling agents, antioxidants, hardened fatty acids, zinc oxide (zinc white), tackifiers, vulcanization accelerators, vulcanizing agents, etc., as necessary, appropriately selected within ranges that do not impair the objects of the present invention.
• Commercially available products can be suitably used as these compounding agents.
• the antioxidants include N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (6C), 2,2,4-trimethyl-1,2-dihydroquinoline polymer (TMDQ), etc. These antioxidants may be used alone or in combination of two or more. There are no particular restrictions on the content of the antioxidant, and it is preferably in the range of 0.1 to 5 parts by mass, more preferably 1 to 4 parts by mass, per 100 parts by mass of the rubber component.
• the hardened fatty acid may be stearic acid or the like. There are no particular restrictions on the content of the hardened fatty acid, but it is preferably in the range of 0.1 to 5 parts by mass, and more preferably 1 to 4 parts by mass, per 100 parts by mass of the rubber component.
• the amount of zinc oxide (zinc white) is not particularly limited, but is preferably in the range of 0.1 to 10 parts by mass, and more preferably 1 to 8 parts by mass, per 100 parts by mass of the rubber component.
• the tackifier examples include rosin-based resins, terpene-based resins, petroleum-based resins, phenol-based resins, coal-based resins, xylene-based resins, etc., and among these, petroleum-based resins are preferred.
• the petroleum-based resins include C5 -based resins, C5 - C9- based resins, C9 -based resins, dicyclopentadiene resins, etc.
• the content of the tackifier is not particularly limited, and is preferably in the range of 0.1 to 5 parts by mass, more preferably 0.5 to 3 parts by mass, per 100 parts by mass of the rubber component.
• the vulcanization accelerator may be a sulfenamide-based vulcanization accelerator, a guanidine-based vulcanization accelerator, a thiazole-based vulcanization accelerator, a thiuram-based vulcanization accelerator, a dithiocarbamate-based vulcanization accelerator, or the like. These vulcanization accelerators may be used alone or in combination of two or more. There are no particular limitations on the content of the vulcanization accelerator, and the content is preferably in the range of 0.1 to 5 parts by mass, and more preferably in the range of 0.2 to 4 parts by mass, per 100 parts by mass of the rubber component.
• the vulcanizing agent may be sulfur.
• the content of the vulcanizing agent is preferably in the range of 0.1 to 6 parts by mass, more preferably 0.5 to 3 parts by mass, in terms of sulfur content per 100 parts by mass of the rubber component.
• the method for producing the rubber composition for tires is not particularly limited, but for example, the rubber composition can be produced by blending various components appropriately selected as necessary with the above-mentioned rubber component and filler, and kneading, heating, extruding, etc.
• the obtained rubber composition can be vulcanized to produce a vulcanized rubber.
• kneading there are no particular limitations on the conditions for the kneading, and the input volume of the kneading device, the rotation speed of the rotor, the ram pressure, etc., as well as the conditions for the kneading temperature, kneading time, type of kneading device, etc., can be appropriately selected according to the purpose.
• kneading devices include Banbury mixers, intermixes, kneaders, rolls, etc., which are typically used for kneading rubber compositions.
• heat-in process temperature heat-in process time
• heat-in process equipment heat-in process equipment
• other conditions can be appropriately selected according to the purpose.
• the heat-in process equipment include a heat-in process roll machine typically used for heat-in process of rubber compositions.
• extrusion conditions there are no particular limitations on the extrusion conditions, and various conditions such as extrusion time, extrusion speed, extrusion equipment, and extrusion temperature can be appropriately selected depending on the purpose.
• extrusion equipment include extruders that are typically used for extruding rubber compositions.
• the extrusion temperature can be appropriately determined.
• Typical vulcanization equipment includes a mold vulcanizer that uses a mold used to vulcanize rubber compositions.
• the vulcanization temperature is, for example, about 100 to 190°C.
• the tire of the present embodiment is characterized by including the above-mentioned rubber composition for tires. Since the tire of the present embodiment includes the above-mentioned rubber composition for tires, the tire has a good balance of fuel efficiency, abrasion resistance, and productivity.
• the rubber composition is applied to the tread rubber of the tire.
• the tire of this embodiment may be obtained by molding an unvulcanized rubber composition and then vulcanizing it, depending on the type of tire to which it is applied, or by molding a semi-vulcanized rubber that has been subjected to a pre-vulcanization process or the like, and then further vulcanizing it.
• the tire of this embodiment is preferably a pneumatic tire, and the gas to be filled in the pneumatic tire may be normal air or air with an adjusted oxygen partial pressure, or an inert gas such as nitrogen, argon, or helium.
• ⁇ Method for synthesizing modified BR1> 283 g of cyclohexane, 50 g of 1,3-butadiene, 0.0057 mmol of 2,2-ditetrahydrofurylpropane, and 0.513 mmol of hexamethyleneimine (HMI) were added to a dried, nitrogen-purged pressure-resistant glass vessel of about 900 mL, and 0.57 mmol of n-butyllithium (BuLi) was further added, followed by polymerization for 4.5 hours in a 50°C warm water bath equipped with a stirrer. The polymerization conversion rate at this time was nearly 100%.
• HMI hexamethyleneimine
• modified butadiene rubber (modified BR1) obtained, the vinyl bond amount in the butadiene portion was measured from the integral ratio of the 1 H-NMR spectrum to be 14%, the glass transition temperature (Tg) was calculated from the inflection point of the DSC curve to be ⁇ 95° C., and the coupling rate was calculated from the ratio of the peak area on the highest molecular weight side to the entire area of the molecular weight distribution curve by gel permeation chromatography (GPC) to be 65%.
• GPC gel permeation chromatography
• reaction conversion rate of 1,3-butadiene was almost 100%. 200 g of this polymer solution was withdrawn, and a methanol solution containing 1.5 g of 2,4-di-tert-butyl-p-cresol was added to terminate the polymerization, after which the solvent was removed by steam stripping and the mixture was dried with a roll at 110° C. to obtain a pre-modified polymer (butadiene rubber).
• a toluene solution of tetra 2-ethylhexyl titanate (EHOTi) (13.5 mmol) was added and mixed for 30 minutes.
• a methanol solution containing 1.5 g of 2,4-di-tert-butyl-p-cresol was added to obtain 2.5 kg of a modified polymer solution.
• the modified polymer solution was added to 20 L of an aqueous solution adjusted to pH 10 with sodium hydroxide, and a condensation reaction was carried out at 110° C. for 2 hours while removing the solvent, and the mixture was dried with a roll at 110° C. to obtain a modified butadiene rubber (modified BR2).
• modified butadiene rubber modified BR2
• Mw/Mn molecular weight distribution
• Mooney viscosity ML 1+4 , 125° C.
• this polymer solution was extracted into a methanol solution containing 1.3 g of 2,6-di-tert-butyl-p-cresol to terminate the polymerization, and the solvent was removed by steam stripping and dried with a roll at 110°C to obtain polybutadiene before modification.
• the microstructure (vinyl bond amount) of the obtained polybutadiene before modification was measured, and the vinyl bond amount was 30 mass%.
• the obtained polymer solution was kept at a temperature of 50° C.
• modified BR3 a primary amine-modified butadiene rubber
• the microstructure (vinyl bond amount) of the obtained modified butadiene rubber (modified BR3) was measured, and the vinyl bond amount was 30 mass%.
• ⁇ Method for synthesizing copolymer 1> In a nitrogen atmosphere, 65 parts by mass of cyclopentene, 35 parts by mass of 2-norbornene, 300 parts by mass of cyclohexane, and 0.066 parts by mass of 1-hexene were added to a glass reaction vessel equipped with a stirrer. Next, 0.024 parts by mass of the ring-opening polymerization catalyst dichloro-(3-phenyl-1H-inden-1-ylidene)bis(tricyclohexylphosphine)ruthenium(II) dissolved in 1 part by mass of toluene was added, and the polymerization reaction was carried out at 20°C for 2 hours.
• ⁇ Method for synthesizing copolymer 2> In a nitrogen atmosphere, 77 parts by mass of cyclopentene, 23 parts by mass of dicyclopentadiene, 300 parts by mass of cyclohexane, and 0.069 parts by mass of 1-hexene were added to a glass reaction vessel equipped with a stirrer. Next, 0.024 parts by mass of the ring-opening polymerization catalyst dichloro-(3-phenyl-1H-inden-1-ylidene)bis(tricyclohexylphosphine)ruthenium(II) dissolved in 1 part by mass of toluene was added, and the polymerization reaction was carried out at 40°C for 2 hours.
• each rubber composition further contains the following compounding ingredients per 100 parts by mass of rubber component: 2 parts by mass of hardened fatty acid, 3.5 parts by mass of zinc oxide, 2.5 parts by mass of antioxidant (total amount of two types), 1 part by mass of resin, 1.4 parts by mass of sulfenamide vulcanization accelerator, and 1.05 parts by mass of sulfur.
• the rubber compositions of Comparative Examples 1 and 2 which contain a copolymer of cyclopentene and a norbornene-based compound but no modified polymer, show a significant deterioration in processability, and the rubber composition of Comparative Example 5 shows a significant deterioration in abrasion resistance.

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