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  • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
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  • C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
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  • 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
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  • C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
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  • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
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  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D165/00—Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Coating compositions based on derivatives of such polymers
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  • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G2261/10—Definition of the polymer structure
  • C08G2261/13—Morphological aspects
  • C08G2261/135—Cross-linked structures
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  • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
  • C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
  • C08G2261/332—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
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  • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
  • C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
  • C08G2261/332—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
  • C08G2261/3324—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms derived from norbornene
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  • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
  • C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
  • C08G2261/332—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
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  • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G2261/40—Polymerisation processes
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  • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G2261/70—Post-treatment
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  • C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
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  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
  • C08J3/247—Heating methods

Definitions

• the present invention relates to a rubber composition and a crosslinked rubber product, and more particularly, a rubber composition that can provide a crosslinked rubber product with excellent fracture resistance, wet grip properties, and low heat build-up, and such a rubber.
• the present invention relates to a rubber crosslinked product obtained using the composition.
• cyclopentene and norbornene compounds are so-called Ziegler-Natta compounds consisting of transition metal compounds from Group 6 of the periodic table, such as WCl 6 and MoCl 5 , and organometallic activators such as triisobutylaluminum, diethylaluminum chloride, and tetrabutyltin.
• organometallic activators such as triisobutylaluminum, diethylaluminum chloride, and tetrabutyltin.
• ring-opening metathesis polymerization in the presence of a catalyst yields an unsaturated linear ring-opening polymer.
• a method is known in which the affinity of a polymer for inorganic particles is improved by introducing a functional group containing a heteroatom at the end of a polymer chain.
• Patent Document 1 discloses a composition for a fracture-resistant material that includes an inorganic material and a ring-opened copolymer containing a structural unit derived from a monocyclic cyclic olefin and a structural unit derived from a norbornene compound. According to the technique of Patent Document 1, it is possible to provide a rubber crosslinked product that has excellent fracture resistance and chipping resistance and is suitable for use in tires and the like. On the other hand, in recent years, there has been a strong demand for cross-linked rubber products used in tires to have low fuel consumption (low heat build-up) due to environmental and resource issues. They are also expected to excel.
• the present invention was made in view of the above circumstances, and an object of the present invention is to provide a rubber composition capable of providing a rubber crosslinked product with excellent fracture resistance, wet grip properties, and low heat build-up. do.
• the present inventors conducted studies to achieve the above object, and found that the above problems could be solved by a rubber composition containing a copolymer having a specific structural unit and a filler.
• the present invention has now been completed.
• a rubber composition containing a copolymer represented by the following general formula (1) and a filler is provided.
• R 1 to R 4 are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, a silicon atom, an oxygen an atom or a substituent containing a nitrogen atom, x is 0 to 2, R 5 is a hydrogen atom or a methyl group, p is 30 to 2000, and n is 200 to 5000.
• R 1 and R 2 , R 3 and R 4 may each be combined to form a ring.
• the values of R 1 to R 5 and x that are included in plurality are the same, respectively. may also be different.
• the filler is preferably a carbon material.
• the filler is preferably silica.
• a crosslinked rubber product obtained by crosslinking the above rubber composition is provided. Further, according to the present invention, there is provided a method for producing the above rubber composition, comprising: A first ethylenically unsaturated polymer having an alicyclic structure and having an unsaturated bond carbon content of 10 to 40 mol%; and a first ethylenically unsaturated polymer having no alicyclic structure and having an unsaturated bond carbon content of 20 to 50 mol%.
• a method for producing a rubber composition which includes a step of blending a filler into the copolymer.
• the rubber composition of the present invention is a rubber composition containing a copolymer represented by the general formula (1) described below and a filler.
• R 1 to R 4 are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a silicon atom or an oxygen atom. or a substituent containing a nitrogen atom, x is 0 to 2, R 5 is a hydrogen atom or a methyl group, p is 30 to 2000, and n is 200 to 5000. R 1 and R 2 and R 3 and R 4 may be bonded to each other to form a ring. In the above general formula (1), the values of multiple R 1 to R 5 and x may be the same or different.
• the copolymer used in the present invention is a copolymer represented by the above general formula (1), and as represented by the above general formula (1), p structural units A, n structural units B, and these structural units A and B are randomly bonded together to form a random copolymer.
• the copolymer represented by the above general formula (1) is not particularly limited in its randomness, but for example, the structural unit A may have about 2 to 40 consecutive blocks, The structural unit B may include about 2 to 40 consecutive blocks.
• the carbon-carbon double bond structure contained in structural unit A and the carbon-carbon double bond structure contained in structural unit B have either a cis structure or a trans structure. It can be either a cis structure or a trans structure, and is not particularly limited (in the above general formula (1), a trans structure is exemplified, but a cis structure or trans structure).
• Structural unit B has a double bond in the polymer main chain, and some of them have double bonds in the side chains shown in the following formula (B') and the following formula (B''). It may be a structural unit. That is, the copolymer represented by the above general formula (1) has a structural unit A, a structural unit B, a structural unit represented by the following formula (B') and/or a structural unit represented by the following formula (B''). It may also be provided with a structural unit.
• R 1 to R 4 are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a silicon atom or an oxygen atom. or a substituent containing a nitrogen atom, preferably a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms which may have a substituent.
• halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and the like.
• hydrocarbon group having 1 to 20 carbon atoms which may have a substituent include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert- Alkyl groups such as butyl group, pentyl group, isopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group; cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group; Alkenyl groups such as vinyl group, 1-propenyl group, allyl group, 1-butenyl group, 2-butenyl group, pentenyl group, hexenyl group, cyclohexenyl group; ethynyl group, 1-propynyl group, 2-propyl
• x is 0 to 2, preferably 0 or 1.
• p is 30 to 2000, preferably p is 45 to 1900, more preferably p is 60 to 1800.
• the resulting rubber crosslinked product can have excellent fracture resistance, wet grip properties, and low heat generation properties.
• the values of R 1 to R 4 and x that are included in plurality may be the same or different. That is, when p is 2 or more, two or more structural units A are included, but the values of R 1 to R 4 and x in two or more structural units A are the same.
• R 5 is a hydrogen atom or a methyl group, preferably a hydrogen atom.
• n is 200 to 5,000, preferably 250 to 4,500, more preferably 300 to 4,000.
• the resulting rubber crosslinked product can have excellent fracture resistance, wet grip properties, and low heat generation properties.
• a plurality of R 5 's may be the same or different, but it is preferable that all R 5 's are the same.
• the ratio of structural unit A to structural unit B in the above general formula (1) is preferably 30:70 to 75:25 in weight ratio of structural unit A: structural unit B, and 35 :65 to 70:30 is more preferable, and even more preferably 40:60 to 65:35.
• the weight average molecular weight (Mw) of the copolymer represented by the general formula (1) used in the present invention is not particularly limited, but is preferably 50,000 to 1,000,000, more preferably 100,000 to 500. ,000, more preferably 150,000 to 300,000. By setting the weight average molecular weight (Mw) within the above range, the resulting rubber crosslinked product can have better fracture resistance, wet grip properties, and low heat generation properties.
• the molecular weight distribution (Mw/Mn) of the copolymer represented by general formula (1) is not particularly limited, but is preferably 1.0 to 5.0, more preferably 1.5 to 3.0. be.
• the weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw/Mn) are determined as polystyrene equivalent values by gel permeation chromatography (GPC) measurement using tetrahydrofuran as a solvent. be able to.
• the glass transition temperature (Tg) of the copolymer represented by the general formula (1) used in the present invention is preferably -80 to 10°C, more preferably -70 to 0°C, and even more preferably - The temperature is 65 to -5°C.
• the method for producing the copolymer represented by the general formula (1) used in the present invention is not particularly limited, the first ethylene having an alicyclic structure and an unsaturated bond carbon content of 10 to 40 mol%
• the ethylenically unsaturated polymer and the second ethylenically unsaturated polymer, which does not have an alicyclic structure and has an unsaturated bond carbon content of 20 to 50 mol%, are subjected to a cross-metathesis reaction in the presence of a metathesis catalyst. It can be suitably manufactured by performing the following steps.
• the unsaturated bond carbon content of the first ethylenically unsaturated polymer is preferably 10 to 38 mol%, more preferably 11 to 35 mol%
• the unsaturated bond content of the second ethylenically unsaturated polymer is preferably 10 to 38 mol%, more preferably 11 to 35 mol%.
• the carbon content is preferably 25 to 50 mol%, more preferably 30 to 50 mol%.
• the unsaturated bond carbon content refers to carbon-carbon double bonds and carbon-carbon triple bonds among the carbon atoms constituting the first ethylenically unsaturated polymer and the second ethylenically unsaturated polymer. is the proportion of carbon atoms that make up .
• the unsaturated bond carbon content does not include carbon atoms forming aromatic double bonds.
• the copolymer represented by the general formula (1) used in the present invention is obtained by combining a first ethylenically unsaturated polymer and a second ethylenically unsaturated polymer in the presence of a metathesis catalyst. It can be suitably produced by carrying out a cross metathesis reaction. According to the cross metathesis reaction, due to the action of the metathesis catalyst, the carbon-carbon double bond constituting the first ethylenically unsaturated polymer and the carbon-carbon double bond constituting the second ethylenically unsaturated polymer A copolymer represented by the general formula (1) can be obtained by carrying out an exchange reaction of carbon-carbon double bonds.
• a polymer represented by the following general formula (2) can be suitably used
• the following general A polymer represented by formula (3) can be suitably used.
• a case where a polymer represented by the following general formula (2) and a polymer represented by the following general formula (3) are used will be described as an example.
• R 1 to R 4 are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, a silicon atom, an oxygen an atom or a substituent containing a nitrogen atom, x is 0 to 2, and p' is 100 to 10,000.
• R 1 and R 2 and R 3 and R 4 are each bonded to form a ring.
• the values of R 1 to R 4 and x, which are present in plurality may be the same or different.
• R 5 is a hydrogen atom or a methyl group, and n' is 500 to 20,000. In the general formula (3), multiple R 5s are the same. (It may be different or different.)
• the polymer represented by the above general formula (2) and the polymer represented by the above general formula (3) are used, the polymer represented by the above general formula (2) is used.
• the block may have a continuous block of about 2 to 40 structural units derived from the polymer represented by the above general formula (3), and may have 2 to 40 structural units derived from the polymer represented by the above general formula (3). It may also include blocks that are somewhat continuous.
• R 1 to R 4 are each independently a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and are preferably The range and specific examples thereof are the same as those in general formula (1) above.
• x is 0 to 2, preferably 0 or 1.
• p' is 100 to 10,000, preferably 150 to 7,500, more preferably 200 to 5,000.
• the polymer represented by the above general formula (2) can be produced, for example, by ring-opening polymerization of a compound represented by the following general formula (4).
• R 1 to R 4 are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a silicon atom or an oxygen atom. Alternatively, it is a substituent containing a nitrogen atom, and its preferred range and specific examples are the same as those in the above general formula (1).
• x is 0 to 2, preferably 0 or 1.
• 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 .
• Tetradeca-3,5,7,12-tetraene also referred to as 1,4-methano-1,4,4a,9a-tetrahydro-9H-fluorene
• Tetracyclo[10.2.1.0 2 , 11 Tetracyclo[10.2.1.0 2 , 11 .
• Pentadeca-4,6,8,13-tetraene also referred to as 1,4-methano-1,4,4a,9,9a,10-hexahydroanthracene
• dicyclopentadiene methyldicyclopentadiene
• bicyclo[2.2.1]hept-2-ene unsubstituted or with a hydrocarbon substituent, such as dihydrodicyclopentadiene (tricyclo[5.2.1.0 2,6 ]dec-8-ene).
• Class
• Tetracyclo[6.2.1.1 3,6 . 0 2,7 ] Dodec-4-ene (tetracyclododecene), 9-methyltetracyclo[6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, 9-ethyltetracyclo[6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, 9-cyclohexyltetracyclo[6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, 9-cyclopentyltetracyclo[6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene, 9-methylenetetracyclo[6.2.1.1 3,6 .
• Alkoxy such as methyl 5-norbornene-2-carboxylate, ethyl 5-norbornene-2-carboxylate, methyl 2-methyl-5-norbornene-2-carboxylate, ethyl 2-methyl-5-norbornene-2-carboxylate, etc.
• Bicyclo[2.2.1]hept-2-enes having a carbonyl group Tetracyclo[6.2.1.1 3,6 . 0 2,7 ] methyl dodec-9-ene-4-carboxylate, and 4-methyltetracyclo[6.2.1.1 3,6 . 0 2,7 ] Tetracyclo[6.2.1.1 3,6 . 0 2,7 ] dodec-4-enes;
• Bicyclo[2.2 .1] Hept-2-enes Tetracyclo[6.2.1.1 3,6 . 0 2,7 ] dodec-9-ene-4-carboxylic acid, tetracyclo[6.2.1.1 3,6 . 0 2,7 ] dodec-9-ene-4,5-dicarboxylic acid, and tetracyclo[6.2.1.1 3,6 . 0 2,7 ] dodec-9-ene-4,5-dicarboxylic anhydride or other tetracyclo[6.2.1.1 3,6 . 0 2,7 ] dodec-4-enes;
• Bicyclo[2.2.1]hept-2-enes having a hydrocarbonyl group such as 5-norbornene-2-carbaldehyde; Tetracyclo[6.2.1.1 3,6 . 0 2,7 ] dodec-9-ene-4-carbaldehyde and other tetracyclo[6.2.1.1 3,6 . 0 2,7 ] dodec-4-enes;
• Bicyclo[2.2.1]hept-2-enes having an alkoxycarbonyl group and a hydroxycarbonyl group such as 3-methoxycarbonyl-5-norbornene-2-carboxylic acid;
• Bicyclos having a carbonyloxy group such as 5-norbornen-2-yl acetate, 2-methyl-5-norbornen-2-yl acetate, 5-norbornen-2-yl acrylate, and 5-norbornen-2-yl methacrylate.
• Hept-2-enes Acetic acid 9-tetracyclo[6.2.1.1 3,6 . 0 2,7 ] dodec-4-enyl, 9-tetracyclo[6.2.1.1 3,6 . 0 2,7 ] dodec-4-enyl, and 9-tetracyclo[6.2.1.1 3,6 . 0 2,7 ] dodec-4-enyl and other tetracyclo[6.2.1.1 3,6 . 0 2,7 ] dodec-4-enes;
• 5-norbornene-2-carbonitrile and bicyclo[2.2.1]hept-2 having a nitrogen atom-containing functional group such as 5-norbornene-2-carboxamide and 5-norbornene-2,3-dicarboxylic acid imide.
• -enes Tetracyclo[6.2.1.1 3,6 . 0 2,7 ] dodec-9-ene-4-carbonitrile, tetracyclo[6.2.1.1 3,6 . 0 2,7 ] dodec-9-ene-4-carboxamide, and tetracyclo[6.2.1.1 3,6 . 0 2,7 ] dodec-9-ene-4,5-dicarboxylic acid imide and other tetracyclo[6.2.1.1 3,6 . 0 2,7 ] dodec-4-enes;
• Bicyclo[2.2.1]hept-2-enes having a halogen atom such as 5-chloro-2-norbornene; 9-chlorotetracyclo[6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene and other tetracyclo[6.2.1.1 3,6 . 0 2,7 ] dodec-4-enes;
• Bicyclo[2.2.1]hept-2-enes having a functional group containing a silicon atom such as 5-trimethoxy-2-norbornene and 5-triethoxy-2-norbornene; 4-trimethoxysilyltetracyclo[6.2.1.1 3,6 . 0 2,7 ] dodec-9-ene, 4-triethoxysilyltetracyclo[6.2.1.1 3,6 . 0 2,7 ] dodec-9-ene and other tetracyclo[6.2.1.1 3,6 . 0 2,7 ] dodec-4-enes;
• Examples of the compound represented by the above general formula (4) include bicyclo[2.2.1]hept-2-enes which are unsubstituted or have a hydrocarbon substituent, and tetracyclo[6 .2.1.1 3,6 . 0 2,7 ] dodec-4-enes are preferred, especially 2-norbornene, dicyclopentadiene, tetracyclo[6.2.1.1 3,6 . 0 2,7 ] dodec-4-ene (tetracyclododecene), tetracyclo[9.2.1.0 2,10 . 0 3,8 ]tetradeca-3,5,7,12-tetraene (1,4-methano-1,4,4a,9a-tetrahydro-9H-fluorene, MTHF) is more preferred.
• the compound represented by the above general formula (4) may be used alone or in combination of two or more. That is, it may be a copolymer of two or more types of monomers.
• the method of ring-opening polymerization of the compound represented by the above general formula (4) is not particularly limited, but for example, the compound represented by the above general formula (4) is subjected to ring-opening polymerization in a solvent in the presence of a ring-opening polymerization catalyst.
• a method of ring-opening polymerization is mentioned.
• the ring-opening polymerization catalyst include a combination of a group 6 transition metal compound of the periodic table as a main catalyst and an organometallic compound as a co-catalyst, and a metathesis catalyst such as a ruthenium carbene complex.
• an olefin compound or diolefin compound may be added to the polymerization reaction system as a molecular weight regulator.
• the weight average molecular weight (Mw) of the polymer represented by the above general formula (2) is not particularly limited, but is preferably 50,000 to 1,000,000, more preferably 50,000 to 750,000, and Preferably it is 100,000 to 500,000. Further, the molecular weight distribution (Mw/Mn) of the polymer represented by the above general formula (2) is not particularly limited, but is preferably 1.0 to 5.0, more preferably 1.5 to 3.0. be.
• the polymer represented by the above general formula (3) is not particularly limited, but includes polybutadiene, polyisoprene, a copolymer of butadiene and isoprene, and the like.
• R 5 is a hydrogen atom or a methyl group
• n' is 500 to 20,000.
• n' is preferably 750 to 20,000, more preferably 1,000 to 15,000.
• the amount of vinyl bonds is not particularly limited.
• polybutadiene, polyisoprene, and a copolymer of butadiene and isoprene for example, anionically polymerizable organic active metals such as organic alkali metal compounds, organic alkaline earth metal compounds, and organic lanthanide series rare earth metal compounds are used. Those obtained by polymerization can be used.
• synthetic polyisoprene natural rubber can also be used as the polyisoprene.
• the weight average molecular weight (Mw) of the polymer represented by the above general formula (3) is not particularly limited, but is preferably 50,000 to 1,000,000, more preferably 50,000 to 750,000, and Preferably it is 100,000 to 500,000. Further, the molecular weight distribution (Mw/Mn) of the polymer represented by the above general formula (3) is not particularly limited, but is preferably 1.0 to 5.0, more preferably 1.5 to 3.0. be.
• a copolymer represented by the general formula (1) used in the present invention is produced by subjecting them to a cross-metathesis reaction in the presence of a metathesis catalyst.
• the polymer represented by the above general formula (2) (first ethylenically unsaturated polymer) and the polymer represented by the above general formula (3) (second ethylenically unsaturated polymer) may be used in combination of two or more.
• the polymer represented by the above general formula (2) (first ethylenically unsaturated polymer) and the polymer represented by the above general formula (3) (second ethylenically unsaturated polymer) The amount used is not particularly limited and may be selected depending on the ratio of p and n in the above general formula (1).
• a complex formed by bonding a plurality of ions, atoms, polyatomic ions, and/or compounds with a transition metal atom as a central atom is used.
• the transition metal atoms atoms of groups 5, 6, and 8 of the periodic table (long periodic table, the same applies hereinafter) are used.
• Such transition metal atoms are not particularly limited, but examples of Group 5 atoms include vanadium, niobium, and tantalum; examples of Group 6 atoms include molybdenum and tungsten; and examples of Group 6 atoms include molybdenum and tungsten; Examples of atoms in the group include ruthenium and osmium.
• complexes of molybdenum and tungsten in group 6, and ruthenium and osmium in group 8 are particularly preferable.
• complex catalysts of molybdenum and tungsten, and carbene complexes of molybdenum, tungsten, and ruthenium are particularly preferable.
• Ruthenium carbene complexes are preferable because they are relatively stable against oxygen and moisture in the air, are less likely to be deactivated, and have excellent catalytic activity.
• examples of complex catalysts containing transition metals in Group 6 of the periodic table include tungsten hexachloride, tungsten oxytetrachloride, tungsten (ethylimide) (tetrachloride) (diethyl ether), and tungsten (ethylimide) (tetrachloride).
• the complex catalyst containing a transition metal from Group 6 of the periodic table is used as a metathesis catalyst. It is preferable to use it in combination with a catalyst other than the complex catalyst.
• organometallic compounds include known organometallic compounds.
• the organometallic compound is preferably an organometallic compound belonging to Groups 1, 2, 12, 13 or 14 of the periodic table, which has a hydrocarbon group having 1 to 20 carbon atoms, and includes organolithium compounds, organomagnesium compounds, and organic Zinc compounds, organoaluminum compounds, and organotin compounds are more preferred, and organolithium compounds and organoaluminum compounds are particularly preferred.
• Examples of the organic lithium compound include n-butyllithium, methyllithium, phenyllithium, neopentyllithium, neophyllithium, and the like.
• Examples of the organic magnesium compound include butylethylmagnesium, butyloctylmagnesium, dihexylmagnesium, ethylmagnesium chloride, n-butylmagnesium chloride, allylmagnesium bromide, neopentylmagnesium chloride, neophyllmagnesium chloride, and the like.
• Examples of organic zinc compounds include dimethylzinc, diethylzinc, and diphenylzinc.
• organoaluminum compound examples include trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, diethylaluminum ethoxide, ethylaluminum dichloride, ethylaluminum diethoxide, and the like.
• organic tin compound examples include tetramethyltin, tetra(n-butyl)tin, and tetraphenyltin.
• catalysts may be used alone or in combination of two or more.
• a complex catalyst containing a transition metal of Group 6 of the periodic table for example, a compound represented by the following general formula (5) can be mentioned.
• M represents a molybdenum atom or a tungsten atom.
• R 6 and R 7 each independently represent a hydrogen atom; a carbon number of 1 to 1, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, etc.; 12 alkyl group; cycloalkyl group having 3 to 20 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group; or aryl group having 6 to 20 carbon atoms which may have a substituent; Examples of the aryl group of the aryl group which may have a substituent include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, and the like.
• Substituents for aryl groups include alkyl groups having 1 to 12 carbon atoms such as methyl and ethyl groups; halogen atoms such as fluorine, chlorine and bromine; methoxy, ethoxy and isopropoxy groups.
• Alkoxy group having 1 to 12 carbon atoms haloalkyl group having 1 to 12 carbon atoms such as trifluoromethyl group; haloalkoxy group having 1 to 12 carbon atoms such as trifluoromethoxy group; phenyl group, 4-methylphenyl group, 2 , 4-dimethylphenyl group, 2-chlorophenyl group, 3-methoxyphenyl group, and an aryl group having 6 to 12 carbon atoms, which may have a substituent.
• L 1 is an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms which may have a substituent, and a cycloalkyl group having 3 to 20 carbon atoms which may have a substituent.
• the alkyl group having 1 to 12 carbon atoms contained in the nitrogen atom and oxygen atom of L 1 may be linear, branched, or cyclic. Specific examples thereof include methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, pentyl group, hexyl group, and the like.
• Examples of the cycloalkyl group having 3 to 20 carbon atoms in the nitrogen atom and oxygen atom of L 1 include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, and an adamantyl group.
• examples of the aryl group having 6 to 12 carbon atoms contained in the nitrogen atom and oxygen atom of L 1 include phenyl group, 1-naphthyl group, and 2-naphthyl group.
• the substituents that the cycloalkyl group having 3 to 20 carbon atoms and the aryl group having 6 to 12 carbon atoms that the nitrogen atom and oxygen atom of L 1 can have are not particularly limited.
• alkyl groups having 1 to 12 carbon atoms such as methyl group and ethyl group; halogen atoms such as fluorine atom, chlorine atom, and bromine atom; alkoxy groups having 1 to 12 carbon atoms such as methoxy group, ethoxy group, isopropoxy group, etc.
• Haloalkyl group having 1 to 12 carbon atoms such as trifluoromethyl group
• Haloalkoxy group having 1 to 12 carbon atoms such as trifluoromethoxy group
• Amino group Monosubstituted amino group such as methylamino group; Disubstituted such as dimethylamino group Amino group; Imino group, etc. are mentioned.
• L 2 and L 3 are a conjugated heterocyclic group having at least one nitrogen atom and having 5 to 15 ring members and optionally having a substituent, or consisting of OR 8 is an alkoxy group, and R 8 is a group selected from an alkyl group having 1 to 12 carbon atoms which may have a substituent, and an aryl group having 6 to 30 carbon atoms which may have a substituent. It is.
• Examples of the conjugated heterocyclic group for L 2 and L 3 include a 5-membered conjugated heterocyclic group such as a pyrrolyl group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, and a thiazolyl group; a pyridyl group, a pyridazinyl group, a pyrimidinyl group, a pyrazinyl group, and a triazinyl group.
• Six-membered ring conjugated heterocyclic groups such as groups; condensed ring conjugated heterocyclic groups such as quinazolinyl group, phthalazinyl group, pyrrolopyridyl group; and the like.
• the substituents that the conjugated heterocyclic group may have are not particularly limited.
• alkyl groups having 1 to 12 carbon atoms such as methyl group and ethyl group
• halogen atoms such as fluorine atom, chlorine atom, and bromine atom
• alkoxy groups having 1 to 12 carbon atoms such as methoxy group, ethoxy group, isopropoxy group, etc.
• Haloalkyl group having 1 to 12 carbon atoms such as trifluoromethyl group
• Haloalkoxy group having 1 to 12 carbon atoms such as trifluoromethoxy group
• Amino group Monosubstituted amino group such as methylamino group; Disubstituted such as dimethylamino group Amino group; Imino group, etc. are mentioned.
• alkyl group having 1 to 12 carbon atoms in the alkyl group having 1 to 12 carbon atoms which may have a substituent in R 8 include methyl group, ethyl group, propyl group, isopropyl group, butyl group, t- Examples include butyl group and pentyl group. Further, when both L 2 and L 3 consist of O--R 8 , the alkyls of R 8 may be bonded to each other.
• the substituents that the alkyl group having 1 to 12 carbon atoms in R 8 may have are not particularly limited.
• halogen atoms such as fluorine atoms, chlorine atoms, and bromine atoms
• alkoxy groups having 1 to 12 carbon atoms such as methoxy, ethoxy, and isopropoxy groups
• haloalkyl groups having 1 to 12 carbon atoms such as trifluoromethyl
• Haloalkoxy group having 1 to 12 carbon atoms such as trifluoromethoxy group
• having a substituent such as phenyl group, 4-methylphenyl group, 2,4-dimethylphenyl group, 2-chlorophenyl group, 3-methoxyphenyl group, etc.
• Examples thereof include an aryl group having 6 to 12 carbon atoms which may be substituted; an amino group; a monosubstituted amino group such as a methylamino group; a disubstituted amino group such as a dimethylamino group; and an imino group.
• R 8 examples include 1,1,1,3,3,3-hexafluoro-2-propoxy group, 2-methyl-2-propoxy group, 1,1,1-trifluoro-2-methyl -2-propoxy group, 1,1,1-trifluoro-2-trifluoromethyl-2-propoxy group, 2-trifluoromethyl-2-phenyl-1,1,1-trifluoroethoxy group. I can do it.
• aryl group having 6 to 30 carbon atoms which may have a substituent examples include 2,6-bis(2,4,6-trimethylphenyl)phenoxy group, 2,6-bis(2,4 , 6-triisopropylphenyl) phenoxy group, 2,4,6-trimethylphenoxy group, 2,3,5,6-tetraphenolphenoxy group, and the like.
• An example of a case where the alkyl groups of R 8 are bonded to each other is 3,3'-di(t-butyl)-5,5',6,6'-tetramethyl-2,2'-biphenoxy group.
• L 4 is a neutral conjugated heterocyclic ligand having at least one nitrogen atom, ie, a conjugated heterocyclic group having 12 to 24 ring members.
• neutral conjugated heterocyclic ligands having a nitrogen atom include pyridine, 2-methylpyridine, 2,4-lutidine, 2,6-lutidine, 2,2'-bipyridine, 5, 5'-dimethyl-2,2'-bipyridyl, 4,4'-dimethyl-2,2'-bipyridyl, 4,4'-dibromo-2,2'-bipyridyl, 2,2'-biquinoline, 1,10 -Phenanthroline and terpyridine are included. When it has multiple nitrogen atoms, it can be a bidentate rather than a monodentate ligand.
• conjugated heterocyclic group of L 4 may have a substituent.
• substituents include the same substituents as those listed as the substituents that the conjugated heterocyclic group L2 may have.
• Specific examples of the compound represented by the general formula (5) include bis(1,1,1,3,3,3-hexafluoro-2-propoxy)neophylidene tungsten(VI)(2,6-dimethyl (phenylimide), bis(1,1,1,3,3,3-hexafluoro-2-propoxy)neophylidenemolybdenum(VI) (2,6-dimethylphenylimide), bis(1,1,1, 3,3,3-hexafluoro-2-propoxy) neophylidene tungsten (VI) (2,6-diisopropylphenylimide), (2,3,5,6-tetraphenylphenoxy)2,6-dimethylphenylimide Tungsten (VI) (2,5-dimethylpyrrolid) (neophylidene), ⁇ 3,3'-di(t-butyl)-5,5',6,6'-tetramethyl-2,2'-biphenoxy ⁇ Neophylidene molyb
• ruthenium carbene complex a complex compound represented by the following general formula (6) or general formula (7) is preferable.
• R 9 and R 10 are each independently a hydrogen atom; a halogen atom; or a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom A hydrocarbon group having 1 to 20 carbon atoms that may contain.
• X 1 and X 2 are each independently any anionic ligand
• L 5 and L 6 are each independently a heteroatom-containing carbene compound or a neutral electron donating compound.
• R 9 , R 10 , X 1 , X 2 , L 5 and L 6 may be combined in any combination, and may be bonded to each other to form a multidentate chelating ligand.
• heteroatom refers to atoms belonging to Groups 15 and 16 of the periodic table, and specifically includes N, O, P, S, As, and Se atoms. Among these, from the viewpoint of obtaining a stable carbene compound, N, O, P, and S atoms are preferred, and N atom is particularly preferred.
• the hetero atom-containing carbene compound is preferably one in which hetero atoms are bonded adjacent to both sides of a carbene carbon, and more preferably one in which a hetero ring containing a carbene carbon atom and hetero atoms on both sides is formed.
• the hetero atom adjacent to the carbene carbon has a bulky substituent.
• a compound represented by the following general formula (8) or general formula (9) is preferable.
• R 13 to R 16 are each independently a hydrogen atom; a halogen atom; or a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom A hydrocarbon group having 1 to 20 carbon atoms that may contain. Furthermore, R 13 to R 16 may be combined in any combination, and may be bonded to each other to form a multidentate chelating ligand.
• the anionic ligands X 1 and X 2 are ligands that have a negative charge when separated from the central metal, such as F, Cl , Br, I, and other halogen atoms; diketonate groups, substituted cyclopentadienyl groups, alkoxy groups, aryloxy groups, carboxyl groups, and the like.
• halogen atoms are preferred, and chlorine atoms are more preferred.
• the neutral electron-donating compound may be any ligand that has a neutral charge when separated from the central metal, such as carbonyl, amines, pyridines, ethers, nitriles, etc.
• Examples include esters, phosphines, thioethers, aromatic compounds, olefins, isocyanides, and thiocyanates.
• phosphines, ethers and pyridines are preferred, and trialkylphosphines are more preferred.
• complex compounds represented by the above general formulas (6) and (7) include benzylidene (1,3-dimesitylimidazolidin-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, (1 , 3-dimesitylimidazolidin-2-ylidene) (3-methyl-2-buten-1-ylidene) (tricyclopentylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityl-2,3-dihydrobenzimidazole- 2-ylidene)(tricyclohexylphosphine)ruthenium dichloride, tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene][3-methyl-2 Ruthenium complex compounds in which L 5 and L 6 are a hetero atom-containing carbene compound and a neutral electron
• Ruthenium compounds such as benzylidene bis( 1,3 - dicyclohexylimidazolidin-2-ylidene) ruthenium dichloride, benzylidene bis(1,3-diisopropyl-4-imidazolin-2-ylidene) ruthenium dichloride, etc.
• Examples include ruthenium complex compounds, both of which are heteroatom-containing carbene compounds.
• specific examples of the compounds represented by the above general formulas (8) and (9) include 1,3-dimesitylimidazolidin-2-ylidene, 1,3-dimesityl-4-imidazoline-2 -ylidene, 1,3-di(1-phenylethyl)-4-imidazolin-2-ylidene, 1,3-dimesityl-2,3-dihydrobenzimidazol-2-ylidene, and the like.
• 1,3,4-triphenyl-2,3,4,5-tetrahydro-1H-1,2,4- Hetero atom-containing carbene complex compounds such as triazol-5-ylidene and 1,3,4-triphenyl-4,5-dihydro-1H-1,2,4-triazol-5-ylidene can also be used.
• the metathesis catalyst can be used alone or in combination of two or more.
• the amount of the metathesis catalyst used is determined between the polymer represented by the above general formula (2) (first ethylenically unsaturated polymer) and the polymer represented by the above general formula (3). It is preferably 0.001 to 10 parts by weight, more preferably 0.002 to 5 parts by weight, and even more preferably 0.001 to 10 parts by weight, based on a total of 100 parts by weight of the combined material (second ethylenically unsaturated polymer). 0.005 to 1 part by weight.
• the amount of the metathesis catalyst within the above range, the randomness of the structural units constituting the copolymer represented by the general formula (1) obtained by the cross metathesis reaction and the weight average molecular weight can be suitably controlled. I can do it.
• a polymer represented by the above general formula (2) (first ethylenically unsaturated polymer) and a polymer represented by the above general formula (3) are mixed in a solvent. It is preferable to proceed with the cross-metathesis reaction in a state in which the coalescence (second ethylenically unsaturated polymer) and the metathesis catalyst are dispersed or dissolved, and the cross-metathesis reaction may proceed under stirring.
• a polymer represented by the above general formula (2) (first ethylenically unsaturated polymer), a polymer represented by the above general formula (3) (second ethylenically unsaturated polymer), etc.
• aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; hexane, n-heptane, n-octane, etc., but are not particularly limited.
• aliphatic hydrocarbons such as cyclohexane, cyclopentane, and methylcyclohexane
• haloalkanes such as dichloromethane and chloroform
• aromatic halogens such as chlorobenzene and dichlorobenzene.
• the polymer represented by the above general formula (2) first ethylenically unsaturated polymer
• the polymer represented by the above general formula (3) second ethylenically unsaturated polymer
• the cross-metathesis reaction is carried out in a state where the metathesis catalyst is dispersed or dissolved
• the reaction temperature is preferably 0 to 100°C, more preferably 10 to 80°C, more preferably 20 to 70°C.
• the reaction time is preferably 1 minute to 100 hours, more preferably 10 minutes to 24 hours.
• the copolymer represented by general formula (1) can be isolated using conventional methods such as filtration, distillation, extraction, extractive distillation, and adsorption. .
• the rubber composition of the present invention is made by blending a filler with the copolymer represented by the above-mentioned general formula (1).
• the filler may be either an organic filler or an inorganic filler, but carbon materials or silica are preferred.
• the resulting crosslinked rubber product can have excellent fracture resistance, wet grip properties, and low heat build-up, as well as excellent abrasion resistance. Therefore, it can be suitably used, for example, in heavy-duty tire applications.
• carbon black is preferable, and examples of the carbon black include furnace black, acetylene black, thermal black, channel black, and graphite.
• furnace black is preferred, and specific examples thereof include SAF, ISAF, ISAF-HS, ISAF-LS, IISAF-HS, HAF, HAF-HS, HAF-LS, FEF, and the like.
• SAF SAF
• ISAF ISAF-HS
• ISAF-LS ISAF-LS
• IISAF-HS High Speed F-HS
• HAF HAF-HS
• HAF-LS HAF-LS
• FEF FEF
• the nitrogen adsorption specific surface area (N 2 SA) of carbon black is preferably 5 to 200 m 2 /g, more preferably 70 to 120 m 2 /g, and the adsorption amount of dibutyl phthalate (DBP) is preferably 5 to 200 m 2 /g.
• the amount is 300 ml/100 g, more preferably 80 to 160 ml/100 g.
• silica examples include dry process white carbon, wet process white carbon, colloidal silica, and precipitated silica disclosed in JP-A No. 62-62838.
• wet process white carbon containing hydrated silicic acid as a main component is preferred.
• a carbon-silica dual phase filler in which silica is supported on the surface of carbon black may be used. These silicas can be used alone or in combination of two or more.
• the nitrogen adsorption specific surface area of silica (measured by the BET method according to ASTM D3037-81) is preferably 50 to 400 m 2 /g, more preferably 100 to 220 m 2 /g. Further, the pH of silica is preferably less than pH 7, and more preferably from pH 5 to 6.9.
• silane coupling agent examples include vinyltriethoxysilane, ⁇ -(3,4-epoxycyclohexyl)ethyltrimethoxysilane, N-( ⁇ -aminoethyl)- ⁇ -aminopropyltrimethoxysilane, bis(3- (triethoxysilyl)propyl)tetrasulfide, bis(3-(triethoxysilyl)propyl)disulfide, and ⁇ -trimethoxysilylpropyldimethylthiocarbamyltetrasulfide described in JP-A No.
• Tetrasulfides such as ⁇ -trimethoxysilylpropylbenzothiazyl tetrasulfide can be mentioned. Among these, tetrasulfides are preferred.
• These silane coupling agents can be used alone or in combination of two or more.
• the blending amount of the silane coupling agent is preferably 0.1 to 30 parts by weight, more preferably 1 to 15 parts by weight, based on 100 parts by weight of silica.
• the content of the filler in the rubber composition of the present invention is preferably 10 to 150 parts by weight, more preferably 10 to 150 parts by weight, based on 100 parts by weight of the rubber component containing the copolymer represented by general formula (1) above. is 20 to 100 parts by weight, more preferably 40 to 85 parts by weight.
• the content of the carbon material should be 40 to 60 parts by weight with respect to 100 parts by weight of the rubber component containing the copolymer represented by the above general formula (1). is particularly preferable, and when silica is used as a filler, the content of silica is 60 to 85 parts by weight based on 100 parts by weight of the rubber component containing the copolymer represented by the above general formula (1). It is particularly preferable that there be.
• the rubber composition of the present invention may contain a rubber other than the copolymer represented by the above general formula (1) as a rubber component.
• the rubber component refers to a copolymer represented by the above-mentioned general formula (1) and a rubber other than the copolymer represented by the above-mentioned general formula (1).
• examples of rubbers other than the copolymer represented by the above-mentioned general formula (1) include natural rubber (NR), polyisoprene rubber (IR), emulsion polymerization SBR (styrene-butadiene copolymer rubber), and solution polymerization random rubber.
• SBR bound styrene 5-50% by weight, 1,2-bond content in the butadiene moiety 10-80%), high trans SBR (trans bond content in the butadiene moiety 70-95%), low cis BR (polybutadiene rubber) , high cis BR, high trans BR (trans bond content in the butadiene moiety 70-95%), ethylene-propylene-diene rubber (EPDM), styrene-isoprene copolymer rubber, butadiene-isoprene copolymer rubber, emulsion polymerized styrene-acrylonitrile -Butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubber, high vinyl SBR-low vinyl SBR block copolymer rubber, polyisoprene-SBR block copolymer rubber, polystyrene-polybutadiene-polystyrene block copolymer, acrylic rubber, epichloro
• the rubber composition of the present invention contains a crosslinking agent, a crosslinking accelerator, a crosslinking activator, a filler other than inorganic materials, an anti-aging agent, an activator, a process oil, and a plasticizer according to a conventional method.
• lubricants and other compounding agents can be added in the required amounts.
• sulfur such as powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, and highly dispersed sulfur; halogenated sulfur such as sulfur monochloride and sulfur dichloride; dicumyl peroxide, ditertiary butyl peroxide, etc.
• Organic peroxides Quinone dioximes such as p-quinone dioxime and p,p'-dibenzoylquinone dioxime; Organics such as triethylenetetramine, hexamethylene diamine carbamate, and 4,4'-methylenebis-o-chloroaniline Examples include polyvalent amine compounds; alkylphenol resins having methylol groups; and the like.
• crosslinking agents may be used alone or in combination of two or more.
• the amount of the crosslinking agent blended is preferably 0.1 to 15 parts by weight, more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the rubber component in the rubber composition.
• crosslinking accelerator examples include N-cyclohexyl-2-benzothiazolylsulfenamide, N-(tert-butyl)-2-benzothiazolylsulfenamide, and N-oxyethylene-2-benzothiazolylsulfenamide.
• Sulfenamide crosslinking accelerators such as amide, N-oxyethylene-2-benzothiazolylsulfenamide, N,N'-diisopropyl-2-benzothiazolylsulfenamide; 1,3-diphenylguanidine, 1, Guanidine-based crosslinking promoters such as 3-diorthotolylguanidine and 1-orthotolylbiguanidine; Thiourea-based crosslinking promoters such as diethylthiourea; 2-mercaptobenzothiazole, dibenzothiazyl disulfide, 2-mercaptobenzothiazole zinc salt, etc.
• thiazole-based crosslinking promoters thiazole-based crosslinking promoters
• thiuram-based crosslinking promoters such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide
• dithiocarbamate-based crosslinking promoters such as sodium dimethyldithiocarbamate and zinc diethyldithiocarbamate
• xanthate-based crosslinking promoters such as zinc acid and zinc butylxanthate.
• crosslinking accelerators may be used alone or in combination of two or more.
• the amount of the crosslinking accelerator is preferably 0.1 to 15 parts by weight, more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the rubber component in the rubber composition.
• crosslinking activator for example, higher fatty acids such as stearic acid, zinc oxide, etc. can be used.
• the amount of the crosslinking activator is selected as appropriate, but the amount of the higher fatty acid is preferably 0.05 to 15 parts by weight, more preferably 0.05 to 15 parts by weight, based on 100 parts by weight of the rubber component in the rubber composition.
• the amount of zinc oxide is preferably 0.05 to 10 parts by weight, more preferably 0.5 to 3 parts by weight, based on 100 parts by weight of the rubber component in the rubber composition. be.
• mineral oil or synthetic oil may be used.
• mineral oil aroma oil, naphthenic oil, paraffin oil, etc. are usually used.
• Other compounding agents include activators such as diethylene glycol, polyethylene glycol, and silicone oil; fillers other than inorganic materials such as calcium carbonate, talc, and clay; tackifiers such as petroleum resin and coumaron resin; and wax. .
• the rubber composition of the present invention can be obtained by kneading each component according to a conventional method. For example, after kneading the compounding ingredients excluding the crosslinking agent and the crosslinking accelerator and a rubber component such as a copolymer represented by the above general formula (1), the crosslinking agent and the crosslinking accelerator are mixed into the kneaded product. A rubber composition can be obtained.
• the kneading temperature of the compounding agents excluding the crosslinking agent and the crosslinking accelerator and the rubber component such as the copolymer represented by the above general formula (1) is preferably 20 to 200°C, more preferably 30 to 180°C.
• the kneading time is preferably 30 seconds to 30 minutes.
• the crosslinking agent and the crosslinking accelerator are usually mixed at a temperature of 100°C or lower, preferably 80°C or lower.
• the crosslinked rubber product of the present invention is obtained by crosslinking the rubber composition of the present invention described above.
• the rubber crosslinked product of the present invention can be produced by molding the rubber composition of the present invention using a molding machine corresponding to a desired shape, such as an extruder, an injection molding machine, a compressor, a roll, etc., and then heating the product. It can be manufactured by performing a crosslinking reaction and fixing the shape as a crosslinked product. In this case, the crosslinking may be performed after pre-forming or at the same time as the molding.
• the molding temperature is usually 10 to 200°C, preferably 25 to 120°C.
• the crosslinking temperature is usually 100 to 200°C, preferably 130 to 190°C
• the crosslinking time is usually 1 minute to 24 hours, preferably 2 minutes to 12 hours, particularly preferably 3 minutes to 6 hours. .
• the heating method a general method used for crosslinking rubber such as press heating, steam heating, oven heating, hot air heating, etc. may be appropriately selected.
• the rubber crosslinked product of the present invention thus obtained is obtained using the above-described rubber composition of the present invention, and therefore has excellent fracture resistance, wet grip properties, and low heat build-up. Therefore, the rubber crosslinked product of the present invention takes advantage of its excellent properties and can be used, for example, as a material for each part of the tire such as the cap tread, base tread, carcass, sidewall, and bead; hoses, belts, mats, and It can be used for various purposes such as swing rubber and other materials for various industrial products; impact resistance improvers for resins; resin film cushioning agents; shoe soles; rubber shoes; golf balls; toys; In particular, the rubber crosslinked product of the present invention has excellent fracture resistance, wet grip properties, and low heat build-up, and is therefore suitable as a tire material.
• the crosslinked rubber product of the present invention contains a carbon material as a filler constituting the rubber composition, it has excellent wear resistance in addition to fracture resistance, wet grip property, and low heat generation property. Therefore, it can be suitably used as a material for heavy-duty tires.
• Tg Glass transition temperature of each polymer> The glass transition temperature (Tg) of each polymer was measured at 10°C/min in the range of -150 to 100°C using a differential scanning calorimeter (product name "X-DSC7000", manufactured by Hitachi High-Tech Science). It was determined by measuring at elevated temperature conditions.
• a crosslinked rubber composition in the form of a sheet is produced by press crosslinking the crosslinkable rubber composition used as a sample, and the crosslinked rubber product obtained in the form of a sheet is subjected to JIS K6251:2010 in a direction parallel to the grain direction.
• a dumbbell-shaped test piece was obtained by punching out a dumbbell-shaped No. 6 shape specified by . Then, the obtained dumbbell-shaped test piece was tested at 23°C and 500 mm/min in accordance with JIS K6251:2010 using a tensile tester (product name "TENSOMETER 10K", manufactured by ALPHA TECHNOLOGIES) as a testing machine.
• a tensile test was conducted under the following conditions, and the tensile strength and elongation were measured. The higher the tensile strength, the better the fracture resistance.
• ⁇ Wet grip> A test piece was prepared by press-crosslinking a crosslinkable rubber composition as a sample at 160°C for 20 minutes. tan ⁇ was measured at 0° C. under the conditions of a dynamic strain of 0.5% and a frequency of 10 Hz. Then, the obtained measurement results are calculated using an index with the measured value of Comparative Example 1 as 100 for Examples 1 to 10, and the measured value of Comparative Example 3 as 100 for Examples 11 to 20. Calculated using an index. The larger this index is, the better the wet grip property is.
• a test piece was prepared by press-crosslinking a crosslinkable rubber composition as a sample at 160°C for 20 minutes.
• tan ⁇ was measured at 60° C. under the conditions of dynamic strain of 2.0% and 10 Hz. Then, the obtained measurement results are calculated using an index with the measured value of Comparative Example 1 as 100 for Examples 1 to 10, and the measured value of Comparative Example 3 as 100 for Examples 11 to 20. Calculated using an index. The smaller this index is, the better the low heat generation property is.
• ⁇ DIN wear test> A sample crosslinkable rubber composition was press-molded under pressure using a mold to obtain a cylindrical crosslinked rubber product with a diameter of 16 mm and a thickness of 6 mm. The obtained cylindrical rubber crosslinked product was then tested in accordance with JIS K6264-2:2005 using a DIN abrasion tester (product name "AB-6110", manufactured by Ueshima Seisakusho Co., Ltd.) as a tester. The specific wear volume was measured under the conditions of method A, additional force of 10 N, friction distance of 40 m, 23° C., and reference test piece D1. Note that the DIN abrasion test was conducted for Examples 1 to 10 and Comparative Examples 1 and 2. The smaller the specific wear volume, the better the wear resistance.
• ⁇ Polymerization example 1> Under a nitrogen atmosphere, 100 parts of 2-norbornene (NB), 567 parts of cyclohexane, and 0.065 parts of 1-hexene were added as a norbornene compound to a glass reaction vessel equipped with a stirrer. Next, 0.009 parts of dichloro-(3-phenyl-1H-inden-1-ylidene)bis(tricyclohexylphosphine)ruthenium(II) dissolved in 10 parts of toluene was added, and a polymerization reaction was carried out at room temperature for 2 hours. . After the polymerization reaction, excess vinyl ethyl ether was added to stop the polymerization.
• the obtained polymer solution was poured into a large excess of methanol containing 2,6-di-t-butyl-p-cresol (BHT), the precipitated polymer was collected, washed with methanol, and then It was vacuum dried at °C for 3 days to obtain 100 parts of ring-opened copolymer (2-A).
• the resulting ring-opened copolymer (2-A) had a number average molecular weight (Mn) of 340,000, a weight average molecular weight (Mw) of 885,000, a glass transition temperature (Tg) of 35°C, and an unsaturated bond of carbon.
• the content was 28.6 mol%. Note that the unsaturated bond carbon content was determined by 1 H-NMR.
• ⁇ Polymerization example 2> Under a nitrogen atmosphere, 100 parts of 2-norbornene (NB), 567 parts of cyclohexane, and 0.35 parts of 1-hexene were added as a norbornene compound to a glass reaction vessel equipped with a stirrer. Next, 0.009 parts of dichloro-(3-phenyl-1H-inden-1-ylidene)bis(tricyclohexylphosphine)ruthenium(II) dissolved in 10 parts of toluene was added, and a polymerization reaction was carried out at room temperature for 2 hours. . After the polymerization reaction, excess vinyl ethyl ether was added to stop the polymerization.
• the obtained polymer solution was poured into a large excess of methanol containing 2,6-di-t-butyl-p-cresol (BHT), the precipitated polymer was collected, washed with methanol, and then It was vacuum dried at °C for 3 days to obtain 100 parts of ring-opened copolymer (2-B).
• the resulting ring-opened copolymer (2-B) had a number average molecular weight (Mn) of 95,200, a weight average molecular weight (Mw) of 233,000, a glass transition temperature (Tg) of 35°C, and an unsaturated bond of carbon. The content was 28.6 mol%.
• the resulting ring-opened copolymer (2-C) had a number average molecular weight (Mn) of 125,000, a weight average molecular weight (Mw) of 268,000, a glass transition temperature (Tg) of 151°C, and an unsaturated bond of carbon. The content was 40.0 mol%.
• ⁇ Polymerization example 4 100 parts of a ring-opened copolymer (2-D) was obtained in the same manner as in Polymerization Example 3, except that 50 parts of dicyclopentadiene (DCPD) and 50 parts of 2-norbornene (NB) were used as the norbornene compounds.
• the number average molecular weight (Mn) of the obtained ring-opened copolymer (2-D) was 199,000, the weight average molecular weight (Mw) was 439,000, and the ratio of dicyclopentadiene structural unit/norbornene structural unit was 50/ 50 (weight ratio), the glass transition temperature (Tg) was 83° C., and the unsaturated bond carbon content was 33.3 mol%.
• Dodec-4-ene tetracyclododecene, TCD was used in the same manner as in Polymerization Example 3 to obtain 100 parts of ring-opened copolymer (2-E).
• the resulting ring-opened copolymer (2-E) had a number average molecular weight (Mn) of 129,000, a weight average molecular weight (Mw) of 277,000, a glass transition temperature (Tg) of 200°C, and an unsaturated bond of carbon.
• the content was 16.7 mol%.
• a ring-opened copolymer (2-F) was produced in the same manner as in Polymerization Example 3, except that 100 parts of 1,4-methano-1,4,4a,9a-tetrahydro-9H-fluorene (MTHF) was used as the norbornene compound. Got 100 copies.
• the resulting ring-opened copolymer (2-F) had a number average molecular weight (Mn) of 128,000, a weight average molecular weight (Mw) of 275,000, a glass transition temperature (Tg) of 201°C, and an unsaturated bond of carbon. The content was 14.3 mol%.
• ⁇ Polymerization example 7> Under a nitrogen atmosphere, 599 parts of 2-norbornene (NB) as a norbornene compound, 703 parts of cyclopentene (CPE) as a monocyclic olefin, 2411 parts of toluene, and 1.05 parts of 1-hexene were placed in a glass reaction vessel equipped with a stirrer under a nitrogen atmosphere. added. Next, 0.154 parts of dichloro-(3-phenyl-1H-inden-1-ylidene)bis(tricyclohexylphosphine)ruthenium(II) dissolved in 35 parts of toluene was added, and a polymerization reaction was carried out at room temperature for 3 hours. .
• ⁇ Polymerization example 8> Under a nitrogen atmosphere, 45 parts of dicyclopentadiene (DCPD) as a norbornene compound, 55 parts of cyclopentene (CPE) as a monocyclic olefin, 233 parts of toluene, and 0.5 parts of 1-hexene were placed in a glass reaction vessel equipped with a stirrer under a nitrogen atmosphere. 08 parts were added. Next, 0.011 part of dichloro-(3-phenyl-1H-inden-1-ylidene)bis(tricyclohexylphosphine)ruthenium(II) dissolved in 6 parts of toluene was added, and a polymerization reaction was carried out at room temperature for 3 hours. .
• DCPD dicyclopentadiene
• CPE cyclopentene
• 1-hexene 1-hexene
• the number average molecular weight (Mn) of the obtained ring-opened copolymer (1'-L) was 119,000, the weight average molecular weight (Mw) was 238,000, and the weight average molecular weight (Mw) and number average molecular weight (Mn) (Mw/Mn) is 2.00, the ratio of dicyclopentadiene structural unit/cyclopentene structural unit is 55/45 (weight ratio), the glass transition temperature (Tg) is -25°C, and the unsaturated bond carbon The content was 40.0 mol%.
• ⁇ Polymerization example 9> Into an autoclave with an internal volume of 2000 ml and equipped with a stirrer, 2.0 x 10 -5 mol of cobalt octenoate was charged, and 162.3 g of 1,3-butadiene, 900 ml of benzene, and 0.18 g of 1,5-cyclooctadiene were added. Then 8.0 ⁇ 10 ⁇ 4 moles of water were added. Further, while stirring, 10 ml of a benzene solution containing 2.7 ⁇ 10 ⁇ 3 mol of diethylaluminium chloride was added, and polymerization was carried out at 50° C. for 2 hours.
• the polymerization reaction was stopped by adding 20 ml of methanol, and the obtained polymer solution was poured into 5000 ml of methanol, and the precipitated polymer was collected by filtration and dried. Furthermore, the obtained polymer was dissolved in 1500 ml of toluene, the polymer solution was poured into 5000 ml of methanol, and the precipitated polymer was collected by filtration and dried to obtain polybutadiene rubber (3-A). The polymer yield was 85%.
• the vinyl bond content in the obtained polybutadiene rubber (3-A) was 0.2 mol%, and the unsaturated bond carbon content was 50.0 mol%.
• the mixture was vacuum dried for 3 days to obtain 98 parts of polybutadiene rubber (3-C).
• the obtained polybutadiene rubber (3-C) had a number average molecular weight (Mn) of 132,000, a weight average molecular weight (Mw) of 278,000, a glass transition temperature (Tg) of -90°C, and a vinyl bond content of The unsaturated bond carbon content was 0.7 mol% and 50.0 mol%.
• cross-metathesis reaction was carried out at room temperature for 24 hours while stirring. After the reaction, the reaction was stopped by adding excess vinyl ethyl ether. Then, the obtained cross-metathesis reaction solution was poured into a large excess of methanol containing 2,6-di-t-butyl-p-cresol (BHT), and the precipitated copolymer was collected and washed with methanol. The mixture was vacuum dried at 50° C. for 3 days to obtain 164 parts of cross metathesis copolymer (1-A).
• BHT 2,6-di-t-butyl-p-cresol
• a crosslinkable rubber composition in the form of a sheet was obtained by kneading 1 part of crosslinking accelerator (manufactured by Co., Ltd.). Then, each of the above-mentioned measurements was performed using the obtained crosslinkable rubber composition. The results are shown in Table 1.
• a crosslinkable rubber composition was prepared in the same manner as in Example 1, except that 100 parts of the cross-metathesis copolymer (1-C) obtained above was used, and measurements were carried out in the same manner. The results are shown in Table 1.
• Example 4 (Synthesis of cross metathesis copolymer (1-D)) Example 3 except that 96 parts of the ring-opening copolymer (2-C) polymerized in Polymerization Example 3 was replaced with 96 parts of the ring-opening copolymer (2-D) polymerized in Polymerization Example 4. In the same manner, 152 parts of cross metathesis copolymer (1-D) was obtained.
• the obtained cross metathesis copolymer (1-D) had a number average molecular weight (Mn) of 121,000, a weight average molecular weight (Mw) of 244,000, and a 2-norbornene structural unit/dicyclopentadiene structural unit/butadiene structure.
• the unit ratio was 27/27/44 (weight ratio), and the glass transition temperature (Tg) was -23°C.
• Example 5 (Synthesis of cross metathesis copolymer (1-E)) Example 3 except that 96 parts of the ring-opening copolymer (2-C) polymerized in Polymerization Example 3 was replaced with 96 parts of the ring-opening copolymer (2-E) polymerized in Polymerization Example 5. In the same manner, 147 parts of cross metathesis copolymer (1-E) was obtained.
• the obtained cross-metathesis copolymer (1-E) had a number average molecular weight (Mn) of 119,000, a weight average molecular weight (Mw) of 241,000, and a ratio of tetracyclododecene structural units/butadiene structural units to 44.
• a crosslinkable rubber composition was prepared in the same manner as in Example 1, except that 100 parts of the cross-metathesis copolymer (1-E) obtained above was used, and measurements were carried out in the same manner. The results are shown in Table 1.
• Example 6 (Synthesis of cross metathesis copolymer (1-F)) Example 3 except that 96 parts of the ring-opened copolymer (2-F) polymerized in Polymerization Example 6 was used instead of 96 parts of the ring-opened copolymer (2-C) polymerized in Polymerization Example 3. In the same manner, 147 parts of cross metathesis copolymer (1-F) was obtained.
• the number average molecular weight (Mn) of the obtained cross metathesis copolymer (1-F) was 117,000, the weight average molecular weight (Mw) was 239,000, and 1,4-methanol-1,4,4a,9a-
• the ratio of tetrahydro-9H-fluorene (MTHF) structural unit/butadiene structural unit was 43/57 (weight ratio), and the glass transition temperature (Tg) was -24°C.
• a crosslinkable rubber composition was prepared in the same manner as in Example 1, except that 100 parts of the cross-metathesis copolymer (1-F) obtained above was used, and measurements were carried out in the same manner. The results are shown in Table 1.
• a crosslinkable rubber composition was prepared in the same manner as in Example 1, except that 100 parts of the cross-metathesis copolymer (1-G) obtained above was used, and measurements were carried out in the same manner. The results are shown in Table 1.
• Example 8> (Synthesis of cross metathesis copolymer (1-H)) A cross-metathesis copolymer (1 -H) 147 parts were obtained.
• the obtained cross-metathesis copolymer (1-H) had a number average molecular weight (Mn) of 130,000, a weight average molecular weight (Mw) of 242,000, and a ratio of 2-norbornene structural units/butadiene structural units of 61/ 39 (weight ratio), and the glass transition temperature (Tg) was -25°C.
• a crosslinkable rubber composition was prepared in the same manner as in Example 1, except that 100 parts of the cross-metathesis copolymer (1-H) obtained above was used, and measurements were carried out in the same manner. The results are shown in Table 1.
• Example 10 Synthesis of cross metathesis copolymer (1-J)
• the procedure was the same as in Example 1, except that the amount of ring-opening copolymer (2-A) polymerized in Polymerization Example 1 was changed to 96 parts, and the amount of polybutadiene rubber (3-A) was changed to 114 parts. Thus, 165 parts of cross metathesis copolymer (1-J) was obtained.
• a crosslinkable rubber composition was prepared in the same manner as in Example 1, except that 100 parts of the cross-metathesis copolymer (1-J) obtained above was used, and measurements were carried out in the same manner. The results are shown in Table 1.
• Example 1 The same procedure as in Example 1 was carried out, except that 100 parts of the ring-opened copolymer (1'-K) obtained in Polymerization Example 7 was used instead of 100 parts of the cross-metathesis copolymer (1-A). A crosslinkable rubber composition was prepared and measured in the same manner. The results are shown in Table 1.
• Example 2 The same procedure as in Example 1 was carried out, except that 100 parts of the ring-opened copolymer (1'-L) obtained in Polymerization Example 8 was used instead of 100 parts of the cross-metathesis copolymer (1-A). A crosslinkable rubber composition was prepared and measured in the same manner. The results are shown in Table 1.
• the resulting rubber crosslinked product has high tensile strength and fracture resistance. Furthermore, since it used a carbon material as a filler, it also had excellent abrasion resistance (Examples 1 to 3). 10). On the other hand, when a ring-opened copolymer of a norbornene compound and cyclopentene is used instead of the copolymer represented by the above general formula (1), the resulting rubber crosslinked product has low tensile strength, The fracture resistance was insufficient, and the wet grip properties and low heat generation properties were also insufficient (Comparative Examples 1 and 2).
• Example 11 In a Banbury mixer, 100 parts of the cross metathesis copolymer (1-A) obtained in Example 1, silica (trade name "Zeosil 1165MP", manufactured by Rhodia, nitrogen adsorption specific surface area (BET method): 163 m 2 / g) 50 parts, and 10 parts of process oil (trade name "Aromax T-DAE", manufactured by Nippon Oil Co., Ltd.), silane coupling agent (bis(3-(triethoxysilyl)propyl)tetrasulfide, trade name 6.0 parts of "Si69” (manufactured by Degussa) were added and kneaded for 1.5 minutes at a starting temperature of 110°C.
• silica trade name "Zeosil 1165MP", manufactured by Rhodia, nitrogen adsorption specific surface area (BET method): 163 m 2 / g) 50 parts
• process oil trade name "Aromax T-DAE”
• silane coupling agent
• silica trade name "Zeosil 1165MP", manufactured by Rhodia
• 3 parts of zinc oxide zinc white No. 1
• stearic acid trade name "SA-300", manufactured by Asahi Denka Kogyo Co., Ltd.
• anti-aging agent N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine, trade name "Nocrac 6C", manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.
• the temperature of the rubber composition at the end of kneading was 150°C. After this rubber composition was cooled to room temperature, it was kneaded again in the Banbury mixer for 3 minutes, and then the rubber composition was discharged from the Banbury mixer. Next, the obtained rubber composition was mixed with 1.5 parts of sulfur and a crosslinking accelerator (Nt-butyl-2-benzothiazolesulfenamide (trade name "Noxela NS", Ouchi Co., Ltd.) in an open roll at 50°C.
• a crosslinking accelerator Nt-butyl-2-benzothiazolesulfenamide (trade name "Noxela NS", Ouchi Co., Ltd.)
• Example 12 to 20 Except that in place of 100 parts of the cross metathesis copolymer (1-A), 100 parts of the cross metathesis copolymers (1-B) to (1-J) synthesized in Examples 2 to 10, respectively, were used.
• a crosslinkable rubber composition was prepared in the same manner as in Example 1 and measured in the same manner. The results are shown in Table 2.

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