JP2007270158A - Ethylene oxide/propylene oxide/unsaturated epoxide terpolymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new ethylene oxide/propylene oxide/unsaturated epoxide terpolymer which is useful as a raw material for a rubber composition with the excellent characteristics. <P>SOLUTION: The ethylene oxide/propylene oxide/unsaturated epoxide terpolymer comprises 50-98.9% by weight of ethylene oxide, 1-35% by weight of propylene oxide and 0.1-15% by weight of an unsaturated epoxide, and has Mooney viscosity (ML<SB>1+4</SB>, 100°C) of 70-150. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an ethylene oxide / propylene oxide / unsaturated epoxide terpolymer which is a novel polyether polymer useful as a raw material of a rubber composition. The rubber composition using the ethylene oxide / propylene oxide / unsaturated epoxide terpolymer of the present invention has excellent heat resistance, tensile strength and processability. Moreover, since the rubber composition using the ethylene oxide / propylene oxide / unsaturated epoxide terpolymer of the present invention has low heat generation, it is suitable as a rubber material for automobile tires having low rolling resistance.

  In recent years, with the emphasis on resource saving and environmental measures, the demand for lower fuel consumption of automobiles has become stricter, and automobile tires can contribute to lower fuel consumption by reducing rolling resistance. It has been demanded. In order to reduce the rolling resistance of a tire, it is generally effective to use a rubber material that can provide a vulcanized rubber having low heat generation.

  Generally, a rubber composition in which carbon black is blended with diene rubber such as natural rubber (NR), polybutadiene (BR), polyisoprene (IR), styrene-butadiene copolymer rubber (SBR) as a rubber material for tires. Is widely used. However, a rubber composition in which carbon black is blended with a diene rubber does not have sufficient heat resistance.

  Therefore, conventionally, in order to improve the heat resistance, it has been proposed to use, as a tire rubber material, a rubber composition in which silica is blended instead of carbon black as a reinforcing agent in a diene rubber. However, the silica-containing rubber composition has problems such as insufficient heat resistance due to poor processability compared to the carbon black-containing rubber composition, and insufficient tensile strength. . One of the causes is considered to be that the affinity of silica with diene rubber is smaller than that of carbon black, so that the processability is poor and a sufficient reinforcing effect cannot be exhibited.

  Conventionally, a method of using a silane coupling agent has been proposed in order to increase the affinity between silica and diene rubber (Patent Document 1, Patent Document 2). However, the effect of improving heat resistance, tensile strength, and workability is not yet sufficient only by using a silane coupling agent.

  In addition, in order to increase the affinity between silica and diene rubber, it has been studied to use a diene rubber into which a substituent having a high affinity with silica is introduced. For example, as a diene rubber by an emulsion polymerization method, a diene rubber having a tertiary amino group introduced has been proposed (Patent Document 3). In the diene rubber by the anionic polymerization method, the diene rubber introduced with a substituent having a polar group such as an alkylsilyl group (Patent Document 4), a halogenated silyl group (Patent Document 5), a substituted amino group (Patent Document 6) Has been proposed. However, the diene rubber introduced with a substituent having these polar groups has disadvantages that it is inferior in processability when mixed with silica, and properties such as heat resistance and tensile strength are not sufficiently improved. .

  On the other hand, rubber-like or resin-like polymers are known for polyether polymers. As a rubber composition mainly composed of polyether polymer rubber, for example, it is excellent in paper feeding performance consisting of 70 parts by weight of epichlorohydrin-allyl glycidyl ether copolymer rubber and 30 parts by weight of low nitrile rubber and useful for a platen roll. A rubber composition (Patent Document 7), a rubber composition (Patent Document 8) excellent in chargeability composed of 50 to 70% by weight of epichlorohydrin rubber and 50 to 30% by weight of butadiene rubber, and suitable for a charging roller, epihalohydrin rubber and silica A conductive rubber composition (Patent Document 9), a rubber composition (Patent Document 10) excellent in anti-oxidation resistance composed of an epichlorohydrin rubber and hydrous silicic acid, and suitable for hoses, an epichlorohydrin-propylene oxide copolymer rubber, and Rubber composition excellent in oil resistance, ozone resistance and cold resistance composed of hydrous silicic acid (Patent Document 1) ) And the like have been reported. Polyether polymers useful as resin modifiers include, for example, copolymers of ethylene oxide and epichlorohydrin (Patent Document 12) that improve the negative electrode radiation of polyolefin and other resins, and plastics such as ABS resins. An epihalohydrin copolymer rubber (Patent Document 13) that improves the antistatic property of the material has been reported. However, conventionally, it has not been known that these polyether polymers have an excellent modifying effect on rubber compositions of diene rubber and silica.

JP-A-3-252431 JP-A-3-252433 Japanese Patent Laid-Open No. 1-1101344 JP-A-1-188501 Japanese Patent Laid-Open No. 5-230286 Japanese Unexamined Patent Publication No. 64-22940 Japanese Patent Laid-Open No. 1-261436 JP 7-164571 A JP-A-62-112653 Japanese Examined Patent Publication No. 4-71946 Japanese Patent Publication No. 5-62147 Japanese Patent Laid-Open No. 3-52986 Japanese Patent Publication No. 7-84564

  An object of the present invention is to provide a rubber composition excellent in exothermic resistance (low exothermic property) as an index of rolling resistance when silica is blended, and excellent in tensile strength and workability, and a diene rubber and a reinforcing agent. In order to provide a rubber composition having excellent heat resistance, tensile strength and processability, it is useful as a raw material for a rubber composition having such excellent characteristics. The object is to provide a propylene oxide / unsaturated epoxide terpolymer.

  As a result of intensive studies in order to overcome the problems of the prior art, the inventors have excellent processability with silica by blending a specific amount of a polyether polymer with a diene rubber, Moreover, it has been found that a rubber composition excellent in heat resistance and tensile strength can be obtained.

  The polyether polymer is preferably a copolymer of two or more alkylene oxides or a copolymer of alkylene oxide and unsaturated epoxide. The copolymer of alkylene oxide and unsaturated epoxide is preferably a copolymer of two or more types of alkylene oxide and unsaturated epoxide. Among them, ethylene oxide / propylene oxide / unsaturated epoxide terpolymer is more preferable. Although preferred, this terpolymer is a novel polymer.

Thus, according to the present invention, it is composed of 50 to 98.9% by weight of ethylene oxide, 1 to 35% by weight of propylene oxide and 0.1 to 15% by weight of unsaturated epoxide, and has a Mooney viscosity (ML _{1 + 4} , 100 ° C.) of 70. An ethylene oxide / propylene oxide / unsaturated epoxide terpolymer of .about.150 is provided.

  Embodiments of the rubber composition using the ethylene oxide / propylene oxide / unsaturated epoxide terpolymer of the present invention as a raw material include the following modes.

1. A terpolymer of 50 to 98.9% by weight of ethylene oxide, 1 to 35% by weight of propylene oxide and 0.1 to 15% by weight of unsaturated epoxide with respect to 100 parts by weight of diene rubber (i), A rubber composition containing 0.1 to 25 parts by weight of a polyether polymer (ii) having a Mooney viscosity (ML _{1 + 4} , 100 ° C.) of 10 to 200, and 10 to 200 parts by weight of silica.

  If the ethylene oxide / propylene oxide / unsaturated epoxide terpolymer of the present invention is used as a raw material, it was regarded as a defect without impairing the good rolling resistance (heat generation resistance) that is characteristic of the silica-containing rubber material. A rubber composition having greatly improved tensile strength and processability is provided. In addition, this rubber composition has a sufficiently excellent antistatic property.

  The diene rubber (i), polyether polymer (ii), silica, and silane coupling agent, which are the components of the rubber composition, will be described.

Diene rubber (i)
As the diene rubber (i), a homopolymer of a conjugated diene, a copolymer of two or more conjugated dienes, or a rubber form of at least one conjugated diene and a monomer copolymerizable with the conjugated diene. The copolymer is not particularly limited, but the content of the conjugated diene unit is usually 40% by weight or more, preferably 50 to 100% by weight, more preferably 55 to 100% by weight (copolymer). ) A polymer is desirable.

  In order to highly balance the characteristics of heat resistance, tensile strength and processability, it is preferable to use a diene rubber (i-A) having a polar group in the molecule. The polar group of the polar group-containing diene rubber (i-A) is not particularly limited, but a polar group containing a hetero atom is preferably used. Examples of the hetero atom include atoms belonging to the second to fourth periods of the periodic table and belonging to Group 5B or Group 6B, such as a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. Among these, a nitrogen atom and an oxygen atom are preferable. Specific examples of the polar group having a hetero atom include hydroxyl group, oxy group, carboxyl group, carbonyl group, oxycarbonyl group, sulfide group, disulfide group, sulfonyl group, sulfinyl group, thiocarbonyl group, imino group, amino group, Examples thereof include a nitrile group, an ammonium group, an imide group, an amide group, a hydrazo group, an azo group, and a diazo group. Among these, a hydroxyl group, an oxy group, a sulfide group, a disulfide group, an imino group, and an amino group are preferable, a hydroxyl group, an amino group, and an oxy group are more preferable, and a hydroxyl group and an amino group are most preferable.

  Examples of the diene rubber (i-A) containing such a polar group include (1) a diene heavy comprising a conjugated diene monomer unit and other copolymerizable monomer units as required. A polar group-containing diene rubber (i-A-1) having a polar group bonded to a part of the polymer chain, preferably a molecular chain end, (2) a conjugated diene monomer unit, a polar group-containing vinyl monomer unit, and Examples thereof include diene rubbers (i-A-2) containing other copolymerizable monomer units as required.

  Examples of the conjugated diene include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene, 1,3-pentadiene, and the like. Is mentioned. Among these, 1,3-butadiene and 2-methyl-1,3-butadiene are preferable, and 1,3-butadiene is more preferable. These conjugated dienes can be used alone or in combination of two or more.

  The polar group-containing vinyl monomer is not particularly limited as long as it is a polymerizable monomer having at least one polar group in the molecule. Specific examples include amino group-containing vinyl monomers, hydroxyl group-containing vinyl monomers, oxy group-containing vinyl monomers, and preferably hydroxyl group-containing vinyl monomers, amino acids. It is a group-containing vinyl monomer. These polar group-containing vinyl monomers can be used alone or in combination of two or more.

  Examples of the amino group-containing vinyl monomer include polymerizable monomers having at least one amino group selected from the group consisting of primary, secondary, and tertiary amino groups in one molecule. Among these, tertiary amino group-containing vinyl monomers are particularly preferable. These amino group-containing vinyl monomers can be used alone or in combination of two or more.

  Examples of the primary amino group-containing vinyl monomer include acrylamide, methacrylamide, p-aminostyrene, aminomethyl (meth) acrylate, aminoethyl (meth) acrylate, aminopropyl (meth) acrylate, aminobutyl ( And (meth) acrylate.

  Examples of the secondary amino group-containing vinyl monomer include anilinostyrenes disclosed in JP-A No. 61-130355; and anilinophenyl disclosed in JP-A No. 61-130356. Butadienes; and N-monosubstituted (meth) acrylamides such as N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-methylolacrylamide, N- (4-anilinophenyl) methacrylamide; It is done.

  Examples of tertiary amino group-containing vinyl monomers include N, N-disubstituted aminoalkyl acrylates, N, N-disubstituted aminoalkylacrylamides, N, N-disubstituted aminoaromatic vinyl compounds, and pyridyl. And vinyl compounds having a group.

  Examples of the N, N-disubstituted aminoalkyl acrylate include N, N-dimethylaminomethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-dimethylaminobutyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, N, N-diethylaminobutyl (meth) acrylate, N-methyl-N -Ethylaminoethyl (meth) acrylate, N, N-dipropylaminoethyl (meth) acrylate, N, N-dibutylaminoethyl (meth) acrylate, N, N-dibutylaminopropyl (meth) acrylate, N, N- Dibutylaminobutyl (meth) acrylate DOO, N, N-dihexylaminoethyl (meth) acrylate, N, N-dioctyl aminoethyl (meth) acrylate, acrylic acid or methacrylic esters of acrylic acid such acryloyl morph Olin like. Among these, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dipropylaminoethyl (meth) acrylate, N, N-dioctylaminoethyl (meth) An acrylate, N-methyl-N-ethylaminoethyl (meth) acrylate is preferred.

  Examples of the N, N-disubstituted aminoalkylacrylamide include N, N-dimethylaminomethyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-dimethylaminobutyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-diethylaminopropyl (meth) acrylamide, N, N-diethylaminobutyl (meth) acrylamide, N-methyl-N -Ethylaminoethyl (meth) acrylamide, N, N-dipropylaminoethyl (meth) acrylamide, N, N-dibutylaminoethyl (meth) acrylamide, N, N-dibutylaminopropyl (meth) acrylamide, N, N- Dibutylamino Acrylamide compounds or methacrylamide compounds such as butyl (meth) acrylamide, N, N-dihexylaminoethyl (meth) acrylamide, N, N-dihexylaminopropyl (meth) acrylamide, N, N-dioctylaminopropyl (meth) acrylamide, etc. Is mentioned. Among these, N, N-dimethylaminopropyl (meth) acrylamide, N, N-diethylaminopropyl (meth) acrylamide, and N, N-dioctylaminopropyl (meth) acrylamide are preferable.

  Examples of the N, N-disubstituted aminoaromatic vinyl compound include N, N-dimethylaminoethylstyrene, N, N-diethylaminoethylstyrene, N, N-dipropylaminoethylstyrene, and N, N-dioctylaminoethyl. Examples include styrene derivatives such as styrene.

  Examples of the vinyl compound having a pyridyl group include 2-vinylpyridine, 4-vinylpyridine, 5-methyl-2-vinylpyridine, 5-ethyl-2-vinylpyridine, and the like. Among these, 2-vinylpyridine and 4-vinylpyridine are preferable.

  Examples of the hydroxyl group-containing vinyl monomer include polymerizable monomers having at least one primary, secondary, or tertiary hydroxyl group in one molecule. Examples of such hydroxyl group-containing vinyl monomers include unsaturated carboxylic acid monomers, vinyl ether monomers, and vinyl ketone monomers each containing a hydroxyl group. Hydroxyl group-containing unsaturated carboxylic acid monomers are preferred. Examples of hydroxyl group-containing unsaturated carboxylic acid monomers include, for example, esters of α, β-unsaturated acids such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid, amides, and anhydrides. Preferred are ester compounds such as acrylic acid and methacrylic acid.

  Specific examples of the hydroxyl group-containing vinyl monomer include, for example, hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, glycerol mono (meth) acrylate, hydroxybutyl (meth) acrylate, 2-chloro-3-hydroxypropyl (meth) ) Acrylate, hydroxyhexyl (meth) acrylate, hydroxyoctyl (meth) acrylate, hydroxymethyl (meth) acrylamide, 2-hydroxypropyl (meth) acrylamide, 3-hydroxypropyl (meth) ) Acrylamide, di- (ethylene glycol) itaconate, di- (propylene glycol) itaconate, bis (2-hydroxypropyl) itaconate, bis (2-hydroxyethyl) itaconate, bis (2-hydroxyethyl) fumarate, bis (2- Hydroxyethyl) malate, 2-hydroxyethyl vinyl ether, hydroxymethyl vinyl ketone, allyl alcohol and the like are exemplified. Among these, hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate Glycerol mono (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyhexyl (meth) acrylate, hydroxyoctyl (meth) acrylate, hydroxymethyl (meth) acrylamide, 2-hydroxypropyl (meth) acrylamide, 3-hydroxypropyl ( Meth) acrylamide is preferred.

  Examples of the oxy group-containing vinyl monomer include trimethoxyvinylsilane, triethoxyvinylsilane, tri (2-methylbutoxy) vinylsilane disclosed in JP-A-1-188501 and JP-A-7-188356, Alkoxysilyl group-containing vinyl-based monomers such as 6-trimethoxysilyl-1,2-hexene, p-trimethoxysilylstyrene, triphenoxyvinylsilane, 3-trimethoxysilylpropyl methacrylate, 3-triethoxysilylpropyl acrylate, etc. Examples include a polymer.

  These polar group-containing vinyl monomers are used alone or in combination of two or more.

  Other copolymerizable monomers are not particularly limited as long as they do not impair the object of the present invention. However, when importance is placed on the balance between heat resistance and wet skid resistance, aromatic vinyl is usually used. Used. Examples of the aromatic vinyl include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-diisopropylstyrene, 2,4-dimethylstyrene, and 4-t-butylstyrene. , 5-t-butyl-2-methylstyrene, monochlorostyrene, dichlorostyrene, monofluorostyrene and the like. Among these, styrene is preferable. These other copolymerizable monomers can be used alone or in combination of two or more.

  The content of each monomer unit in the polar group-containing diene rubber (i-A) is appropriately selected according to the purpose of use.

  Each monomer in the case where the polar group-containing diene rubber (i-A-1) in which the polar group is bonded to a part of the polymer is a copolymer comprising a conjugated diene and another copolymerizable monomer The conjugated diene bond unit is usually 45 to 95% by weight, preferably 50 to 90% by weight, more preferably 55 to 85% by weight, and other copolymerizable monomer units ( Preferably, the aromatic vinyl bond unit) is in the range of 55-5 wt%, preferably 50-10 wt%, more preferably 45-15 wt%.

  The content of each monomer in the polar group-containing diene rubber (i-A-2) obtained by copolymerizing the polar group-containing vinyl monomer is conjugated diene and polar group-containing vinyl monomer. And a copolymerization of a conjugated diene, a polar group-containing diene monomer and another copolymerizable monomer. In the case of a copolymer of a conjugated diene and a polar group-containing vinyl monomer, the content of the conjugated diene bond unit is usually 80 to 99.99% by weight, preferably 85 to 99.95% by weight, more preferably The content of the polar group-containing vinyl monomer bond unit is usually 0.01 to 20% by weight, preferably 0.05 to 15% by weight, more preferably 0. .1 to 10% by weight. In the case of a copolymer of a conjugated diene, a polar group-containing vinyl monomer and another copolymerizable monomer (preferably an aromatic vinyl), the content of each monomer bond unit is conjugated diene bond. The content of the unit is usually 45 to 94.99% by weight, preferably 50 to 85% by weight, more preferably 55 to 80% by weight, and the content of the polar group-containing vinyl monomer binding unit is usually 0.01 to 20% by weight, preferably 0.05 to 15% by weight, more preferably 0.1 to 10% by weight, and the content of other copolymerizable monomer units is usually 5%. It is -55 weight%, Preferably it is 10-50 weight%, More preferably, it is the range of 15-45 weight%.

  These polar group-containing diene rubbers (i-A) can be produced according to a conventional method. The polar group-containing diene rubber (i-A-1) in which a polar group is bonded to a part of the polymer is, for example, (1) a conjugated diene using an organic active metal compound as an initiator in a hydrocarbon solvent. Alternatively, a polymer is obtained by reacting an active (co) polymer obtained by (co) polymerizing a conjugated diene and another copolymerizable monomer with an active metal bonded to a polymer chain end and a modifier. A method of introducing a polar group at the chain end (production method a), (2) a conjugated diene or a conjugated diene and another copolymerizable monomer in a hydrocarbon solvent using a polar group-containing organic active metal compound as an initiator Can be produced by a (co) polymerization method (production method b). The polar group-containing diene rubber (i-A-2) is, for example, (3) conjugated diene and polar group-containing vinyl monomer, or conjugated diene and polar group-containing vinyl monomer and other copolymers. It can be produced by a method of copolymerizing with a possible monomer (production method c).

  Hereinafter, these production methods (ac) will be described in detail.

  As the organic active metal compound used in the production method a, those generally used in anionic polymerization are used, and examples thereof include organic alkali metals, organic alkaline earth metals, and organic acid lanthanoid series rare earth metals. Among these, an organic alkali metal is preferable.

  Examples of the organic alkali metal include monoorganolithium compounds such as n-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, phenyllithium and stilbenelithium; dilithiomethane, 1,4-dilithiobutane, 1,4- Polyfunctional organolithium compounds such as dilithio-2-ethylcyclohexane and 1,3,5-trilithiobenzene; sodium naphthalene, potassium naphthalene and the like. Among these, an organolithium compound is preferable, and a monoorganolithium compound is particularly preferable.

  Examples of the organic alkaline earth metal include n-butylmagnesium bromide, n-hexylmagnesium bromide, ethoxy calcium, calcium stearate, t-butoxystrontium, ethoxybarium, isopropoxybarium, ethyl mercaptobarium, t-butoxybarium, phenoxy Examples include barium, diethylaminobarium, barium stearate, and ethylbarium.

  Examples of the organic acid lanthanoid series rare earth metal include composite catalysts composed of neodymium versatate / triethylaluminum hydride / ethylaluminum sesquichloride as described in JP-B-63-64444.

  These organic active metal compounds can be used alone or in combination of two or more. The amount of the organic active metal compound used is appropriately selected according to the required molecular weight of the produced polymer, and is usually 0.01 to 20 mmol, preferably 0.05 to 15 mmol, more preferably 0.00 per 100 g of monomer. It is in the range of 1-10 mmol.

  The polymerization reaction using the organic active metal compound as an initiator is performed in a hydrocarbon solvent that does not destroy the initiator. The suitable hydrocarbon solvent is not particularly limited as long as it is used for usual solution polymerization. For example, n-butane, n-pentane, iso-pentane, n-hexane, n-heptane, iso- Aliphatic hydrocarbons such as octane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene and toluene; and preferably n-hexane, cyclohexane, toluene, etc. is there. Moreover, you may use unsaturated hydrocarbons with low polymerizability, such as 1-butene, cis-2-butene, and 2-hexene, as needed. These hydrocarbon solvents are each used alone or in combination of two or more, and are usually used in an amount ratio such that the monomer concentration is 1 to 30% by weight.

  In the polymerization reaction, a Lewis basic compound can be used to adjust the microstructure of the conjugated diene bond unit or the distribution of the aromatic vinyl copolymerized with the conjugated diene in the copolymer chain. The Lewis basic compound is not particularly limited as long as it is used in ordinary anionic polymerization using an organic active metal compound as an initiator. For example, tetrahydrofuran, diethyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol dibutyl ether Ethers such as diethylene glycol dimethyl ether and diethylene glycol dibutyl ether; tertiary amines such as tetramethylethylenediamine, trimethylamine, triethylamine, pyridine and quinuclidine; alkali metal alkoxides such as potassium tert-amyl oxide and potassium tert-butyl oxide; Phosphines such as triphenylphosphine; and the like. Among these, ethers and tertiary amines are preferable.

  These Lewis basic compounds can be used alone or in combination of two or more. The amount of the Lewis basic compound used is usually 0 to 200 mol, preferably 0.1 to 100 mol, more preferably 0.5 to 50 mol, most preferably 1 mol of initiator (organic active metal compound). Is 0.8 to 20 mol.

  The polymerization reaction is performed by (co) polymerizing a conjugated diene alone or a conjugated diene and another copolymerizable monomer (preferably aromatic vinyl). Two or more conjugated dienes and other copolymerizable monomers may be used in combination. When the conjugated diene and other copolymerizable monomer are used in combination, the proportion of each monomer in the total monomer is generally 45 to 95% by weight, preferably 50 to 90% by weight, based on the conjugated diene. More preferably, it is in the range of 55 to 85% by weight, and the other copolymerizable monomer is usually in the range of 55 to 5% by weight, preferably 50 to 10% by weight, more preferably 45 to 15% by weight. It is.

  The polymerization reaction is usually performed in a batch or continuous polymerization mode in the range of −78 to 150 ° C. When aromatic vinyl is copolymerized as another copolymerizable monomer, for example, in order to improve the randomness of the aromatic vinyl unit, for example, Japanese Patent Laid-Open Nos. 59-140221 and 56- As described in Japanese Patent No. 143209, the conjugated diene or the conjugated diene and the aromatic vinyl are mixed so that the aromatic vinyl content in the composition ratio of the aromatic vinyl and the conjugated diene in the polymerization system falls within a specific concentration range. It is desirable to feed the mixture continuously or intermittently to the reaction system.

  Specific examples of the polymer produced by the polymerization reaction include polybutadiene, polyisoprene, butadiene-isoprene copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-butadiene-isoprene copolymer, and the like. Can be illustrated. Thus, a polymer in which an active metal is bonded to the end of the polymer chain (that is, an active polymer) is obtained.

  Modification agents that can be reacted with such an active polymer to introduce a polar group at the end of the polymer chain are known. For example, JP 59-191705 A, JP 60-137913 A, and JP 62 A Various modifiers disclosed in JP-A-86074, JP-A-62-109801, JP-A-62-149708, JP-A-64-22940, and the like can be used.

  Specific examples of the modifying agent include, for example, a compound having at least one reactive polar group that reacts with an active metal such as a carbonyl group, a thiocarbonyl group, an aziridine group, and an epoxy group in the molecule (hereinafter referred to as a modifying agent X). ); Having at least one reactive group that reacts with an active metal such as a carbonyl group, a thiocarbonyl group, an aziridine group, an epoxy group, a halogen atom, or a carbon-carbon unsaturated bond group and at least one polar group in the molecule. Compound (hereinafter referred to as modifier Y); and the like.

  Examples of the modifier X include ketones such as acetone, benzophenone, and acetylacetone; aldehydes such as benzaldehyde; oxiranes; carbodiimides; N-ethylethylideneimine, N-methylbenzylideneimine, N-hexylcinnamideneimine, N-decyl-2-ethyl-1,2-diphenylbutylideneimine, N-phenylbenzylideneimine, N-dodecylcyclohexaneimine, N-propyl-2,5-cyclohexadienimine, N-methyl-1-naphthaleneimine, etc. Or a cyclic imine compound having 2 to 3 carbon atoms; and the like. Among these, oxiranes; carbodiimides; C2-C3 cyclic imine compounds; and the like are particularly preferable.

  Examples of oxiranes include ethylene oxide, propylene oxide, 1,2-epoxybutane, 1,2-epoxy-iso-butane, 2,3-epoxybutane, 1,2-epoxyhexane, 1,2-epoxyoctane, 1,2-epoxydecane, 1,2-epoxytetradecane, 1,2-epoxyhexadecane, 1,2-epoxyoctadecane, 1,2-epoxyeicosane, 1,2-epoxy-2-pentylpropane, 3,4 -Epoxy-1-butene, 1,2-epoxy-5-hexene, 1,2-epoxy-9-decene, 1,2-epoxycyclopentane, 1,2-epoxycyclohexane, 1,2-epoxycyclododecane, 1,2-epoxyethylbenzene, 1,2-epoxy-1-methoxy-2-methylpropane, glycidyl Chill ether, glycidyl ethyl ether, glycidyl isopropyl ether, glycidyl allyl ether, glycidyl phenyl ether, glycidyl butyl ether, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, epichlorohydrin, Epibromohydrin, epiiodohydrin, 2,3-epoxy-1,1,1-trifluoropropane, 1,2-epoxy-1H, 1H, 2H, 3H, 3H, -heptadecafluoroundecane, etc. It is done.

  Among these, ethylene oxide, propylene oxide, 1,2-epoxybutane, 1,2-epoxy-iso-butane, 2,3-epoxybutane, 1,2-epoxyhexane, 3,4-epoxy-1-butene, 1,2-epoxy-5-hexene, glycidyl methyl ether, glycidyl ethyl ether, glycidyl isopropyl ether, glycidyl allyl ether, glycidyl phenyl ether, glycidyl butyl ether, 3-glycidyloxypropyltrimethoxysilane, epichlorohydrin, epi Bromohydrin is preferred.

  Examples of carbodiimides include dimethylcarbodiimide, diethylcarbodiimide, dipropylcarbodiimide, dibutylcarbodiimide, dihexylcarbodiimide, dicyclohexylcarbodiimide, dibenzylcarbodiimide, diphenylcarbodiimide, methylpropylcarbodiimide, butylcyclohexylcarbodiimide, ethylbenzylcarbodiimide, propylphenylcarbodiimide, Examples thereof include benzyl carbodiimide. Of these, dicyclohexylcarbodiimide, diphenylcarbodiimide and the like are preferable.

  Examples of the cyclic imine compound having 2 to 3 carbon atoms include N-unsubstituted aziridine compounds such as ethyleneimine and propyleneimine, and N-unsubstituted azetidine compounds such as trimethyleneimine.

  Examples of the modifier Y include a compound having a vinyl group and a hydroxyl group in the molecule; a compound having a vinyl group and an amino group in the molecule; a compound having a vinyl group and an alkoxysilyl group in the molecule; And compounds having a halogen atom and an alkoxysilyl group; compounds having a carbonyl group and an amino group in the molecule; and the like. Among these, compounds having vinyl and hydroxyl groups in the molecule; compounds having vinyl and amino groups in the molecule; compounds having vinyl and alkoxysilyl groups in the molecule; halogen atoms in the molecule Compounds having an alkoxysilyl group; compounds having a carbonyl group and an amino group in the molecule are preferred, and compounds having a carbonyl group and an amino group in the molecule are particularly preferred.

  Examples of the compound having a vinyl group and a hydroxyl group, an amino group or an alkoxy group in the molecule are the same as the specific examples of the polar group-containing vinyl monomer.

  Examples of the compound having a vinyl group or a halogen atom and an alkoxysilyl group in the molecule include trimethoxychlorosilane, triethoxychlorosilane, diethoxymethylchlorosilane, triphenoxy disclosed in JP-A-1-188501. Monohalogenated alkoxysilane compounds such as chlorosilane and diphenoxyphenyliodosilane; and the like. These compounds are used singly or in combination of two or more, but it is necessary to determine the amount of the compound added so that the amount of functional groups such as vinyl groups and halogen atoms is equal to or greater than the active metal. is there.

  In a compound having a carbonyl group and an amino group in the molecule, preferably a compound having a carbonyl group and a tertiary amino group in the molecule, both groups may be adjacent to each other or may be separated from each other. . Examples of the compound in which both groups are adjacent include N-substituted amides, N-substituted imides, N-substituted ureas, N-substituted isocyanuric acids and the like, and these cyclic compounds are preferable. Examples of the compound in which both groups are separated include N-substituted aminoketones and N-substituted aminoaldehydes, and N-substituted aminoketones are preferred.

  Examples of N-substituted cyclic amides include N-methyl-β-propiolactam, N-phenyl-β-propiolactam, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, and N-phenyl. -2-pyrrolidone, Nt-butyl-2-pyrrolidone, N-methyl-5-methyl-2-pyrrolidone, N-methyl-2-piperidone, N-vinyl-2-piperidone, N-phenyl-2-piperidone N-methyl-ε-caprolactam, N-phenyl-ε-caprolactam, N-methyl-ω-laurylactam, N-vinyl-ω-laurylactam and the like. Among these, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N-phenyl-2-pyrrolidone, N-methyl-piperidone, N-vinyl-2-piperidone, N-methyl-ε-caprolactam, N-phenyl-ε-caprolactam is preferred.

  Examples of N-substituted cyclic ureas include 1,3-dimethylethyleneurea, 1,3-divinylethyleneurea, 1,3-diethyl-2-imidazolidinone, 1-methyl-3-ethyl-2-imidazole. Lizinone and the like can be mentioned, and 1,3-dimethylethyleneurea and 1,3-divinylethyleneurea are preferable.

  Examples of N-substituted aminoketones include 4-N, N-dimethylaminoacetophenone, 4-N-methyl-N-ethylaminoacetophenone, 4-N, N-diethylaminoacetophenone, 1,3-bis (diphenylamino) 2-propanone, 1,7-bis (methylethylamino) -4-heptanone, 4-N, N-dimethylaminobenzophenone, 4-N, N-di-t-butylaminobenzophenone, 4-N, N- Examples include diphenylaminobenzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (diphenylamino) benzophenone. Among these, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, and 4,4′-bis (diphenylamino) benzophenone are particularly preferable.

  Examples of N-substituted aminoaldehydes include N-substituted aminoaldehydes such as 4-N, N-dimethylaminobenzaldehyde, 4-N, N-diphenylaminobenzaldehyde and 4-N, N-divinylaminobenzaldehyde. Can be mentioned.

  These modifiers are used alone or in combination of two or more. The amount of the modifier used is appropriately selected according to the required properties of the diene rubber, but is usually in the range of 1 to 50 equivalents, preferably 1 to 20 equivalents, more preferably 1 to 10 equivalents per organic active metal compound. It is.

  Further, the polar group-containing diene rubber (i-A-1) may be obtained by reacting the active polymer in combination with a modifier and a polyfunctional coupling agent. In the reaction of the active polymer with the modifying agent and the polyfunctional coupling agent, the modifying agent and the polyfunctional coupling agent may be reacted separately at the same time or before and after the both. The amount of the modifier used in these cases is usually 0.1 to 0.9 equivalents, preferably 0.1 to 0.9 equivalents per organic active metal compound when reacting simultaneously with the polyfunctional coupling agent or before the polyfunctional coupling agent. In the range of 0.2 to 0.8 equivalent, more preferably 0.3 to 0.7 equivalent, when the reaction is carried out after the polyfunctional coupling agent, usually 0.1 to 50 equivalent, preferably 0.2 It is -20 equivalent, More preferably, it is the range of 0.3-10 equivalent. The amount of the polyfunctional coupling agent used is usually 0.1 to 0.9 equivalent, preferably 0.2 to 0, based on the organic active metal compound when the polyfunctional coupling agent is reacted simultaneously with the modifier or before the modifier. .8 equivalents, more preferably in the range of 0.3 to 0.7 equivalents. When the reaction is carried out after the modifier, it is usually 0.1 to 50 equivalents, preferably 0.2 to 20 equivalents, more preferably 0. .3 to 10 equivalents.

  Examples of the polyfunctional coupling agent are disclosed in JP-A-56-143209, JP-A-56-17362, JP-A-57-55912, JP-A-58-162605, and the like. Various polyfunctional coupling agents can be used.

  Specific examples of the polyfunctional coupling agent include, for example, tin dichloride, tin tetrachloride, tin tetrabromide, monomethyltrichlorotin, monoethyltrichlorotin, monobutyltrichlorotin, monohexyltrichlorotin, dimethyldichlorotin, diethyl Tin coupling agents such as dichlorotin, dibutyldichlorotin, dibutyldibromotin, tetramethoxytin, tetraethoxytin, tetrabutoxytin, bistrichlorostannylethane; silicon dichloride, silicon dibromide, silicon tetrachloride, Silicon tetrabromide, silicon tetraiodide, monomethyltrichlorosilicon, monoethyltrichlorosilicon, monobutyltrichlorosilicon, monohexyltrichlorosilicon, monomethyltribromosilicon, dimethyldichlorosilicon, diethyldichlorosilicon, butyltrick Silicon, dibutyldichlorosilicon, dihexyldichlorosilicon, dimethyldibromosilicon, tetramethoxysilicon, tetraethoxysilicon, tetrabutoxysilicon, diphenyldimethoxysilicon, diphenyldiethoxysilicon, monochlorotrimethoxysilicon, monobromotrimethoxysilicon, dichlorodimethoxysilicon , Dibromodimethoxysilicon, trichloromethoxysilicon, tribromomethoxysilicon, alkyltriphenoxysilicon, bistrichlorosilylethane, and other silicon-based coupling agents; lead dichloride, germanium tetrachloride, and other halogenated metal-based coupling agents; ethylacrylonitrile Unsaturated nitrile coupling agents such as dichloromethane, dibromomethane, dichloroethane, dibromoethane, dichloropropane, Halogenated hydrocarbon coupling agents such as bromopropane, dibromobenzene, dichlorobenzene, chloroform, tribromomethane, trichloroethane, trichloropropane, tribromopropane, carbon tetrachloride, tetrachloroethane; methyl formate, ethyl formate, methyl acetate, Ethyl acetate, propyl acetate, isopropyl acetate, amyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, ethyl trimethyl acetate, methyl caproate, ethyl caproate, methyl benzoate, ethyl benzoate, dimethyl adipate, Ester coupling agents such as diethyl adipate, ethyl benzoate, dimethyl terephthalate, diethyl terephthalate, dimethyl phthalate, dimethyl isophthalate; terephthalic acid dichloride, diphthalic acid And halide coupling agents such as chloride, isophthalic acid dichloride, and adipic acid dichloride; phosphorus coupling agents such as trisnonylphenyl phosphite, trimethyl phosphite, and triethyl phosphite; Among these, a tin coupling agent, a silicon coupling agent, an ester coupling agent, a halogenated hydrocarbon coupling agent, and the like are preferable, and a tin coupling agent and a silicon coupling agent are particularly preferable.

  These polyfunctional coupling agents can be used alone or in combination of two or more.

  In the modification reaction and the coupling reaction, an active polymer having an active metal may be brought into contact with a modifying agent and / or a polyfunctional coupling agent. When an active polymer is produced by a polymerization reaction, the reaction can usually be carried out by adding a predetermined amount of a modifier and / or a polyfunctional coupling agent to the active polymer solution before the polymerization is stopped. The reaction temperature and reaction time can be selected within a wide range, but are generally from room temperature to 120 ° C. and from several seconds to several hours. The modification rate is usually selected appropriately from the range of 10 to 100%. The degree of modification can be determined by measuring each absorption intensity with a differential refractometer (RI) of GPC and an ultraviolet-visible spectrophotometer (UV), obtaining the (UV / RI) value, and using a calibration curve prepared in advance. . The coupling rate can be selected as appropriate, but is usually in the range of 10 to 100%. The coupling rate can be determined from the area ratio between the high molecular weight and the low molecular weight of the differential refractometer by GPC measurement.

  There is no restriction | limiting in particular as a polar group containing organic active metal compound used by the manufacturing method b, What is used as an initiator of normal anion polymerization can be used. In general, an organic active metal amide is used. As the organic active metal amide, one obtained by previously reacting an organic active metal compound with a secondary amine may be used, or at least 1 as in the method disclosed in JP-A-6-199921. It may be produced in the polymerization reaction system by adding an organic active metal compound in the presence of a part of the monomer and secondary amine.

  Examples of secondary amines include aliphatic secondary amine compounds, aromatic secondary amine compounds, and cyclic imine compounds, with aliphatic secondary amine compounds and cyclic imine compounds being preferred.

  Examples of the aliphatic secondary amine compound include dimethylamine, methylethylamine, methylpropylamine, methylbutylamine, methylamylamine, amylhexylamine, diethylamine, ethylpropylamine, ethylbutylamine, ethylhexylamine, dipropylamine, and diisopropyl. Examples include amine, propylbutylamine, dibutylamine, diamylamine, dihexylamine, diheptylamine, dioctylamine, methylcyclopentylamine, ethylcyclopentylamine, methylcyclohexylamine, dicyclopentylamine, dicyclohexylamine and the like. Among these, dimethylamine, methylethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diamylamine, dihexylamine, diheptylamine, and dioctylamine are preferable.

  Examples of the aromatic secondary amine compound include diphenylamine, N-methylaniline, N-ethylaniline, dibenzylamine, N-methylbenzylamine, N-ethylphenethylamine and the like.

  Examples of cyclic imine compounds include aziridine, acetylidine, pyrrolidine, piperidine, 2-methylpiperidine, 3-methylpiperidine, 4-methylpiperidine, 3,5-dimethylpiperidine, 2-ethylpiperidine, hexamethyleneimine, heptamethyleneimine. , Dodecamethyleneimine, coniine, morpholine, oxazine, pyrroline, pyrrole, azepine and the like. Among these, pyrrolidine, piperidine, 3-methylpiperidine, 4-methylpiperidine, 3,5-dimethylpiperidine, 2-ethylpiperidine, hexamethyleneimine and heptamethyleneimine are preferable.

  These secondary amines may be used alone or in combination of two or more.

  The amount of the organic active metal amide used in the case of using the organic active metal amide prepared by reacting the organic active metal compound with the secondary amine in advance is appropriately selected depending on the required molecular weight of the produced polymer. The amount is usually 0.1 to 30 mmol, preferably 0.2 to 15 mmol, more preferably 0.3 to 10 mmol per 100 g of the monomer.

  When the organic active metal compound and the secondary amine are added to the polymerization system to produce the organic active metal amide in the system, the amount of the organic active metal used is appropriately selected depending on the required molecular weight of the produced polymer. The amount is usually 0.1 to 30 mmol, preferably 0.2 to 15 mmol, more preferably 0.3 to 10 mmol per 100 g of monomer. The amount of secondary amine used at this time is usually 0.5 to 2 equivalents, preferably 0.8 to 1.5 equivalents, more preferably 1 to 1.2 equivalents, relative to the organic active metal compound. .

  The polymerization reaction of the production method b may be carried out according to a conventional method. For example, in the presence of at least a part of the monomer according to the method disclosed in JP-A-6-199921, the organic active metal compound and It can be carried out by contacting with a secondary amine compound. Other polymerization conditions are the same as the polymerization conditions of the production method a.

  In the method b, after the polymerization reaction is completed, it can be reacted with a modifier and / or a polyfunctional coupling agent. The amount of the modifier / polyfunctional coupling used and the reaction conditions are the same as in the specific example of production method a.

  Thus, the vinyl bond (1,2-vinyl bond and 3,4-vinyl bond) ratio of the conjugated diene bond unit of the polar group-containing diene rubber (i-A-1) obtained by the method a or b is as follows: Although there is no special limitation, it is usually 10% or more, preferably 10 to 90%, more preferably 30 to 85%, and most preferably 50 to 80%. When the amount of vinyl bonds in the conjugated diene bond unit is within this range, the wear resistance and heat generation resistance are highly balanced and suitable. The remaining conjugated diene bond unit other than the vinyl bond is a 1,4-bond and may be a 1,4-cis bond or a 1,4-trans bond.

  The method of copolymerizing the conjugated diene and the polar group-containing vinyl monomer or the conjugated diene, the polar group-containing vinyl monomer and other copolymerizable monomers in the production method c is not particularly limited, Usually, an emulsion polymerization method is employed. In the emulsion polymerization method, a normal emulsion polymerization method can be employed. For example, a predetermined amount of at least one monomer is emulsified and dispersed in an aqueous medium in the presence of an emulsifier, and the emulsion polymerization is performed using a radical polymerization initiator. The method of doing is mentioned.

  As the emulsifier, for example, a long-chain fatty acid salt and / or rosinate having 10 or more carbon atoms is used. Specific examples include potassium salts such as capric acid, lauric acid, myristic acid, palmitic acid, oleic acid, stearic acid, and sodium salts.

  Examples of the radical polymerization initiator include persulfates such as ammonium persulfate and potassium persulfate; a combination of ammonium persulfate and ferric sulfate, a combination of organic peroxide and ferric sulfate, and peroxidation. A redox initiator such as a combination of hydrogen and ferric sulfate;

  A chain transfer agent can be added to adjust the molecular weight of the copolymer. As the chain transfer agent, for example, mercaptans such as t-dodecyl mercaptan and n-dodecyl mercaptan, α-methylstyrene dimer, carbon tetrachloride, thioglycolic acid, diterpene, terpinolene, γ-terpinene and the like can be used.

  Although the temperature of emulsion polymerization can be suitably selected according to the kind of radical polymerization initiator used, it is 0-100 degreeC normally, Preferably it is 0-60 degreeC. The polymerization mode may be any of continuous polymerization, batch polymerization and the like.

  When the polymerization conversion rate of the monomer in emulsion polymerization increases, a tendency to gel is observed. Therefore, it is preferable to suppress the conversion rate to 90% or less, and it is particularly preferable to stop the polymerization in the range of the conversion rate of 50 to 80%. The termination of the polymerization reaction is usually performed by adding a polymerization terminator to the polymerization system when a predetermined conversion rate is reached. Examples of the polymerization terminator include amine compounds such as diethylhydroxylamine and hydroxylamine, quinone compounds such as hydroquinone and benzoquinone, and compounds such as sodium nitrite and sodium dithiocarbamate.

  After termination of the emulsion polymerization reaction, unreacted monomers are removed from the obtained polymer latex as necessary, and then an acid such as nitric acid or sulfuric acid is added and mixed as necessary to bring the latex pH to a predetermined value. After the adjustment, a salt such as sodium chloride, calcium chloride or potassium chloride is added and mixed as a coagulant to coagulate the polymer as crumb. The crumb can be washed and dehydrated and then dried with a band dryer or the like to obtain the desired polar group-containing diene rubber.

  Examples of other polar group-containing diene rubbers (i-A-3) include natural rubber, emulsion-polymerized styrene / acrylonitrile / butadiene copolymer rubber, acrylonitrile / butadiene copolymer rubber, chloroprene rubber, and the like. Of these, natural rubber is preferable.

  Other diene rubbers (i-B) that do not contain a polar group are not particularly limited, but diene rubbers used in the normal rubber industry can be used. Specifically, for example, polyisoprene rubber (IR), emulsion-polymerized styrene-butadiene copolymer rubber (SBR), solution polymerization random SBR (bonded styrene 5 to 50% by weight, 1,2-vinyl bond of butadiene bond unit part) 10-80%), high trans SBR (1,4-trans bond amount 70-95% of butadiene bond unit part), low cis polybutadiene rubber (BR), high cis BR, high trans BR (butadiene bond unit part) 1,4-trans bond amount 70-95%), styrene-isoprene copolymer rubber (SIR), butadiene-isoprene copolymer rubber, solution polymerization random styrene-butadiene-isoprene copolymer rubber (SIBR), emulsion polymerization SIBR, High vinyl SBR-low vinyl SBR block copolymer rubber, polystyrene-polybutadiene-poly Block copolymers such as Chi Ren block copolymer. Can be appropriately selected according to the required characteristics. Among these, BR, IR, SBR, and SIBR are preferable.

The Mooney viscosity (ML _{1 + 4} , 100 ° C.) of the diene rubber (i) is not particularly limited, but is usually 10 to 200, preferably 20 to 150, and more preferably 25 to 120. When the Mooney viscosity is in this range, the heat resistance and workability are highly balanced and suitable.

  There is no particular limitation on the aromatic vinyl chain distribution when the diene rubber (i) contains an aromatic vinyl unit, but the content of the independent chain of one aromatic vinyl unit is the amount of the combined aromatic vinyl unit. Usually 40 wt% or more, preferably 60 wt% or more, more preferably 75 wt% or more, and the content of the aromatic vinyl long chain in which 8 or more aromatic vinyl units are linked is the amount of bonded aromatic vinyl In general, it is 5% by weight or less, preferably 2.5% by weight or less, more preferably 1.5% by weight or less in order to balance characteristics such as heat resistance, wear resistance, and wet skid resistance to a high value. Is appropriate.

  As the diene rubber (i), at least one selected from polar group-containing diene rubber (i-A) and other diene rubber (i-B) may be used alone or in combination of two or more. Can do.

Polyether polymer (ii)
As the polyether polymer (ii) as a component of the rubber composition, a polymer having an ether bond (—C—O—C—) in the main chain is used without any particular limitation. As the polyether polymer (ii), an oxirane compound such as alkylene oxide, epihalohydrin, unsaturated epoxide or the like is preferably used by block polymerization or random addition polymerization alone or in combination of two or more.

  Specific examples of the polyether polymer (ii) obtained by addition polymerization of oxirane compounds alone or in combination of two or more thereof include, for example, alkylene oxide homopolymers, copolymers of two or more alkylene oxides, and alkylene oxides. A copolymer of an alkylene oxide and an unsaturated epoxide, a copolymer of an alkylene oxide, an epihalohydrin and an unsaturated epoxide, a homopolymer of an epihalohydrin, a copolymer of two or more epihalohydrins, Examples include a copolymer of an epihalohydrin and an unsaturated epoxide, a homopolymer of an unsaturated epoxide, a copolymer of two or more unsaturated epoxides, and the like. Among these, a copolymer of two or more alkylene oxides or a copolymer of alkylene oxide and unsaturated epoxide is preferable, and a copolymer of alkylene oxide and unsaturated epoxide is particularly preferable.

  Examples of the alkylene oxide include ethylene oxide, propylene oxide, 1,2-epoxybutane, 1,2-epoxy-iso-butane, 2,3-epoxybutane, amylene oxide, 1,2-epoxyhexane, 1,2 -Epoxyoctane, 1,2-epoxydecane, 1,2-epoxytetradecane, 1,2-epoxyhexadecane, 1,2-epoxyoctadecane, 1,2-epoxyeicosane, 1,2-epoxy-2-pentylpropane 1,2-epoxycyclopentane, 1,2-epoxycyclohexane, 1,2-epoxycyclododecane and the like. Among these, lower alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, and amylene oxide are preferable, and ethylene oxide and propylene oxide are particularly preferable.

  Examples of the epihalohydrin include epichlorohydrin, epibromohydrin, epiiodohydrin, 2,3-epoxy-1,1,1-trifluoropropane, 1,2-epoxy-1H, 1H, 2H, 3H. , 3H-heptadecafluoroundecane, etc., and epichlorohydrin is usually used.

  The unsaturated epoxide is not particularly limited as long as it is a compound having at least one carbon-carbon unsaturated bond and at least one epoxy group in the molecule. For example, allyl glycidyl ether, butenyl glycidyl ether, octenyl Alkenyl glycidyl ethers such as glycidyl ether; alkenyl epoxides such as 3,4-epoxy-1-butene, 1,2-epoxy-5-hexene, 1,2-epoxy-9-decene; styrene epoxides, glycidyl phenyl ether, etc. Aryl epoxides; and the like. Among these, alkenyl glycidyl ether is preferable and allyl glycidyl ether is particularly preferable.

  Examples of other oxirane compounds include 1,2-epoxy-1-methoxy-2-methylpropane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, and the like. be able to.

  These oxirane compounds can be used alone or in combination of two or more.

  The kind and content of the oxirane compound in the polyether polymer (ii) are appropriately selected depending on the purpose of use. For example, when the heat resistance and the tensile strength are highly balanced, generally a polyether polymer (ii-A) obtained by copolymerizing an alkylene oxide and an unsaturated epoxide is used. The alkylene oxide content is usually 85 to 99.9% by weight, preferably 90 to 99% by weight, and more preferably 95 to 99% by weight. The unsaturated epoxide content is usually 15 to 9% by weight, respectively. The range is 0.1% by weight, preferably 10 to 1% by weight, and more preferably 5 to 1% by weight. In order to improve the processability to a high degree, a polyether polymer (ii-B) containing an alkylene oxide of usually 50% by weight or more, preferably 70% by weight or more, more preferably 90% by weight or more is suitable. Used for. Further, when antistatic properties are required in addition to heat resistance, tensile strength and workability, the alkylene oxide contains 50% by weight or more, preferably 60% by weight or more, more preferably 70% by weight or more as an alkylene oxide. The polyether polymer (ii-C) is preferably used. In order to highly balance all the properties of heat resistance, tensile strength, workability and antistatic properties, the alkylene oxide in the polyether polymer (ii-A) is usually 50 to 100% by weight of ethylene oxide. , Preferably 60 to 99% by weight, more preferably 70 to 97% by weight, and propylene oxide usually consisting of 50 to 0% by weight, preferably 40 to 1% by weight, more preferably 30 to 3% by weight Are preferably used. A preferred copolymer is a copolymer comprising 50 to 99% by weight of ethylene oxide, 0 to 49% by weight of propylene oxide, and 1 to 15% by weight of allyl glycidyl ether.

  Among the polyether polymers (ii), (1) 50 to 98.9% by weight of ethylene oxide, preferably, in order to highly balance all the characteristics of heat resistance, tensile strength, workability and antistatic properties 60-97.5 wt%, more preferably 70-96 wt%, (2) propylene oxide 1-35 wt%, preferably 2-30 wt%, more preferably 3-25 wt%, and (3) no An ethylene oxide / propylene oxide / unsaturated epoxide terpolymer having a bond amount of 0.1 to 15% by weight, preferably 0.5 to 10% by weight, more preferably 1 to 5% by weight, is particularly preferable. . In this terpolymer, the unsaturated epoxide is preferably an alkenyl glycidyl ether such as allyl glycidyl ether.

  The (co) polymer of the oxirane compound containing the ternary copolymer can be usually obtained by a solution polymerization method or a solvent slurry polymerization method. Examples of the catalyst include a system in which water and acetylacetone are reacted with organic aluminum (Japanese Patent Publication No. 35-15797), a system in which phosphoric acid and triethylamine are reacted with triisobutylaluminum (Japanese Patent Publication No. 46-27534), A homogeneous catalyst such as a system in which an organic acid salt of phosphoric acid or diazabicycloundecene is reacted with triisobutylaluminum (Japanese Examined Patent Publication No. 56-51171); consisting of a partially hydrolyzed aluminum alkoxide and an organic zinc compound System (Japanese Examined Patent Publication No. 43-2945), system composed of an organic zinc compound and a polyhydric alcohol (Japanese Examined Patent Publication No. 45-7751), system composed of dialkylzinc and water (Japanese Patent Publication No. 36-3394), etc. Examples include heterogeneous catalysts. When the solvent slurry polymerization method is employed, a catalyst that has been pretreated with both a monomer that gives a polymer soluble in the polymerization solvent and a monomer that gives a polymer insoluble in the polymerization solvent is used. Is preferable from the viewpoint of the stability of the polymerization reaction system.

  Examples of the solvent include aromatic hydrocarbons such as toluene; pentanes such as n-pentane; hexanes such as n-hexane; alicyclic hydrocarbons such as cyclopentane;

  When employing a solvent slurry polymerization method using a solvent such as n-pentane, n-hexane, or cyclopentane, for example, ethylene oxide that gives a polymer insoluble in the solvent and propylene that gives a polymer soluble in the solvent. As described above, it is preferable to treat the catalyst with oxide in advance from the viewpoint of the stability of the polymerization reaction system. In the treatment of the catalyst, the catalyst component and a small amount of each monomer are mixed and aged at a temperature of 0 to 100 ° C., preferably 30 to 50 ° C.

  In the polymerization reaction, a monomer component, a catalyst component, a polymerization solvent, and the like are charged into a reactor, and at a temperature of 0 to 100 ° C., preferably 30 to 70 ° C., in any manner such as batch, semi-batch, and continuous. It can be carried out.

The Mooney viscosity (ML _{1 + 4} , 100 ° C.) of the polyether polymer (ii) is in the range of 10 to 200, preferably 20 to 150, more preferably 25 to 120. In the present invention, when the Mooney viscosity (ML _{1 + 4} , 100 ° C.) is in the range of 70 to 150, preferably 80 to 140, more preferably 85 to 120, the heat resistance, tensile strength and workability are high. Balanced and suitable.

It consists of 50 to 98.9% by weight of ethylene oxide, 1 to 35% by weight of propylene oxide and 0.1 to 15% by weight of unsaturated epoxide as described above, and has a Mooney viscosity (ML _{1 + 4} , 100 ° C.) of 70 to 150. The ethylene oxide / propylene oxide / unsaturated epoxide terpolymer is the ethylene oxide / propylene oxide / unsaturated epoxide terpolymer of the present invention and is a novel substance.

  These polyether polymers (ii) can be used alone or in combination of two or more. The amount of the polyether polymer used is appropriately selected according to the intended use, but is usually 0.1 to 25 parts by weight, preferably 1 to 25 parts by weight, more preferably 100 parts by weight of the diene rubber. The range is 3 to 15 parts by weight. If the amount of the polyether polymer used is too small, the effect of improving the heat resistance, tensile strength, workability, etc. is not sufficient, and conversely if too large, the heat generation is not sufficient, both of which are preferable. Absent.

The silica silica is not particularly limited, for example, dry process white carbon, wet process white carbon, colloidal silica, and the like precipitated silica and the like disclosed in JP-62-62838 JP. Among these, wet method white carbon mainly containing hydrous silicic acid is particularly preferable.

The specific surface area of silica is not particularly limited, a nitrogen adsorption specific surface area (BET method) is usually 50 to 400 m ² / g, preferably from 100 to 250 m ² / g, more preferably in the range of 120~190m ² / g In this case, improvement in heat resistance, tensile strength, workability, etc. is sufficiently achieved, which is preferable. Here, the nitrogen adsorption specific surface area is a value measured by the BET method according to ASTM D3037-81.

  These silicas can be used alone or in combination of two or more. The mixing ratio of silica is appropriately selected according to the purpose of use, and is usually 10 to 200 parts by weight, preferably 20 to 150 parts by weight, more preferably 30 to 120 parts by weight with respect to 100 parts by weight of the diene rubber. .

  Silica and carbon black can be used in combination.

  The carbon black is not particularly limited, and for example, furnace black, acetylene black, thermal black, channel black, graphite and the like can be used. Among these, furnace black is particularly preferable, and specific examples thereof include those of various grades such as SAF, ISAF, ISAF-HS, ISAF-LS, IISAF-HS, HAF, HAF-HS, HAF-LS, and FEF. Is mentioned. These carbon blacks can be used alone or in combination of two or more.

The nitrogen adsorption specific surface area (N ₂ SA) of carbon black is not particularly limited, but is usually in the range of ^{5 to} 200 m ² / g, preferably 50 to 150 m ² / g, more preferably 80 to 130 m ² / g. . The DBP adsorption amount of carbon black is not particularly limited, but is usually in the range of 5 to 300 ml / 100 g, preferably 50 to 200 ml / 100 g, more preferably 80 to 160 ml / 100 g.

As carbon black, cetyltrimethylammonium bromide adsorption (CTAB) disclosed in JP-A-5-230290 has a specific surface area of 110 to 170 m ² / g, and after being repeatedly compressed 4 times at a pressure of 24,000 psi. Wear resistance can be improved by using high structure carbon black having a DBP (24M4DBP) oil absorption of 110 to 130 ml / 100 g.

  The mixing ratio when silica and carbon black are used in combination is appropriately selected according to the application and purpose, but the silica: carbon black (weight ratio) is usually 10:90 to 99: 1, preferably 30:70 to 95: 5, more preferably 50:50 to 90:10.

The addition of the silane coupling agent silane coupling agent, since耐発heat is further improved, which is preferable.

  The silane coupling agent is not particularly limited. For example, vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ- Glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane N-phenyl-γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, bis (3- (triethoxysilyl) propyl) tetrasulfide , And JP It is described in 6-248116 JP γ- trimethoxysilylpropyl dimethylthiocarbamoyl tetrasulfide, and the like tetrasulfide such as γ- trimethoxysilylpropyl benzothiazyl tetrasulfide.

  These silane coupling agents can be used alone or in combination of two or more. The blending ratio of the silane coupling agent is usually in the range of 0.1 to 30 parts by weight, preferably 1 to 20 parts by weight, and more preferably 2 to 10 parts by weight with respect to 100 parts by weight of silica.

Rubber composition In addition to the above-mentioned components, the rubber composition is a vulcanizing agent, a vulcanization accelerator, a vulcanization activator, an anti-aging agent, an activator, a plasticizer, a lubricant, a filler and the like according to a conventional method. The other compounding agents can be contained in necessary amounts.

  There are no particular limitations on the vulcanizing agent, but examples include sulfur such as powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, and highly dispersible sulfur; sulfur halides such as sulfur monochloride and sulfur dichloride; Organic peroxides such as oxide and ditertiary butyl peroxide; quinone dioximes such as p-quinone dioxime and p, p'-dibenzoylquinone dioxime; triethylenetetramine, hexamethylenediamine carbamate, 4,4'- Organic polyvalent amine compounds such as methylenebis-o-chloroaniline; alkylphenol resins having a methylol group; and the like. Among these, sulfur is preferable, and powdered sulfur is particularly preferable. These vulcanizing agents are used alone or in combination of two or more.

  The blending ratio of the vulcanizing agent is usually 0.1 to 15 parts by weight, preferably 0.3 to 10 parts by weight, and more preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the diene rubber. is there. When the blending ratio of the vulcanizing agent is within this range, the tensile strength is excellent, and the characteristics such as heat resistance and residual strain are also particularly preferable.

  Examples of the vulcanization accelerator include N-cyclohexyl-2-benzothiazole sulfenamide, Nt-butyl-2-benzothiazole sulfenamide, N-oxyethylene-2-benzothiazole sulfenamide, N- Sulfenamide vulcanization accelerators such as oxyethylene-2-benzothiazole sulfenamide and N, N'-diisopropyl-2-benzothiazole sulfenamide; such as diphenylguanidine, diortolylguanidine, orthotolylbiguanidine Guanidine vulcanization accelerators; thiourea vulcanization accelerators such as thiocarboanilide, diortolylthiourea, ethylenethiourea, diethylthiourea and trimethylthiourea; 2-mercaptobenzothiazole, dibenzothiazyl disulfide, 2-mercaptobe Thiazole vulcanization accelerators such as zothiazole zinc salt, 2-mercaptobenzothiazole sodium salt, 2-mercaptobenzothiazolecyclohexylamine salt, 2- (2,4-dinitrophenylthio) benzothiazole; tetramethylthiuram monosulfide, tetra Thiuram vulcanization accelerators such as methyl thiuram disulfide, tetraethyl thiuram disulfide, tetrabutyl thiuram disulfide, dipentamethylene thiuram tetrasulfide; sodium dimethyldithiocarbamate, sodium diethyldithiocarbamate, sodium di-n-butyldithiocarbamate, dimethyldithiocarbamic acid Lead, zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc di-n-butyldithiocarbamate, pentamethy Zinc dithiocarbamate, zinc ethylphenyldithiocarbamate, tellurium diethyldithiocarbamate, selenium dimethyldithiocarbamate, selenium diethyldithiocarbamate, copper dimethyldithiocarbamate, iron dimethyldithiocarbamate, diethylamine diethyldithiocarbamate, piperidine pentamethylenedithiocarbamate, methylpentamethylene And vulcanization accelerators such as dithiocarbamate vulcanization accelerators such as pipecoline dithiocarbamate; xanthogenic vulcanization accelerators such as sodium isopropylxanthate, zinc isopropylxanthate, and zinc butylxanthate;

  These vulcanization accelerators are used alone or in combination of two or more, and those containing at least a sulfenamide vulcanization accelerator are particularly preferred. The blending ratio of the vulcanization accelerator is usually 0.1 to 15 parts by weight, preferably 0.3 to 10 parts by weight, more preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the diene rubber. It is.

  The vulcanization activator is not particularly limited, and for example, higher fatty acids such as stearic acid and zinc oxide can be used. As zinc oxide, for example, it is preferable to use one having a high surface activity particle size of 5 μm or less, and specific examples thereof include active zinc white having a particle size of 0.05 to 0.2 μm or 0.3 to 1 μm, for example. Can be mentioned. In addition, zinc oxide that has been surface-treated with an amine-based dispersant or wetting agent can be used.

  These vulcanization activators can be used alone or in combination of two or more. The mixing ratio of the vulcanization activator is appropriately selected depending on the type of the vulcanization activator. When a higher fatty acid is used, it is usually 0.05 to 15 parts by weight, preferably 0.1 to 10 parts by weight, and more preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the diene rubber. When using a zinc oxide, it is 0.05-10 weight part normally with respect to 100 weight part of diene rubbers, Preferably it is 0.1-5 weight part, More preferably, it is 0.5-2 weight part. When the blending ratio of zinc oxide is within this range, the tensile strength and workability characteristics are highly balanced and suitable.

  Examples of other compounding agents include, for example, coupling agents other than silane coupling agents; activators such as diethylene glycol, polyethylene glycol, and silicone oil; fillers such as calcium carbonate, talc, and clay; process oils, waxes, and the like. Can be mentioned.

  The rubber composition can be obtained by kneading each component according to a conventional method. For example, a rubber composition can be obtained by mixing a compounding agent excluding a vulcanizing agent and a vulcanization accelerator and a diene rubber and then mixing a vulcanizing agent and a vulcanization accelerator in the mixture. The mixing temperature of the compounding agent excluding the vulcanizing agent and the vulcanization accelerator and the diene rubber is usually 80 to 200 ° C, preferably 100 to 190 ° C, more preferably 140 to 180 ° C, and the mixing time is usually It is 30 seconds or more, preferably 1 to 30 minutes. Mixing of the vulcanizing agent and the vulcanization accelerator is usually performed after cooling to 100 ° C. or lower, preferably from room temperature to 80 ° C., and then press vulcanized at a temperature of usually 120 to 200 ° C., preferably 140 to 180 ° C. .

  Hereinafter, the present invention will be described more specifically with reference to production examples, examples, reference examples, and comparative examples. Parts and% in these examples are based on weight unless otherwise specified.

  Various physical properties were measured according to the following methods.

(1) The amount of bound styrene in the polymer was measured according to JIS K6383 (refractive index method).

(2) The vinyl bond ratio of the butadiene bond unit in the polymer was measured by infrared spectroscopy (Hampton method).

(3) Mooney viscosity (ML _{1 + 4} , 100 ° C.) was measured according to JIS K6301.

(4) As for the tensile strength, 300% stress (Kgf / cm ² ) was measured according to JIS K6301. This property was expressed as an index (tensile strength index). A higher value is more preferable.

(5) For heat resistance, RDA-II manufactured by Rheometrics was used, and 1% twist and tan δ at 20 ° C. and 0 ° C. and 60 ° C. were measured. This characteristic was expressed as an index (exothermic index) with a value of tan δ 0 ° C./tan δ 60 ° C. as Comparative Example 100. A higher value is more preferable.

(6) The workability was judged by evaluating the winding property on the roll and the dispersibility of the silica according to the following criteria, and ranking it in 3 ranks based on the total score.
○: 7-8 points,
Δ: 5 to 6 points
×: 2 to 4 points

(I) Roll winding property:
4 points;
3 points;
2 points; wraps around, but often floats,
1 point: hardly wound.

(Ii) Dispersibility of silica: (Evaluated by SEM photograph of sample surface)
4 points; uniformly dispersed,
3 points: There is a slight difference in particle size, but it is uniformly dispersed.
2 points; large difference in particle size occurs
1 point: Almost no dispersion.

(7) Antistatic property is measured with a neostometer on the surface voltage of the sample after 10 kV discharge (measurement conditions: 23 ° C. ± 1 ° C., relative humidity 50 ± 5%, sample 40 × 40 × 2 mm, with electrode The distance was 20 mm) and evaluated according to the following criteria.
○;
Δ: Less than +0.5 kV,
X: +0.5 kV or more.

[Production Example 1] (Production of diene rubber Nos. 1 to 12)
Diene rubber No. 1 and 2 are polar groups containing a polar group such as N, N-dimethylaminopropylacrylamide (DAP) or 2-vinylpyridine (2VP) according to the emulsion polymerization method disclosed in JP-A-1-101344. The body was copolymerized and produced. Diene rubber No. Properties of 1 and 2 are shown in Table 1.

  Diene rubber No. 3-12 are polar group-containing after (co) polymerizing butadiene or butadiene and styrene using n-butyllithium as an initiator according to the anionic polymerization method disclosed in JP-B-6-18933 This was produced by reacting a modifying agent and a polyfunctional coupling agent. Diene rubber No. The properties of 3 to 12 are shown in Table 1.

footnote:
(* 1) A: emulsion polymerization, B: anionic polymerization (* 2) modifier:
DAP; N, N-dimethylaminopropylacrylamide,
EAB; 4,4′-bis (dimethylamino) benzophenone,
AST; N, N-dimethylaminostyrene,
EO; ethylene oxide,
NMC; N-methyl-ε-caprolactam,
NMP; N-methylpyrrolidone,
NPP; N-phenylpyrrolidone.

(* 3) modifier / n-butyllithium (equivalent ratio)
(* 4) Coupling agent:
TMSi; tetramethoxysilane,
TCSn; tin tetrachloride.

(* 5) Coupling agent / n-butyllithium (equivalent ratio)
(* 6) DAP; N, N-dimethylaminopropylacrylamide (* 7) 2VP; 2-vinylpyridine

[Production Example 2] (Production of polyether polymer Nos. 1 to 6)
Polyether polymer No. No. 1 according to the method described in Japanese Patent Publication No. 35-15797, and polyether polymer no. Nos. 2 to 3 were produced according to the method described in JP-B-56-51171. Polyether polymer No. Nos. 4 to 6 were produced according to the slurry polymerization method described in JP-A-61-58488. More specifically, it is as follows.

<Polyether polymer No. 1>
(Preparation of catalyst solution)
A pressure-resistant glass bottle with an inner volume of 800 ml that was sealed was replaced with nitrogen, and 180 g of toluene and 60 g of triisobutylaluminum were charged. After the glass bottle was immersed in ice water and cooled, 109.1 g of tetrahydrofuran was added and stirred. Next, while cooling with ice water, 2.72 g of distilled water was added and stirred. At this time, the pressure in the bottle increased due to the reaction between the organic aluminum and water, and therefore depressurization was carried out in a timely manner. Next, 15.1 g of acetylacetone was added and stirred while cooling with ice water. The resulting reaction mixture was aged for 20 hours in a warm water bath at 30 ° C. to obtain a catalyst solution.

(Preparation of polymer)
An autoclave equipped with a stirrer with an internal volume of 5 liters was purged with nitrogen, and charged with 2250 g of toluene, 180 g of ethylene oxide, and 70 g of propylene oxide. The internal temperature was set to 50 ° C., and 5 ml of the catalyst solution was added to initiate the reaction. Further, 5 ml of the catalyst solution was added every 30 minutes to allow the reaction to proceed. After the catalyst solution was added 10 times, a post reaction was performed for 2 hours. The polymerization reaction rate was 85%. 42.5 g of a 5% toluene solution of 4,4′-thiobis (6-tertiarybutyl-cresol) was added to the polymer solution taken out and stirred. The polymer solution was dropped into a large amount of n-hexane to precipitate the polymer. The polymer was separated from the solvent and vacuum dried at 60 ° C. overnight.

(Analysis of polymer)
The composition of the polymer was determined by ¹ H-NMR analysis. All the polyether polymers described below were similarly subjected to composition determination by ¹ H-NMR analysis.

<Polyether polymer No. 2>
(Preparation of catalyst solution)
A pressure-resistant glass bottle with an inner volume of 800 ml that was sealed was replaced with nitrogen, and 180 g of toluene and 60 g of triisobutylaluminum were charged. The glass bottle was immersed in ice water and cooled, and then 224.2 g of diethyl ether was added and stirred. Next, 8.89 g of normal phosphoric acid was added and stirred while cooling with ice water. At this time, the pressure in the bottle increased due to the reaction between organoaluminum and orthophosphoric acid. Next, 8.98 g of 1,8-diaza-bicyclo (5,4,0) undecene-7 formate was added. The resulting reaction mixture was aged for 1 hour in a warm water bath at 30 ° C. to obtain a catalyst solution.

(Preparation of polymer)
An autoclave equipped with a stirrer with an internal volume of 5 liters was purged with nitrogen, and charged with 2250 g of toluene, 225 g of ethylene oxide, and 25 g of allyl glycidyl ether. The internal temperature was set to 50 ° C., and 4 ml of the catalyst solution was added to initiate the reaction. Further, 4 ml of the catalyst solution was added every 30 minutes to allow the reaction to proceed. After the catalyst solution was added 10 times, a post reaction was performed for 2 hours. The polymerization reaction rate was 92%. To the polymer solution taken out, 46 g of a 5% toluene solution of 4,4′-thiobis (6-tertiarybutyl-cresol) was added and stirred. The polymer solution was dropped into a large amount of n-hexane to precipitate the polymer. The polymer was separated from the solvent and vacuum dried at 60 ° C. overnight.

<Polyether polymer No. 3>
(Preparation of polymer)
An autoclave equipped with a stirrer with an internal volume of 5 liters was purged with nitrogen, and charged with 2250 g of toluene, 235 g of propylene oxide, and 15 g of allyl glycidyl ether. When the internal temperature was set to 50 ° C., the polyether polymer No. The reaction was started by adding 3 ml of the catalyst solution used in 2. Further, 3 ml of the catalyst solution was added every 30 minutes to allow the reaction to proceed. After the catalyst solution was added 10 times, a post reaction was performed for 2 hours. The polymerization reaction rate was 94%. 47 g of a 5% toluene solution of 4,4′-thiobis (6-tertiarybutyl-cresol) was added to the polymer solution taken out and stirred. Steam was blown into the polymer solution to remove the solvent and unreacted monomer by steam stripping. The obtained polymer was vacuum-dried overnight at 60 ° C.

<Polyether polymer No. 4>
(Preparation of catalyst solution)
The autoclave with a stirrer having an internal volume of 3 liters was purged with nitrogen, and 158.7 g of triisobutylaluminum, 1170 g of toluene, and 296.4 g of diethyl ether were charged. The internal temperature was set to 30 ° C., and 23.5 g of normal phosphoric acid was gradually added while stirring. Further, 12.1 g of triethylamine was added, and a ripening reaction was performed at 60 ° C. for 2 hours to obtain a catalyst solution.

(Preparation of polymer)
The autoclave with a stirrer having an internal volume of 5 liters was purged with nitrogen, and 2100 g of n-hexane and 63 g of the catalyst solution were charged. The internal temperature was set to 30 ° C., and 5% of a mixed solution consisting of 264 g of ethylene oxide, 30 g of propylene oxide, 6 g of allyl glycidyl ether, and 300 g of n-hexane was added with stirring. After the reaction for 1 hour, the internal temperature was set to 60 ° C., and the remaining 95% of the mixed solution was continuously added over 5 hours. After completion of the addition, the reaction was performed after 2 hours. The polymerization reaction rate was 90%. When the inside of the polymerization can was confirmed, almost the entire amount of the polymer was attached to the wall of the polymerization can and the stirring blade, but the polymer attached to the wall and the stirring blade was recovered. The obtained polymer was subjected to vacuum drying at 60 ° C. overnight after separating the solvent with a wire mesh.

<Polyether polymer No. 5>
(Preparation of catalyst solution)
An autoclave with a stirrer with an internal volume of 5 liters was purged with nitrogen, and 2100 g of n-hexane and a polyether polymer No. 4g catalyst solution 63g was charged. The internal temperature was set to 30 ° C., and a mixed solution consisting of 2 g of ethylene oxide, 4 g of propylene oxide and 6 g of n-hexane was added with stirring, and aged for 1 hour.

(Preparation of polymer)
The internal temperature of the catalyst solution after the above treatment was set to 60 ° C., and a mixed solution consisting of 260 g of ethylene oxide, 25 g of propylene oxide, 15 g of allyl glycidyl ether and 300 g of normal hexane was continuously added over 5 hours. After completion of the addition, the reaction was performed after 2 hours. The polymerization reaction rate was 96%. Polyether polymer No. The polymer obtained in comparison with No. 4 was in a clean slurry state, and the inner wall surface of the autoclave and the stirring blade were very clean. To the obtained slurry, 57.6 g of a 5% toluene solution of 4,4′-thiobis (6-tertiarybutyl-cresol) was added and stirred. After separating the solvent with a wire mesh, the powdery polymer was vacuum-dried overnight at 40 ° C. A clean powdery polymer sample was obtained.

<Polyether polymer No. 6>
(Preparation of catalyst solution)
An autoclave with a stirrer with an internal volume of 5 liters was purged with nitrogen, and 2100 g of n-hexane and a polyether polymer No. 4g catalyst solution 63g was charged. The internal temperature was set to 30 ° C., and a mixed solution consisting of 2 g of ethylene oxide, 4 g of propylene oxide and 6 g of n-hexane was added with stirring, and aged for 1 hour.

(Preparation of polymer)
The internal temperature of the catalyst solution after the above treatment was set to 60 ° C., and a mixed solution consisting of 260 g of ethylene oxide, 20 g of propylene oxide, 20 g of allyl glycidyl ether, and 300 g of n-hexane was continuously added over 5 hours. After completion of the addition, the reaction was performed after 2 hours. The polymerization reaction rate was 95%. Polyether polymer No. Compared to 4, the obtained polymer was in a clean slurry state, and the inner wall surface of the autoclave and the stirring blade were very clean. To the obtained slurry, 57 g of a 5% toluene solution of 4,4′-thiobis (6-tertiarybutyl-cresol) was added and stirred. After separating the solvent with a wire mesh, the powdery polymer was vacuum-dried overnight at 40 ° C. A clean powdery polymer sample was obtained. These results are shown in Table 2.

footnote:
(* 1) EO; ethylene oxide (* 2) PO; propylene oxide (* 3) AGE; allyl glycidyl ether

[Examples 1-9, Comparative Examples 1-2]
As the raw rubber, the diene rubbers listed in Table 4 of commercial products and the diene rubber No. 1 prepared in Production Example 1 were used. 1 to 6 and polyether polymer No. 1 prepared in Production Example 2. 5 and mixing the total amount of raw rubber, half of silica and half of silane coupling agent at 170 ° C. for 2 minutes in a 250 ml Brabender type mixer, and then added with sulfur. The remaining compounding agents except for the sulfur accelerator were added and kneaded for 2 minutes at the same temperature.

  Next, the obtained mixture, sulfur and a vulcanization accelerator were added to a 50 ° C. open roll and kneaded, and then press vulcanized at 160 ° C. for 30 minutes to prepare a test piece, and each physical property was measured. The results are shown in Table 4.

footnote:
(* 1) Si69 (Degussa)
(* 2) Sunsen 410 (Nippon Oil Co., Ltd.)
(* 3) Nocrack 6C (Ouchi Shinsei Co., Ltd.)
(* 4) Noxeller CZ (made by Ouchi Shinsei)

footnote:
(* 1) Styrene butadiene copolymer rubber [styrene content 23.5%, Mooney viscosity (ML _{1 + 4} , 100 ° C.) = 50; manufactured by Nippon Zeon Co., Ltd.]
(* 2) Z1165MP (nitrogen adsorption specific surface area = 175 m ² / g; manufactured by Rhône Poulenc)
(* 3) Nipsil AQ (nitrogen adsorption specific surface area = 200 m ² / g; manufactured by Nippon Silica)
(* 4) These indices were set to 100 in Comparative Example 2.

  From the results of Table 4, it can be seen that the rubber compositions (Examples 1 to 9) are excellent in all of the properties of tensile strength, heat resistance and workability, and sufficiently excellent in antistatic properties. Further, the blending amount of the polyether-based polymer is such that the effect of modification is exhibited even at 1 part by weight with respect to 100 parts by weight of the diene rubber (Example 1), and the polar group-containing diene rubber as the diene rubber. The properties of tensile strength, heat resistance and workability are more highly balanced when using (Examples 4 to 9). Further, when silica having a small specific surface area is blended, the tensile strength, heat resistance and It can be seen that the workability is more highly balanced (Examples 2 to 8). On the other hand, the rubber composition of diene rubber and silica (Comparative Examples 1 and 2) to which no polyether polymer is added is inferior in processability, has insufficient tensile strength and heat resistance, and is charged. It turns out that there is a problem.

[Examples 10 to 14, Comparative Example 3]
As the raw rubber, diene rubbers listed in Table 6 as commercially available products, diene rubber No. 1 prepared in Production Example 1 were used. 7 to 11 and polyether polymer No. 1 prepared in Production Example 2. 5 and mixing the total amount of raw rubber, half of silica and half of silane coupling agent at 170 ° C. for 2 minutes in a 250 ml Brabender type mixer, and then added with sulfur. The remaining ingredients except for the sulfur accelerator were added and kneaded for 3 minutes at the same temperature.

  Next, the obtained mixture, sulfur and a vulcanization accelerator were added to a 50 ° C. open roll and kneaded, and then press vulcanized at 160 ° C. for 30 minutes to prepare a test piece, and each physical property was measured. The results are shown in Table 6.

footnote:
(* 1) Ultrazil VN3 (nitrogen adsorption specific surface area = 175 m ² / g; manufactured by Degussa)
(* 2) Si69
(* 3) Fukkor M (Fuji Kosan Co., Ltd.)
(* 4) Nocrack 6C
(* 5) Noxeller D (made by Ouchi Shinsei)
(* 6) Noxeller CZ

footnote:
(* 1) Polyisoprene rubber [Mooney viscosity (ML _{1 + 4} , 100 ° C.) = 100; manufactured by Zeon Corporation]
(* 2) These indices were set to 100 in Comparative Example 3.

  From the results of Table 6, even when various styrene-butadiene copolymer rubbers having different styrene content and vinyl bond content of the butadiene bond portion are used as the diene rubber, the rubber compositions (Examples 10 to 14) have a tensile strength, It can be seen that both the heat resistance and the workability are sufficiently excellent and the antistatic property is also sufficiently excellent. It can also be seen that when the styrene content of the styrene-butadiene copolymer rubber is in the range of 10 to 50%, more preferably 15 to 40%, the tensile strength and the heat resistance are highly balanced.

[Reference Examples 1 and 2, Examples 15 to 19, Comparative Example 4]
As raw rubbers, diene rubbers described in Table 8 as commercially available products, diene rubber No. 1 prepared in Production Example 1 were used. 4 and 12, and the polyether polymer No. 1 prepared in Production Example 2. 1 and no. 3 to 6, and based on the formulation of Table 7, in a Brabender type mixer with a capacity of 250 ml, all the raw rubber, half of the silica and half of the silane coupling agent were mixed at 170 ° C. for 2 minutes, and then sulfur And the rest of the ingredients except for the vulcanization accelerator were added and kneaded for 3 minutes at the same temperature.

  Next, the obtained mixture, sulfur and a vulcanization accelerator were added to a 50 ° C. open roll and kneaded, and then press vulcanized at 160 ° C. for 30 minutes to prepare a test piece, and each physical property was measured. The results are shown in Table 8.

footnote:
(* 1) Z1165MP
(* 2) Si69
(* 3) Nocrack 6C
(* 4) Noxeller D
(* 5) Noxeller CZ

footnote:
(* 1) Polybutadiene rubber [Mooney viscosity (ML _{1 + 4} , 100 ° C.) = 45; manufactured by Zeon Corporation]
(* 2) Natural rubber [Mooney viscosity (ML _{1 + 4} , 100 ° C.) = 60]
(* 3) The index of Comparative Example 4 was 100.

  From the results of Table 8, the rubber compositions (Reference Examples 1 and 2 and Examples 15 to 19) are excellent in all of the properties of tensile strength, heat resistance, and processability, and sufficiently excellent in antistatic properties. You can see that Further, as a polyether polymer to be blended, a copolymer obtained by copolymerizing an unsaturated epoxide such as allyl glycidyl ether markedly improved properties such as tensile strength and heat resistance (Reference Example 2, Examples 15 to 19). ), When the content of allyl glycidyl ether is 1 to 5% by weight, the effect of improving them is the highest (Examples 15 to 17), and when an ethylene oxide content is high, antistatic properties are high. (Reference example 1, Examples 15-19) etc. are understood. On the other hand, the rubber composition (Comparative Example 4) to which diethylene glycol is added instead of the polyether polymer is inferior in processability, is not sufficient in improving effects such as tensile strength and heat resistance, and has an antistatic effect. I understand that there is no.

[Reference Examples 3 and 4, Comparative Examples 5 and 6]
As the raw rubber, diene rubbers listed in Table 10 as commercially available products, diene rubber No. 1 prepared in Production Example 1 were used. 10 and the polyether polymer No. 1 prepared in Production Example 2. 2 and based on the formulation of Table 9, in a Brabender type mixer with a capacity of 250 ml, the total amount of raw rubber, the total amount of polyether polymer, the half amount of silica and the half amount of silane coupling agent at 170 ° C. After mixing for 2 minutes, the remaining ingredients except for sulfur and vulcanization accelerator were added and kneaded for 3 minutes at the same temperature.

  Next, the obtained mixture, sulfur and a vulcanization accelerator were added to a 50 ° C. open roll and kneaded, and then press vulcanized at 160 ° C. for 30 minutes to prepare a test piece, and each physical property was measured. The results are shown in Table 10.

footnote:
(* 1) Z1165MP
(* 2) Seast KH (Tokai Carbon Co., Ltd.)
(* 3) Si69: 8% by weight of silica
(* 4) Nocrack 6C
(* 5) Noxeller CZ

footnote:
(* 1) Natural rubber [Mooney viscosity (ML _{1 + 4} , 100 ° C.) = 50]
(* 2) The index of Comparative Example 5 was 100.

  From the results shown in Table 10, it can be seen that the rubber composition (Reference Examples 3 and 4) is excellent in all of the properties of tensile strength, heat resistance, and processability, and sufficiently excellent in antistatic properties. On the other hand, it is possible to improve the antistatic property by adding carbon black without adding a polyether polymer, but the heat resistance is inferior, and the tensile strength and workability are not sufficiently improved. Example 6)

  When the ethylene oxide / propylene oxide / unsaturated epoxide terpolymer of the present invention is used, the tensile strength, which has been regarded as a defect, is maintained without impairing the good rolling resistance (heat resistance) characteristic of the silica-containing rubber material. And a rubber composition having greatly improved processability. In addition, this rubber composition has a sufficiently excellent antistatic property. Therefore, this rubber composition is used in various applications that make use of these characteristics, for example, in various parts of tires such as treads, carcass, sidewalls, bead parts, or hoses, window frames, belts, shoe soles, vibration-proof rubbers. It can be used for rubber products such as automobile parts, and further as resin reinforced rubber for impact-resistant polystyrene, ABS resin, and the like. In particular, this rubber composition is excellent in tire treads of low fuel consumption tires by taking advantage of the above characteristics, but also other tire treads such as all-season tires, high performance tires, studless tires, side walls, under treads, carcass. Can be used for beat part etc.

Claims (1)

Ethylene oxide / propylene oxide comprising 50 to 98.9% by weight of ethylene oxide, 1 to 35% by weight of propylene oxide and 0.1 to 15% by weight of unsaturated epoxide, and having a Mooney viscosity (ML _{1 + 4} , 100 ° C.) of 70 to 150 Unsaturated epoxide terpolymer.