JPH09291121A - Butene/butadiene copolymer, its production, and vulcanized rubber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a copolymer desirably used for tire treads satisfying all of low fuel consumption, low heat buildup, abrasion resistance, wet skid resistance and grip during continuous high-speed running while keeping them at high levels by selecting a copolymer having a structure in which a plurality of specified monomer components are bonded to each other at random. SOLUTION: This copolymer comprises 10-90mol% 1-butene structures (A), 90-10mol% 1,4-butadiene structures (B), 3mol% or below 1,2-butadiene structures (C), and 3mol% or below ethylene structures (D). The copolymer has a manner of random bonding of components, a molecular weight of 10,000-1,000,000, and a molecular weight distribution (Mw/Mn) of 1-5. When it further contains 1-30mol% styrene structure in addition to components A to D, it has improved tensile strength, abrasion resistance and wet skid resistance.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a tire tread which is more excellent in satisfying fuel saving, low heat generation, wear resistance, wet skidability, grip performance in continuous high speed operation, etc. at an extremely high level at the same time. The present invention relates to a novel butene-butadiene copolymer capable of providing the above, a method for producing the same, and a vulcanized rubber using the same.

[0002]

2. Description of the Related Art Conventionally, in comparison with automobile tires, rolling resistance is reduced in terms of fuel efficiency, steering stability and wet skidability (braking performance on wet road surface) from the aspect of automobile safety. In terms of improvement of tire quality and productivity of tires, it has been demanded to improve quality by improving workability. However, these characteristics tend to conflict with each other, and it was quite difficult to improve all the characteristics.

In recent years, there has been an increasing demand for tires with higher fuel efficiency that lead to energy saving due to environmental protection problems, and at the same time, due to the development of the expressway network, grip at high level in continuous high speed driving. Performance is required. As a method of reducing rolling resistance while maintaining the wet skid properties of tires, methods such as weight reduction of tires, optimization of tire structure, improvement of tread pattern, improvement of rubber compound used for tire tread, etc. are tried. Has been. Among these, as a method of improving the rubber compound used for the tire tread and reducing rolling resistance, a method of using a raw material rubber with less hysteresis loss, a method of using a carbon black having a large particle size, carbon Various methods have been proposed, such as a method of reducing the amounts of black and oil.

On the other hand, the rubber to be used has been improved, and the present inventors have previously proposed that the vinyl bond selectively has partial hydrogen with high modulus, impact resilience, low exothermicity and heat aging resistance. A selected partially hydrogenated rubber having a specific structure was proposed (Japanese Patent Publication No. 5-20442).

[0005]

However, future automobile tires will have a high level of fuel saving characteristics, and at the same time will have low heat generation, wear resistance, wet skid, and grip performance in continuous high speed operation. There is a need for even better rubbers that satisfy extremely high standards, but rubbers that meet these requirements have not yet been obtained.

[0006]

As a result of extensive studies to solve the above-mentioned problems, polybutadiene and butadiene-containing 1,2-butadiene having a highly selectively hydrogenated structure.
A styrene copolymer was obtained. That is, the present invention is a copolymer of 1-butene and 1,3-butadiene, or 1-butene.
A copolymer of butene, 1,3-butadiene and styrene, a method for producing the same, and a vulcanized rubber using the same.

The present invention has a high level of fuel efficiency, and has low heat build-up, abrasion resistance, wet skid, and grip performance in continuous high-speed operation at an extremely high level at the same time. A rubber with excellent performance is obtained, which is industrially excellent. Hereinafter, the present invention will be described in detail. The first aspect of the present invention is that the constituent monomer components are 1-butene structure (A), 1,4-butadiene structure (B), 1,
It consists of a 2-butadiene structure (C) and an ethylene structure (D), and the composition ratio of each component is such that (A) component is 10 to 90 mol%, (B) component is 90 to 10 mol%, and (C) component and Component (D) is 3 mol% or less, and the binding mode of each component is random. The molecular weight is 10,000 to 1,
It is a copolymer having a molecular weight distribution Mw / Mn of 1 to 5,000,000.

In the second aspect of the present invention, the constituent monomer components are 1-butene structure (A), 1,4-butadiene structure (B), 1,2-butadiene structure (C) and ethylene structure (D). ) And a styrene structure (S), the composition ratio of each component is such that (A) component is 10 to 89 mol%, (B) component is 89 to 10 mol%, and (C) component and (D) component are respectively. 3 mol% or less, the (S) component is 1 to 30 mol%, and the binding mode of each component is random and the molecular weight is 10,
It is a copolymer having a molecular weight distribution Mw / Mn of 1 to 5 and 000 to 1,000,000.

In a third aspect of the present invention, the constituent monomer component comprises a 1,2-butadiene structure (C) and a 1,4-butadiene structure (B), and the component (C) is 10 to 90 mol. %, The content of the component (B) is 90 to 10 mol%, and polybutadiene having a random bonding mode of the component (C) and the component (B) is used, and 90 of the double bonds of the 1,2-butadiene structure is used.
When the ratio r1 / r2 of the hydrogenation rate r1 of 1,2-butadiene when 1% is hydrogenated and the hydrogenation rate r2 of the double bond of the 1,4-butadiene structure is 5 or more, 1,2 A method for obtaining the copolymer of the first invention, characterized in that the hydrogenation is stopped when the butadiene structure is consumed to 3 mol% or less.

In a fourth aspect of the present invention, the constituent monomer components are composed of a 1,2-butadiene structure (C), a 1,4-butadiene structure (B) and a styrene structure (S),
Component (C) is 10 to 89 mol%, component (B) is 89 to 1
0 mol%, (S) component is 1 to 30 mol%, a butadiene-styrene copolymer in which the bonding mode of each component is random is used, and 90 of double bonds of 1,2-butadiene structure is used.
When the ratio r1 / r2 of the hydrogenation rate r1 of 1,2-butadiene when 1% is hydrogenated and the hydrogenation rate r2 of the double bond of the 1,4-butadiene structure is 5 or more, 1,2 -A method for obtaining the copolymer of the second invention, which is characterized in that the hydrogenation is stopped when the butadiene structure is consumed to 3 mol% or less.

A fifth aspect of the present invention is the third aspect of the invention, wherein the dicyclopentadienyl titanium compound and a reducing agent or their reaction products are used as hydrogenation catalysts and the temperature during hydrogenation is 80 to 140 ° C. It is a method for obtaining the described copolymer. 6th of this invention uses the dicyclopentadienyl titanium compound and a reducing agent or these reaction products as a hydrogenation catalyst, The temperature at the time of hydrogenation is 80-140 degreeC. It is a method of obtaining a polymer.

In a seventh aspect of the present invention, the constituent monomer components are 1-butene structure (A), 1,4-butadiene structure (B), 1,2-butadiene structure (C) and ethylene structure (D). ), The composition ratio of each component is such that (A) component is 10 to 90 mol%, (B) component is 90 to 10 mol%,
The component (C) and the component (D) are each 3 mol% or less, and the binding mode of each component is random and the molecular weight is 1
10,000 to 1,000,000, molecular weight distribution Mw / M
It is a vulcanized rubber obtained by using 10% by weight or more of the copolymer according to the first invention, wherein n is 1 to 5, in the rubber component.

In the eighth aspect of the present invention, the constituent monomer components are 1-butene structure (A), 1,4-butadiene structure (B), 1,2-butadiene structure (C), ethylene structure (D). ) And a styrene structure (S), the composition ratio of each component is such that (A) component is 10 to 89 mol%, (B) component is 89 to 10 mol%, and (C) component and (D) component are respectively. 3 mol% or less, the (S) component is 1 to 30 mol%, and the binding mode of each component is random and the molecular weight is 10,
It is a vulcanized rubber in which the copolymer described in the second invention having a molecular weight distribution Mw / Mn of 000 to 1,000,000 and 1 to 5 is used in an amount of 10% by weight or more in the rubber component.

In the present invention, the constituent monomer components are 1-butene structure (A), 1,4-butadiene structure (B), 1,
2-butadiene structure (C) and ethylene structure (D) or 1-butene structure (A), 1,4-butadiene structure (B), 1,2-butadiene structure (C), ethylene structure (D) and styrene structure It is composed of the component (S), and the composition ratio of each component is within the above range. If these composition ratios are deviated from, it is impossible to satisfy the high fuel saving characteristics, low heat generation, wet skid characteristics, and grip performance in continuous high-speed operation, which are the features of the present invention, at an extremely high level at the same time. When the styrene structure (S) is 0, low temperature performance and fuel economy are excellent, and compatibility with natural rubber is particularly excellent, and performance such as fuel economy when using a blend is good. When the styrene structure (S) is 1 to 30 mol%, the tensile strength, abrasion resistance and wet skid property are excellent. The 1,2-butadiene structure (C) component and the ethylene structure (D) component are each 3 mol% or less, preferably 1 mol% or less. In terms of production, preferably 0.01 mol% each
That is all. If the ratio of these components is high, the grip performance in continuous high-speed operation, which is particularly important among the effects of the present invention, deteriorates.

The binding mode of each component of the present invention needs to be random. If the specific components continuously form a block, the excellent performance of the present invention cannot be obtained. The composition may be distributed continuously or discontinuously within the composition ratio within the range of the present invention. The molecular weight of the present invention is 10,000-1,
If the molecular weight is less than 10,000, the strength and other properties of the vulcanized rubber are poor, and the molecular weight is 1,000,
If it exceeds 000, processing becomes difficult. Molecular weight distribution Mw /
Mn is 1 to 5. If it is 1 or less, it does not exist, and if it is 5 or more, the wear resistance and other properties are poor.

In the present invention, the constituent monomer components are
Consisting of a 2-butadiene structure (C) and a 1,4-butadiene structure (B), the component (C) being 10 to 90 mol%,
The component (B) is 90 to 10 mol%, and the polybutadiene or the 1,2-butadiene structure (C) or the 1,4-butadiene structure (B) in which the bonding mode of the component (C) and the component (B) is random. ) And a styrene structure (S),
Component (C) is 10 to 89 mol%, component (B) is 89 to 1
0 mol%, (S) component is 1 to 30 mol%, the bonding mode of each component is random, and the double bond of 1,2-butadiene structure is selectively hydrogenated. It can be obtained by converting. The copolymer of the present invention cannot be obtained from any other polybutadiene or butadiene-styrene copolymer.

The polybutadiene or butadiene-styrene copolymer used in the present invention is preferably one obtained by solution polymerization in a hydrocarbon solvent. The solution-polymerized polybutadiene or butadiene-styrene copolymer is preferably a lithium initiator such as alkyl lithium, lithium amide, alkyl tin lithium, or alkylamino tin lithium, or an organic alkaline earth metal compound-based initiator, preferably , Ethers, tertiary amines, alkali metal alcoholates or sulfonates.

The method of polymerization may be either batch polymerization or continuous polymerization. By the way, as a method for hydrogenating the butadiene portion of polybutadiene and butadiene-styrene copolymer, nickel, cobalt, platinum, a catalyst in which a metal such as palladium is supported on carbon, silica, alumina, diatomaceous earth, iron, Although catalysts containing an organometallic compound of nickel, cobalt or rhodium as a main component are known, all of them have low hydrogenation activity,
Since the hydrogenation selectivity of 2-butadiene is low, the copolymer of the present invention has not been obtained.

The present inventors have previously proposed a selected partially hydrogenated rubber having a specific structure in which a vinyl bond is selectively partially hydrogenated by a highly active hydrogenation catalyst containing an organometallic compound of titanium as a main component. (Japanese Patent Publication No. 5-20442). However, the high degree of selectivity of the 1,2-butadiene structure in hydrogenation still has room for improvement. This is 1,2 when 90% of the double bonds in the 1,2-butadiene structure are hydrogenated.
Hydrogenation is carried out at a ratio r1 / r2 of the hydrogenation rate r1 of butadiene and the hydrogenation rate r2 of the double bond of the 1,4-butadiene structure of 5 or more, and the 1,2-butadiene structure is consumed to 3 mol% or less. This is achieved by the method for producing a copolymer of the present invention in which hydrogenation is stopped at a certain point, whereby the copolymer of the present invention is obtained. When r1 / r2 is less than 5, the ethylene structure (D) exceeds 3 mol%, so that the copolymer of the present invention cannot be obtained. If the hydrogenation is stopped before the 1,2-butadiene structure is consumed to 3 mol% or less, the copolymer of the present invention cannot be obtained. On the other hand, when the 1,2-butadiene structure is consumed to 3 mol% or less and the hydrogenation reaction is continued even after the 1,2-butadiene structure becomes 0, the ethylene structure increases and the copolymerization of the present invention increases. I can't get a coalescence.

In the method for producing the copolymer of the present invention, preferably, a dicyclopentadienyl titanium compound and a reducing agent or a reaction product of these are used as a hydrogenation catalyst at a hydrogenation temperature of 80 to 140 ° C. A method of selective hydrogenation. More preferably, the dicyclopentadienyl titanium compound is preferably at least one of the specific compounds represented by the following general formula.

[0021]

Embedded image

R1, R2, R3, R4 and R5 each represent hydrogen or a hydrocarbon group having 1 to 12 carbon atoms, and 3 or more and 5 or more of them are hydrocarbon groups, which may be the same. It can be different. R6 and R7 are groups selected from a hydrocarbon group having 1 to 12 carbon atoms, an aryloxy group, an alkoxy group, a halogen group and a carbonyl group, and R6 and R7 may be the same or different. As the organic titanium compound, for example, di-p-tolylbis (η
5-trimethylcyclopentadienyl) titanium, di-p
-Tolylbis (η5-tributylcyclopentadienyl) titanium, di-p-tribis (η5-tetramethylcyclopentadienyl) titanium, di-p-tolylbis (η
5-pentamethylcyclopentadienyl) titanium, diphenylbis (η5-penta-n-butylcyclopentadienyl) titanium, dichlorobis (η5-pentamethylcyclopentadienyl) titanium, dibromobis (η5-pentamethylcyclopentadiene) (Phenyl) titanium, difluorobis (η5-pentamethylcyclopentadienyl) titanium, diiodobis (η5-pentamethylcyclopentadienyl) titanium, dichlorobis (η5-tetramethylcyclopentadienyl) titanium, dichlorobis (η5-pentabutylcyclo) Pentadienyl) titanium, dimethylbis (η5-tetramethylcyclopentadienyl) titanium, dimethylbis (η5-pentamethylcyclopentadienyl) titanium, diethylbis (η5-tetramethylcyclopentadienyl) titanium, dihexylbis (Η5-
Pentamethylcyclopentadienyl) titanium, dioctylbis (η5-tetramethylcyclopentadienyl) titanium, dibenzylbis (η5-pentamethylcyclopentadienyl) titanium, dimethoxybis (η5-pentamethylcyclopentadienyl) titanium, Diethoxybis (η5-pentamethylcyclopentadienyl) titanium,
Di-n-butoxybis (η5-tributylcyclopentadienyl) titanium, diphenoxybis (η5-pentamethylcyclopentadienyl) titanium, dimethoxybis (η5-trimethylcyclopentadienyl) titanium, dimethoxybis (η5-tetra Methylcyclopentadienyl) titanium, methylbis (η5-pentamethylcyclopentadienyl) titanium chloride, methoxybis (η5-
Pentamethylcyclopentadienyl) titanium chloride,
Phenoxybis (η5-trimethylcyclopentadienyl) titanium chloride, and the like.

Of these, particularly preferred are di-m-tolylbis (η5-pentamethylcyclopentadienyl) titanium, di-p-tolylbis (η5-pentamethylcyclopentadienyl) titanium and di-p-tolylbis (η5). -
Tetramethylcyclopentadienyl) titanium, dichlorobis (η5-pentamethylcyclopentadienyl) titanium, and dichlorobis (η5-tetramethylcyclopentadienyl) titanium.

The reducing agent is preferably an alkali metal, alkaline earth metal, aluminum or zinc organometallic compound or hydride, and the organometallic compound is, for example, a living anion polymer or the above-mentioned polymerization initiator. An organolithium compound, an organosodium compound,
Organic potassium compounds, 2 organic substituted magnesium, organic substituted magnesium halides, 3 organic substituted aluminum, organic substituted aluminum halogenides, organic substituted aluminum hydrides, 2 organic substituted zinc and the like.

Specifically, methyllithium, ethyllithium, n-propyllithium, n-butyllithium, se
c-butyl lithium, tert-butyl lithium, hexyl lithium, octyl lithium, phenyl lithium,
Trilyl lithium, methyl sodium, ethyl sodium, n-propyl sodium, n-butyl sodium,
sec-butyl sodium, tert-butyl sodium, hexyl sodium, octyl sodium, phenyl sodium, tolyl sodium, sodium naphthalene, methyl potassium, ethyl potassium, n-propyl potassium, n-butyl potassium, sec-butyl potassium, tert-butyl potassium. , Hexyl potassium, octyl potassium, phenyl potassium, tolyl potassium,
Potassium naphthalene, dimethyl magnesium, diethyl magnesium, di-n-butyl magnesium, n-butyl-i-butyl magnesium, n-butyl-ethyl magnesium, tributyl sodium magnesium, methyl magnesium bromide, ethyl magnesium bromide, ethyl magnesium chloride, t- Butyl magnesium bromide, t-butyl magnesium chloride, phenyl magnesium bromide, triethyl aluminum, tri-i-butyl aluminum, triphenyl aluminum, diethyl aluminum chloride, diethyl aluminum hydride, di-i-butyl aluminum hydride, diethyl zinc, bis (η5 -Cyclopentadienyl) zinc, diphenyl zinc and the like.

As another preferable combination of the dicyclopentadienyl titanium compound and the reducing agent or the reaction product thereof, the dicyclopentadienyl titanium compound is at least one of the specific compounds represented by the following general formula. , The following specific reducing agents.

[0027]

Embedded image

R1, R2, R3, R4 and R5 each represent hydrogen or a hydrocarbon group having 1 to 12 carbon atoms, and include those having all hydrogen and those having all hydrocarbon groups, They may be the same or different.
At least one of R6 and R7 is a halogen group, and the others are groups selected from a hydrocarbon group having 1 to 12 carbon atoms, an aryloxy group, an alkoxy group and a carbonyl group, and R6
And R7 may be the same or different. Examples of the organic titanium compound include dichlorobis (η5-cyclopentadienyl) titanium, dibromobis (η5-cyclopentadienyl) titanium, difluorobis (η5-cyclopentadienyl) titanium, diiodobis (η5-cyclopentadienyl) titanium. Titanium, dichlorobis (η5-methylcyclopentadienyl) titanium, dichlorobis (η5-n-
Butylcyclopentadienyl) titanium, dichlorobis (η5-tetramethylcyclopentadienyl) titanium,
Dichlorobis (η5-pentamethylcyclopentadienyl) titanium, methoxybis (η5-cyclopentadienyl) titanium chloride, phenoxybis (η5-cyclopentadienyl) titanium chloride, phenylbis (η5-
Cyclopentadienyl) titanium chloride, and the like.

Examples of the reducing agent include 3 organic-substituted aluminum having 3 to 20 carbon atoms, organic-substituted aluminum halogenide, and organic-substituted aluminum hydride. Specifically, tri-i-propylaluminum, tri-i-butylaluminum, tri-n-butylaluminum, tri-n-
Examples include octyl aluminum, triphenyl aluminum, di-i-propyl aluminum hydride, di-i-butyl aluminum hydride, di-n-butyl aluminum hydride and di-n-octyl aluminum hydride.

Of these, a particularly preferred combination is dichlorobis (η5-cyclopentadienyl) titanium and di-i.
-Butyl aluminum hydride. Regarding the ratio of the organic titanium compound and the reducing agent, the reducing agent is preferably used in an amount of 0.5 to 20 mol, more preferably 0, 8 to 5 mol, based on 1 mol of titanium.

Further, preferably, as the third component, a small amount of a substance that stabilizes the organotitanium compound, for example, polybutadiene containing a side chain vinyl bond, polyisoprene, or an oligomer thereof is present. As the method of using the hydrogenation catalyst, a method in which an organotitanium compound is added to a living anion polymer after polymerization, and the living anion polymer after polymerization is temporarily stopped with an equivalent amount of alcohols, phenols, water or hydrogen and then organic A method of adding a titanium compound, a method of adding an organotitanium compound and a reducing agent to a stopped polymer solution, a method of previously reacting an organotitanium compound and a reducing agent in an inert solvent, and then adding to a stopped polymer solution, an organic After reacting the titanium compound with the reducing agent in an inert solvent, immediately add alcohol etc. to stop the reaction and add it to the termination polymer solution.Organic titanium compound and reducing agent in an inert solvent vinyl bond Immediately after reacting in the presence of a small amount of polybutadiene containing alcohol, the reaction is stopped by adding alcohol etc., and it is added to the terminated polymer solution. Method, and the like.

The hydrogenation is carried out in a solvent which is inert to the catalyst and in which the butadiene-based polymer is soluble. Preferred solvents include aliphatic hydrocarbons such as n-pentane, n-hexane and n-octane, alicyclic hydrocarbons such as cyclohexane and cycloheptane, aromatic hydrocarbons such as benzene and toluene, diethyl ether. , An ether such as tetrahydrofuran, or a mixture containing them as a main component.

The most preferred method of the present invention is to solution polymerize butadiene or butadiene and styrene using a lithium compound initiator, and use the obtained polymer solution as it is in the next hydrogenation reaction. Extremely useful. The hydrogenation reaction is generally carried out by adding a hydrogenation catalyst to a butadiene-based polymer solution under hydrogen or an inert atmosphere,
Then, hydrogen gas is introduced, the pressure is increased to a predetermined pressure, and the mixture is vigorously stirred. An inert atmosphere means an atmosphere that does not react with any of the participants in the hydrogenation reaction such as helium, neon, argon and nitrogen. Air and oxygen are not preferred because they oxidize the catalyst and cause deactivation of the catalyst.

The hydrogenation reaction can be stopped by consuming and eliminating hydrogen, depressurizing to remove hydrogen, or adding excess alcohols or water to deactivate the hydrogenation catalyst.
The temperature during the hydrogenation reaction is from 0 ° C to 150 ° C. If the temperature is too low, the hydrogenation reaction is slow, and if too high, the activity of the hydrogenation catalyst is lost. In addition, the higher the hydrogenation temperature, the higher the hydrogenation selectivity of the vinyl part in the butadiene unit, and the faster the hydrogenation rate. Therefore, it is preferable to carry out hydrogenation at a temperature as high as possible within the range where the activity of the hydrogenation catalyst is not lost. More preferably, it is from 80 ° C to 140 ° C.

The hydrogenation reaction process is a batch process,
Either a continuous process or a combination thereof can be used. The amount of catalyst added is 100% of the pre-hydrogenation polymer.
It is preferably 0.001 to 20 mmol per g. It is more preferably 0.01 to 1 mmol. The copolymer of the present invention, in the copolymer solution after hydrogenation, preferably water,
It can be obtained by adding a reaction terminator such as alcohol and a stabilizer, removing the solvent, and isolating the polymer. As a method for removing the solvent, steam stripping and dehydration / drying methods which are commonly used can be used.

The copolymer of the present invention can be made to have a large molecular weight to improve the performance such as abrasion resistance, but if necessary, process oil is added to adjust the processability as an oil-extended polymer. You can do it. In addition, it is preferable that there is appropriate branching for workability. On the other hand, the non-oil-extended copolymer has a molecular weight distribution Mw / Mn of 1 to 2 and is subjected to coupling using a polyfunctional tin compound, alkyl tin terminal modification,
Terminal modification such as amine terminal modification is preferable in terms of fuel economy.

The copolymer obtained in the present invention is singly or blended with another rubber, and is kneaded with a reinforcing agent such as carbon black or silica, and if necessary, a process oil, and further kneaded. Add sulfur accelerator, crosslinking agent, etc.,
It becomes a vulcanized rubber composition. The rubber used in the blend includes natural rubber, polyisoprene rubber, other butadiene rubber, butadiene-styrene rubber, butadiene-isoprene rubber, butadiene-isoprene-styrene rubber, butyl rubber, halogenated butyl rubber, ethylene-propylene rubber and the like. It is used by blending two or more components, and the copolymer of the present invention is used in a blend ratio of 10% by weight or more in the rubber component.

There are various carbon blacks used as a reinforcing agent, but those which meet the purpose are used. Specific types include SAF, ISAF and HA.
Furnace black such as F and FEF can be used. Physically preferable is carbon black with small particles, and also small particles / high aggregation type (high surface area / high oil absorption).
Those having good dispersibility in rubber are particularly preferable in terms of physical properties and processability.

As the reinforcing agent, silica is used alone or in combination with carbon black, and in this case, a silane coupling agent is used in combination. As the silane coupling agent, a compound having in one molecule a group compatible with or bonded to silica and a group compatible with or bonded to a polymer is used. For example, a trialkoxysilane group and polysulfide (-SS- in one molecule). ) Compounds in which both groups are present. For example, bis (3-triethoxy-silylpropyl) -tetrasulfide. In addition, similar compounds include mercaptopropyltriethoxysilane, vinyltriethoxysilane, and thiocyanatotriethoxysilane. The amount of the silane coupling agent used is preferably 0.5 to 20 parts by weight per 100 parts by weight of the raw rubber.

The amount of the reinforcing agent is preferably 5 to 100 parts by weight with respect to 100 parts by weight of the raw rubber. The required amount of process oil in the composition is 0 to 75 parts by weight based on 100 parts by weight of the raw rubber. Examples of the process oil include paraffin type process oil, naphthene type process oil, aromatic (aromatic) type process oil and the like, and economically advantageous aromatic type process oil is preferable. On the other hand, when importance is attached to low-temperature performance and fuel efficiency, naphthene-based process oil is preferable.

As the vulcanizing agent, sulfur, sulfur chloride compounds,
Organic sulfur compounds and the like can be used. The required amount of vulcanizing agent is
It is 0.1 to 10 parts by weight with respect to 100 parts by weight of the raw rubber. When the amount is less than 0.1 parts by weight or exceeds 10 parts by weight, good rubber elasticity is not exhibited, which is not preferable. Besides, it is also possible to use a vulcanization accelerator and a crosslinking agent together. As the vulcanization accelerator, guanidine type, aldehyde-amine type,
Aldehyde-ammonia type, thiazole type, sulfenamide type, thiourea type, thiuram type, dithiocarbamate type, xanthate type compounds and the like can be used.

As the crosslinking agent, in addition to radical generators such as organic peroxide compounds and azo compounds, oxime compounds, nitroso compounds and polyamine compounds can be used. Further, if necessary, a reinforcing agent, a softening agent, a filler, a vulcanization aid, a colorant, a flame retardant, a lubricant, a foaming agent, a plasticizer, a processing aid, an antioxidant, an antiaging agent, an anti-scorch agent. It is also possible to add an anti-UV agent, an antistatic agent, an anti-coloring agent, and other compounding agents.

As other reinforcing agents to be added as required, inorganic reinforcing agents such as activated calcium carbonate, high styrene resin, phenol-formaldehyde resin, etc. are used. These inorganic or organic reinforcing agents are It is used in an amount of 50 parts by weight or less based on 100 parts by weight of the raw rubber.
As the filler, calcium carbonate, clay, talc, aluminum hydroxide, zeolite, diatomaceous earth, aluminum sulfate, barium sulfate or the like can be used.

Examples of antioxidants or antioxidants include diphenylamine-based and p-phenylenediamine-based amine derivatives, quinoline derivatives, hydroquinone derivatives,
Monophenols, diphenols, thiobisphenols, hindered phenols, phosphites, etc. can be used, and these are used per 100 parts by weight of raw rubber.
0.001 to 10 parts by weight may be added, and two or more kinds may be used in combination.

UV inhibitors, lubricants, foaming agents, foaming aids,
As the flame retardant, antistatic agent, anti-coloring agent and other rubber compounding chemicals, known chemicals can be used depending on the intended purpose. The vulcanized rubber of the present invention is suitable for various automobile tires by taking advantage of its characteristics, and more specifically, a tire tread portion, a cap tread portion, an undertread portion,
Suitable for side wall and carcass.

[0046]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below with reference to Examples and Comparative Examples, but these do not limit the scope of the present invention.

[0047]

Example 1 [Polymerization of butadiene-styrene copolymer] Using an autoclave having an inner volume of 10 liters, an inlet at the bottom and an outlet at the top, a stirrer and a jacket as a polymerization reactor, butadiene, styrene, Hexane is 6 by weight
It was continuously introduced at a residence time of 40 minutes at 5: 35: 400, and 0.038 parts by weight of normal butyl lithium and 2,2-bis (2-oxolanylpropane) as a polymerization initiator were added per 100 parts by weight of the monomer. 0.10 parts by weight was continuously added to maintain the reactor internal temperature at 100 ° C. The copolymer solution was continuously withdrawn from the top of the reactor, and 0.95 equivalent of ethanol was continuously added to the pipe with respect to the fed initiator to stop the reaction.

The copolymer solution was sampled, dried in a drum dryer and analyzed. The constituent components of the copolymer were 35% by weight of styrene, that is, 21.8 mol%, 65% by weight of butadiene, 40 mol% of 1,2-butadiene structure in butadiene, and 1,4-butadiene structure of butadiene. 60 mol%, 1,2-based on the whole copolymer
The butadiene structure was 31.3 mol% and the 1,4-butadiene structure was 46.9 mol%. The bonding mode of each component in the copolymer was random. When the chain distribution of styrene was measured by the Tanaka method, that is, the ozonolysis-GPC method, the block styrene, that is, the chain of 8 or more chains was 0.5% by weight with respect to the total styrene, and the result was extremely high in randomness.

[Butadiene Hydrogenation] A copolymer solution was added to
It was continuously introduced into an atomizer having an internal volume of 2.5 liters, and dichlorobis (η5-pentamethylcyclopentadienyl) titanium and n-butyllithium were previously used as hydrogenation catalysts in cyclohexane at a molar ratio of 1: 1 at room temperature. 10
What was reacted for 5 minutes was used as titanium for the copolymer.
An amount equivalent to 0 ppm was continuously added, the amount of hydrogen introduced was gradually increased while vigorously stirring, and cooling was performed with a jacket so that the internal temperature became 100 ° C, and hydrogenation was performed.
2 per 100 parts by weight of copolymer after exiting the atomizer
Water and 0.5 parts by weight of BHT were added, and 37.5 parts by weight of aromatic oil was further added, followed by drying with a drum dryer to obtain an oil-extended copolymer.

The constituent component of the copolymer is styrene 21.
8 mol%, 1-butene structure 30.9 mol%, 1,4-
The butadiene structure was 46.3 mol%, the 1,2-butadiene structure was 0.4 mol%, and the ethylene structure was 0.6 mol%. The bonding mode of each component in the copolymer was random. The weight average molecular weight was 380,000 and the molecular weight distribution Mw / Mn was 2.2.

In order to measure the hydrogenation selectivity, 7 liters of the above butadiene-styrene copolymer solution was sampled in a 10 liter autoclave, the same hydrogenation catalyst was added, and the bottom portion was vigorously stirred. Hydrogen is introduced from the above, hydrogenation is performed while controlling the internal temperature to 100 ° C., the hydrogenation rate of each component is measured by sampling, and 90% of the double bonds of the 1,2-butadiene structure are hydrogen. It was found that the ratio r1 / r2 of the hydrogenation rate r1 of 1,2-butadiene when converted to the hydrogenation rate r2 of the double bond of the 1,4-butadiene structure was 18. [Analysis Method of Copolymer Before Hydrogenation] The styrene content and the vinyl bond content of the butadiene portion were measured by the following methods.

1) Styrene content The polymer before hydrogenation was used as a chloroform solution, and the styrene content [S] (wt%) was measured by absorption of UV at 254 nm by the phenyl group of styrene. 2) Content of butadiene When the polymer before hydrogenation contains styrene, it was calculated as 100% -styrene content (wt%).

3) Vinyl bond content of butadiene part The polymer before hydrogenation was made into a heavy chloroform solution, and FT-N
1H- at MR (270MHz, JEOL Ltd.)
The NMR spectrum is measured, and the chemical shift is 4.7 to 5.2.
Proton (= CH2) due to vinyl bond (ppm as signal C0) and chemical shift of 5.2 to 5.8 ppm
From the integrated intensity ratio of protons (= CH-) due to 1,4 bonds (denoted as signal D0), vinyl bond content [V]
(%) Was calculated by the following formula.

[V] = [2C0 / (C0 + 2D0)] × 100 [Method for measuring hydrogenation rate] FT-NMR (270 MHz, manufactured by JEOL Ltd.) was prepared by using the polymer before hydrogenation as a heavy chloroform solution. , 1H-NMR spectrum is measured, and chemical shift is 4.7 to 5.2 ppm (signal C0)
(= CH2) due to the vinyl bond (1,2-butadiene structure) and chemical shift of 5.2 to 5.8 ppm
The integrated intensity of the proton (= CH-) due to the 1,4 bond (denoted as signal D0) was obtained. Similarly, the 1H-NMR spectrum of the hydrogenated polymer was measured and the chemical shift was 0.6 to 1.0 ppm (signal A1).
Methyl protons (-CH3) due to hydrogenated vinyl bond (butene structure), chemical shift 4.7-5.2 ppm
Proton (= CH2) due to non-hydrogenated vinyl bond (designated as signal C1), chemical shift 5.2-
The integrated intensity of 5.8 ppm (denoted as signal D1) of unhydrogenated 1,4 bond protons (= CH-) was determined, and the hydrogenation rate was calculated as follows.

P = 3C0 / (3C1 + 2A1) A11 = p × A1, C11 = p × C1, D11 = p × D1, and the hydrogenation rate of vinyl bond [B]
(%) Was calculated by the following formula.

[B] = [2A11 / (2A11 + 3C11)] × 100 The hydrogenation rate [C] (%) of the 1,4 bond was calculated by the following formula. [C] = [(2D0-C0-2D11 + C11) / (2D0
-C0)] × 100 The hydrogenation rate [A] (%) of the entire butadiene part was calculated by the following formula. [A] = [[V] × [B] + (100− [V]) ×
[C]] / 100 The content (mol%) of butene bonds, vinyl bonds, ethylene bonds, and 1,4 bonds in the hydrogenated copolymer is [h]
v], [v], [hb], and [b] can be calculated as follows. Note that [S] is defined as mol% in the copolymer.

[Hv] = (100− [S]) × [V] × [B] ÷ 10000 [v] = (100− [S]) × [V] ÷ 100− [hv] [hb] = ( 100- [S]) x (100- [V]) x [C] / 10000 [b] = (100- [S]) x (100- [V]) / 100- [hb] [Weight average molecular weight and Method for measuring molecular weight distribution (Mw / Mn)] The copolymer was used as a THF solution, and GPC (pump:
The chromatogram was measured by LC-5A manufactured by Shimadzu Corporation, column: polystyrene gel HSG-40, 50, 60 each, detector: differential refractometer. The weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of butadiene-polystyrene copolymer were calculated and calculated by a standard method using a calibration curve of the relationship between the molecular weight of the peak of standard polystyrene and the retention volume. [Blend of Copolymer and Vulcanized Rubber] The above oil-extended copolymer was blended and vulcanized as a raw rubber to evaluate the performance.

The impact resilience at 70 ° C. was measured as a measure of fuel economy. 0 ℃ as a measure of wet skid resistance
The impact resilience of was measured. As the grip performance in continuous high speed operation, the degree of decrease in dynamic elastic modulus at high temperature, that is, 100 ° C
E ′ / 70 ° C. E ′ was measured. The higher the better. Goodrich heat generation (HB
U) was measured.

Pico wear was measured as a measure of wear resistance. Table 1 shows the measurement results. The performance evaluation was performed by kneading by the following compounding and kneading methods, vulcanization molding at 160 ° C. for 20 minutes, and measurement. [Blending] Copolymer (oil-extended copolymer) 137.5 parts by weight Aroma oil (addition) 12.5 〃 carbon black * 1 85 〃 zinc flower 5 〃 stearic acid 2 〃 anti-aging agent (810NA) * 2 1 〃 Vulcanization accelerator (CZ) * 3 1.6 〃 Sulfur 2.4 〃 * 1 N234 Showa Cabot * 2 N-Isopropyl-N'-phenyl-p-phenylenediamine Ouchi Shinko Chemical Co., Ltd. Nocrac 810-NA * 3 N-cyclohexyl-2-benzothiazylsulfenamide Ouchi Shinko Chemical Co., Ltd. Nocrac CZ [kneading method] Banbury mixer (capacity 1.7 liters, temperature 1
Knead the oil-extended copolymer with carbon black, zinc white, stearic acid, and antioxidant at 60 ° C.

Open roll (10 inches, 80
Knead sulfur and vulcanization accelerator at (° C). [Vulcanization molding] The composition was put into a mold and press-heated at 160 ° C for 20 minutes for vulcanization molding. Each performance of the vulcanizate was measured as follows.

1) Impact resilience: Lupke method according to JIS-K-6301, after preheating the sample in an oven at 70 ° C. for 1 hour and then quickly taking it out for measurement. The impact resilience represents rolling resistance and is an index representing fuel efficiency characteristics. The larger the value, the better the fuel efficiency. 2) Wet skid resistance: The impact resilience was measured at 0 ° C., and the lower the value, the better the wet skid resistance.

3) Measurement of dynamic elastic modulus: VEst manufactured by Iwamoto
The measurement was performed by changing the temperature at 10 Hz using ypeF-3. 4) Goodrich heat generation: measured at 50 ° C. The lower the value, the better the heat generation. 5) Pico wear measurement: It is expressed by the wear amount cc of 80 times, and the lower the value, the better the wear resistance.

[0063]

Comparative Examples 1 to 3 [Polymerization of butadiene-styrene copolymer] The same method as in Example 1 was carried out. [Butadiene hydrogenation] The copolymer solution was continuously introduced into an atomizer having an internal volume of 2.5 liters, and di-p-tolylbis (η5-cyclopentadienyl) titanium n-butyl was previously used as a hydrogenation catalyst. Lithium was reacted at a molar ratio of 1: 1 in cyclohexane for 5 minutes at room temperature, and a continuous amount of 50 ppm as titanium was added to the copolymer, and the amount of hydrogen introduced was gradually increased with vigorous stirring. Hydrogenation was carried out by cooling with a jacket so that the internal temperature became 100 ° C. After leaving the atomizer,
2 parts by weight of water and 0.5 parts by weight of BHT were added per 100 parts by weight of the copolymer, and further 37.5 of aromatic oil was added.
Parts by weight were added and dried with a drum dryer to obtain an oil-extended copolymer. Three types of copolymers having different hydrogen contents were obtained.

The constituents of the first copolymer are styrene 21.8 mol%, 1-butene structure 15.7 mol%,
1,4-butadiene structure 44.4 mol%, 1,2-butadiene structure 15.6 mol%, ethylene structure 2.5
Mole%. Many unhydrogenated 1,2-butadiene structures are outside the scope of the present invention. This is referred to as Comparative Example 1.
The constituents of the second copolymer were styrene 21.8 mol%, 1-butene structure 25.1 mol%, 1,4-butadiene structure 40.7 mol% and 1,2-butadiene structure. The content was 6.2 mol% and the ethylene structure was 6.2 mol%.
The degree of hydrogenation of all butadiene is the same as in Example 1, but
There are many 1,2-butadiene structures and ethylene structures, which are outside the scope of the present invention. This is referred to as Comparative Example 2.

The constituents of the third copolymer are styrene 21.8 mol%, 1-butene structure 28.7 mol%,
1,4-butadiene structure 33.4 mol%, 1,2-butadiene structure 2.6 mol%, ethylene structure 13.5
Mole%. Although the degree of hydrogenation of 1,2-butadiene is the same as in Example 1, it has a large ethylene structure and is outside the scope of the present invention. This is referred to as Comparative Example 3.

The bonding mode of each component in these copolymers was random. The weight average molecular weight was 380,000 and the molecular weight distribution Mw / Mn was 2.2. Also,
In order to measure the hydrogenation selectivity, 7 liters of the above butadiene-styrene copolymer solution was sampled in a 10 liter autoclave in the same manner as in Example 1, the same hydrogenation catalyst was added, and the mixture was stirred vigorously. Hydrogen was introduced from the bottom, hydrogenation was performed while controlling the internal temperature to 100 ° C., the hydrogenation rate of each component was measured by sampling, and the hydrogenation rate of the double bond of 1,2-butadiene was 9
The ratio r1 / r2 of the hydrogenation rate r1 of 1,2-butadiene when 0% was hydrogenated and the hydrogenation rate r2 of the double bond of the 1,4-butadiene structure was 1.5.

[Blend of Copolymer and Vulcanized Rubber] The same procedure as in Example 1 was carried out. Table 1 shows the measurement results.

[0068]

[Table 1]

[0069]

Example 2 [Polymerization of Polybutadiene] Using an autoclave equipped with a stirrer and a jacket as a polymerization reactor with an internal volume of 100 liters, butadiene, hexane, and tetrahydrofuran were charged at 6 kg, 34 kg, and 0.2 kg, respectively, and the internal temperature was adjusted. After the temperature was set to 40 ° C., normal butyl lithium 0.060 was used as a polymerization initiator per 100 parts by weight of the monomer.
When the temperature in the reactor reached the peak temperature of 70 ° C., 0.75 equivalent of tin tetrachloride (1 mol as 4 equivalents), 0.2 equivalent was added to the added initiator when the temperature in the reactor reached a peak temperature of 70 ° C. Ethanol was added to stop.

The copolymer solution was sampled, dried in a drum dryer and analyzed. The components of the polymer are
The 1,2-butadiene structure was 52 mol% and the 1,4-butadiene structure was 48 mol%. [Butadiene Hydrogenation] Next, the polymer solution was kept at 90 ° C., and dichlorobis (η5-cyclopentadienyl) titanium and di-i-butylaluminum hydride were previously used as hydrogenation catalysts in cyclohexane at a molar ratio of 1: 3. After reacting at room temperature for 3 days, 50 ppm of titanium was added to the copolymer, and hydrogen was added from the bottom with vigorous stirring to carry out hydrogenation. The internal temperature during hydrogenation rose to almost 120 ° C. To measure the hydrogenation selectivity, the hydrogenation rate of each component was measured by sampling, and the hydrogen of 1,2-butadiene when 90% of the double bonds in the 1,2-butadiene structure were hydrogenated. Conversion rate r1
And the hydrogenation rate r of the double bond of the 1,4-butadiene structure
The ratio r2 / r2 of 2 was 10.

After the desired hydrogenation was achieved, the stirring was stopped and the hydrogen was depressurized. Then, 2 parts by weight of water and 0.5 parts by weight of BHT were added to 100 parts by weight of the copolymer, and dried by a drum dryer to obtain a copolymer. The constituent components of the copolymer were 51.1 mol% of 1-butene structure, 47.3 mol% of 1,4-butadiene structure, 0.9 mol% of 1,2-butadiene structure and 0. It was 7 mol%. The bonding mode of each component in the copolymer was random. The weight average molecular weight was 330,000 and the molecular weight distribution Mw / Mn was 1.4.

[Blend of Copolymer and Vulcanized Rubber] The butene-butadiene copolymer was blended and vulcanized as a raw material rubber to evaluate the performance. As a raw material rubber, a copolymer and a natural rubber were blended at a ratio of 50/50 (weight ratio), and the performance was measured by vulcanization molding at 160 ° C. for 20 minutes with the following formulation. Table 2 shows the results.

[Compounding] Raw rubber 100 parts by weight Carbon black * 1 50 〃 Aroma oil 10 〃 Zinc white 5 〃 Stearic acid 2 〃 Anti-aging agent (810NA) * 2 1 〃 Vulcanization accelerator (CZ) * 3 1 〃 Sulfur 1.8 〃 * 1 Seast KH * 2 N-isopropyl-N'-phenyl-p-phenylenediamine Ouchi Shinko Chemical Industry Co., Ltd. Nocrac 810-NA * 3 N-cyclohexyl-2-benzothiazylsulfene Amido Ouchi Shinko Chemical Co., Ltd. Nocrac CZ

[0074]

Comparative Example 4 [Polymerization of polybutadiene] The same method as in Example 1 was carried out. [Butadiene Hydrogenation] As a hydrogenation catalyst, dichlorobis (η5-cyclopentadienyl) titanium and trimethylaluminum were mixed in cyclohexane at a molar ratio of 1: 3,
The same procedure as in Example 2 was carried out except that the one reacted at room temperature for 3 days was used.

90 of 1,2-butadiene double bonds
The ratio r1 / r2 of the hydrogenation rate r1 of 1,2-butadiene at the time of hydrogenation of 1% and the hydrogenation rate r2 of the double bond of the 1,4-butadiene structure was 0.8. The constituent component of the obtained copolymer is 42.1 mol% of 1-butene structure,
The 1,4-butadiene structure was 38.1 mol%, the 1,2-butadiene structure was 9.9 mol%, and the ethylene structure was 9.9 mol%. The bonding mode of each component in the copolymer was random. The weight average molecular weight was 330,000 and the molecular weight distribution Mw / Mn was 1.4. The degree of hydrogenation of all butadienes is the same as in Example 2, but there are many 1,2-butadiene structures and ethylene structures, which is outside the scope of the present invention.

[Blend of Copolymer and Vulcanized Rubber] The same procedure as in Example 2 was carried out. The measurement results are shown in Table 2.

[0077]

[Table 2]

[0078]

According to the present invention, fuel economy, wet skid resistance, grip performance during continuous high speed operation,
It provides unprecedented rubber with excellent internal heat generation and abrasion resistance at the same time, and is useful as a material for automobile tires that require advanced fuel consumption characteristics, especially fuel-saving automobile tires suitable for high-speed running. Is.

Claims (8)

[Claims] 1. A monomer component which is composed of a 1-butene structure (A), a 1,4-butadiene structure (B), a 1,2-butadiene structure (C) and an ethylene structure (D),
The constituent ratio of each component is such that the component (A) is 10 to 90 mol%,
The component (B) is 90 to 10 mol%, the components (C) and (D) are each 3 mol% or less, and the binding mode of each component is random and the molecular weight is 10,000 to 1.0.
A copolymer having a molecular weight distribution Mw / Mn of 0,000 from 1 to 5. 2. The constituent monomer components are 1-butene structure (A), 1,4-butadiene structure (B), 1,2-butadiene structure (C), ethylene structure (D) and styrene structure ( S), and the composition ratio of each component is such that the component (A) is 10 to 89 mol% and the component (B) is 89 to 10 mol%.
Component (C) and component (D) are each 3 mol% or less,
The component (S) is 1 to 30 mol%, and the binding mode of each component is random, and the molecular weight is 10,000 to 1,000,
000, a copolymer having a molecular weight distribution Mw / Mn of 1 to 5. 3. The constituent monomer components are 1,2-butadiene structure (C) and 1,4-butadiene structure (B).
A polybutadiene in which the component (C) is 10 to 90 mol%, the component (B) is 90 to 10 mol%, and the bonding mode of the component (C) and the component (B) is random.
The hydrogenation rate r1 of 1,2-butadiene when 90% of double bonds in the 2-butadiene structure are hydrogenated, and 1,4-
Ratio of hydrogenation rates r2 of double bonds of butadiene structure r1 /
When r2 is 5 or more, it is hydrogenated and the 1,2-butadiene structure is 3
The hydrogenation is stopped when it is consumed to a mol% or less, and the constituent monomer components are 1-butene structure (A), 1,4-butadiene structure (B), 1,2- Consisting of a butadiene structure (C) and an ethylene structure (D),
The constituent ratio of each component is such that the component (A) is 10 to 90 mol%,
The component (B) is 90 to 10 mol%, the components (C) and (D) are 3 mol% or less, respectively, and the bonding mode of each component is random, and the molecular weight is 10,000 to 1,0.
A method for obtaining a copolymer having a molecular weight distribution Mw / Mn of 0,000 from 1 to 5. 4. The constituent monomer component comprises a 1,2-butadiene structure (C), a 1,4-butadiene structure (B) and a styrene structure (S), and the component (C) is 10-8.
Using a butadiene-styrene copolymer in which 9 mol%, (B) component is 89 to 10 mol%, (S) component is 1 to 30 mol%, and the bonding mode of each component is random, 1,2-
The ratio r1 / r2 of the hydrogenation rate r1 of 1,2-butadiene when 90% of the double bonds of the butadiene structure is hydrogenated and the hydrogenation rate r2 of the double bond of the 1,4-butadiene structure
Is hydrogenated at 5 or more, and the hydrogenation is stopped when the 1,2-butadiene structure is consumed to 3 mol% or less, and the monomer component constituted is a 1-butene structure (A). , 1,4-butadiene structure (B), 1,2-butadiene structure (C), ethylene structure (D) and styrene structure (S), and the composition ratio of each component is from 10 to 89 for the component (A). Mol%, the component (B) is 89 to 10 mol%,
Component (C) and component (D) are each 3 mol% or less,
The component (S) is 1 to 30 mol%, and the binding mode of each component is random, and the molecular weight is 10,000 to 1,000,
000, a method for obtaining a copolymer having a molecular weight distribution Mw / Mn of 1 to 5. 5. The copolymer according to claim 3, wherein the dicyclopentadienyl titanium compound and a reducing agent or a reaction product thereof are used as a hydrogenation catalyst, and the temperature during hydrogenation is 80 to 140 ° C. How to get. 6. The copolymer according to claim 4, wherein the dicyclopentadienyl titanium compound and a reducing agent or a reaction product thereof are used as a hydrogenation catalyst, and the temperature during hydrogenation is 80 to 140 ° C. How to get. 7. The constituent monomer component comprises a 1-butene structure (A), a 1,4-butadiene structure (B), a 1,2-butadiene structure (C) and an ethylene structure (D),
The constituent ratio of each component is such that the component (A) is 10 to 90 mol%,
The component (B) is 90 to 10 mol%, the components (C) and (D) are each 3 mol% or less, and the binding mode of each component is random and the molecular weight is 10,000 to 1.0.
A vulcanized rubber in which a copolymer having a molecular weight distribution Mw / Mn of 0,000 of 1 to 5 is used in an amount of 10% by weight or more in a rubber component. 8. The constituent monomer components are 1-butene structure (A), 1,4-butadiene structure (B), 1,2-butadiene structure (C), ethylene structure (D) and styrene structure ( S), and the composition ratio of each component is such that the component (A) is 10 to 89 mol% and the component (B) is 89 to 10 mol%.
Component (C) and component (D) are each 3 mol% or less,
The component (S) is 1 to 30 mol%, and the binding mode of each component is random, and the molecular weight is 10,000 to 1,000,
000, a vulcanized rubber using a copolymer having a molecular weight distribution Mw / Mn of 1 to 5 in an amount of 10% by weight or more in a rubber component.