JPH04227648A - Selectively and partially hydrogenated polymer composition - Google Patents

Abstract

PURPOSE:To increase the hardness and modulus and improve the impact resilience, heat build-up and aging resistance by mixing a raw rubber containing a specific selectively and partially hydrogenated polymer, carbon black and a vulcanizing agent. CONSTITUTION:A butadiene polymer or styrene-butadiene copolymer having a total styrene content (S) of 0-40wt.%, a vinyl bond content (V) of 1-80% in the butadiene portion, a weight average molecular weight of 1-1,000,000, and a molecular weight distribution of 1.2-5.0 is selectively and partially hydrogenated in the presence of a hydrogenation catalyst to obtain a selectively and partially hydrogenated polymer (i) which has a hydrogenation rate (A) of 3-60% in the whole butadiene portion and a hydrogenation rate (B) of 30% or more in the vinyl bond part of the butadiene portion, wherein A/(S+V)<1/2> is 2-8 and B.V<1/2>/A is 10-16. The title composition is obtained by mixing 100 pts.wt. raw rubber comprising 30wt.% or more of the component (i) and natural rubber and other synthetic rubbers as required, 10-150 pts.wt. carbon black and 0.5-10 pts.wt. vulcanizing agent.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a selectively hydrogenated polymer composition having high hardness and modulus, excellent rebound and heat generation properties, and improved heat aging resistance. More specifically, the present invention relates to a rubber composition of a selectively hydrogenated polymer having a specific structure, which is obtained by selectively partially hydrogenating a butadiene polymer or a styrene-butadiene copolymer having a specific structure.

0002

[Prior art and its problems] Polymers obtained by partially hydrogenating styrene-butadiene copolymers have been known for a long time, and they can be blended with other diene elastomers or ethylene-propylene copolymer rubber. Proposal for obtaining a composition with improved green strength (Japanese Patent Publication No. 46-3549)
No. 7) has been done. In addition, a proposal regarding a composition with excellent breaking strength and rubber-like elasticity consisting of this and a specific inorganic filler (Japanese Patent Publication No. 47-8928) and a proposal regarding a method for producing oil-extended rubber with excellent heat aging resistance and rebound resilience (Japanese Patent Publication No. 1989-8928) Kosho 46
-29020) etc. have been made.

However, with conventional catalysts mainly composed of organic compounds of iron, nickel, and cobalt, it is difficult to preferentially select vinyl bonds for partial hydrogenation, and it is difficult to hydrogenate vinyl bonds to a certain degree. It was also necessary to highly hydrogenate the 1,4 bonds (there are cis and trans bonds). Moreover, in this method, when a crystalline copolymer is produced to improve the intended impact resilience and heat aging resistance, it only results in an undesirable significant increase in hardness or a decrease in exothermic property.

On the other hand, a method has also been proposed in which only the side chain components of a diene polymer (in the case of a butadiene polymer, the vinyl bond) are selectively hydrogenated, and a selectively hydrogenated diene polymer having ozone resistance and oxidation stability has been produced. A method for obtaining the same is also known (Japanese Unexamined Patent Publication No. 52-41690). However, although it is true that the polymer produced by this method has some improvement in heat aging resistance or rebound resilience, it is insufficient and there is no improvement in hardness or modulus at all.

[0005]

[Means for Solving the Problems] The present invention proposes a novel polymer that solves the above-mentioned problems all at once. That is, (1) the bound styrene content [S] is 0 to 40% by weight (2) the vinyl bond content [V] of the butadiene part is 1 to 8
0% (3) Weight average molecular weight (Mw) is 1 to 1 million (4
) Made by selectively partially hydrogenating a butadiene polymer or styrene-butadiene copolymer having a molecular weight distribution (Mw/Mn) of 1.2 to 5.0 (5) Hydrogenation rate of the entire butadiene part [A
] is 3 to 60% (6) The hydrogenation rate [B] of the vinyl bond part of the butadiene part is 30% or more, and [A], [B], [S
], [V] is (7) [A] / ([S] + [V]) 1/2
is 2~8 (8) [B]・[V]1/2 / [A] is 1
A rubber composition consisting of 100 parts by weight of raw rubber containing at least 30% by weight of a selected partially hydrogenated polymer satisfying the relationship of 0 to 16, 10 to 150 parts by weight of carbon black, and 0.1 to 10 parts by weight of a vulcanizing agent. The present invention was achieved by discovering that the material has high hardness, high modulus, and excellent impact resilience, heat generation property, and heat aging resistance.

By the way, as hydrogenation catalysts for butadiene polymers and styrene-butadiene copolymers, in addition to the above-mentioned catalysts mainly composed of organic compounds of iron, nickel, and cobalt and composed of organometallic compounds, nickel, cobalt, platinum, and palladium can also be used. Catalysts in which a metal such as rutinium is supported on a carrier such as carbon, silica, alumina, or diatomaceous earth are also known, but their activity is low and hydrogenation at low temperature and low pressure has not been industrially possible. Moreover, the vinyl bond of the butadiene moiety was not partially hydrogenated more selectively.

[0007] Recently, a highly active hydrogenation method using an organometallic compound of titanium as a main component has become known (Japanese Patent Laid-Open No.
9-133203, Japanese Patent Application Publication No. 60-220147),
Industrially, it has become possible to easily hydrogenate only the butadiene portion under mild conditions at low temperature and pressure. The present invention applies this to the partial hydrogenation of a butadiene polymer or a styrene-butadiene polymer with a specific structure to obtain a selectively hydrogenated polymer with a specific structure, thereby solving the problems of the prior art at once. .

The butadiene polymer and styrene-butadiene copolymer, which are the base polymers of the selectively hydrogenated polymer of the present invention, are required to have a specific structure. That is (1)
Bound styrene content [S] is 0 to 40% by weight (2) Vinyl bond content [V] of the butadiene moiety is 1 to 80% (3) Weight average molecular weight (Mw) is 1 to 1 million (4) Molecular weight distribution (
Mw/Mn) is required to be 1.2 to 5.0.

Here, the bound styrene content [S] is defined as the content (% by weight) of bound styrene units relative to the total amount of the raw polymer before hydrogenation, and the bound styrene content is 4%.
If it exceeds 0% by weight, even if the other requirements of the present invention are met, the improvements in rebound and heat generation that are the objectives of the present invention are insufficient. The bound styrene content is preferably limited to 30% or less. Further, it is preferable that the bonding mode of styrene is random. The bonding mode of the butadiene moiety in the raw polymer before hydrogenation has a structural formula that is based on 1,4 bonds.

0010

[Chemical formula 1] Cis (c) and structural formula represented by

[0011]

[Chemical formula 2] A structural formula consisting of trans (t) and 1,2 bonds

0012

[Chemical formula 3] There are three types of vinyl (v) shown in .

Therefore, the vinyl bond content [V] of the butadiene moiety is the above cis (c), which is the entire butadiene moiety.
It is defined as the content (mol %) of vinyl (v) relative to the total amount of trans (t) and vinyl (v). The vinyl bond content of this butadiene moiety is limited to 1 to 80%. Outside this range, there will be too many or too few vinyl bonds, and the selective partial hydrogenation of vinyl bonds in the present invention will be meaningless and will not produce any effect.

[0014] The vinyl bond content is preferably 5 to 60%,
More preferably, it is limited to 10 to 50%. In addition, the weight molecular weight (Mw) is 1 to 1 million, and the molecular weight distribution is Mw/M
It needs to be 1.2 to 5.0 expressed as n. If the molecular weight is less than 10,000 or the molecular weight distribution is more than 5, the physical properties of the raw polymer itself that should be improved, such as hardness, modulus, rebound, and heat generation properties, are significantly inferior, and the present invention is not applicable. However, a sufficient amount of polymer cannot be obtained.

On the other hand, if the molecular weight exceeds 1,000,000 or the molecular weight distribution is less than 1.2, it becomes difficult to process or obtain the polymer as a rubber, and the present invention cannot be applied. The preferred range of molecular weight is 5-
800,000, more preferably 100,000 to 600,000. Moreover, the preferable range of molecular weight distribution is 1.5 to 3.0. Molecular weight and molecular weight distribution are measured using a gel permeation chromatograph according to a standard method and defined using this method.

The butadiene polymer and styrene-butadiene copolymer having the above-specified structure can be produced by solution polymerization using an organic compound of nickel, cobalt or titanium and an organometallic catalyst or an organolithium alone or a combination of this and a Lewis base. Can be easily manufactured. A part of the butadiene component of the polymer may be replaced with another conjugated diene component copolymerizable therewith, for example, within a range of 30% by weight or less. Other conjugated diene components include isoprene, 2,3 dimethyl-1,3-butadiene, 1,3 pentadiene, and the like. Similarly, a portion of the styrene component may be replaced with a vinyl-substituted aromatic hydrocarbon such as t-butylstyrene, α-methylstyrene, p-methylstyrene, or divinylbenzene.

The polymer of the present invention is obtained by selectively partially hydrogenating the above-specified butadiene polymer or styrene-butadiene copolymer (5) hydrogenation rate of the entire butadiene portion [A
] is 3 to 60% (6) The hydrogenation rate [B] of the vinyl bond part of the butadiene part is 30% or more, and [A], [B], [S
], [V] is (7) [A] / ([S] + [V]) 1/2
is 2~8 (8) [B]・[V]1/2 / [A] is 1
It is a selective partially hydrogenated polymer that satisfies the relationship of 0 to 16. When the butadiene moiety is hydrogenated, the butadiene unit due to the 1,4 bond has the structural formula

[0018]

[Chemical formula 4] Tetramethylene (m) is shown, and the one with 1,2 bonds has the structural formula

[0019]

[C5] It becomes butylene (b) shown by

[0020] Therefore, the hydrogenation rate of the entire butadiene part [A]
represents the entire butadiene moiety, i.e. cis (c), trans (t
) and the total content (mol%) of hydrogenated units tetramethylene (m) and butylene (b) relative to the total amount of vinyl (v), tetramethylene (m) and butylene (b) be done.

[0021] The hydrogenation rate [A] of the entire butadiene portion is 3
-60%, preferably 5-50%, more preferably 8-60%
40%, with a particularly preferred range of 10-30%. If the hydrogenation rate [A] is lower than this range, the polymer of the present invention with high hardness and modulus and excellent impact resilience cannot be obtained. On the other hand, if the hydrogenation rate [A] is too high, the resulting polymer will partially have crystallinity, resulting in excessively high hardness and poor exothermic properties in terms of physical properties.

[0022] The hydrogenation rate [B] of the vinyl bonded portion of the butadiene portion is the hydrogenated unit of butylene (b) relative to the entire vinyl bonded portion of the butadiene portion, that is, the total amount of vinyl (v) and butylene (b). is defined as the content (mol%) of the butadiene moiety and the hydrogenation rate of the vinyl bond part [B
] is limited to 30% or more, preferably 30 to 95%, more preferably 45 to 95%, even more preferably 60 to 90%. If the hydrogenation rate [B] is lower than this, the effect of improving heat aging resistance and impact resilience of the present invention is small.

In the present invention, the range of the hydrogenation rate [A] of the entire butadiene moiety is determined by the bound styrene content [S] of the butadiene polymer or styrene-butadiene copolymer, which is the original polymer, and the vinyl content of the butadiene moiety. It is determined as a function of the binding content [V]. That is, [A]/([S]+
[V])1/2 is required to be 2 to 8, preferably 3 to 7, and more preferably 4 to 6. If this value is less than 2, the effects of the present invention, especially the increase in hardness and modulus, will not be realized, and on the contrary, if this value is 8 or more, the heat generation property will be poor.

The hydrogenation rate [B] of the vinyl bond in the butadiene moiety is determined by the vinyl bond content in the butadiene moiety [V] of the raw polymer.
] and the hydrogenation rate of the entire butadiene portion [A]. That is, [B].[V]1/2/[A] is 10 to 16, preferably 11 to 15, more preferably 12
~14. Outside this range, the polymer will not have the effects of the present invention, which are excellent in hardness, modulus, heat generation properties, rebound resilience, and heat aging resistance. Generally, when this value exceeds 16, although other physical properties are improved, there is an increase in hardness/modulus or heat aging resistance.
On the other hand, if it is less than 10, the physical properties will be insufficient in terms of rebound resilience and heat generation, and the overall physical properties will be unbalanced, which is undesirable.

[0025] If the butadiene polymer or styrene-butadiene polymer with a specific structure, which is the base polymer of the selectively partially hydrogenated polymer of the present invention, falls under the above-mentioned limited structure, the manufacturing method thereof may be It can be anything. Typical manufacturing methods for obtaining these polymers are as follows.

That is, the raw polymer is prepared in an inert solvent such as hexane, cyclohexane, or benzene, using an organic lithium such as n-butyllithium or sec-butyllithium or other alkali metal compound as a polymerization catalyst, and as necessary. As co-catalyst components, alkoxides such as potassium butoxide, dodecylbenzenesulfonate,
Using an organic compound typified by an organic acid salt such as sodium stearate, we can further use ether, polyether, tertiary amine, polyamine, thioether, hexamethylphosphorotris as a compound to adjust the vinyl bond content as necessary. It can be obtained by monopolymerizing butadiene as a monomer and, optionally, styrene in a predetermined ratio using a polar organic compound such as an amide or by copolymerizing it. The vinyl bond content can be controlled by the amount of the polar organic compound added and the polymerization temperature.

[0027] Furthermore, the polymer chain having an active end obtained by the above method is coupled with a polyfunctional compound such as silicon tetrachloride, tin tetrachloride, or a polyepoxy compound, or with a branched polymer chain such as divinylbenzene. By adding the agent to the polymerization system, branched or radial polymers or copolymers can be obtained. Furthermore, in the polymerization method, various polymerization conditions such as adjusting the addition method of the monomer, changing the amount of the compound for adjusting the vinyl bond content, the addition method, and the polymerization temperature in the middle of the polymerization reaction can be used. Polymers or copolymers in which the styrene content or vinyl bond content increases or decreases in the molecular chain, or have a block shape can be obtained.

In addition, various compounds such as acetylene, 1,2-butadiene, fluorene, primary amines, secondary amines, etc. can also be used as molecular weight regulators in the polymerization. The polymerization process for obtaining the above polymers can be a batch process, a continuous process, or a combination thereof.

[0029] The raw polymer of the present invention can also be produced by polymerization methods other than using a lithium catalyst, such as organic compounds such as nickel, cobalt, titanium, etc., and organometallic components such as lithium, magnesium, aluminum, etc. A method using a Ziegler catalyst or an emulsion polymerization method can also be used.

The raw polymer obtained by the above method is then selectively partially hydrogenated. Hydrogenation catalysts that can be suitably used in the present invention include catalysts containing titanium as a metal component alone or in combination with organometallic compounds such as lithium, magnesium, aluminum, etc. -133203 or JP-A-60-220
It is described in No. 147. The selective partial hydrogenation of the present invention must be carried out using the above-mentioned catalyst under extremely mild reaction conditions.

The hydrogenation reaction is carried out in a solvent in which the raw polymer inert to the catalyst is soluble. Suitable solvents are n-pentane,
aliphatic hydrocarbons such as n-hexane, n-octane,
It is either a single alicyclic hydrocarbon such as cyclohexane or cycloheptane, or an ether such as diethyl ether or tetrahydrofuran, or a mixture thereof as a main component.

[0032] In the hydrogenation reaction of the present invention, the above raw polymer is generally maintained at a predetermined temperature under hydrogen or an inert atmosphere, a hydrogenation catalyst is added with or without stirring, and then This is carried out by introducing hydrogen gas and pressurizing it to a predetermined pressure. Inert atmospheres include, for example, helium, neon,
This means an atmosphere that does not react with any participating bodies in the hydrogenation reaction, such as argon.

Further, when a titanocene diaryl compound is used as a hydrogenation catalyst, it may be added alone to the reaction solution as it is, or it may be added as a solution in an inert organic solvent. As the inert organic solvent used when the catalyst is used as a solution, any of the above-mentioned various solvents that do not react with any of the participants in the hydrogenation reaction can be used. Preferably, it is the same solvent as used in the hydrogenation reaction. Further, the amount of the catalyst added is 0.02 to 20 mmol per 100 g of the raw polymer.

The most preferable method for obtaining the polymer of the present invention is to carry out solution polymerization of the raw polymer using an organolithium catalyst, and use the obtained polymer solution as it is in the next hydrogenation reaction, which is suitable for industrial use. extremely useful. The selectively partially hydrogenated polymer of the present invention can be obtained by removing the solution obtained above and drying it.

Taking advantage of its properties, the polymer of the present invention can be widely used in applications where butadiene polymers and styrene-butadiene copolymers are currently used. A particularly preferred application is for automobile tires, where the polymer of the present invention is used alone or blended with natural rubber or other synthetic rubber, and subjected to predetermined "compounding,""molding," and "vulcanization" before being used for final use. Ru. In this case, in order for the polymer of the present invention to exhibit its effects, at least 30% of the raw rubber needs to be the polymer of the present invention.

Examples of synthetic rubbers that can be used as a blend include butadiene polymer, styrene-butadiene copolymer, isoprene-butadiene copolymer, acrylonitrile-butadiene copolymer, chloroprene polymer, and ethylene-propylene copolymer. Examples include polymers, isoprene-isobutylene copolymers, and the like. In addition, the compounding agents added to the raw material rubber in "compounding" include reinforcing agents, softeners, fillers, vulcanizing agents, vulcanization accelerators, and vulcanization accelerators. There are sulfur auxiliaries, colorants, flame retardants, lubricants, blowing agents, and other compounding agents, which are appropriately selected and used depending on the intended use of the composition.

Carbon black is a typical reinforcing agent, and various types of reinforcing agents with different particle sizes or structures obtained by various manufacturing methods are used, but carbon blacks such as ISAF, HAF, and FEF are used. is preferably used. The amount of carbon black to be added is 10 to 150 parts by weight, preferably 40 to 10 parts by weight, based on 100 parts by weight of raw rubber.
0 parts by weight are used. The type and amount of carbon black added are appropriately adjusted depending on the intended use of the rubber composition, and two or more types may be used in combination.

Other reinforcing agents that may be added as necessary include inorganic reinforcing agents such as silica and activated calcium carbonate, high styrene resins, and phenol-formaldehyde resins. The agent is 1 to 100 parts by weight per 100 parts by weight of raw rubber,
Preferably 5 to 50 parts by weight are used.

Typical softeners that can be added as needed include process oils, including paraffinic and
Various types of naphthenic and aromatic compounds are suitably used in the rubber composition, and are used in an amount of 2 to 100 parts by weight, preferably 5 to 70 parts by weight, per 100 parts by weight of raw rubber. It is also possible to use an oil-extended polymer in which process oil is added to the raw rubber in advance. Other softeners include liquid paraffin, coal tar, fatty oils, and sub.

[0040] Examples of the filler include calcium carbonate, clay, talc, and aluminum hydroxide. The typical vulcanizing agent is sulfur, and raw rubber 10
0.1 to 10 parts by weight, preferably 0.0 parts by weight.
2 to 5 parts by weight are used. Other vulcanizing agents include sulfur compounds such as sulfur chloride, morpholine disulfide, and alkylphenol disulfide, and peroxides, which may be used alone or in combination with sulfur.

[0041] There are a wide variety of vulcanization accelerators, and these can be used in amounts ranging from 0.01 to 100 parts by weight of raw rubber.
5 parts by weight is used, and two or more types may be used in combination. Typical vulcanization accelerators include guanidine-based, aldehyde-amine and aldehyde-ammonia-based, thiazole-based, imidazoline-based, thiourea-based, thiuram-based, dithiocarbamate-based, xanthate-based, and mixed accelerators. Examples of vulcanization aids include metal oxides such as zinc oxide, fatty acid compounds such as stearic acid, and amines.
~10 parts by weight are used.

Typical anti-aging agents or antioxidants are amine-based, phenol-based, phosphorus-based, sulfur-based, etc., and these contain 0.0% per 100 parts by weight of raw rubber.
001 to 10 parts by weight, and two or more types may be used in combination. Typical scorch inhibitors include phthalic anhydride, salicylic acid, and N-nitroso-diphenylamine. Examples of the tackifier include coumaron-indene resin, terpene-phenol resin, and rosin ester. Furthermore, various other compounding agents may be used as necessary.

The rubber composition of the present invention can be produced by mixing raw rubber and various compounding agents using various mixing devices generally used for mixing rubber compositions, such as open rolls, Banbury mixers, kneaders, extruders, etc. Then, after molding into the desired shape, it is vulcanized. The rubber composition of the present invention is suitably used for various automobile tires, belts, hoses, industrial goods such as anti-vibration rubber, footwear, daily necessities, construction materials, and various other uses by taking advantage of its characteristics.

[0044]

EXAMPLES The present invention will now be explained in more detail with reference to Examples and Comparative Examples, but these are not intended to limit the scope of the present invention.

Example 1, Comparative Example 3 A butadiene/n-hexane mixture (butadiene concentration 20% by weight) was reacted at a rate of 20 l/hr using a jacketed autoclave with an internal volume of 10 l and equipped with a stirrer as a reactor. 60ml n-butyllithium/n-hexane solution (concentration 5% by weight)
/hr, and the coupling polymerization of butadiene was carried out at a polymerization temperature of 110°C.

The obtained activated polymer was deactivated with methanol,
Transfer 8 liters of the polymer solution to another jacketed reactor with internal volume of 10 liters and add di-p-tolylbis(1-cyclopentadienyl)titanium/cyclohexane as a hydrogenation catalyst at a temperature of 60°C. 250 ml of solution (concentration 1 mmol/l) and n-butyllithium solution (
50 ml (concentration 5 mmol/l) at 0°C, 2.
The mixture was added under a hydrogen pressure of 0 kg/cm2, and the mixture was reacted for 30 minutes at a hydrogen partial pressure of 2.5 kg/cm2.

To the resulting selective partially hydrogenated polymer solution, 0.5 part of 2,6-ditertiarybutylhydroxytoluene was added per polymer as an antioxidant, and the solvent was removed. Table 1 shows the analytical values of the raw polymer (butadiene polymer of Comparative Example 3) obtained by sampling after methanol deactivation and the analytical values of the selective partially hydrogenated polymer. In addition, the analysis method was performed by the method shown below.

1) The original polymer containing bound styrene is dissolved in chloroform, and UV2 caused by the phenyl nucleus of styrene is
Bound styrene content (wt%) by absorption at 54 nm
was measured.

2) Vinyl bond content The original polymer was dissolved in deuterated chloroform, and 1,2- Proton due to vinyl (=
CH2 ) and chemical shift 5.2 ppm to 5.8 ppm
The vinyl proton (=CH
-) was calculated using the following formula.

[0050]

[Math 1]

3) Weight average molecular weight and molecular weight distribution The polymer was dissolved in tetrahydrofuran (THF) and subjected to GPC (LC-5A column PS Gel 104, 10, manufactured by Shimadzu Corporation).
5 and 106 were connected in series, and a differential refractometer was used as a detector. ), and the average molecular weight was calculated using a calibration curve previously determined from the relationship between the molecular weight of the peak of standard polystyrene and the GPC count number.

4) Hydrogenation rate of the entire butadiene part and hydrogenation rate of the vinyl bond part The original polymer was dissolved in deuterated chloroform, and F
T-NMR (270 mega, manufactured by JEOL Ltd.) revealed protons (=CH2) due to 1,2-vinyl with a chemical shift of 4.7 ppm to 5.2 ppm (signal C0) and chemical shifts of 5.2 ppm to 5.2 ppm. 8ppm (signal D0
The integrated intensity of the vinyl proton (=CH-) of
1.0 ppm (signal A1) of hydrogenated 1,
Methyl group proton (-CH3) due to 2 bonds, proton due to unhydrogenated 1,2 vinyl with a chemical shift of 4.7 ppm to 5.2 ppm (signal C1) (signal C1)
=CH2), chemical shift 5.2ppm-5.8ppm
It was calculated using the following formula from the integrated intensity of non-hydrogenated vinyl protons (=CH-) (signal D1). first

[0053]

[Formula 2] A11=pA1, C11=pC1, D11=pD1
and the hydrogenation rate of the 1,2-vinyl bond part is

[0054]

[Math 3] Hydrogenation rate of 1,4-double bond part

[0055]

[Math 4] Hydrogenation rate of the entire butadiene part

[0056]

##EQU00005## Table 2 also shows the vulcanization properties of a carbon-blended composition of a 75/25 blend of this material and natural rubber. In addition,
The measurement method was as follows.

1) Hardness JIS-K-6301 JIS
-By A hardness tester. 2) Modulus, tensile strength, elongation at break Based on JIS-K-6301 tensile test method.

3) Repulsion Resilience The Lupke method according to JIS-K-6301. However, the repulsion at 70°C is as follows:
After preheating in the oven at 0℃ for 1 hour, quickly take it out and measure.

4) Exothermic Goodrich exotherm; using a Goodrich flexometer, load 24 pounds, displacement 0
．． 225 inches, start 50℃, rotation speed 1800rpm
The test was conducted under the conditions of m, and the difference in temperature increase after 20 minutes is expressed.

5) Heat aging resistance 100°C oven 100h
Comprehensive evaluation was made from the retention of hardness, tensile strength, and elongation after r. The evaluation criteria were as follows. ◎; Excellent ○; Good △; Slightly poor ×; Poor

Examples 2 to 8, Comparative Examples 1, 2, and 4 to
11 A butadiene polymer and a styrene-butadiene polymer obtained by batch polymerization or continuous polymerization using an organolithium catalyst (alone or using tetrahydrofuran as a modifier) under the reaction conditions of Example 1 (hydrogenation pressure, hydrogenation Examples 2 to 8 were hydrogenated by changing the temperature, time, and amount of catalyst.
Selected partially hydrogenated polymers of Comparative Examples 1, 2, 4, 5 and 7 to 9 were obtained.

In Comparative Example 6, the raw polymer used in Example 6 was used without hydrogenation. In Comparative Examples 10 and 11, partially hydrogenated polymers were obtained using a nickel-based catalyst disclosed in Japanese Patent Publication No. 35497/1983 as a hydrogenation catalyst. Table 1 shows the structural analysis values for each polymer. In addition, Tables 2 and 3 show the vulcanized physical properties of carbon compounded compositions of these polymers alone or blended with natural rubber. Note that the measurement method in Table 3 is the same as in Table 2 except for the following method.

Wet skid resistance; AS using a Stanley London portable skid tester and Safety Walk (manufactured by 3M) as the road surface.
It was measured according to the method of TM-E-808-74.

[0064]

[Table 1]

[0065]

[Table 2]

[0066]

[Table 3]

[0067]

[Effects of the Invention] As explained above, the carbon-blended composition of the raw material rubber obtained by using the selectively hydrogenated polymer having the specified structure of the present invention alone or by blending it with other rubbers has a high hardness and modulus. , and has excellent rebound resilience.
Furthermore, it has excellent heat aging resistance and well-balanced physical properties, making it suitable for tires, especially tire treads.

[Brief explanation of the drawing]

FIG. 1 is a diagram showing FT-NMR absorption of the raw polymer of Example 1.

[Figure 2] FT of the polymer after selective partial hydrogenation of Example 1
- It is a figure showing NMR absorption.

Claims (1)

[Claims] Claim 1: (1) Combined styrene content [S] is 0 to 40
Weight% (2) Vinyl bond content [V] of butadiene part is 1
~80% (3) Select a butadiene polymer or styrene-butadiene copolymer with a weight average molecular weight (Mw) of 1 to 1 million (4) Molecular weight distribution (Mw/Mn) of 1.2 to 5.0 with partial water (5) The hydrogenation rate [A] of the entire butadiene part is 3 to 60% (6) The hydrogenation rate [B] of the vinyl bond part of the butadiene part is 30% or more, and [A], [B ],
[S], [V] are (7) [A] / ([S] + [V]) 1
/2 is 2~8 (8) [B]・[V]1/2 /[A]
A rubber composition consisting of 100 parts by weight of raw rubber containing at least 30% by weight of a selectively hydrogenated polymer satisfying the relationship of 10 to 16, 10 to 150 parts by weight of carbon black, and 0.1 to 10 parts by weight of a vulcanizing agent. thing.