JP3102930B2 - Hydrogenated butadiene copolymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to ozone resistance, weather resistance,
The present invention relates to a hydrogenated butadiene copolymer having excellent heat resistance and vulcanizability, and more particularly to a hydrogenated butadiene copolymer containing an alkenyl group-containing conjugated diene and preferentially hydrogenating the butadiene portion.

[0002]

BACKGROUND OF THE INVENTION Hydrogenated butadiene polymers have been known for a long time. For example,
JP-B-3895, JP-B-42-8933, JP-B-42-25304, and JP-B-45-39274 disclose a method for producing a hydrogenated butadiene polymer and a hydrogenated styrene-butadiene copolymer. ing.

[0003] The hydrogenated product of a high vinyl butadiene polymer is disclosed in JP-B-63-14721, and the hydrogenated diene-based polymer composition having improved strength of an unvulcanized product is disclosed in JP-B-46-35497. JP-B-48-39203 discloses a lubricating oil composition of a hydrogenated styrene-butadiene copolymer having a small change in viscosity with respect to temperature. On the other hand, a lubricating oil composition having a high shear stability using a hydrogenated styrene-butadiene copolymer having a star structure is also disclosed in JP-B-61-50120.

Japanese Patent Application Laid-Open No. 60-252643 discloses a hydrogenated styrene-butadiene copolymer composition having a polymodal molecular weight distribution and excellent processability and strength. Japanese Patent Publication No. 62-45883 discloses a diblock type hydrogenated butadiene polymer disclosed in JP-A-1-217069.
Japanese Patent Laid-Open Publication No. Sho 2-2-1 discloses a bituminous composition of a diblock hydrogenated copolymer comprising a crystal block and an amorphous block.
Japanese Patent No. 70735 discloses a hydrogenated butadiene polymer composition.

[0005] These copolymers are intended to improve heat resistance and crystallinity by hydrogenation, but have sufficient ozone resistance, weather resistance, heat resistance and sufficient vulcanization properties. A polymer for vulcanized rubber which satisfies the balance of physical properties of strength, processability and rubber elasticity at the same time has not been obtained.

[0006]

SUMMARY OF THE INVENTION The present invention proposes a novel hydrogenated copolymer which solves the above-mentioned problems. That is, in the present invention, the total of the hydrogenated butadiene units represented by the formulas (1) and (2) and the butadiene units represented by the formulas (3) and (4) is 99 to 10% by weight, and (1) is 0-7
5% by weight, (2) is 8 to 99% by weight, (3) is 0 to 5% by weight, (4) is 0 to 15% by weight, ((2) + (4)) /
((1) + (2) + (3) + (4)) = 0.25-1,
((1) + (2)) / ((1) + (2) + (3) +
(4)) = 0.85 to 1,

[0007]

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The total of the hydrogenated conjugated diene monomer units represented by the formulas (5) to (7) and the conjugated diene monomer units represented by the formulas (8) to (10) is 1 to 90% by weight, 5): 0 to 45% by weight, (6) + (7): 0.5
~ 45% by weight (however, if any of (6) and (7)
%), (8) is 0 to 10% by weight,
(9) + (10) is 0 to 45% by weight, and ((6) +
(7) + (9) + (10)) / ((5) + (6) +
(7) + (8) + (9) + (10)) = 0.5 to 1,

[0009]

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[0010]

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[Where R ^{1 to} R ⁶ are hydrogen and have 1 to 1 carbon atoms.
There are 11 alkyl groups or alkenyl groups, which may be the same or different, but at least one is an alkenyl group or a hydrogenated group thereof, and the degree of hydrogenation is 0 to 90%. The vinyl aromatic compound unit is 0 to 50% by weight, the weight average molecular weight is 10,000 to 1,000,000, and the molecular weight distribution (Mw / M
It is intended to provide a hydrogenated butadiene copolymer in which n) is 10 or less.

The hydrogenated 1,4-butadiene component represented by the formula (1) in the hydrogenated butadiene-based copolymer chain of the present invention contains 0
７５75% by weight, preferably 25-60% by weight. 7
If it exceeds 5% by weight, the rubber elasticity is remarkably reduced, which is not preferable. The hydrogenated 1,2-butadiene component represented by the formula (2) is 8 to 99% by weight, preferably 25 to 80% by weight.
It is. If it is less than 8% by weight, rubber elasticity cannot be exhibited.
The 1,4-butadiene component represented by the formula (3) is 0 to 5
% By weight, preferably 0 to 3% by weight. If it exceeds 5% by weight, the ozone resistance decreases. The 1,2-butadiene component represented by the formula (4) is 0 to 15% by weight, preferably 0 to 5% by weight. If it exceeds 15% by weight, heat resistance is undesirably reduced.

The hydrogenated 1,4-conjugated diene component represented by the formula (5) is 0 to 45% by weight, preferably 0 to 40% by weight.
It is. If it exceeds 45% by weight, the rubber properties at low temperatures are undesirably reduced. The total of the hydrogenated 1,2- and hydrogenated 3,4-conjugated diene components represented by the formulas (6) to (7) is 0.5 to 45% by weight (when any of (6) and (7) is 0%). % By weight), and preferably 2 to 40% by weight. If it exceeds 45% by weight, the rubber properties at low temperatures are undesirably reduced. The 1,4-conjugated diene component represented by the formula (8) is 0 to 10% by weight, preferably 0 to 5% by weight. If it exceeds 10% by weight, the ozone resistance is undesirably reduced. The sum of the 1,2- and 3,4-conjugated diene components represented by the formulas (9) to (10) is 0 to 45.
% By weight, preferably 0 to 40% by weight. 45% by weight
Exceeding the heat resistance is not preferred because the heat resistance decreases. (1)
The components of (10) to (10) may be present in the copolymer chain in a random, block, or increasing or decreasing manner along the copolymer chain.

The hydrogenated butadiene copolymer of the present invention is a hydrogenated product of a copolymer of butadiene, a conjugated diene compound having an alkenyl group and a vinyl aromatic compound. In the hydrogenated butadiene copolymer of the present invention, the hydrogenated butadiene ((1)
-(2) formula) component and butadiene ((3)-(4) formula)
The total of the components is 99 to 10% by weight, preferably 97 to 30%.
%, And less than 10% by weight is not preferred because the rubber properties of the hydrogenated copolymer are greatly reduced.

The total of the components of the hydrogenated alkenyl group-containing conjugated diene compound (formulas (5) to (7)) and the alkenyl group-containing conjugated diene compound (formulas (8) to (10)) is 1 to 9
0% by weight, preferably 3 to 50% by weight, 1% by weight
If it is less than 90%, the effect of improving the ozone resistance of the hydrogenated copolymer will be lost. The content of the vinyl aromatic compound component is from 0 to 50% by weight, preferably from 0 to 40% by weight, and if it exceeds 50% by weight, the rubbery elasticity of the hydrogenated copolymer is lost and the resinous properties are strengthened.

The monomers of butadiene, alkenyl group-containing conjugated diene compound and vinyl aromatic compound are present in the copolymer chain before hydrogenation in a random, block, or increasing or decreasing manner along the copolymer chain. You may. Of the hydrogenated butadiene and butadiene in the hydrogenated butadiene copolymer chain of the present invention, 1,2 represented by the formulas (2) and (4)
It is necessary that 25 to 100% of 2-bonds be present, and preferably 35 to 80%. If it is less than 25%, the rubber elasticity of the hydrogenated copolymer decreases, which is not preferable. The 1,2-linkages may be random, block, or increase or decrease along the copolymer chain in the copolymer chain.

The hydrogenated conjugated diene compound having an alkenyl group and the conjugated diene compound having an alkenyl group in the hydrogenated butadiene copolymer chain of the present invention have a 1,2-bond represented by the formulas (6) and (9). The total of the 3,4-bonds represented by the formulas (7) and (10) needs to be 50% or more, preferably 70% or more, and more preferably 85%.
That is all. The total of 1,2- and 3,4-bonds is 50%
If it is less than 10, the ozone resistance of the hydrogenated copolymer decreases, which is not preferable. The 1,2- and 3,4-bonds may be present in the copolymer chain before hydrogenation in a random, block, or increasing or decreasing manner along the copolymer chain. Are preferred in terms of rubber properties.

The substituents R ^{1 to} R ⁶ of the alkenyl group-containing conjugated diene compound are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, pentyl, hexyl, heptyl, octyl, Nonyl, decyl and the like. Examples of the alkenyl group include, for example, vinyl, propenyl, isopropenyl, butyrenyl, isobutenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, and decenyl groups. Examples of the alkenyl group include ethylene, n-propenyl, isopropenyl, n-
Butyl, isobutyl, pentyl, hexyl, heptyl,
Octyl, nonyl, decyl and the like can be mentioned. Examples of the alkenyl group include, for example, vinyl, propenyl, isopropenyl, butyrenyl, isobutylenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl,
A decenyl group.

R ¹ of an alkenyl group-containing conjugated diene compound
At least one alkenyl group of to R ⁶ is preferably the double bond is an alkenyl group represented by the following equation (11) hydrogenated by structure difficult.

[0020]

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Wherein R ⁷ is an alkylene group having 1 to ⁷ carbon atoms, R ^{8 to} R ¹⁰ are hydrogen or an alkyl group having 1 to 7 carbon atoms, and R ^{8 to} R ¹⁰ are the same or different. (Although it may be different, at least two are alkyl groups.) (11) R of the substituent of the alkenyl group represented by the formula:
⁷ is an alkylene group such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene,
Hexamethylene, heptamethylene, propylene, butylene, amylene, hexylene and the like. R ⁸ ~R
¹⁰ is an alkyl group such as methyl, ethyl, n
-Propyl, isopropyl, n-butyl, isobutyl,
Examples include pentyl, hexyl, and heptyl groups.

An alkenyl group-containing conjugated diene compound is
And specifically, R¹, R^Two, R^Four, R^Five, R⁶But water
Prime, R^ThreeIs -CH_TwoCH_TwoCH = C (CH_Three)_TwoIs
Milsen, R¹, R^TwoIs -CH_Three, R^Three, R^Four, R⁶But
Hydrogen, R^FiveIs -C (CH_Three) = CHCH_ThreeAroo
Shimen, R¹, R^Two, R^Three, R⁶Is hydrogen, R^FourIs -CH
_Three, R^FiveIs -CH_TwoCH_TwoC (CH_Three) = CH_TwoIs
Oshimen, R¹, R^Two, R ^Three, R⁶Is hydrogen, R^FourIs -C
H_Three, R^FiveIs -CH_TwoCH = C (CH_Three)_TwoΒ−
Oshimen and the like. Mill in terms of polymerizability and stability
Sen and alloocimene are preferred.

The vinyl aromatic compound which can be used in the hydrogenated butadiene copolymer of the present invention is styrene, α-
One or more aromatic vinyl compounds selected from aromatic vinyl compounds such as methylstyrene, vinyltoluene, and p-tert-butylstyrene. The hydrogenated butadiene copolymer of the present invention has a low double bond in the main chain and a sufficient double bond in the side chain in order to simultaneously develop ozone resistance, heat resistance and vulcanization. It needs to be present. Therefore, the double bond of the butadiene portion of the hydrogenated butadiene-based copolymer of the present invention needs to be 85% or more, preferably 90% or more, more preferably 95% or more. If it is less than 85%, ozone resistance and heat resistance are poor. In addition, the hydrogenation rate of the double bond of the alkenyl group of the alkenyl group-containing conjugated diene compound needs to be suppressed to 90% or less, and preferably 80% or less. If the hydrogenation exceeds 90%, the vulcanizability decreases.

The hydrogenated butadiene copolymer of the present invention is a random and block copolymer comprising butadiene, an alkenyl group-containing conjugated diene compound and an aromatic vinyl compound, and examples thereof include the following. A: alkenyl group-containing conjugated diene compound polymer B: butadiene polymer A / B: random copolymer or tapered block copolymer of alkenyl group-containing conjugated diene compound and butadiene C: aromatic vinyl compound polymer A / C: When a random copolymer or a tapered block copolymer of an alkenyl group-containing conjugated diene compound and an aromatic vinyl compound is used, A / B random copolymer, A / B / C random copolymer, and A / BC block copolymer are used. Polymer, CA / B
-C block copolymer, A / BC multi-block copolymer, BA / C block copolymer, A / CBAA / C
Block copolymers, BA / C multi-block copolymers,
A / CA / BA / C block copolymer, A / BA
/ C having a structure such as a multi-block copolymer. Further, it may be a copolymer having these structures repeatedly, or a copolymer obtained by coupling these.

The hydrogenated butadiene copolymer of the present invention has a weight average molecular weight (Mw) of 10,000 to 1,000,000 and a molecular weight distribution (Mw).
w / Mn) is 10 or less. Weight average molecular weight of 100
If it exceeds 10,000, the processability is remarkably poor, and if it is less than 10,000, the strength of the hydrogenated copolymer becomes low. If Mw / Mn exceeds 10, the stickiness of the surface due to low molecules becomes severe. The production method of the hydrogenated butadiene copolymer of the present invention may be any as long as it corresponds to the specific structure described above. A typical production method for obtaining these copolymers will be described below. The copolymer before hydrogenation is hexane, cyclohexane,
In an inert solvent such as benzene, n
-Using an organic lithium or other alkali metal compound such as butyllithium, as a co-catalyst component if necessary,
Compounds that use alkoxides such as potassium butoxide, organic compounds such as dodecylbenzenesulfonate, and organic acid salts such as sodium stearate, and further adjust the amount of 1,2- and 3,4-bonds as necessary. As a monomer, butadiene using a polar organic compound such as ether, polyether, tertiary amine, polyamine, thioether, hexamethylphosphortriamide,
In some cases, it is obtained by further copolymerizing styrene at a predetermined ratio. The 1,2- and 3,4-bond amounts can be controlled by the amount of the polar organic compound added and the polymerization temperature.

In the above-mentioned polymerization method, the method of adding the monomer or the amount of the compound for controlling the amount of 1,2- and 3,4-bonds, the method of addition, and the polymerization temperature are changed during the polymerization reaction. By changing various polymerization conditions such as the above, it is possible to obtain a copolymer in which the content of each monomer and the amount of 1,2- and 3,4-bonds are increased or decreased in the molecular chain as described above. . In the polymerization, various compounds such as acetylene, 1,2-butadiene, fluorene, primary amine and secondary amine can be used as a molecular weight regulator. In addition, the copolymer chain having an active terminal obtained above is coupled with a polyfunctional compound such as silicon tetrachloride, tin tetrachloride, or a polyepoxy compound, or a branching agent such as divinylbenzene is polymerized. By adding to the system, a branched or radial copolymer is obtained.

Further, by reacting a functional group-containing compound with the active terminal, an alkyltin, a silyl group, an amino group, a carboxyl group, an acid anhydride group, a hydroxyl group, an epoxy group, an isocyanate group, a sulfonyl group or the like is introduced. Thus, a copolymer having an acidic property is obtained. As the polymerization process for obtaining the above copolymer, any of a batch process, a continuous process, and a combination thereof can be used.

The copolymer before hydrogenation is prepared by a polymerization method other than using a lithium catalyst, for example, an organic compound such as nickel, cobalt or titanium and an organic metal component such as lithium, magnesium or aluminum. A method using a Ziegler catalyst or a radical polymerization method can also be used. Regarding the method and conditions of the hydrogenation reaction, any methods and conditions can be used as long as a copolymer having a hydrogenation rate limited by the present invention can be obtained. Examples of such hydrogenation methods include a method using a catalyst mainly containing an organometallic compound of titanium as a hydrogenation catalyst, and a catalyst comprising an organic compound of iron, nickel, and cobalt and an organometallic compound such as alkylaluminum. How to use, ruthenium, method using an organic complex of an organometallic compound such as rhodium, palladium, platinum, ruthenium,
There is a method using a catalyst in which a metal such as cobalt or nickel is supported on a carrier such as carbon, silica or alumina. Among various methods, a homogeneous catalyst comprising an organometallic compound of titanium alone or an organometallic compound of lithium, magnesium, or aluminum (JP-B-63-48)
No. 41, JP-B1-37970) and hydrogenation under mild conditions of low pressure and low temperature are industrially preferable, and the hydrogenation selectivity to the double bond of butadiene is high. Suitable for the purpose.

The hydrogenation is carried out in a solvent which is inert to the catalyst and in which the copolymer 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, and diethyl ether. And ethers such as tetrahydrofuran alone or a mixture containing them as a main component.

The hydrogenation reaction is generally carried out by maintaining the copolymer at a predetermined temperature in a hydrogen or inert atmosphere, adding a hydrogenation catalyst with stirring or without stirring, and then introducing hydrogen gas. This is performed by applying a predetermined pressure. The inert atmosphere means an atmosphere that does not react with any participant in the hydrogenation reaction, such as helium, neon, or argon. Air and oxygen are not preferred because they oxidize the catalyst and cause deactivation of the catalyst. Also, nitrogen is not preferable because it acts as a catalyst poison during the hydrogenation reaction and lowers the hydrogenation activity. In particular, it is most preferable that the inside of the hydrogenation reactor be an atmosphere containing only hydrogen gas.

The hydrogenation reaction process for obtaining the hydrogenated copolymer is as follows:
Any of a batch process, a continuous process, and a combination thereof can be used. When a titanocene diaryl compound is used as the hydrogenation catalyst, it may be added alone to the reaction solution, or may be added as a solution of an inert organic solvent. As the inert organic solvent used when the catalyst is used as a solution, the above-mentioned various solvents which do not react with any participant in the hydrogenation reaction can be used. Preferably, the same solvent as the solvent used for the hydrogenation reaction is used. Also,
The catalyst was added in an amount of 0.02 to 100 g per 100 g of the copolymer before hydrogenation.
20 mmol.

The most preferred method for obtaining the hydrogenated butadiene copolymer of the present invention is to carry out solution polymerization of the copolymer before hydrogenation using an organolithium catalyst, and then to subject the resulting copolymer solution to the next hydrogenation. It is used for a reaction and is extremely useful industrially. The hydrogenated butadiene copolymer of the present invention is obtained by removing the solvent from the solution obtained above and isolating the copolymer.

The hydrogenated butadiene copolymer of the present invention takes advantage of its properties and is used alone or in a blend with other rubbers for vulcanized rubber applications. Quality use and dynamic vulcanization with PP resin are preferred.

[0034]

EXAMPLES The present invention will now be described specifically with reference to Examples and Comparative Examples, but these do not limit the scope of the present invention.

[0035]

EXAMPLE 1 Using an autoclave equipped with a stirrer and having a capacity of 10 liters and having a jacket as a reactor, 4200 g of n-hexane, 700 g of 1,3-butadiene and 80 g of myrcene were added, and n-butyllithium / n-hexane 9.0 ml of a solution (concentration: 5% by weight) and tetrahydrofuran (THF) were introduced at 50 times the molar amount of lithium, and the mixture was heated at 60 ° C.
For 2 hours. Thereafter, methanol was added in an equimolar amount to living lithium to inactivate the lithium. Di-p-tolylbis (1-cyclopentadienyl) as hydrogenation catalyst
250 ml of a titanium / cyclohexane solution (concentration: 1 mmol / l) and 50 ml of an n-butyllithium solution (concentration: 5 mmol / l) were mixed at 0 ° C and 2.0 kg / cm.
^2. Add the mixed solution under hydrogen and add hydrogen partial pressure 2.5k
The reaction was performed at g / cm ^{2 for} 90 minutes. The obtained hydrogenated copolymer was added with 2,6-di-tert-butylhydroxytoluene as an antioxidant in an amount of 0.5 part per polymer,
The solvent was removed. Table 1 shows the analysis values of the obtained hydrogenated copolymer.
It was shown to.

[0036]

[Table 1]

Table 2 shows the vulcanization properties of the composition evaluated using the hydrogenated copolymer. Hereinafter, the evaluation composition of each example in Table 2 was as follows.

[0038]

[Table 2]

[Evaluation Formulation] Hydrogenated copolymer 100 parts by weight, stearic acid 1.0 part by weight, carbon black
40 parts by weight, sulfur 1.5 parts by weight, paraffinic process oil 40 parts by weight, tetraethylthiuram disulfide
1.5 parts by weight, zinc white 5 parts by weight, 2-mercaptobenzothiazole 0.5 part by weight

[0040]

Examples 2 to 4 and Comparative Example 1 Amount of added monomer and T
A hydrogenated copolymer was obtained under the same conditions as in Example 1 except that the amount of HF was changed to change the monomer composition and the amount of 1,2- and 3,4-bonds. Table 1 shows the analysis values of the hydrogenated copolymer, and Table 2 shows the vulcanization properties.

[0041]

Examples 5 to 7 and Comparative Example 2 A hydrogenated copolymer was obtained under the same conditions as in Example 1 except that styrene was added as a monomer in addition to butadiene and myrcene, and the amount of each monomer was changed. . Table 1 shows the analysis values of the hydrogenated copolymer, and Table 2 shows the vulcanization properties.

[0042]

Examples 8 to 10 and Comparative Example 3 The amounts of butadiene and myrcene were changed to 1,2- and 3,
A hydrogenated copolymer was obtained under the same conditions as in Example 1 except that the amount of 4-bond was changed. Table 1 shows the analysis values of the hydrogenated copolymer.
Table 2 shows the vulcanization properties.

[0043]

Examples 11 to 12 and Comparative Example 4 A hydrogenated copolymer was obtained under the same conditions as in Example 1 except that 1,2-butadiene was added during polymerization in order to change the molecular weight distribution of the copolymer. . Table 1 shows the analysis values of the hydrogenated copolymer, and Table 2 shows the vulcanization properties.

[0044]

Examples 13 and 14 and Comparative Example 5 A hydrogenated copolymer was obtained under the same conditions as in Example 1 except that the hydrogenation reaction time was changed and the hydrogenation rates of the butadiene part and the myrcene part were changed. . Table 1 shows the analysis values of the hydrogenated copolymer, and Table 2 shows the vulcanization properties.

[0045]

Example 15 A hydrogenated copolymer having a star structure was obtained under the same conditions as in Example 1 except for coupling with silicon tetrachloride after the synthesis of the copolymer before hydrogenation. Table 1 shows the analysis values of the hydrogenated copolymer, and Table 2 shows the vulcanization properties.

[0046]

Example 16 70 parts by weight of the hydrogenated copolymer obtained in Example 1 and 30 parts by weight of natural rubber were roll-blended. Next, the vulcanization properties were measured.

[0047]

Example 17 Roll blending of 40 parts by weight of the hydrogenated copolymer obtained in Example 1 and 60 parts by weight of natural rubber was carried out. Next, the vulcanization properties were measured.

[0048]

Comparative Example 6 40 parts by weight of the hydrogenated copolymer obtained in Comparative Example 1 and 60 parts by weight of natural rubber were roll-blended. Next, the vulcanization properties were measured. Monomer composition of the copolymer before hydrogenation,
1,2- and 3,4-bond amounts, weight average molecular weight (M
w), molecular weight distribution (Mw / Mn) and hydrogenation ratio were measured by the following methods.

Content of vinyl aromatic compound: The copolymer before hydrogenation was used as a chloroform solution, and the content was measured by UV 254 nm absorption by a phenyl group of the vinyl aromatic compound.
Amount of 1,2-bond in butadiene portion: The copolymer before hydrogenation was converted into a heavy chloroform solution, and FT-NMR (270 MH
z, manufactured by JEOL Ltd.), the ¹ H-NMR spectrum was measured, and a proton (= CH ₂ ) by a 1,2-bond having a chemical shift of 4.7 ppm to 5.2 ppm and a chemical shift of 5.2 ppm
From the integrated intensity ratio of proton (= CH-) of ~ 5.8 ppm,
Calculated.

Weight average molecular weight and molecular weight distribution (Mw / M
n): The copolymer before hydrogenation was used as a THF solution, and GPC (pump: LC-5A manufactured by Shimadzu Corporation, eluent: TH)
F, column: Shodex GPC A-804, 80
5, 806 each, Detector: Differential refractometer Shode
x RISE-10), the chromatogram was measured. The weight average molecular weight (Mw) and the number average molecular weight (Mn) in terms of polystyrene were determined 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.

Hydrogenation ratio: The copolymer before hydrogenation and the copolymer after hydrogenation were converted into a heavy chloroform solution, and FT-NMR (2
NMR spectra were measured at 70 MHz, manufactured by JEOL Ltd., and the copolymer before hydrogenation was compared with a proton (= CH ₂ ) by a 1,2-bond having a chemical shift of 4.7 ppm to 5.2 ppm. Calculate the integrated intensity of protons (= CH-) with a chemical shift of 5.2 ppm to 5.8 ppm, while for the copolymer after hydrogenation, the hydrogenated 1,2-bonds with a chemical shift of 0.6 ppm to 1.0 ppm Methyl proton (-C
H ₃ ), protons due to unhydrogenated 1,2-bond (= CH ₂ ) having a chemical shift of 4.7 ppm to 5.2 ppm, and non-hydrogenated protons (= CH-) having a chemical shift of 5.2 ppm to 5.8 ppm, respectively And the hydrogenation rate was calculated.

Each performance of the crosslinked product shown in Table 2 was measured as follows. (1) Hardness and tensile test: Measured according to JIS-K-6301. (2) Ozone resistance: 40 in accordance with JIS-K-6301
C, 20% elongation, ozone concentration 20ppm, 50
The state of crack generation (number, size and depth of cracks) after 0 hour ozone exposure was observed.

(3) Aging resistance: Air aging was performed in a gear type aging tester set at 125 ° C. in accordance with JIS-K-6301, and the change in tensile strength was measured. (4) Rebound resilience: Measured with a Lupke rebound tester according to JIS-K-6301. As described above, the hydrogenated copolymer of the present invention (Examples 1 to 4) is particularly superior in strength as compared with the conventional hydrogenated polymer (Comparative Example 1).

[0054]

According to the hydrogenated butadiene copolymer of the present invention, a raw material rubber which simultaneously satisfies weather resistance, heat resistance, ozone resistance and vulcanizability, and has an excellent balance of physical properties between strength and resilience is provided. Is done.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C08F 8/04 C08F 36/06

Claims (1)

(57) [Claims] 1. The total of the hydrogenated butadiene unit represented by the formula (1) or (2) and the butadiene unit represented by the formula (3) or (4) is 99 to 10% by weight, and (1) is 0% by weight. ~ 7
5% by weight, (2) is 8 to 99% by weight, (3) is 0 to 5% by weight, (4) is 0 to 15% by weight, and ((2) +
(4)) / ((1) + (2) + (3) + (4)) = 0.
25-1, ((1) + (2)) / ((1) + (2) +
(3) + (4)) = 0.85 to 1, The total of the hydrogenated conjugated diene monomer units represented by the formulas (5) to (7) and the conjugated diene monomer units represented by the formulas (8) to (10) is 1 to 90% by weight, and (5) is 0 to 45% by weight, (6) + (7) is 0.5 to 45% by weight
(However, the case where either (6) or (7) is 0% by weight is included), (8) is 0 to 10% by weight, (9) +
(10) is 0 to 45% by weight, and ((6) + (7) +
(9) + (10)) / ((5) + (6) + (7) +
(8) + (9) + (10)) = 0.5 to 1, Embedded image [Wherein, R ^{1 to} R ⁶ are hydrogen, an alkyl group or an alkenyl group having 1 to 11 carbon atoms, and may be the same or different, but at least one is an alkenyl group or a hydrogenated group thereof. The hydrogenation rate is 0 to 90%. The vinyl aromatic compound unit is 0 to 50% by weight, the weight average molecular weight is 10,000 to 1,000,000, and the molecular weight distribution (Mw / M
A hydrogenated butadiene copolymer in which n) is 10 or less.