JPH05125108A - Hydrogenated butadienic copolymer - Google Patents

Abstract

PURPOSE:To provide the subject copolymer containing a hydrogenated butadiene, butadiene and a vinyl aromatic compound and having specific 1,2-bond content and hydrogenation degree, excellent heat-resistance, ozone-resistance and vulcanizability and balanced strength and impact resilience. CONSTITUTION:1,3-Butadiene, myrcene and styrene, etc., are charged into a reactor containing n-hexane solvent, polymerized in the presence of n- butyllithium initiator and incorporated with methanol to inactivate the initiator. The produced polymer is hydrogenated in hydrogen atmosphere in the presence of di-tolylbis(1-cyclopentadienyl)titanium as a hydrogenation catalyst to obtain the objective copolymer containing 99-10wt.% of the hydrogenated butadiene unit of formula I and II and butadiene unit of formula III and IV, having 1,2-bond content of >=25wt.%, a hydrogenation degree of >=85%, containing 1-90wt.% of conjugated diene having hydrogenated alkenyl group and conjugated diene having alkenyl group and >=50wt.% of 1,2-bond and 3,4-bond in total and having an alkenyl-hydrogenation-degree of 90% and a vinyl aromatic compound content of 0-50wt.%.

Description

Detailed Description of the Invention

[0001]

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

[0002]

BACKGROUND OF THE INVENTION Hydrogenated products of butadiene-based polymers have long been known. For example, Japanese Patent Publication Sho 36
JP-A-3895, JP-B-42-8933, JP-B-42-25304, and JP-B-45-39274 disclose methods for producing hydrogenated butadiene polymers and hydrogenated styrene-butadiene copolymers. ing.

A hydrogenated product of a high vinyl butadiene polymer is disclosed in JP-B-63-14721, and a hydrogenated diene polymer composition having improved strength of an unvulcanized product is disclosed in JP-B-46-35497. Japanese Patent Publication No. 48-39203 discloses a hydrogenated styrene-butadiene copolymer lubricating oil composition having a small viscosity change with temperature. On the other hand, a high shear stability lubricating oil composition using a hydrogenated styrene-butadiene copolymer having a star structure is also disclosed in JP-B-61-50120.

JP-A-60-252643 discloses a hydrogenated styrene-butadiene copolymer composition having a polymodal molecular weight distribution and excellent processability and strength. Japanese Examined Patent Publication No. 62-45883 discloses diblock type hydrogenated butadiene polymer.
Japanese Unexamined Patent Application Publication No. Sho 2 (1989) discloses a bituminous composition of a diblock hydrogenated copolymer comprising a crystalline block and an amorphous block.
Japanese Patent No. 70735 discloses a hydrogenated butadiene-based polymer composition.

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

[0006]

The present invention proposes a novel hydrogenated copolymer which solves the above 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) 8 to 99% by weight, (3) 0 to 5% by weight, (4) 0 to 15% by weight, ((2) + (4)) /
((1) + (2) + (3) + (4)) = 0.25-1,
((1) + (2)) / ((1) + (2) + (3) +
(4)) = 0.85-1

[0007]

[Chemical 4]

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
~ 45% by weight (however, either (6) or (7) is 0
(Including the case where it is wt%), (8) is 0 to 10 wt%,
(9) + (10) is 0 to 45% by weight, and ((6) +
(7) + (9) + (10)) / ((5) + (6) +
(7) + (8) + (9) + (10)) = 0.5 to 1,

[0009]

[Chemical 5]

[0010]

[Chemical 6]

[Wherein R ^{1 to} R ⁶ are hydrogen, and the number of carbon atoms is 1 to
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 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
It is intended to provide a hydrogenated butadiene-based copolymer having n) of 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 is 0.
˜75 wt%, preferably 25-60 wt%. 7
If it exceeds 5% by weight, rubber elasticity is significantly lowered, 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.
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 0-3% by weight. If it exceeds 5% by weight, ozone resistance is deteriorated. 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, the heat resistance is lowered, which is not preferable.

The hydrogenated 1,4-conjugated diene component represented by the formula (5) is 0 to 45% by weight, preferably 0 to 40% by weight.
Is. If it exceeds 45% by weight, the rubber properties at low temperatures deteriorate, which is not preferable. The total of hydrogenated 1,2- and hydrogenated 3,4-conjugated diene components represented by the formulas (6) to (7) is 0.5 to 45% by weight (any one of (6) and (7) is 0). (Including the case where it is wt%), preferably 2 to 40 wt%. If it exceeds 45% by weight, the rubber properties at low temperatures deteriorate, which is not preferable. 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, ozone resistance is deteriorated, which is not preferable. The total of 1,2- and 3,4-conjugated diene components represented by formulas (9) to (10) is 0 to 45.
% By weight, preferably 0-40% by weight. 45% by weight
If it exceeds the range, heat resistance decreases, which is not preferable. (1)
Each of the components (10) to (10) may be present in the copolymer chain in a random, block, or increased or decreased manner along the copolymer chain.

The hydrogenated butadiene-based copolymer of the present invention is a hydrogenated product of a copolymer of butadiene, an alkenyl group-containing conjugated diene compound and a vinyl aromatic compound. In the hydrogenated butadiene-based copolymer of the present invention, 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 if it is less than 10% by weight, the rubber properties of the hydrogenated copolymer are significantly reduced, which is not preferable.

The total of the hydrogenated alkenyl group-containing conjugated diene compound ((5) to (7) formula) component and the alkenyl group-containing conjugated diene compound ((8) to (10) formula) component is 1 to 9
0% by weight, preferably 3 to 50% by weight, 1% by weight
If it is less than 90% by weight, the effect of improving the ozone resistance of the hydrogenated copolymer is lost. The content of the vinyl aromatic compound component is 0 to 50% by weight, preferably 0 to 40% by weight. If it exceeds 50% by weight, the rubber elasticity of the hydrogenated copolymer is lost and the resinous property is enhanced, which is not preferable.

The respective 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. May be. Among the hydrogenated butadiene and butadiene in the hydrogenated butadiene-based copolymer chain of the present invention, 1, which are represented by the formulas (2) and (4),
It is necessary that 25-100% of 2-bonds be present, preferably 35-80%. If it is less than 25%, the rubber elasticity of the hydrogenated copolymer decreases, which is not preferable. The 1,2-bonds may be present in the copolymer chain in a random, block, or increasing or decreasing manner along the copolymer chain.

The hydrogenated alkenyl group-containing conjugated diene compound and the alkenyl group-containing conjugated diene compound in the hydrogenated butadiene-based copolymer chain of the present invention have 1,2-bonds represented by the formulas (6) and (9). It is necessary that the total of 3,4-bonds represented by the formulas (7) and (10) is 50% or more, preferably 70% or more, and more preferably 85%.
That is all. 50% total of 1,2- and 3,4-bonds
When it is less than 1, the ozone resistance of the hydrogenated copolymer is reduced, which is not preferable. 1,2- and 3,4-bonds may be present in the copolymer chain before hydrogenation at random, in blocks, or increased or decreased along the copolymer chain; Is preferable in rubber properties.

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

R ¹ of the conjugated diene compound containing an alkenyl group
At least one alkenyl group of R ⁶ to R ⁶ is preferably an alkenyl group represented by the following formula (11) having a structure in which a double bond is less likely to be hydrogenated.

[0020]

[Chemical 7]

(In the formula, 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 they 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 groups and the like can be mentioned. R ⁸ ~ R
¹⁰ is an alkyl group, for example, methyl, ethyl, n
-Propyl, isopropyl, n-butyl, isobutyl,
Examples thereof include pentyl, hexyl and heptyl groups.

As a conjugated diene compound containing an alkenyl group
Specifically, R¹, R², R^Four, R^Five, R⁶But water
Elementary, R³Is -CH₂CH₂CH = C (CH₃)₂Is
Mirsen, R¹, R²Is -CH₃, R³, R^Four, R⁶But
Hydrogen, R^FiveIs -C (CH₃) = CHCH₃Is aloo
Simene, R¹, R², R³, R⁶Is hydrogen, R^FourIs -CH
₃, R^FiveIs -CH₂CH₂C (CH₃) = CH₂Is
Ocimen, R¹, R², R ³, R⁶Is hydrogen, R^FourIs -C
H₃, R^FiveIs -CH₂CH = C (CH₃)₂Β-
Examples include ocimen. Mill in terms of polymerizability and stability
Sen and aloocimene are preferred.

Vinyl aromatic compounds that can be used in the hydrogenated butadiene-based copolymer of the present invention include styrene and α-
One or more aromatic vinyl compounds selected from aromatic vinyl compounds such as methylstyrene, vinyltoluene, and p-tert-butylstyrene. The hydrogenated butadiene-based copolymer of the present invention has a small number of double bonds in the main chain and sufficient double bonds in the side chains in order to simultaneously exhibit ozone resistance / heat resistance and vulcanization. Must exist Therefore, the double bond of the butadiene portion of the hydrogenated butadiene-based copolymer of the present invention needs to be 85% or more hydrogenated, preferably 90% or more, and more preferably 95% or more. If it is less than 85%, the ozone resistance and heat resistance are poor. Further, 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, preferably 80% or less. If the hydrogenation exceeds 90%, the vulcanizability will decrease.

The hydrogenated butadiene-based copolymer of the present invention is a random or block copolymer composed of 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: A random copolymer or taper block copolymer of an alkenyl group-containing conjugated diene compound and an aromatic vinyl compound is referred to as an A / B random copolymer, an A / B / C random copolymer, or an A / BC block copolymer. Polymer, CA / B
-C block copolymer, A / B-C multi-block copolymer, B-A / C block copolymer, A / C-B-A / C
Block copolymer, BA / C multi-block copolymer,
A / C-A / B-A / C block copolymer, A / B-A
/ C has 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-based copolymer of the present invention has a weight average molecular weight (Mw) of 10,000 to 1,000,000 and a molecular weight distribution (M
w / Mn) is 10 or less. Weight average molecular weight is 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. When Mw / Mn exceeds 10, surface stickiness due to low molecules becomes severe. The hydrogenated butadiene-based copolymer of the present invention may be produced by any method as long as it corresponds to the above-mentioned specific structure. Typical production methods for obtaining these copolymers are shown below. The copolymer before hydrogenation is hexane, cyclohexane,
In an inert solvent such as benzene, n as a polymerization catalyst
-Using organolithium such as butyllithium or another alkali metal compound, as a co-catalyst component, if necessary,
A compound that uses an organic compound represented by an alkoxide such as potassium butoxide, an organic acid salt such as dodecylbenzene sulfonate, and sodium stearate as a representative example, and further adjusts the 1,2- and 3,4-bond amount as necessary. As the monomer, butadiene of a polar organic compound such as ether, polyether, tertiary amine, polyamine, thioether, hexamethylphosphortriamide,
In some cases, it can be obtained by further copolymerizing styrene in a predetermined ratio. The 1,2- and 3,4-bond amounts can be controlled by the addition amount of the polar organic compound and the polymerization temperature.

In addition, in the above-mentioned polymerization method, the amount of the compound for adjusting the monomer addition method, the amount of 1,2- and 3,4-bonds, the addition method, 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 in the molecular chain are increased or decreased. .. Further, in the polymerization, various compounds such as acetylene, 1,2-butadiene, fluorene, primary amine and secondary amine can be used as a molecular weight modifier. Further, the copolymer chain having an active end 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 can be obtained.

Further, by reacting a compound having a functional group at the active terminal, an alkyl tin, 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 as a terminal functional group. A copolymer having a positive polarity is obtained. The polymerization process for obtaining the above copolymer may be a batch process, a continuous process, or a combination thereof.

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 type catalyst or a radical polymerization method can also be used. As for the method and conditions of the hydrogenation reaction, any method and conditions can be used as long as the copolymer having the hydrogenation rate limited by the present invention can be obtained. Examples of those hydrogenation methods include a method in which a catalyst containing an organometallic compound of titanium as a main component is used as a hydrogenation catalyst, and a catalyst comprising an organic compound of iron, nickel, cobalt and an organometallic compound such as alkylaluminum. Method used, ruthenium, method using an organic complex of an organometallic compound such as rhodium, palladium, platinum, ruthenium,
There is a method of 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 composed of an organometallic compound of titanium alone or an organometallic compound of lithium, magnesium or aluminum (Japanese Patent Publication No. 63-48).
No. 41, Japanese Patent Publication No. 1-37970), the method of hydrogenating under mild conditions of low pressure and low temperature is industrially preferable, and the hydrogenation selectivity to the double bond of butadiene is high. Suitable for the purpose.

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, diethyl ether. , An ether such as tetrahydrofuran, 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 hydrogen or an inert atmosphere, adding a hydrogenation catalyst with or without stirring, and then introducing hydrogen gas. It is carried out by applying a predetermined pressure. An 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 preferable because they may oxidize the catalyst and deactivate the catalyst. Further, nitrogen acts as a catalyst poison during the hydrogenation reaction and reduces the hydrogenation activity, which is not preferable. In particular, the hydrogenation reactor is most preferably an atmosphere of hydrogen gas alone.

The hydrogenation reaction process for obtaining the hydrogenated copolymer is as follows:
Either a batch process, a continuous process or 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 that do not react with any participants in the hydrogenation reaction can be used. It is preferably the same solvent as that used for the hydrogenation reaction. Also,
The amount of catalyst added is 0.02 to 100 g of the copolymer before hydrogenation.
20 mmol.

The most preferred method for obtaining the hydrogenated butadiene-based copolymer of the present invention is to solution polymerize the copolymer before hydrogenation using an organic lithium catalyst, and obtain the resulting copolymer solution as it is for the next hydrogenation. It is used for the reaction and is extremely useful industrially. The hydrogenated butadiene-based copolymer of the present invention is obtained by removing the solvent from the solution obtained above and isolating the copolymer.

The hydrogenated butadiene-based copolymer of the present invention is used not only for vulcanized rubber applications alone or in a blend with other rubbers, but also for impact-resistant styrene-based resin applications and blending into resins. Suitable for quality applications and dynamic vulcanization with PP resin.

[0034]

EXAMPLES 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.

[0035]

Example 1 An autoclave equipped with a stirrer and having an internal volume of 10 liters was used 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 was added. A solution (concentration 5% by weight) 9.0 ml and tetrahydrofuran (THF) were introduced in a molar amount 50 times that of lithium, and the temperature was 60 ° C.
It was polymerized for 2 hours. Thereafter, methanol was added to the living lithium in an equimolar amount to deactivate it. Di-p-tolylbis (1-cyclopentadienyl) as hydrogenation catalyst
A titanium / cyclohexane solution (concentration 1 mmol / liter) 250 ml and an n-butyllithium solution (concentration 5 mmol / liter) 50 ml were added at 0 ° C. and 2.0 kg / cm.
^2. Add the mixed solution under hydrogen, hydrogen partial pressure 2.5k
The reaction was performed for 90 minutes at g / cm ² . The resulting hydrogenated copolymer was prepared by adding 0.5 parts of 2,6-di-tert-butylhydroxytoluene as an antioxidant per polymer,
The solvent was removed. Table 1 shows the analytical values of the obtained hydrogenated copolymer.
It was shown to.

[0036]

[Table 1]

Further, the vulcanized physical properties of the evaluation compounding composition using this hydrogenated copolymer are shown in Table 2. Hereinafter, the evaluation composition of each example in Table 2 was as follows.

[0038]

[Table 2]

[Evaluation Mixture] 100 parts by weight of hydrogenated copolymer, 1.0 part by weight of stearic acid, 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 parts by weight

[0040]

Examples 2 to 4 and Comparative Example 1 Addition amount of monomer and T
A hydrogenated copolymer was obtained under the same conditions as in Example 1 except that the amount of HF added was changed to change the monomer composition and the 1,2- and 3,4-bond amounts. The analytical values of the hydrogenated copolymer are shown in Table 1, and the vulcanized physical properties are shown in Table 2.

[0041]

Examples 5 to 7 and Comparative Example 2 Hydrogenated copolymers were obtained under the same conditions as in Example 1 except that styrene was added in addition to butadiene and myrcene as monomers, and the addition amount of each monomer was changed. .. The analytical values of the hydrogenated copolymer are shown in Table 1, and the vulcanized physical properties are shown in Table 2.

[0042]

Examples 8 to 10 and Comparative Example 3 By changing the amount of THF added, 1,2- and 3, of the butadiene part and the myrcene part were changed.
A hydrogenated copolymer was obtained under the same conditions as in Example 1 except that the 4-bond amount was varied. Table 1 shows the analysis values of the hydrogenated copolymer.
The vulcanized physical properties are shown in Table 2.

[0043]

Examples 11 to 12 and Comparative Example 4 Hydrogenated copolymers were obtained under the same conditions as in Example 1 except that 1,2-butadiene was added during the polymerization in order to change the molecular weight distribution of the copolymer. .. The analytical values of the hydrogenated copolymer are shown in Table 1, and the vulcanized physical properties are shown in Table 2.

[0044]

Examples 13 to 14 and Comparative Example 5 Hydrogenated copolymers were obtained under the same conditions as in Example 1 except that the hydrogenation reaction time was changed to change the hydrogenation rates of the butadiene part and the myrcene part. .. The analytical values of the hydrogenated copolymer are shown in Table 1, and the vulcanized physical properties are shown in Table 2.

[0045]

Example 15 A star-structured hydrogenated copolymer was obtained under the same conditions as in Example 1 except that after coupling of the copolymer before hydrogenation, coupling with silicon tetrachloride was performed. The analytical values of the hydrogenated copolymer are shown in Table 1, and the vulcanized physical properties are shown in Table 2.

[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 vulcanized physical properties were measured.

[0047]

Example 17 40 parts by weight of the hydrogenated copolymer obtained in Example 1 and 60 parts by weight of natural rubber were roll-blended. Next, the vulcanized physical 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 vulcanized physical properties were measured. Monomer composition of the copolymer before hydrogenation,
1,2- and 3,4-bond amount, weight average molecular weight (M
w), molecular weight distribution (Mw / Mn), and hydrogenation rate were measured by the following methods.

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

Weight average molecular weight and molecular weight distribution (Mw / M
n): a 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 1 each, Detector: Differential refractometer Shode
The chromatogram was measured by x RI SE-10). The polystyrene-reduced weight average molecular weight (Mw) and number average molecular weight (Mn) were 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.

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

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

(3) Aging resistance: According to JIS-K-6301, air aging was carried out in a gear type aging tester set at 125 ° C., and changes in tensile strength were measured. (4) Rebound resilience: Measured with a Lupke repulsion tester according to JIS-K-6301. As described above, the strength of the hydrogenated copolymers of the present invention (Examples 1 to 4) is particularly excellent as compared with the conventional hydrogenated polymer (Comparative Example 1).

[0054]

EFFECTS OF THE INVENTION The hydrogenated butadiene-based copolymer of the present invention provides a raw material rubber that simultaneously satisfies weather resistance, heat resistance, ozone resistance and vulcanization property and has an excellent balance of physical properties of strength and impact resilience. To be done.

Claims (1)

[Claims] 1. The total of hydrogenated butadiene units represented by formulas (1) to (2) and butadiene units represented by formulas (3) to (4) is 99 to 10% by weight, and (1) is 0. ~ 7
5% by weight, (2) 8 to 99% by weight, (3) 0 to 5% by weight, (4) 0 to 15% by weight, and ((2) +
(4)) / ((1) + (2) + (3) + (4)) = 0.
25-1, 1, ((1) + (2)) / ((1) + (2) +
(3) + (4)) = 0.85 to 1, and The total of the hydrogenated conjugated diene-based monomer units represented by the formulas (5) to (7) and the conjugated diene-based monomer units represented by the formulas (8) to (10) is 1 to 90% by weight, and (5) is 0-45% by weight, (6) + (7) 0.5-45% by weight
(However, it includes 0% by weight of either (6) or (7)), 0 to 10% by weight of (8), (9) +
(10) is 0 to 45% by weight, and ((6) + (7) +
(9) + (10)) / ((5) + (6) + (7) +
(8) + (9) + (10)) = 0.5 to 1, and [Chemical 3] [Wherein R ^{1 to} R ⁶ are hydrogen, an alkyl group or an alkenyl group having 1 to 11 carbon atoms, and they 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
Hydrogenated butadiene-based copolymers in which n) is 10 or less.