JP2625878B2 - Method for producing modified diene polymer rubber - Google Patents

Description

The present invention relates to a method for producing a modified diene-based polymer rubber, and more specifically, an active conjugated diene-based polymer rubber having an alkali metal terminal, tin or The present invention relates to a method for producing a modified diene polymer rubber, which comprises reacting a silicon compound and an aminovinylsilane compound.

<Conventional Technology> Conventionally, conjugated diene-based polymer rubbers such as polybutadiene and butadiene-styrene copolymer rubber have been used as rubber for automobile tire treads. As a result, there has been a demand for a rubber material having a small rolling resistance and a large road grip on snow and ice as a rubber for an automobile tire tread.

The rolling resistance has a correlation with the rebound resilience of the polymer, and the higher the rebound resilience, the lower the rolling resistance. On the other hand, it is known that the lower the JIS hardness at low temperatures, the greater the road grip on snow and ice on snow and ice. However, these properties have been unsatisfactory in practical use with existing rubber materials.

The present inventors have previously conducted intensive studies to increase the rebound resilience of the conjugated diene polymer rubber and lower the JIS hardness at low temperature, and as a result, the alkali metal-containing diene polymer rubber and the aminovinylsilane compound It has been found that the above object can be achieved by reacting and introducing a specific atomic group into the polymer. (Japanese Patent Application No. 63-0444859, Japanese Patent Application No. 63-04448)
60) However, the conjugated diene-based polymer rubber modified with the above compound has a serious practical disadvantage that its processability typified by rollability and the like is poor.

<Problems to be Solved by the Invention> An object of the present invention is to provide a method for producing a conjugated diene-based polymer rubber having improved rebound resilience, reduced JIS hardness at a low temperature, and good workability.

<Means for Solving the Problems> The present inventors have intensively studied to increase the rebound resilience of the conjugated diene-based polymer rubber, reduce the JIS hardness at low temperatures, and improve the processability and storage properties. As a result, the active conjugated diene-based polymer rubber having an alkali metal terminal is reacted with a tin or silicon compound and an aminovinylsilane compound, and a specific atomic group is introduced into the polymer. Have been achieved, and the present invention has been completed.

That is, the present invention relates to (1) an active conjugated diene having an alkali metal terminal obtained by polymerizing a conjugated diene monomer or a conjugated diene monomer and an aromatic vinyl monomer in a hydrocarbon solvent using an alkali metal catalyst. (A) General formula R _a MX _b (where R is an alkyl group, alkenyl group, cycloalkenyl group or aromatic hydrocarbon group, M is a silicon or tin atom, and X is a halogen Atom, a
Is an integer of 0 to 2, b is an integer of 2 to 4), and (b) a general formula (Wherein R ₁ , R ₂ , R ₃ , R ₄ and R ₅ represent an alkyl group) and a method for producing a modified diene-based polymer rubber characterized by reacting Things.

The active conjugated diene polymer rubber having an alkali metal terminal used in the present invention (hereinafter referred to as “active diene polymer rubber”) is a conjugated diene monomer or a conjugated diene monomer and an aromatic vinyl monomer in a hydrocarbon solvent. Refers to a diene-based polymer rubber having an alkali metal bonded to a polymer terminal obtained by performing polymerization using an alkali metal-based catalyst.

Examples of the diene polymer rubber include polymers of conjugated diene monomers such as 1,3-butadiene, isoprene, 1,3-pentadiene (piperylene), 2,3-dimethyl-1,3-butadiene, and 1,3-hexadiene. Or a copolymer rubber, or a conjugated diene monomer and styrene copolymerizable with the monomer, α-methylstyrene, vinyltoluene, vinylnaphthalene, divinylbenzene, trivinylbenzene, aromatic vinyl compounds such as divinylnaphthalene, acrylonitrile and the like. Examples include, but are not limited to, unsaturated nitriles, (meth) acrylic acid esters or copolymer rubbers with vinylpyridine and the like.

Specific examples thereof include polybutadiene rubber, polyisoprene rubber, butadiene-isoprene copolymer rubber, and butadiene-citylene copolymer rubber.

The active diene-based polymer rubber is a diene-based polymer rubber obtained by polymerizing a diene-based polymer rubber with an alkali metal-based catalyst, wherein an alkali metal is bonded to at least one end of a polymer chain, before termination of polymerization. Of living polymers. It is possible to use commonly used ones such as an alkali metal catalyst, a polymerization solvent, a randomizer, and a microstructure modifier of a conjugated diene unit, and the production method of the polymer is not particularly limited.

The amount of the polar compound as a randomizer or a conjugated diene unit as a microstructure modifier is usually 0.1 to 10 mol, preferably 0.5 to 2 mol, per 1 mol of the alkali metal catalyst.

Illustrative alkali metal catalysts used in the polymerization reaction are as follows.

Lithium, sodium, potassium, rubidium, cesium metals or complexes thereof with hydrocarbon compounds or polar compounds, preferably lithium or sodium compounds having 2 to 20 carbon atoms.

For example, ethyl lithium, n-propyl lithium, is
o-propyl lithium, n-butyl lithium, sec-butyl lithium, ter-octyl lithium, n-decyl lithium, phenyl lithium, 2-naphthyl lithium, 2-
Butyl-phenyllithium, 4-phenyl-butyllithium, cyclohexyllithium, 4-cyclopentyllithium, 1,4-dilithio-butene-2, sodium naphthalene, sodium biphenyl, potassium-tetrahydrofuran complex, potassium diethoxyethane complex, α-methyl And sodium salts of styrene tetramer.

The polymerization reaction is a hydrocarbon solvent or tetrahydrofuran,
The reaction is performed in a solvent that does not destroy alkali metal-based catalysts such as tetrahydropyran and dioxane.

Suitable hydrocarbon solvents are selected from aliphatic hydrocarbons, aromatic hydrocarbons, and alicyclic hydrocarbons.
Propa, n-butane, iso-butane, n
-Pentane, iso-pentane, n-hexane, cyclohexane, propene, 1-butene, iso-butene, trans-2-butene, cis-2-butene, 1-pentene,
-Pentene, 1-hexene, 2-hexene, benzene,
Preferred are toluene, xylene, ethylbenzene and the like.
These solvents can be used as a mixture of two or more kinds.

Next, the general formula R _a MX _b (where to be reacted with the active diene polymer rubber used in the present invention, wherein R is an alkyl group, alkenyl group, cycloalkenyl group or an aromatic hydrocarbon group, M is A silicon or tin atom, X is a halogen atom, a is an integer of 0 to 2, b is an integer of 2 to 4), and the silicon compound is tetrachlorosilicon, tetrabromosilicon, Methyltrichlorosilicon, butyltrichlorosilicon, dichlorosilicon, bistrichlorosilylsilicon, and the like are used. Tin or the like is used. The silicon or tin compound acts as a coupling agent for the active diene polymer rubber, and the halogen atom of the silicon or tin compound is 0.2 to 1 equivalent of the terminal lithium atom of the active diene polymer rubber.
Used in a ratio of 3 equivalents. Coupling reaction is 50-12
It is performed at a temperature in the range of 0 ° C.

Next, the compound to be reacted with the active diene polymer rubber used in the present invention is represented by the general formula (Wherein, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ represent an alkyl group).

Specific examples of such an aminovinylsilane compound are shown below.

Bis- (dimethylamino) methylvinylsilane, bis (ethylmethylamino) methylvinylsilane, bis (diethylamino) methylvinylsilane, bis (ethylpropylamino) methylvinylsilane, bis (dipropylamino) methylvinylsilane, bis (butylpropylamino) methyl Vinyl silane, bis (dibutylamino) methylvinylsilane, bis (dimethylamino) ethylvinylsilane, bis (ethylmethylamino) ethylvinylsilane, bis (diethylamino) ethylvinylsilane, bis (ethylpropylamino) ethylvinylsilane, bis (dipropylamino) ethyl Vinylsilane, bis (butylpropylamino) ethylvinylsilane, bis (dibutylamino) ethylvinylsilane, bis (dimethylamino) propylvinylsila , Bis (ethylmethylamino) propylvinylsilane, bis (diethylamino) propylvinylsilane, bis (ethylpropylamino) propylvinylsilane, bis (dipropylamino) propylvinylsilane, bis (butylpropylamino) propylvinylsilane, bis (dibutylamino) propyl Vinylsilane, bis (dimethylamino) butylvinylsilane, bis (ethylmethylamino) butylvinylsilane,
Bis (diethylamino) butylvinylsilane, bis (ethylpropylamino) butylvinylsilane, bis (dipropylamino) butylvinylsilane, bis (butylpropylamino) butylvinylsilane, bis (dibutylamino) butylvinylsilane, etc., are particularly preferred. Is bis (dimethylamino) methylvinylsilane.

The amount of the aminovinylsilane compound to be used is generally 0.05 to 10 mol, preferably 0.1 mol, per 1 mol of the alkali metal catalyst used in producing the active diene polymer rubber.
2 to 2 moles.

Since the reaction between the aminovinylsilane compound and the active diene-based polymer rubber occurs rapidly, the reaction temperature and the reaction time can be selected from a wide range.
° C, several seconds to several hours.

The reaction may be carried out by contacting the active diene polymer rubber with the aminovinylsilane compound.For example, the diene polymer rubber is polymerized using an alkali metal catalyst, and the aminovinylsilane compound is added to the polymer rubber solution. Can be exemplified as a preferred method, but the method is not limited to this method. The resulting modified diene polymer rubber has an aminovinylsilane compound introduced at the molecular end.

After completion of the reaction, the modified diene-based polymer rubber is used as it is in the coagulation method used in the production of rubber by ordinary solution polymerization such as addition of a coagulant or steam coagulation from the reaction solution, and the coagulation temperature is not limited at all. .

For drying the crumb separated from the reaction system, band dryers, extrusion dryers and the like used in the production of ordinary synthetic rubber can be used, and the drying temperature is not limited at all.

The modified diene polymer rubber thus obtained is excellent in rebound resilience and JIS hardness at low temperature compared to unmodified rubber, and has improved workability, and is particularly preferably used for automobile tires. However, it can also be used as various industrial raw rubbers such as for shoe soles, flooring materials, and vibration-proof rubber.

In the present invention, it is necessary that the modified diene-based polymer rubber is contained in the rubber composition as a rubber component at least 10% by weight, preferably at least 20% by weight. If the content of the rubber component is less than 10% by weight, improvement in rebound resilience cannot be expected.

When the modified diene polymer rubber and another rubber are used in combination, the other rubber may be emulsion-polymerized styrene-
Includes butadiene copolymer rubber, polybutadiene rubber by solution polymerization (anion polymerization catalyst, Ziegler type catalyst, etc.), styrene-butadiene copolymer rubber, polyisoprene rubber, butadiene-isoprene copolymer rubber, and natural rubber. Depending on the type, one or more of these rubbers are selected and used.

Mooney viscosity of modified diene polymer rubber (ML ₁ + ₄ = 10
0 ° C.) is usually in the range of 10 to 200, preferably 20 to 150
Range. If it is less than 10, the mechanical properties such as tensile strength are inferior, and if it exceeds 200, the miscibility is poor when used in combination with other rubbers, processing operability becomes difficult, and the vulcanized product of the obtained rubber composition Is not preferred because the mechanical properties of

All or a part of the rubber component used in the present invention can be used as an oil-extended rubber.

The rubber composition of the present invention is produced by mixing a rubber component and various compounding agents using a mixer such as a roll Banbury. Various compounding agents to be used may be selected from those commonly used in the rubber industry and those suitable for the purpose of use of the rubber composition, and are not particularly limited.

Usually, sulfur, stearic acid, zinc white,
Various vulcanization accelerators (thiazole, thiuram, sulfenamide, etc.) or organic peroxides, various grades of carbon black and silica such as HAF and ISAF as reinforcing agents, and carbonic acid as filler Calcium, talc and the like are used, and as other compounding agents, process oils, processing aids, anti-aging agents and the like are used. The type and amount of these compounding agents are selected according to the purpose of use of the rubber composition, and are not particularly limited in the present invention.

The modified rubber composition of the present invention has rebound resilience and low temperature.
Excellent in JIS hardness and improved workability, so it is particularly preferably used for automobile tires, but is also used as a raw rubber for various industrial purposes such as shoe soles, flooring materials, and vibration-proof rubber You can also.

<Examples> Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples.

Example 1 A stainless-steel polymerization reactor having an internal volume of 10 l was washed, dried, and purged with dry nitrogen, and then 850 g of 1,3-butadiene was added.
150 g of styrene, 4300 g of n-hexane, 9 g of tetrahydrofuran and 4.4 mmol of n-butyllithium (n-hexane solution) were added, and polymerization was carried out at 50 ° C. for 1 hour with stirring.

After completion of the polymerization, 0.55 mmol of silicon tetrachloride was added, and the mixture was reacted for 30 minutes with stirring. Then, bis (dimethylamino)
2.2 mmol of methylvinylsilane was added, and 30
After reacting for 10 minutes, 10 ml of methanol was added and the mixture was further stirred for 5 minutes.

Thereafter, the contents of the polymerization reactor were taken out, 5 g of 2,6-di-t-butyl-p-cresol (Sumitomo Chemical Co., Ltd. Sumilizer BHT) was added, and most of n-hexane was evaporated, and then 60 ° C. For 24 hours under reduced pressure.

The Mooney viscosity and vinyl content (by infrared spectrophotometry) of the resulting polymer rubber were measured.

The resulting polymer rubber has a Mooney viscosity of 85 and a vinyl content of 31.
%, Styrene content was 15%.

Comparative Example 1 A polymer was obtained in the same manner as in Example 1 except that silicon tetrachloride was not added and bis (dimethylamino) methylvinylsilane was used in an amount of 4.4 mmol.

The resulting polymer rubber has a Mooney viscosity of 72 and a vinyl content of
31%, styrene content 15%.

Comparative Example 2 A polymer was obtained in the same manner as in Example 1 except that silicon tetrachloride and bis (dimethylamino) methylvinylsilane were not added.

The resulting polymer rubber has a Mooney viscosity of 55 and a vinyl content of 31.
%, Styrene content was 15%.

Comparative Example 3 Tin tetrachloride and bis (dimethylamino) methylvinylsilane were not added, and n-butyllithium was changed to 4.
A polymer was obtained in the same manner as in Example 1 except that the amount was changed to 1 mmol.

The resulting polymer rubber has a Mooney viscosity of 72 and a vinyl content of 31.
%, Styrene content was 15%.

Example 2 A stainless steel polymerization reactor having an inner volume of 10 l was washed, dried, and purged with dry nitrogen, and then 850 g of 1,3-butadiene was added.
150 g of styrene, 4300 g of n-hexane, 9 g of tetrahydrofuran and 4.4 mmol of n-butyllithium (n-hexane solution) were added, and polymerization was carried out at 50 ° C. for 1 hour with stirring.

After the completion of the polymerization, 0.55 mmol of tin tetrachloride was added, and the reaction was carried out for 30 minutes with stirring. Subsequently, 2.2 mmol of bis (dimethylamino) methylvinylsilane was added, followed by a reaction for 30 minutes with stirring, and 10 ml of methanol was added. And further stirred for 5 minutes.

After that, the content of the polymerization reactor was taken out, 5 g of 2,6-di-t-butyl-p-cresol (Sumitomo Chemical Co., Ltd. Sumilizer BHT) was added, and most of n-hexane was evaporated. For 24 hours under reduced pressure.

The Mooney viscosity, vinyl content (by infrared spectrophotometry) and styrene content (by refractive index method) of the resulting polymer rubber were measured.

The resulting polymer rubber has a Mooney viscosity of 85 and a vinyl content of 31.
%, Styrene content was 15%.

Comparative Example 4 A polymer was obtained in the same manner as in Example 2 except that tin tetrachloride was not added and bis (dimethylamino) methylvinylsilane was used in an amount of 4.4 mmol.

The resulting polymer rubber has a Mooney viscosity of 72 and a vinyl content of 31.
%, Styrene content was 15%.

Comparative Example 5 A polymer was obtained in the same manner as in Example 2 except that tin tetrachloride and bis (dimethylamino) methylvinylsilane were not added.

The resulting polymer rubber has a Mooney viscosity of 55 and a vinyl content of 31.
%, Styrene content was 15%.

Comparative Example 6 Tin tetrachloride and bis (dimethylamino) methylvinylsilane were not added, and n-butyllithium was changed to 4.
A polymer was obtained in the same manner as in Example 2 except that the amount was changed to 1 mmol.

The resulting polymer rubber has a Mooney viscosity of 72 and a vinyl content of 31.
%, Styrene content was 15%. (Compounding / vulcanized rubber physical properties) The produced polymer rubbers of Examples 1 and 2 and Comparative Examples 1 to 6 were kneaded on a roll according to the compounding recipe shown in Table 1 to obtain a compounded rubber, which was then heated at 160 ° C for 30 minutes. Press vulcanization was performed under the following conditions.

The rebound resilience of the vulcanized rubber was measured at 60 ° C. using a Lupke Jiriens tester. JIS hardness is -20 according to JIS K6301
Measured in ° C. The roll processability is adjusted by adjusting the temperature of the 6 "roll to 50 ° C, changing the roll gap to 0.7 mm, 1.0 mm, and 2.0 mm, winding a polymer or a mixture of polymers, observing the state, The scores are given in Table 2 and the results are shown in Table 3.

<Effects of the Invention> As described above, according to the present invention, a modified diene polymer rubber having high rebound resilience, low JIS hardness at low temperature, and excellent workability, and a modified rubber composition comprising the polymer are provided. Things can be provided.

Claims (1)

(57) [Claims] An active conjugated diene-based polymer rubber having an alkali metal terminal obtained by polymerizing a conjugated diene monomer or a conjugated diene monomer and an aromatic vinyl monomer in a hydrocarbon solvent using an alkali metal-based catalyst. And (a) a general formula R _a MX _b (where R is an alkyl group, alkenyl group, cycloalkenyl group or aromatic hydrocarbon group, M is a silicon or tin atom, X is a halogen atom, a
Is an integer of 0 to 2; b is an integer of 2 to 4); and (b) a general formula: (Wherein, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ represent an alkyl group.) A method for producing a modified diene polymer rubber, characterized by reacting an aminovinylsilane compound represented by the formula: .