JP5034297B2 - Modified diene polymer rubber and rubber composition - Google Patents

Description

The present invention relates to modified diene polymer rubber及 beauty rubber composition. More particularly, the present invention is excellent in impact resilience, thus relates rubber composition using the excellent modified diene polymer rubber及 beauty polymer rubber fuel economy.

  As a rubber for automobile tires, a styrene-butadiene copolymer obtained by an emulsion polymerization method is known. However, since the rebound resilience of the copolymer is inferior, the automobile tire made of the copolymer has a problem that it does not have excellent fuel economy.

  As an attempt to obtain a rubber having excellent rebound resilience, Patent Document 1 includes butadiene and styrene, an organolithium compound as a polymerization initiator, and a Lewis base such as ether as a microstructure modifier. A method of copolymerizing in a hydrocarbon solvent is disclosed.

  Patent Document 2 proposes a method of obtaining a modified diene copolymer rubber having improved rebound resilience by reacting a specific acrylamide with the alkali metal terminal of the diene polymer rubber. Was insufficient.

JP-A-60-72907 Japanese Patent No. 2540901

  In recent years, the demand for fuel economy of automobile tires has become more sophisticated against the background of environmental considerations, and the above polymer rubber cannot sufficiently meet this demand.

  An object of the present invention is to provide a modified diene polymer rubber having excellent rebound resilience, a method for producing the same, and a rubber composition using the modified diene polymer rubber.

（（１）式中、Ｒ¹〜Ｒ⁴は独立に炭素数が１〜８のアルキル基を表し、Ｒ⁵は炭素数が１〜８のアルキル基又は置換基を有してよいフェニル基を表す。） The first invention of the present invention is an active conjugate having an alkali metal terminal obtained by polymerizing a conjugated diene monomer or a conjugated diene monomer and an aromatic vinyl monomer using an alkali metal catalyst in a hydrocarbon solvent. A modified diene polymer rubber obtained by reacting a compound represented by the following formula (1) with a diene polymer.

(In formula (1), R ^{1 to} R ⁴ independently represent an alkyl group having 1 to 8 carbon atoms, and R ⁵ represents a phenyl group that may have an alkyl group having 1 to 8 carbon atoms or a substituent. Represents )

The second aspect of the present invention, the aforementioned modified diene polymer rubber, it relates to a rubber composition containing 10 wt% or more in the rubber component.

The present invention, excellent impact resilience, thus it is possible to provide a rubber composition using the excellent modified diene polymer rubber及 beauty polymer rubber fuel economy.

  Examples of the conjugated diene monomer used in the present invention include 1,3-butadiene, isoprene, 1,3-pentadiene (piperine), 2,3-dimethyl-1,3-butadiene, 1,3-hexadiene, and the like. Among these, 1,3-butadiene and isoprene are preferred from the viewpoints of physical properties of the polymer obtained and availability for industrial implementation.

  Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, vinyl toluene, vinyl naphthalene, divinyl benzene, trivinyl benzene, divinyl naphthalene and the like. Among these, the physical properties of the resulting polymer, industrial Styrene is preferable from the viewpoint of availability in carrying out.

  The hydrocarbon solvent does not deactivate the alkali metal catalyst, and the suitable hydrocarbon solvent is selected from aliphatic hydrocarbons, aromatic hydrocarbons, and alicyclic hydrocarbons, and particularly has 3 to 12 carbon atoms. Propane, n-butane, iso-butane, n-pentane, iso-pentane, n-hexane, cyclohexane, propene, 1-butene, iso-butene, trans-2-butene, cis-2-butene, 1 -Pentene, 2-pentene, 1-hexene, 2-hexene, benzene, toluene, xylene, ethylbenzene and the like. Moreover, these solvents can be used in mixture of 2 or more types.

  Examples of the alkali metal catalyst include metals such as lithium, sodium, potassium, rubidium, and cesium, hydrocarbon compounds containing these metals, and complexes of the metal and polar compounds. Of these, lithium or sodium compounds having 2 to 20 carbon atoms are preferred. For example, ethyl lithium, n-propyl lithium, iso-furopyl lithium, n-butyl lithium, sec-butyl lithium, t-octyl lithium, n-decyl lithium, phenyl lithium, 2-naphthyl lithium, 2-butyl-phenyl lithium 4-phenyl-butyl lithium, cyclohexyl lithium 4-cyclopentyl lithium, 1,4-dilithio-butene-2, sodium naphthalene, sodium biphenyl, potassium-tetrahydrofuran complex, potassium diethoxyethane complex, sodium salt of α-methylstyrene tetramer Etc.

As the modifying compound to be reacted with the active diene polymer rubber, a compound represented by the following formula (1) is used.

In formula (1), R ^{1 to} R ⁴ independently represent an alkyl group having 1 to 8 carbon atoms, and R ⁵ represents an alkyl group or phenyl group having 1 to 8 carbon atoms or an alkyl group having 1 to 8 carbon atoms. Represents a phenyl group having a group as a substituent. As the compound of formula (1), 4- (dimethylamino) -2,3-dimethyl-1-phenyl-3-pyrazolin-5-one, 4- (diethylamino) -2,3-dimethyl-1-phenyl-3 -Pyrazolin-5-one, 4- (dimethylamino) -2-ethyl-3-methyl-1-phenyl-3-pyrazolin-5-one, 4- (dimethylamino) -1,2,3-trimethyl-3 -Pyrazolin-5-one and the like can be mentioned, but 4- (dimethylamino) -2,3-dimethyl-1-phenyl-3-pyrazolin-5-one is preferred from the viewpoint that fuel economy can be remarkably improved.

From the viewpoint of kneadability of the resulting modified polymer rubber, a coupling agent represented by the following formula (2) is added to the active polymer before or after the reaction between the compound of formula (1) and the active polymer. It is preferable to do this.

(2) In the formula, R ⁶ represents an alkyl group, an alkenyl group, a cycloalkenyl group or an aromatic hydrocarbon group, M represents a silicon or tin atom, X represents a halogen atom, and m is an integer of 0 to 2. N represents an integer of 2-4. Compounds of formula (2) include tetrachlorosilicon, tetrabromosilicon, methyltrichlorosilicon, butyltrichlorosilicon, dichlorosilicon, bistrichlorosilylsilicon, tetrachlorotin, tetrabromotin, methyltrichlorotin, butyltrichlorotin, dichlorotin, bis Trichlorosilyl tin or the like is used. The coupling agent of the silicon or tin compound is used in the range of 0.01 to 0.4 equivalent of halogen atom with respect to 1 equivalent of the active diene polymer rubber terminal lithium atom. The coupling reaction is not particularly limited, but is usually performed at a temperature in the range of 20 ° C to 100 ° C.

  As the polymerization monomer, only a conjugated diene monomer may be used, or a conjugated diene monomer and an aromatic vinyl monomer may be used in combination. When a combination of a conjugated diene monomer and an aromatic vinyl monomer is used, the weight ratio of conjugated diene monomer / aromatic vinyl monomer is preferably 50/50 to 90/10, and more preferably 55/45 to 85/15. When the ratio is less than 50/50, the resulting modified polymer rubber becomes insoluble in the hydrocarbon solvent, and as a result, uniform polymerization may not be possible. When this ratio exceeds 90/10, the strength of the resulting modified polymer rubber may be lowered. The copolymer obtained by the combination is desirably a random copolymer from the viewpoint of improving fuel economy. In the case of a block copolymer, fuel economy may be reduced when a vulcanized rubber is used.

  In the polymerization, it is possible to use commonly used ones such as alkali metal catalysts, hydrocarbon solvents, randomizers, vinyl bond content regulators of conjugated diene units, and the method for producing the copolymer is particularly Not restricted.

  In order to adjust the vinyl bond content of the conjugated diene part, various compounds can be used as the Lewis basic compound. However, ether compounds or tertiary amines are easily available in industrial implementation. preferable. Examples of ether compounds include cyclic ethers such as tetrahydrofuran, tetrahydropyran, and 1,4-dioxane; aliphatic monoethers such as diethyl ether and dibutyl ether; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, Examples thereof include aliphatic ethers such as diethylene glycol dibutyl ether; aromatic ethers such as diphenyl ether and anisole. Examples of tertiary amine compounds include triethylamine, tripropylamine, tributylamine, N, N, N ′, N′-tetramethylethylenediamine, N-diethylaniline, pyridine, quinoline and the like. be able to.

  The amount used when the compound (1) of the present invention is added to the active conjugated diene polymer having an alkali metal terminal is usually produced per 1 mol of the alkali metal catalyst used when adding the alkali metal. It is 0.06-10 mol, Preferably it is 0.1-5 mol. More preferably, it is 0.2-2 mol. If the amount used is too small, the effect of improving fuel economy is small. Conversely, if the amount used is too large, it remains in the polymerization solvent. Therefore, when the solvent is recycled, a separation step from the solvent is required. Etc., not economically desirable.

  Since the reaction between the compound (1) and the active conjugated diene polymer having an alkali metal terminal occurs rapidly, the reaction temperature and reaction time can be selected in a wide range, but generally room temperature to 100 ° C., It is several seconds to several hours. The reaction may be carried out by bringing the alkali metal-containing diene polymer and the compound (1) into contact. For example, the diene polymer is polymerized using an alkali metal catalyst, and the compound ( Although the method of adding 1) predetermined amount can be illustrated as a preferable aspect, it is not limited to this method.

  For the resulting modified diene polymer rubber, 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 solvent is used as it is, and the coagulation temperature is not limited at all.

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

  Thus, the modified diene polymer rubber of the present invention is obtained.

The Mooney viscosity (ML _{1 + 4} ) of the modified diene polymer rubber is preferably 10 to 200, more preferably 20 to 150. If the Mooney viscosity is too low, mechanical properties such as the tensile strength of the vulcanizate may be reduced. On the other hand, if the viscosity is too high, the miscibility is poor when used in combination with other rubbers, making it difficult to process. Thus, the mechanical properties of the vulcanizate of the obtained rubber composition may be deteriorated.

  The content of vinyl bonds derived from conjugated diene monomer units in the modified diene polymer rubber is preferably 10 to 70%, more preferably 15 to 60%. When the content is less than 10%, the glass transition temperature of the polymer rubber is lowered, and as a result, the grip performance of a tire made of the polymer rubber may be inferior. When the content exceeds 70%, the glass transition temperature of the polymer rubber increases, and as a result, the rebound resilience of the polymer rubber may be inferior.

  The modified diene polymer rubber of the present invention is a rubber composition containing other rubber components, various additives and the like.

  Other rubber components include emulsion-polymerized styrene-butadiene copolymer rubber, polybutadiene rubber by solution polymerization (anionic polymerization catalyst, Ziegler type catalyst), butadiene-isoprene rubber copolymer rubber, styrene-butadiene copolymer rubber, and Natural rubber is included, and one or more of these rubbers are selectively used depending on the purpose. Here, when other rubber components are used, the proportion of the modified diene polymer rubber of the present invention in the total rubber components is preferably 10% by weight or more, more preferably 20% by weight or more. If the proportion of the modified diene polymer rubber of the present invention is too small, the degree of improvement in rebound resilience will be small.

  The additive may be selected from those commonly used in the rubber industry and suitable for the intended use of the rubber composition, and is not particularly limited. Usually, sulfur, stearic acid, zinc white, various vulcanization accelerators (thiazole type, thiuram type, sulfenamide type, etc.) or organic peroxides are used as vulcanizing systems, and HAF, ISAF, etc. are used as reinforcing agents. Various grades of carbon black, silica and the like, calcium carbonate, talc and the like are used as fillers, and extension oils, processing aids, anti-aging agents and the like are used as other additives. The type and amount of these additives are selected according to the purpose of use of the rubber composition and are not particularly limited in the present invention.

  In order to obtain a rubber composition, the rubber component and various additives may be kneaded using a mixer such as a roll or a banbury. The rubber composition is vulcanized and used for use.

  Since the rubber composition of the present invention is excellent in rebound resilience, it can be optimally used for an automobile tire excellent in fuel economy. Further, the rubber composition of the present invention can be used as various industrial raw material rubbers for shoe soles, flooring agents, anti-vibration rubbers and the like.

  EXAMPLES The present invention will be specifically described below 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 20 liters was washed, dried and replaced with dry nitrogen, and then 1,3-butadiene 1560 g, styrene 440 g, tetrahydrofuran 328 g, hexane 10.2 kg, n-butyllithium (n-hexane solution 9 .76 mmol) was added and polymerization was carried out at 65 ° C. for 3 hours with stirring. After completion of the polymerization, 9.76 mmol (2.33 g) of 4- (dimethylamino) -2,3-dimethyl-1-phenyl-3-pyrazolin-5-one was added. After reacting for 15 minutes with stirring, 10 ml of methanol was added, and the mixture was further stirred for 5 minutes. Thereafter, the contents of the polymerization reaction vessel were taken out, 10 g of 2,6-di-t-butyl-p-cresol (Sumitizer BHT manufactured by Sumitomo Chemical Co., Ltd.) was added, and most of hexane was evaporated. The polymer rubber was obtained by drying under reduced pressure at 55 ° C. for 12 hours.

Comparative Example 1
The n-hexane solution of n-butyllithium was changed to 8.5 mmol, 0.16 mmol of silicon tetrachloride was added, and 4- (dimethylamino) -2,3-dimethyl-1-phenyl-3-pyrazoline A polymer rubber was obtained in the same manner as in Example 1 except that N, N-dimethylaminopropylacrylamide was changed to 7.65 mmol (1.26 g) and added instead of -5-one.

Measurement Method The following measurements were performed on the polymer rubbers obtained in Example 1 and Comparative Example 1.
1. Mooney viscosity Measured at 100 ° C. according to JIS K-6300 (1994).
2. Vinyl content Measured by infrared spectroscopy. Specifically, it was determined from the absorption intensity in the vicinity of 910 Kaiser, which is the vinyl group absorption peak in an infrared spectrometer.
3. Styrene unit content Measured according to JIS K-6383 (refractive index method).
4). Coupling rate It calculated | required from the area ratio of the area for high molecular weight in the measurement curve, and the area for low molecular weight by the gel permeation chromatography.
5. Rebound resilience of vulcanized rubber The modified polymer rubber or polymer rubber was kneaded with a lab plast mill, and the kneaded product was molded with a 6-inch roll to obtain a sheet. The sheet was heated at 160 ° C. for 15 minutes to vulcanize, and then the rebound resilience of the vulcanized sheet at 60 ° C. was measured with a Lupke Resilience Tester.

  Table 2 shows the measurement and evaluation results.

* 1: N-339 (Mitsubishi Carbon Corporation)
* 2: X-140 (Aroma oil manufactured by Kyodo Oil Co., Ltd.)
* 3: Antigen 3C (Anti-aging agent manufactured by Sumitomo Chemical Co., Ltd.)
* 4: Soxinol CZ (vulcanization accelerator manufactured by Sumitomo Chemical Co., Ltd.)
* 5: Sunnock N (Ouchi Shinsei Chemical Co., Ltd.)

* 1 Modified compound A: 4- (dimethylamino) -2,3-dimethyl-1-phenyl-3-pyrazolin-5-one B: N, N-dimethylaminopropylacrylamide

Claims (4)

For an active conjugated diene polymer having an alkali metal terminal obtained by polymerizing a conjugated diene monomer or a conjugated diene monomer and an aromatic vinyl monomer using an alkali metal catalyst in a hydrocarbon solvent, the following formula: A modified diene polymer rubber obtained by reacting the compound represented by (1).

(In formula (1), R ^{1 to} R ⁴ independently represent an alkyl group having 1 to 8 carbon atoms, and R ⁵ represents a phenyl group that may have an alkyl group having 1 to 8 carbon atoms or a substituent. To express.) The modified diene polymer rubber according to claim 1, wherein the active conjugated diene polymer is reacted with a coupling agent represented by the following formula (2) before or after the above formula (1) is reacted.

(In the formula (2), R ⁶ represents an alkyl group, an alkenyl group, a cycloalkenyl group or an aromatic hydrocarbon group, M represents a silicon or tin atom, X represents a halogen atom, and m represents 0-2. Represents an integer, and n represents an integer of 2 to 4.) The modified diene polymer rubber according to claim 1 or 2, wherein R ^{1 to} R ⁴ are a methyl group, an ethyl group, a propyl group, or a butyl group, and R ⁵ is a phenyl group. A rubber composition containing 10% by weight or more of the modified diene polymer rubber according to any one of claims 1 to 3 in a rubber component.