JP2014189676A - Modified cis-1,4-polybutadiene, method for manufacturing the same, and rubber composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a modified cis-1,4-polybutadiene capable, while ameliorating workability, which is an important characteristic for a rubber material, of also improving the low-loss profile and abrasion resistance performance; a method for manufacturing the same; and a rubber composition.SOLUTION: The provided modified cis-1,4-polybutadiene is obtained by adding, as an additive, an organohalogen compound immediately after the production of a cis-1,4-polybutadiene (A) by polymerizing 1,3-butadiene in the presence of a transition metal polymerization catalyst, whereas (a) the difference of the Mooney viscosity ((ML, 100°C) thereof from that of the cis-1,4-polybutadiene (A) is at least 10, whereas (b) the ratio of the Z average molecular weight thereof with respect to the weight-average molecular weight thereof (Mz/Mw) is 2.3 or higher, whereas (c) the Mooney viscosity ((ML, 100°C) thereof is 100 or less.

Description

  The present invention relates to a modified cis-1,4-polybutadiene, a method for producing the same, and a rubber composition that improve the processability, which is an important characteristic for rubber materials, while improving the performance of low loss and wear resistance.

Many proposals have been made on polymerization catalysts for 1,3-butadiene, and in particular, high cis-1,4-polybutadiene having a high cis-1,4 bond content exhibits excellent thermal and mechanical properties. A number of polymerization catalysts have been developed to draw out.

  For example, Patent Document 1 discloses a method for producing high cis-1,4-polybutadiene in which 1,3-butadiene is polymerized using a catalyst comprising a cobalt compound, an acidic metal halide, an alkylaluminum compound, and water. .

Patent Document 2 discloses a method in which 1,3-butadiene is polymerized in a solvent composed of linear or branched aliphatic hydrocarbons using a catalyst composed of diethylaluminum chloride, water, and cobalt octate. Is disclosed.

In high cis-1,4-polybutadiene, the polymer chain has a small degree of branching, that is, linear type high cis-1,4-polybutadiene has excellent properties such as wear resistance, heat resistance, and resilience. ing. However, compared to branch type high cis-1,4-polybutadiene with a high degree of branching, processability is reduced when producing a compound obtained by compounding carbon black or the like with rubber, resulting in high wear resistance. There has been a demand for a method for improving workability while maintaining the above.

As a method for improving the processability of polybutadiene, Patent Document 3 discloses a method of treating a polybutadiene polymerization solution with an organoaluminum compound and an alkyl halide compound. Patent Document 4 describes a method in which a rubber having an unsaturated bond is dissolved in a solvent and an organic acid halide is reacted in the presence of a Lewis acid to modify the rubber. All of these methods require a step of modifying the polymer after the polymerization step, and it has been desired to develop a method that saves complicated operations.

On the other hand, as a measure for improving the heat build-up of the rubber composition, in recent years, an increasing number of cases are using silica as a reinforcing material instead of carbon black. However, since silica has a polar silanol group on the surface of silica, silica has a poor affinity with hydrocarbon structures such as polybutadiene, which makes it easier for silica particles to aggregate and disperse in rubber containing silica. There was a problem that the sex became worse. As a result, when the silica aggregate breaks down, that is, the Payne effect occurs, a strong silica-silica interaction is observed inside the silica aggregate, and a large hysteresis loss occurs between the silica and rubber, causing exothermic deterioration. It was.

As measures for improving the affinity and interaction between the polar silica surface and the nonpolar rubber matrix, the use of a silane coupling agent having a dual function and chemical modification of rubber have been intensively studied. As a chemical modification technology for rubber, many of the high-cis-1,4-polybutadienes chemically modified use a variety of effective alkoxysilane coupling agents after living polymerization of 1,3-butadiene using a rare earth catalyst. Thus, a method for functionalizing molecular ends has been reported.

Patent Document 5 discloses a method for improving cold flow properties by polymerizing polybutadiene rubber with a cobalt compound and further reacting with an acid halide, a halogen-containing sulfur compound, a mercapto group-containing alkoxysilane compound, etc., if necessary. Have been described.

Thereafter, for the purpose of improving the balance between workability, low loss, and wear resistance, a method is disclosed in which polybutadiene rubber is polymerized with a cobalt compound and then modified with a predetermined amount of an organic halogen compound (Patent Documents 6 and 6). 7).
However, from the viewpoint of recent environmental and energy savings, there is a demand for further improving the overall performance while maintaining a balance between workability, low loss, and wear resistance.

Japanese Patent Publication No.38-1243 Japanese Patent Publication No. 61-54808 Japanese Patent Laid-Open No. 51-63891 JP-A-61-225202 Japanese Patent Laid-Open No. 2001-114817 Japanese Patent No. 4123019 JP 2011-79954 A

  The present invention provides a modified cis-1,4-polybutadiene, a process for producing the same, and a rubber composition that improve the performance of low loss and wear resistance while improving processability, which is an important characteristic for rubber materials. It is.

It is obtained by polymerizing 1,3-butadiene in the presence of a transition metal polymerization catalyst to produce cis-1,4-polybutadiene (A), and immediately thereafter adding an organic halogen compound as an additive (a) The difference in Mooney viscosity (ML _{1 + 4} , 100 ° C.) from cis-1,4-polybutadiene (A) is 10 or more, and (b) the ratio (Mz / Mw) of Z average molecular weight to weight average molecular weight is 2.3 or more. And (c) a modified cis-1,4-polybutadiene having a Mooney viscosity (ML _{1 + 4} , 100 ° C.) of 100 or less.

The transition metal polymerization catalyst is (a) cobalt octoate, (b) R ² _3-n AlX _n (wherein R ² represents a hydrocarbon group having 1 to 10 carbon atoms, X represents a halogen, and n represents 1 to 1). A halogen-containing aluminum compound represented by (c) R ³ ₃ Al (wherein R ³ is a hydrocarbon group having 1 to 10 carbon atoms) and (d) The modified cis-1,4-polybutadiene is a catalyst comprising water.

  The modified halogenated cis-1,4-polybutadiene is characterized in that the organic halogen compound is t-butyl chloride.

  The modified cis-1,4-polybutadiene is used for the rubber composition.

(A) cis-1,4-polybutadiene (a) obtained by polymerizing 1,3-butadiene to produce cis-1,4-polybutadiene (A) and immediately after that an organic halogen compound is added as an additive. The difference in Mooney viscosity (ML _{1 + 4} , 100 ° C.) from A) is 10 or more, (b) the ratio of Z average molecular weight to weight average molecular weight (Mz / Mw) is 2.3 or more, and (c) Mooney viscosity ( ML _{1 + 4} , 100 ° C.) relates to a method for producing a modified cis-1,4-polybutadiene having a value of 100 or less.

The modified cis-1,4-polybutadiene obtained in the present invention has a difference in Mooney viscosity (ML _{1 + 4} , 100 ° C.) from (a) cis-1,4-polybutadiene before modification by adding an organic halogen compound. 10 or more, and (b) a polymer structure having a ratio (Mz / Mw) of Z average molecular weight to weight average molecular weight of 2.3 or more and (c) Mooney viscosity (ML _{1 + 4} , 100 ° C.) of 100 or less. Further, the tensile strength, the low loss property and the wear resistance can be improved while improving the workability.

(Modified cis-1,4-polybutadiene)
The modified cis-1,4-polybutadiene referred to in the present invention means that an organic halogen compound is added immediately after production of cis-1,4-polybutadiene by polymerizing 1,3-butadiene in the presence of a transition metal polymerization catalyst. It is polybutadiene obtained by modification.

That is, in the present invention, an organic halogen compound is added by adding an organic halogen compound immediately after the polymerization of 1,3-butadiene to obtain cis-1,4-polybutadiene in the presence of a transition metal polymerization catalyst. By having a high molecular weight component defined by the difference from the previous Mooney viscosity (ML _{1 + 4} , 100 ° C.) and the ratio of the z-average molecular weight to the weight-average molecular weight, workability, tensile strength, low loss and wear resistance Can be obtained.

(Mooney viscosity before and after modification)
The Mooney viscosity (ML _{1 + 4} , 100 ° C.) of the modified cis-1,4-polybutadiene of the present invention is compared with the Mooney viscosity (ML _{1 + 4} , 100 ° C.) of cis-1,4-polybutadiene before adding the organic halogen compound. 10 or more, preferably 15 or more, more preferably 20 or more.
If the difference in Mooney viscosity is smaller than the above range, the effect of improving workability is lowered, which is not preferable.
(Mooney viscosity)
The Mooney viscosity (ML _{1 + 4} , 100 ° C.) of the modified cis-1,4-polybutadiene of the present invention is 40 to 100, preferably 45 to 95, and more preferably 50 to 85. If the Mooney viscosity is larger than the above range, the workability is remarkably deteriorated. If the Mooney viscosity is smaller than the above range, low loss and wear resistance are lowered, which is not preferable.

(Mz / Mw)
The ratio of z-average molecular weight and number-average molecular weight in terms of polystyrene by gel permeation chromatography (GPC) (abbreviated as Mz / Mw) is a value affected by high molecular weight components, and is preferably 2.3 or more. 5 or more is particularly preferable.
If the value of Mz / Mw is less than 2.3, the effect of improving workability is reduced, which is not preferable.

The number average molecular weight, mass average molecular weight, and z average molecular weight are as follows.

Each is represented by Formulas 1-3. Mw is higher than Mn, and Mz is higher than Mw on the high molecular weight side, and Mz / Mw indicates the spread of molecules toward the high molecular weight side.
That is, the larger the value of Mz / Mw, the wider the molecular weight distribution in the high molecular weight region.
The modified cis-1,4 polybutadiene obtained in the present invention has a feature showing the broadening of the molecular weight distribution in this high molecular weight region.

(Cis-1,4-polybutadiene before addition of organic halogen compound)
The cis-1,4-polybutadiene before the addition of the organic halogen compound is a so-called raw material polybutadiene indicating a state before the addition of the organic halogen compound.
The raw polybutadiene has a Mooney viscosity (ML _{1 + 4} , 100 ° C.) of preferably 70 or less, more preferably 60 or less, and still more preferably 60 to 15.
When the Mooney viscosity is above the above range, workability is deteriorated, and when the Mooney viscosity is below the above range, low loss and wear resistance are deteriorated.
Further, T-cp / ML, which is an index indicating the degree of branching of the polybutadiene molecule, is preferably 1.0 or more, and more preferably 1.3 or more.
If it is below the above range, the degree of branching becomes too large, which is not preferable from the viewpoint of low loss.
Further, Mw / Mn is preferably 2.5 or more. If the molecular weight distribution is narrower than the above range, it is not preferable in that the desired processability cannot be obtained.
As the microstructure, the cis-1,4 content is preferably 97% or more.
If it is below the above range, the wear resistance deteriorates, which is not preferable.

(Polymerization catalyst for cis-1,4-polybutadiene before addition of organic halogen compound)
As the polymerization catalyst for the raw polybutadiene rubber, a cobalt catalyst is preferably used.

  As the cobalt compound of the cobalt-based catalyst, a cobalt salt or complex is preferably used. Particularly preferred are cobalt salts such as cobalt chloride, cobalt bromide, cobalt nitrate, cobalt octylate, cobalt naphthenate, cobalt acetate, cobalt malonate, cobalt bisacetylacetonate and trisacetylacetonate. , Ethyl acetoacetate cobalt, cobalt halide triarylphosphine complex, trialkylphosphine complex, organic base complexes such as pyridine complex and picoline complex, or ethyl alcohol complex.

Examples of the halogen-containing aluminum compound in the cobalt-based catalyst composition include R ² _3-n AlX _n (wherein R ² represents a hydrocarbon group having 1 to 10 carbon atoms, X represents a halogen, and n represents a number of 1 to 2). It is preferable to use what is represented by. Examples thereof include dialkylaluminum halides such as dialkylaluminum chloride and dialkylaluminum bromide, alkylaluminum sesquichlorides such as alkylaluminum sesquichloride and alkylaluminum sesquibromide, and alkylaluminum dihalides such as alkylaluminum dichloride and alkylaluminum dibromide. Specific examples of the compound include diethyl aluminum monochloride, diethyl aluminum monobromide, dibutyl aluminum monochloride, ethyl aluminum sesquichloride, ethyl aluminum dichloride, dicyclohexyl aluminum monochloride, diphenyl aluminum monochloride, and the like.

The organoaluminum compound in the cobalt-based catalyst composition is preferably one represented by R ³ ₃ Al (wherein R ³ represents a hydrocarbon group having 1 to 10 carbon atoms). For example, trialkylaluminum compounds such as triethylaluminum, trimethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum and the like can be mentioned.

  Aluminoxane may also be used. The aluminoxane is obtained by bringing an organoaluminum compound and a condensing agent into contact with each other, and includes a chain aluminoxane represented by the general formula (-Al (R ') O-) n or a cyclic aluminoxane. (R ′ is a hydrocarbon group having 1 to 10 carbon atoms, including those partially substituted with a halogen atom and / or an alkoxy group. N is the degree of polymerization and is 5 or more, preferably 10 or more) . Examples of R ′ include methyl, ethyl, propyl, and isobutyl groups, with methyl and ethyl groups being preferred. Examples of the organoaluminum compound used as an aluminoxane raw material include trialkylaluminums such as trimethylaluminum, triethylaluminum, and triisobutylaluminum, and mixtures thereof.

  Among these, a catalyst system composed of a cobalt compound, a halogen-containing aluminum compound, an organic aluminum compound and water, or a catalyst system composed of a cobalt compound, a halogen-containing aluminum compound and water is preferable.

When a cobalt-based catalyst composition comprising a cobalt compound, a halogen-containing organoaluminum compound, water, and an organoaluminum compound is used, 1 × 10 ⁻⁷ to 1 × 10 ⁻⁷ to 1 mol of 1,3-butadiene. A range of 1 × 10 ⁻³ mol is preferred. The halogen-containing organoaluminum compound is preferably in the range of 1 × 10 ⁻⁵ to 1 × 10 ⁻¹ mol. Moreover, about water, it is preferable to exist in the range of 1 * 10 < ^-5 > ^-1 * 10 <^-1> mol. The organoaluminum compound is preferably in the range of 1 × 10 ⁻⁵ to 1 × 10 ⁻¹ mol.

The point of the present invention is that the polymerization conditions of cis-1,4 polybutadiene before modification with an organic halogen compound create effects such as low loss and wear resistance of the final modified cis-1,4 polybutadiene. It becomes important to.
In particular, the “ratio of aluminum compound to water” and “ratio of halogen-containing organoaluminum compound to organoaluminum compound” used in the polymerization step described below are major factors.
It is essential to satisfy these two factors at the same time in the polymerization stage, and if only one of the conditions is satisfied, effects such as low loss and wear resistance of the final modified cis-1,4 polybutadiene can be created. It is difficult.

(Ratio of aluminum compound to water)
The addition amount of the halogen-containing organoaluminum compound and the organoaluminum compound used in the cobalt-based catalyst composition is 0.95 to 1.30 times, especially 0.98 to 1.25 times the amount of water to be added, In particular, it is preferably 1.0 to 1.15 times. If it is larger than this range, desired physical properties cannot be obtained, and if it is smaller than this range, workability is deteriorated.
The addition amount of the halogen-containing organoaluminum compound and the organoaluminum compound and the ratio of water to be added are particularly important in defining the linearity of polybutadiene.

(Ratio of halogen-containing organoaluminum compound to organoaluminum compound)
The halogen-containing organoaluminum compound used in the cobalt-based catalyst composition is preferably 1 to 6 times, particularly preferably 2 to 4 times that of organoaluminum. When it is larger than this range, the gel becomes a problem, and when it is smaller, the polymerization activity decreases.

  As the order of addition of the catalyst components, it is preferable to add water in an inert solvent, mix uniformly, add a halogen-containing organoaluminum compound and an organoaluminum compound, and then add a cobalt compound to initiate polymerization. . It is preferable to add a cobalt compound after aging for a predetermined time after adding the halogen-containing organoaluminum compound. The aging time is preferably from 0.1 to 24 hours. The aging temperature is preferably 0 to 80 ° C.

(Polymerization solvent)
As a polymerization solvent, aromatic hydrocarbons such as toluene, benzene and xylene, aliphatic hydrocarbons such as n-hexane, butane, heptane and pentane, alicyclic hydrocarbons such as cyclopentane and cyclohexane, 1-butene, Olefinic hydrocarbons such as C4 fraction such as cis-2-butene and trans-2-butene, hydrocarbon solvents such as mineral spirit, solvent naphtha, kerosene, halogenated hydrocarbon solvents such as methylene chloride, etc. Can be mentioned. Further, 1,3-butadiene itself may be used as a polymerization solvent.

  Among these, benzene, cyclohexane, or a mixture of cis-2-butene and trans-2-butene is preferably used.

(Molecular weight regulator)
In order to obtain cis-1,4-polybutadiene (raw polybutadiene) having a Mooney viscosity (ML _{1 + 4} , 100 ° C.) of 70 or less before addition of the organic halogen compound in the present invention, it is necessary to apply a molecular weight regulator. .
As the molecular weight modifier, for example, non-conjugated dienes such as cyclooctadiene and allene, or α-olefins such as ethylene, propylene, and butene-1 known at the time of polymerization can be used.
Particularly preferred is cyclooctadiene, preferably 2 to 30 mmol, more preferably 2 to 18 mmol, per mole of 1,3-butadiene. Use of an amount outside this range is not preferable because a problem of Mooney viscosity deviation occurs.

  The polymerization temperature is preferably in the range of -30 to 100 ° C, particularly preferably in the range of 30 to 80 ° C. The polymerization time is preferably in the range of 10 minutes to 12 hours, particularly preferably 30 minutes to 6 hours. The polymerization pressure is carried out under normal pressure or up to about 10 atm (gauge pressure).

(Organic halogen compounds)
Since cis-1,4 polybutadiene not modified with an organic halogen compound does not have a polymer structure containing a desired high molecular weight component defined by Mz / Mn or the like, processability, low loss, wear resistance The effect of improving the balance of sex cannot be obtained.

As the organic halogen compound, an organic halogen compound represented by the general formula R ¹ R ² R ³ CX can be used. In the formula, R ¹ is hydrogen, an alkyl group, an aryl group, a chloro-substituted alkyl group, an alkoxy group, R ² is hydrogen, an alkyl group, an aryl group, chloro, bromo, etc., and R ² + R ³ is oxygen. R ³ is an alkyl group, an aryl group, a vinyl group, chloro, bromo and the like, and X is a halogen such as chloro and bromo. When R ¹ and R ² are hydrogen, R ³ is preferably an aryl group. The above alkyl group may be saturated or unsaturated, and may be linear, branched or cyclic. An aliphatic hydrocarbon group etc. are mentioned.

Specific examples of the compound include chlorinated or brominated compounds such as methyl, ethyl, iso-propyl, iso-butyl, t-butyl, phenyl, benzyl, benzoyl and benzylidene. Further, methyl chloroformate, bromoformate, chlorodiphenylmethane, chlorotriphenylmethane, and the like can be given. Among these, t-butyl chloride or t-butyl bromide is preferable.

A cobalt compound, a halogen-containing aluminum compound, and an organoaluminum compound may be added together with the above-mentioned organohalogen compound. For these, the cobalt compounds, halogen-containing aluminum compounds, and organoaluminum compounds exemplified as the catalyst component can be used.

The addition amount of the organic halogen compound is desirably 0.05 to 0.4 times the total addition amount of the halogen-containing organoaluminum compound and the organoaluminum compound, and 1 × 10 ⁻⁶ to 1 per mole of butadiene. × 10 ⁻³ mol, particularly 1 × 10 ⁻⁵ to 1 × 10 ⁻⁴ mol is preferable. If the amount is more than the above range, gelation of the resulting polybutadiene tends to occur, and if the amount is too small, the effect of this study cannot be obtained.
If the amount is more than the above range, gelation of the resulting polybutadiene tends to occur, and if the amount is too small, the effect of this study cannot be obtained.

About reaction temperature of an organic halogen compound, it is 20-100 degreeC, Preferably it is 30-80 degreeC.

The reaction time of the organic halogen compound is agitated and mixed for 10 minutes to 150 minutes. Preferably, it is desirable to stir and mix for 15 to 30 minutes.

The reaction between the organic halogen compound and cis-1,4-polybutadiene may be carried out after the above-mentioned butadiene polymerization, or after the polymerization reaction is stopped, the solvent remaining in the polymerization product or unreacted You may carry out after dissolving the dried material which removed the monomer by the steam stripping method, the vacuum drying method, etc. with cyclohexane etc. again.

After polymerizing the raw material polybutadiene, the molecules of the polybutadiene are reacted with each other with an organic halogen compound, and a modified cis-1, which has a high molecular weight ML of 100 or less and a wide molecular weight distribution (Mz / Mw) in the high molecular region. 4 Polybutadiene is produced.
The modified cis-1,4 polybutadiene obtained by this method is a raw material for a rubber composition that improves the workability of the rubber material and improves the performance of tensile strength, low loss and wear resistance.

(Rubber composition)
The polybutadiene obtained by the present invention is blended alone or blended with other synthetic rubber or natural rubber, and if necessary, is oil-extended with process oil, and then a filler such as carbon black or silica, a vulcanizing agent, Vulcanization accelerators and other normal compounding agents are added to vulcanize, and various rubber such as industrial articles such as tires, anti-vibration rubber, belts, hoses, seismic isolation rubber, footwear such as men's shoes, women's shoes, and sports shoes. Used for applications. In that case, the rubber component is preferably blended so as to contain at least 10% by weight of the polybutadiene of the present invention.
Thus, the compound obtained by vulcanizing the polybutadiene obtained by the present invention and further compounding various additives is defined as a rubber composition.

(Other synthetic rubber)
Other synthetic rubbers contained in the rubber composition are preferably vulcanizable rubbers, specifically, natural rubber, ethylene propylene diene rubber (EPDM), nitrile rubber (NBR), butyl rubber (IIR), chloroprene rubber. (CR), polyisoprene rubber (IR), high cis polybutadiene rubber, low cis polybutadiene rubber (BR), styrene-butadiene rubber (SBR), butyl rubber, chlorinated butyl rubber, brominated butyl rubber, acrylonitrile-butadiene rubber, etc. Can do. Among these, natural rubber, isoprene rubber, and SBR are preferable.
Further, among SBR, solution-polymerized styrene butadiene copolymer rubber (S-SBR) is particularly preferable. These rubbers may be used alone or in combination of two or more.

The solution-polymerized styrene butadiene copolymer rubber (S-SBR) used in the present invention has the above effect by using 30 to 90 parts by weight, preferably 50 to 80 parts by weight of 100 parts by weight of the rubber component. Expressed. If the blending amount of S-SBR is small, the wet performance decreases, which is not preferable. Conversely, if it is large, the wear resistance and low loss property deteriorate, which is not preferable.
Such S-SBR is known, and for example, commercially available products such as Nippon Zeon Nipol NS110R and Asahi Kasei Asaprene 1204 can be used.

(Silane coupling agent)
As another additive component, the silane coupling agent is an organosilicon compound represented by the general formula R ⁷ nSiX 4 -n, where R ⁷ is a vinyl group, acyl group, allyl group, allyloxy group, amino group, epoxy group. , A mercapto group, a chloro group, an alkyl group, a phenyl group, hydrogen, a styryl group, a methacryl group, an acrylic group, a ureido group and the like, an organic group having 1 to 20 carbon atoms, and X is a chloro group , An alkoxy group, an acetoxy group, an isopropenoxy group, an amino group, and the like, and n represents an integer of 1 to 3.

Among the R ⁷ components of the silane coupling agent, those containing a vinyl group and / or a chloro group are preferable.

Specific examples of silane coupling agents that can be used commercially include, but are not limited to, the following. Bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylpropyl) trisulfide, bis (3-triethoxysilylpropyl) disulfide, bis (2-triethoxysilylpropyl) tetrasulfide, bis (3 -Trimethoxysilylpropyl) tetrasulfide, bis (2-trimethoxysilylpropyl) tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethoxysilane 3-triethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-triethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, 2-triethoxy Rylethyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilylpropylbenzothiazole tetrasulfide, 3-triethoxysilylpropylbenzothiazole tetrasulfide, 3-triethoxysilylpropyl methacrylate monosulfide, 3-trimethoxysilylpropyl Methacrylate monosulfide, vinyltrichlorosilane, methylvinyldichlorosilane, divinyldichlorosilane, dimethylvinylchlorosilane, chloromethyldimethylvinylsilane, methoxydimethylvinylsilane, trimethoxyvinylsilane, dimethyldivinylsilane, ethoxydimethylvinylsilane, diacetoxymethyldinylsilane, allyl Oxydimethylvinylsilane, diethoxymethylvinylsilane, bis (di Tilamino) methylvinylsilane, phenylvinyldichlorosilane, triacetoxyvinylsilane, 3-chloropropylmethyldivinylsilane, diethoxydivinylsilane, dimethylethylmethylketoxyvinylsilane, dimethylisobutoxyvinylsilane, triethoxyvinylsilane, methylphenylvinylchlorosilane, methylphenyl Vinylsilane, dimethylisopentyloxyvinylsilane, 4-bromophenyldimethylvinylsilane, 3-aminophenoxydimethylvinylsilane, 4-aminophenoxydimethylvinylsilane, dimethylpiperidinomethylvinylsilane, dimethyl-2-[(2-ethoxyethoxy) ethoxy] vinylsilane , Divinylmethylphenoxysilane, dimethyl-P-anisylvinylsilane, tris (1 Methylvinyloxy) vinylsilane, triisopropoxyvinylsilane, diethoxy-2-piperidinoethoxyvinylsilane, diphenylvinylchlorosilane, 3-dimethylvinylphenyl N, N-diethylcarbomate, triphenoxyvinylsilane, 1,3-divinyl-1, 1,3,3-tetramethyldisiloxane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, 1- (4-methylpiperidinomethyl) -1,1,3,3- Tetramethyl-3-vinyldisiloxane, 1,4-bis (dimethylvinylsilyl) benzene, 1,4-bis (dimethylvinylsiloxy) benzene, 1,3-bis (dimethylvinylsiloxy) benzene, 1,1,3 , 3-tetraphenyl-, 3-divinyldisiloxane, 1,3,5-trimethyl-1, , 5-trivinylcyclotrisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, tetrakis (dimethylvinylsiloxymethyl) methane, 3-chloropropyltrimethoxysilane ,and so on.

The addition amount of the additive silane coupling agent is preferably 0.2% to 20%, particularly preferably 5% to 15% with respect to the filler amount.
If it is less than the above range, it is not preferable because it causes scorch. Moreover, since it will become the cause of a deterioration of a tensile characteristic and elongation when it exceeds more than said range, it is unpreferable.

It is also possible to produce a rubber-modified impact-resistant polystyrene resin composition that is used as a modifier for plastics, for example, impact-resistant polystyrene.

  As a method for producing the rubber-modified impact-resistant polystyrene resin composition, a method of polymerizing a styrene monomer in the presence of a rubbery polymer is adopted, and a bulk polymerization method or a bulk suspension polymerization method is economical. This is an advantageous method. Examples of styrene monomers include those conventionally used for producing rubber-modified impact-resistant polystyrene resin compositions such as styrene, α-methylstyrene, alkyl-substituted styrene such as p-methylstyrene, and halogen-substituted styrene such as chlorostyrene. One kind or a mixture of two or more kinds of styrenic monomers are used. Of these, styrene is preferred.

  In addition to the rubber-like polymer, a styrene-butadiene copolymer, ethylene-propylene, ethylene-vinyl acetate, acrylic rubber, etc. may be used in combination within 50% by weight with respect to the rubber-like polymer as necessary during production. it can. Moreover, you may blend the resin manufactured by these methods. Furthermore, you may manufacture by mixing the polystyrene-type resin which does not contain the rubber-modified polystyrene-type resin composition manufactured by these methods. As an example of the bulk polymerization method described above, a rubbery polymer (1 to 25% by weight) is dissolved in a styrene monomer (99 to 75% by weight), and in some cases, a solvent, a molecular weight regulator, a polymerization initiator. Etc. are added to convert the rubber-like polymer into particles dispersed to a styrene monomer conversion rate of 10 to 40%. Until the rubber particles are produced, the rubber phase forms a continuous phase. Furthermore, the polymerization is continued until the conversion to a dispersed phase as a rubber particle (particulation step) (polymerization step) to polymerize to a conversion rate of 50 to 99% to produce a rubber-modified impact-resistant polystyrene resin composition.

The dispersed particles (rubber particles) of a rubbery polymer are particles dispersed in a resin, and are composed of a rubbery polymer and a polystyrene resin. The polystyrene resin can be grafted or not grafted to the rubbery polymer. Occluded. The diameter of the dispersed particles of the rubbery polymer referred to in the present invention can be suitably produced in the range of 0.5 to 7.0 μm, preferably in the range of 0.5 to 3.0 μm.

  A graft ratio in the range of 100 to 350 can be preferably produced. It may be a batch type or a continuous production method and is not particularly limited.

The raw material solution mainly composed of the above-mentioned styrene monomer and rubber polymer is polymerized in a complete mixing reactor, and as a complete mixing reactor, the raw material solution maintains a uniform mixed state in the reactor. As long as it is preferable, a stirring blade of a type such as a helical ribbon, a double helical ribbon, or an anchor is preferable. It is preferable that a draft tube is attached to the helical ribbon type stirring blade to further enhance the vertical circulation in the reactor.

The rubber-modified impact-resistant polystyrene-based resin composition includes a stabilizer such as an antioxidant and an ultraviolet absorber, a release agent, a lubricant, a colorant, various fillers, and various fillers as necessary at the time of production and after production. Known additives such as plasticizers, higher fatty acids, organic polysiloxanes, silicone oils, flame retardants, antistatic agents and foaming agents may be added. The rubber-modified impact-resistant polystyrene resin composition of the present invention can be used in various known molded products, but is used in the fields of electrical and industrial applications because of its excellent flame resistance, impact strength, and tensile strength. Suitable for injection molding. For example, it can be used in a wide range of applications such as color televisions, radio cassettes, word processors, typewriters, facsimiles, VTR cassettes, telephone housings, and other household appliances and industrial applications.

Mooney viscosity (ML _{1 + 4} , 100 ° C)
In accordance with JIS-K6300, using a Mooney viscometer (SMV-200) manufactured by Shimadzu Corporation, preheat at 100 ° C for 1 minute, then measure for 4 minutes to obtain the rubber Mooney viscosity (ML _{1 + 4} , 100 ° C) displayed.

Toluene solution viscosity (Tcp)
After dissolving 2.28 g of the polymer in 50 ml of toluene, the standard solution for calibration of the viscometer (JIS Z8809) was used as the standard solution. 400 was used and measured at 25 ° C.

z average molecular weight, weight average molecular weight, number average molecular weight Gel permeation (permeation) chromatography (GPC, manufactured by Tosoh Corporation) was performed at a temperature of 40 ° C using polystyrene as a standard solvent and polystyrene as a standard substance. The z-average molecular weight, weight-average molecular weight, and number-average molecular weight were calculated using a calibration curve obtained from the molecular weight distribution curve.

Mooney viscosity of the formulation (ML _{1 + 4} , 100 ° C.)
In accordance with JIS-K6300, using a Mooney viscometer (SMV-200) manufactured by Shimadzu Corporation, preheated at 100 ° C for 1 minute, then measured for 4 minutes and Mooney viscosity of the compound (ML _{1 + 4} , 100 ° C) And Comparative Example 5 was set as 100 and indicated as an index. The larger the index, the better the workability.

Low loss of vulcanizate : tan δ was measured using EPLEXOR 100N manufactured by GABO under the conditions of a temperature of 50 ° C., a frequency of 10 Hz, and a dynamic strain of 0.3%. The larger the index, the better the low loss property.

According to the rebound resilience BS 903 of the vulcanizate , the rebound resilience was measured at room temperature using a Dunlop trypometer, and Comparative Example 5 was set as 100 and indicated as an index. The larger the index, the better the low loss property.

The abrasion resistance Lambourne wear index of the vulcanizate was measured at a slip rate of 60% according to the measurement method defined in JIS K6264, and the index was displayed with Comparative Example 5 as 100. The higher the index, the better.

Viscosity of vulcanizate Measured in accordance with JIS K6251, measured for tensile strength (TB) and elongation at break (EB), calculated (TB × EB) / 2, and indicated comparative example 5 as 100. did. (TB × EB) / 2 indicates the approximate amount of energy expended before breaking. TB, EB, (TB × EB) / 2 is generally superior in strength as the index increases.

Example 1
In a 1.5 liter stainless steel autoclave sufficiently purged with nitrogen, 1 liter of a cyclohexane-C4 fraction mixed solution containing 38.0% by weight of 1,3-butadiene (cyclohexane 25.5% by weight, cis- 2-butene-containing C4 fraction containing 36.5% by weight), and then added with water 2.22 mmol, diethylaluminum monochloride 2.27 mmol, triethylaluminum 0.76 mmol and stirred And 17.92 mmol of cyclooctadiene was added. After the temperature of the autoclave was raised and the internal temperature reached 49.5 ° C., 0.004 mmol of cobalt octoate was added, and a polymerization reaction was carried out at 50 ° C. for 30 minutes. 30 minutes after the start of polymerization, 0.3 mmol of t-butyl chloride was added and reacted for 20 minutes.
Antiaging agent was added there and it vacuum-dried at 100 degreeC for 1 hour. Table 1 shows the physical properties of the obtained polybutadiene.
Furthermore, a rubber composition was produced in such a manner that the compounding ratio (parts by weight) of the polybutadiene was as follows, and the physical properties thereof were measured. The results are shown in Table 2.
In Table 2, all physical property values are expressed as relative values with Comparative Example 5 as the reference value 100.
70 parts by weight of a commercially available solution polymerized styrene butadiene rubber (s-SBR),
30 parts by weight of the modified cis-1,4 polybutadiene obtained in the present invention,
75 parts by weight of silica (manufactured by Tosoh Silica Co., Ltd., trade name nip seal AQ),
6 parts by weight of silane coupling agent (product name: Si69, manufactured by Degussa Hyrun)
21.5 parts by weight of oil (Sansen Oil 4240)
3 parts by weight of zinc oxide (Sakai Chemical Industry Size 1)
1 part by weight of stearic acid (Kao stearic acid),
1 part by weight of an antioxidant (Sumitomo Chemical Antigen 6C)
1.7 parts by weight of vulcanization accelerator 1 (Noxeller CZ manufactured by Ouchi Shinsei Chemical Co., Ltd.)
2 parts by weight of vulcanization accelerator 2 (Noxeller CZ manufactured by Ouchi Shinsei Chemical Co., Ltd.)
1.4 parts by weight of sulfur (manufactured by Hosoi Chemical Co., Ltd.) was blended.

(Example 2)
Polybutadiene was produced in the same manner as in Example 1 except that 20.36 mmol of cyclooctadiene and 0.9 mmol of t-butyl chloride were added.
Table 1 shows the physical properties of the obtained polybutadiene. Table 2 shows the physical properties of the rubber composition. The compounding ratio of the rubber composition is the same as in Example 1.

(Example 3)
In a 1.5 liter stainless steel autoclave sufficiently purged with nitrogen, 1 liter of a cyclohexane-C4 fraction mixed solution containing 51.0% by weight of 1,3-butadiene (20.5% by weight of cyclohexane, cis- 2-butene-containing C4 fraction containing 27.1% by weight), and then added water 2.06 mmol, diethylaluminum monochloride 2.27 mmol, triethylaluminum 0.76 mmol and stirred And 18.32 mmol of cyclooctadiene was added. After the temperature of the autoclave was raised and the internal temperature reached 49.5 ° C., 0.004 mmol of cobalt octoate was added, and a polymerization reaction was carried out at 50 ° C. for 30 minutes. 30 minutes after the start of polymerization, 0.5 mmol of t-butyl chloride was added and reacted for 20 minutes.

Antiaging agent was added there and it vacuum-dried at 100 degreeC for 1 hour. Table 1 shows the physical properties of the obtained polybutadiene. Table 2 shows the physical properties of the rubber composition. The compounding ratio of the rubber composition is the same as in Example 1.

Example 4
Polybutadiene was produced in the same manner as in Example 3 except that 0.6 mmol of t-butyl chloride was added.
Table 1 shows the physical properties of the obtained polybutadiene. Table 2 shows the physical properties of the rubber composition. The compounding ratio of the rubber composition is the same as in Example 1.

(Comparative Example 1)
Polybutadiene was produced in the same manner as in Example 1 except that 13.84 mmol of cyclooctadiene and 0.30 mmol of t-butyl chloride were added.
Table 1 shows the physical properties of the obtained polybutadiene. Table 2 shows the physical properties of the rubber composition. The compounding ratio of the rubber composition is the same as in Example 1.
From Table 1, it can be seen that the Mooney viscosity, which is an index of processability, is deteriorated.

(Comparative Example 2)
Polybutadiene was produced in the same manner as in Example 1 except that 15.47 mmol of cyclooctadiene and 0.6 mmol of t-butyl chloride were added.
Table 1 shows the physical properties of the obtained polybutadiene. Table 2 shows the physical properties of the rubber composition. The compounding ratio of the rubber composition is the same as in Example 1.

(Comparative Example 3)
In a 1.5 liter stainless steel autoclave sufficiently purged with nitrogen inside, 1 liter of cyclohexane-C4 fraction mixed solution containing 45.5% by weight of 1,3-butadiene (cyclohexane 22.5% by weight, cis- 2-butene-containing C4 fraction containing 31.5% by weight), and then added water 2.06 mmol, diethylaluminum monochloride 2.27 mmol, triethylaluminum 0.76 mmol and stirred And 11.4 mmol of cyclooctadiene was added. After the temperature of the autoclave was raised and the internal temperature reached 49.5 ° C., 0.004 mmol of cobalt octoate was added, and a polymerization reaction was carried out at 50 ° C. for 30 minutes. 30 minutes after the start of polymerization, 0.5 mmol of t-butyl chloride was added and reacted for 20 minutes. Antiaging agent was added there and it vacuum-dried at 100 degreeC for 1 hour. Table 1 shows the physical properties of the obtained polybutadiene. Table 2 shows the physical properties of the rubber composition. The compounding ratio of the rubber composition is the same as in Example 1.

(Comparative Example 4)
A commercially available BR150L manufactured by Ube Industries, Ltd. was used as polybutadiene. The physical properties are shown in Table 1. Table 2 shows the physical properties of the rubber composition. The compounding ratio of the rubber composition is the same as in Example 1.

  In Examples 1 to 4, since the Mooney viscosity difference between the raw material cis-1,4 polybutadiene and the modified cis-1,4 polybutadiene is 10 or more and Mz / Mw is 2.5 or more, these properties are compatible. Compared with Comparative Examples 1 to 5 that do not have, improved low workability and wear resistance while improving workability.

Claims (5)

It is obtained by polymerizing 1,3-butadiene in the presence of a transition metal polymerization catalyst to produce cis-1,4-polybutadiene (A), and immediately thereafter adding an organic halogen compound as an additive (a) The difference in Mooney viscosity (ML _{1 + 4} , 100 ° C.) from cis-1,4-polybutadiene (A) is 10 or more, and (b) the ratio of the Z average molecular weight to the weight average molecular weight (Mz / Mw) is 2.5 or more. And (b) a modified cis-1,4-polybutadiene having a Mooney viscosity (ML _{1 + 4} , 100 ° C.) of 100 or less. The transition metal polymerization catalyst is (a) cobalt octoate, (b) R ² _3-n AlX _n (wherein R ² represents a hydrocarbon group having 1 to 10 carbon atoms, X represents a halogen, and n represents 1 to 1). A catalyst containing a halogen-containing aluminum compound represented by (c) R ³ ₃ Al (wherein R ³ is a hydrocarbon group having 1 to 10 carbon atoms) and (d) water. The modified cis-1,4-polybutadiene according to claim 1.   The modified cis-1,4-polybutadiene according to claim 1 or 2, wherein the organic halogen compound is t-butyl chloride.   A rubber composition comprising the modified cis-1,4-polybutadiene according to any one of claims 1 to 3. (A) cis-1,4-polybutadiene (a) obtained by polymerizing 1,3-butadiene to produce cis-1,4-polybutadiene (A) and immediately after that an organic halogen compound is added as an additive. The difference in Mooney viscosity (ML _{1 + 4} , 100 ° C.) from A) is 10 or more, (b) the ratio of Z average molecular weight to weight average molecular weight (Mz / Mw) is 2.5 or more, and (b) Mooney viscosity ( (ML _{1 + 4} , 100 ° C.) is a process for producing a modified cis-1,4-polybutadiene having a value of 100 or less.