JPH0794517B2 - Transbutadiene-based composite polymer and composite polymer composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention relates to a transbutadiene-based composite polymer as a raw material rubber having excellent physical properties and processability, and a rubber using the transbutadiene-based composite polymer as a raw material rubber. It relates to a composition.

INDUSTRIAL APPLICABILITY The composite polymer of the present invention is a styrene-butadiene copolymer rubber having an improved cold flow property, and is suitably used for all uses where a styrene-butadiene copolymer rubber has been conventionally used. And the rubber composition containing the composite polymer of the present invention is excellent in processability, the vulcanized product has good mechanical strength, shows high wet skid resistance and good abrasion resistance, and has a good balance between both. is there. Therefore, the rubber composition of the present invention is suitable for use in automobile tires, particularly passenger car tires.

[Conventional technology]

BACKGROUND ART Conventionally, a raw material rubber having excellent strength, abrasion resistance, impact resilience, wet skid resistance and the like, and excellent workability has been desired as a general-purpose vulcanized rubber.

However, in order to meet the demand, it is necessary to improve the balance of the mutually conflicting required properties such as wet skid resistance against wear resistance and impact resilience, or workability against strength. , That was extremely difficult. For this reason, various proposals have been made to date on the technique, but none of them have been sufficiently satisfactory.

For example, as one of the improvement methods, there is a proposal to improve the performance and processability by blending several kinds of rubbers each having a characteristic in performance. Part 1
Focusing on trans-bonding, which is one of the bonding modes of butadiene, a butadiene polymer or copolymer having 60-90% of trans-bonding and a butadiene polymer having a glass transition temperature of -60 ° C to -10 ° C or A method of blending a copolymer and using it as a raw rubber (Japanese Patent Laid-Open No. 57-100146)
No.), the workability and wet skid property are greatly improved, but the degree of improvement in tensile strength, impact resilience, and wear resistance is still insufficient, probably because it is a simple blend. As another method, there has been proposed a method of using a block copolymer composed of two or more polymers having different performances as a raw material rubber. For example, a so-called random block copolymer, which is a copolymer of a monovinyl aromatic and a conjugated diene, and which is composed of two types of blocks having different monovinyl aromatic contents (Japanese Patent Publication No. 47-1).
7449, JP-A-57-200413), and a random block copolymer composed of two types of blocks having different vinyl bond contents (Japanese Patent Publication No. 54-26583), monovinyl aromatic content and vinyl bond content. Random block copolymers by combination (JP-A-57-102912, JP-A-57-109817, JP-A-57-109817)
57-109818) is known. However, in these random block copolymers, improvement in the balance of abrasion resistance and wet skid resistance is still insufficient because the block polymer is only a combination of the amount of bound styrene and the amount of vinyl in the butadiene portion, and strength, The improvement in workability had almost no effect. Further, a block copolymer comprising a diblock of high tranulus SBR and high vinyl SBR (JP-A-61-238845).
No.) is also proposed. However, the high-trans SBR block has a high glass transition temperature due to the copolymerization of styrene, and its crystalline melting point is lower than room temperature or does not exist. The physical properties (improvement of cold flow property, hardness, modulus, abrasion resistance, etc.) are not sufficiently expressed. On the other hand, in order to exhibit these effects, it is necessary to include a higher proportion of the high trans block portion, but rather, the heat generation property and the low temperature performance are deteriorated. Moreover, this high transformer SBR
The diblock copolymer of (HTSBR) and high vinyl SBR has an insufficient activity of the catalyst to be used, the activity of the polymerization for obtaining the trans-copolymer portion in the first stage is extremely low, and the molecular weight distribution becomes wide, In addition, the second-stage polymerization also has a poor living property, so that the unfavorable molecular weight distribution is expanded and the proportion of the HTSBR-b-HVSBR type diblock polymer in the produced polymer is decreased, and the proportion of the HTSBR homopolymer is increased. However, the performance improvement expected as a block polymer of a high trans polymer and a low trans polymer was not observed.

[Problems to be Solved by the Invention]

The present invention could not be achieved by the conventional methods described above.
A new styrene-based product with excellent cold flow properties, improved balance between wear resistance and wet skid resistance as a vulcanized rubber, improved strength, and improved processability.
It is intended to provide a transbutadiene-based composite polymer composed of a butadiene copolymer rubber and a composition using the composite polymer.

[Means for Solving the Problems]

That is, the present invention has a glass transition temperature of −80 ° C. or lower, a crystal melting point of 30 to 130 ° C., a trans bond of 80% or higher, and a molecular weight of 1
~ 200,000, Resinous polybutadiene block with molecular weight distribution w / n 1.2 ~ 4 and bound styrene content 1 ~ 50% by weight, trans bond without crystal melting point 40% or less, vinyl bond 40%
~ 80%, block polymer consisting of rubbery butadiene-styrene random copolymer block with a molecular weight of 2 to 400,000 and bound styrene content of 1 to 50% by weight, trans bond having no crystal melting point of 40% or less, vinyl bond 40 to 80%, a rubber-like butadiene-styrene random copolymer having a molecular weight of 2 to 400,000 is the main component, and the high trans resinous polybutadiene portion is 1 to 70% by weight of the whole transbutadiene-based composite polymer, and the Mooney viscosity is ML _{1 + 4} (100 ° C.) of 10 to 150 and molecular weight distribution w / n of 1.2 to 5 transbutadiene-based composite polymer, and raw material containing at least 20% by weight of the transbutadiene-based composite polymer A transbutadiene-based composite polymer composition comprising 100 parts by weight of rubber, 10 to 300 parts by weight of carbon black, and 0.1 to 10 parts by weight of a vulcanizing agent is provided.

The high trans resinous polybutadiene block of the block polymer constituting the composite polymer in the present invention is a resinous polybutadiene having a glass transition temperature of −80 ° C. or lower and a crystal melting point of 30 to 130 ° C. and a trans bond of 80% or more. Outside this range, the excellent effects of the present invention cannot be obtained. That is, when the glass transition temperature exceeds −80 ° C., abrasion resistance and impact resilience are poor, and when the crystal melting point is lower than 30 ° C.,
Cold flow is inferior and abrasion resistance and strength are also reduced. If the crystal melting point exceeds 130 ° C., sufficient cross-linking of the trans polymer block portion cannot be obtained, resulting in deterioration of strength and exothermicity. If the transformer bond is less than 80%, the cold flow property is poor and the wear resistance, strength, modulus and hardness are lowered. In the present invention, the high trans resinous polybutadiene block preferably has a glass transition temperature of -83 ° C or lower, and a crystal melting point of preferably 40 ° C to 120 ° C, more preferably 50 ° C to 110 ° C. Therefore, the transformer coupling is 85
~ 95% is preferred. The high trans resinous polybutadiene block has a molecular weight of 100,000 to 200,000 and a molecular weight distribution w / n of 1.2.
~ 4. If the molecular weight is less than 10,000, the effect of improving the cold flow property, which is a feature of the present invention, cannot be obtained, and the wear resistance,
Performance improvement such as strength improvement cannot be obtained. On the other hand, when the molecular weight is 200,000 or more, the composite polymer becomes too hard at room temperature and rather becomes difficult to process. Here, the molecular weight is the weight average molecular weight w. Molecular weight distribution w / n
When it exceeds 4, not only the effects such as improvement in wear resistance and strength are small, but also the problem that heat generation is deteriorated occurs.

In the present invention, the high trans resinous polybutadiene block preferably has a molecular weight of 30,000 to 150,000 and a molecular weight distribution w /
n is preferably 1.2 to 3.5, more preferably w / n is 1.
2-3.

The low trans rubbery butadiene styrene random copolymer block of the block polymer constituting the composite polymer in the present invention has a bound styrene content of 1 to 50% by weight, a trans bond having no crystal melting point of 40% or less, and a vinyl bond of 40% or less.
It is a rubbery butadiene-styrene random copolymer having a molecular weight of -80% and a molecular weight of 2 to 400,000. If it is out of this range, the excellent effect of the present invention cannot be obtained. That is, when the content of bound styrene exceeds 50% by weight, wear resistance and heat buildup are poor,
Lower bound styrene content results in lower strength. The bound styrene content is preferably 5 to 40% by weight, more preferably 8 to 25% by weight. Further, if the compound has a crystalline melting point or a high trans bond content, the static and dynamic rubber-like properties of the composite polymer are lost. In order to obtain a composite polymer having high wet skid properties, which is the object of the present invention, and high abrasion resistance while having high impact resilience, a low trans rubber-like butadiene-styrene rannum copolymer block is High vinyl content is required. However, when it exceeds 80%, the balance of wear resistance is deteriorated. When the molecular weight is less than 20,000, physical properties such as abrasion resistance, impact resilience and strength are poor, and when the molecular weight exceeds 400,000, roll processability and extrusion processability are poor. In view of the balance between performance and processability, the low-trans rubber-like butadiene-styrene random copolymer block preferably has a molecular weight of 50,000 to 300,000. Here, the molecular weight is a weight average molecular weight.

The low trans rubbery butadiene-styrene random copolymer constituting the butadiene-based composite polymer in the present invention has a bound styrene content of 1 to 50% by weight, a trans bond having no crystal melting point of 40% or less, and a vinyl bond of 40 to 40%. It is a rubbery butadiene-styrene random copolymer with 80% and a molecular weight of 2 to 400,000. If it is out of this range, the excellent effect of the present invention cannot be obtained. That is, the bound styrene content is 50
If it exceeds 5% by weight, abrasion resistance and heat buildup are poor, and if the content of bound styrene is low, strength is reduced. Bound styrene content is 5
-40% by weight is preferable, and 8-25% by weight is more preferable.
If the crystalline polymer has a melting point or the trans bond exceeds 60%, the static and dynamic rubberiness of the composite polymer is lost.

In order to obtain a composite polymer having high wet skid properties and high abrasion resistance while having high impact resilience, which is an object of the present invention, a low trans rubbery butadiene-styrene random copolymer has a high It must be a vinyl content. However, when it exceeds 80%, the balance of wear resistance is deteriorated. When the molecular weight is less than 20,000, physical properties such as abrasion resistance, impact resilience and strength are poor, and when the molecular weight exceeds 400,000, roll processability and extrusion processability are poor. Low trans rubber-like butadiene-in balance of performance and processability
The styrene random copolymer preferably has a molecular weight of 50,000 to 300,000. Here, the molecular weight is the weight average molecular weight.

The low-trans rubber-like butadiene-styrene copolymer portion of the present invention, that is, the low-trans rubber-like copolymer portion of the block polymer and the low-tance rubber-like copolymer portion is required to have styrene polymerized at random. The presence of block polystyrene deteriorates the exothermicity of the composite polymer.
The block polystyrene content is preferably 5% by weight or less, more preferably 2% by weight or less, based on the total amount of the composite polymer. In addition, the measurement of block polystyrene is performed by the osmic acid decomposition method (J.Poly.Sci.1,429 (1946)).

Further, it is more preferably completely random copolymerization, and the isolated styrene analyzed by the ozone decomposition-GPC method is 40% by weight or more of the total bound styrene, more preferably 50% by weight or more, and Chain-block styrene (having 8 or more chains of styrene units) accounts for 5% by weight or less, and more preferably 2.5% by weight or less of the total bound styrene. Completely random copolymerization is carried out by the method described in JP-A-57-100112.

In the present invention, the high trans resinous polybutadiene homopolymer is not contained in the transbutadiene-based composite polymer, or the glass transition temperature is −80 ° C. or lower, and the crystal melting point is 30 to
A resinous polybutadiene homopolymer having a trans bond of 80% or more and a molecular weight of 1 to 200,000 and a molecular weight distribution w / n of 1.2 to 4 at 130 ° C. is used as a high trans resinous polybutadiene block portion in a block polymer and the high trans resinous polybutadiene homopolymer. It is preferably 30% by weight or less based on the total amount of the polymers.

In the present invention, when the amount of the high trans resinous polybutadiene homopolymer in the transbutadiene-based composite polymer is large, the impact resilience is lowered and the heat generation property is deteriorated. In the present invention, the high trans resinous polybutadiene homopolymer in the composite polymer is 20 wt% or less with respect to the total of the high trans resinous polybutadiene block portion in the block polymer and the high trans resinous polybutadiene homopolymer, and further 10 It is preferably not more than weight%. Further, in this case, especially when the glass transition temperature of the high trans resinous polybutadiene homopolymer contained exceeds -80 ° C, abrasion resistance and impact resilience are remarkably reduced, and when the crystal melting point is lower than 30 ° C, cold flow property is lowered. Not only is it inferior, but the wear resistance and strength are also significantly reduced. When the crystal melting point exceeds 130 ° C., the strength decreases and the exothermicity deteriorates. Furthermore, the transformer coupling
If it is less than 80%, the cold flow property is inferior and the wear resistance, strength, modulus and hardness are lowered. Glass transition temperature is −
It is preferably 83 ° C or lower, and the crystal melting point is preferably 40 ° C to 120 ° C.
C., more preferably 50.degree. C. to 110.degree. C., and the trans bond is preferably 85 to 95%. Further, if the molecular weight is less than 10,000, there is a great adverse effect on wear resistance and strength. On the other hand, when the molecular weight is 200,000 or more, the composite polymer becomes too hard and the molecular weight distribution
When w / n exceeds 4, the exothermic property is significantly deteriorated.

In the composite polymer of the present invention, the high trans resinous polybutadiene portion, that is, the total of the high trans resinous polybutadiene block portion and the high trans resinous polybutadiene homopolymer in the block polymer is 1 to 70 of the total trans butadiene-based composite polymer. % By weight. When the total amount is less than 1% by weight, the effect of improving the cold flow property, which is a feature of the present invention, is small, and the performance such as abrasion resistance and strength cannot be improved. On the other hand, if it exceeds 70% by weight, the composite polymer becomes too hard at room temperature to make it difficult to process, or the impact resilience is reduced. The total amount of the high trans resinous polybutadiene block portion and the high trans resinous polybutadiene homopolymer in the block polymer is preferably 3 to 60% by weight, and more preferably 5 to 50% by weight based on the whole composite polymer.

The Mooney viscosity ML _{1 + 4} (100 ° C.) of the transbutadiene-based composite polymer of the present invention is 10 to 150. If the Mooney viscosity is too low, the strength, impact resilience, wear resistance, and heat buildup are poor, while if it is too high, roll formability, extrusion processability, and other processability are reduced, which is not preferable. It is preferably 20 to 130. When the Mooney viscosity is 70 or more, it is possible to add 5 to 100 parts of a normal process oil per 100 parts by weight of the composite polymer to lower the Mooney viscosity and improve the processability.

The molecular weight distribution of the composite polymer of the present invention is w / n 1.2-5. If the molecular weight distribution is too wide, the properties such as impact resilience and heat buildup will be poor. It is preferably 1.2 to 4, and more preferably 1.2 to 3.

The preferred polymer composition constituting the transbutadiene-based composite polymer of the present invention is a component containing a high trans resinous polybutadiene component, that is, a block polymer composed of a high trans resinous polybutadiene block and a low trans rubbery polybutadiene block, and a high trans resinous polybutadiene homopolymer. The total amount of polymer is 5 to 95 with respect to the composite polymer.
% By weight, low trans rubbery polybutadiene is 95 to 5% by weight. When the content of the component including the high trans resinous polybutadiene component is less than 5% by weight, the cold flow property of the present invention and the performance such as strength and abrasion resistance cannot be improved.
On the other hand, when the content of the low trans rubber-like polybutadiene is less than 5% by weight, the rubberiness of the composite polymer is deteriorated and the processability such as roll processability and extrusion processability is deteriorated.

The method for producing the composite polymer of the present invention comprises: (a) a step of preparing a monomer mixture liquid comprising butadiene and an inert solvent; (b) a catalyst comprising a rare earth compound and an organomagnesium compound at a temperature of 0 to 150 ° C. Polymerizing butadiene to a trans bond of 80% or more, (c) subsequently adding an organic lithium compound to the above catalyst, and adding butadiene and styrene to a trans bond of 40% or less at a temperature of 30 to 200 ° C; It is produced by a step of polymerizing to 80% vinyl bond, (d) a step of removing an inert solvent from the obtained composite polymer, and may be a batch method or a continuous method.

The first step is a step of preparing a monomer liquid mixture containing butadiene and an inert solvent. The inert solvent is not particularly limited as long as it does not deactivate the catalyst used, but the solvent used is n Aliphatic or aliphatic hydrocarbons such as -pentane, n-hexane, n-heptane and cyclohexane, and aromatic hydrocarbons such as benzene and toluene are preferable. These may be a mixture of two or more kinds, or may contain a small amount of impurities.

The monomer mixture is prepared to have a monomer concentration of 1 to 50% by weight, preferably 5 to 30% by weight, in which allenes having a molar ratio of 1 or less with respect to the organolithium compound, such as propadiene and 1,2-butadiene. , 1,2-pentadiene, 1,2-
It may include octadiene or the like.

The second step of the present invention is a step of polymerizing butadiene to a trans bond of 80% or more at a temperature of 0 to 150 ° C. with a catalyst composed of a rare earth compound and an organomagnesium compound.
The rare earth compound which is the main component of the catalyst includes lanthanum, cerium, praseodymium, neodymium as rare earth elements,
Element number 57 for samarium, europium, cadmium, etc.
To 71, and preferable elements include lanthanum, cerium, neodymium, and europium, and organic acid salts thereof are used as preferable ones. The rare earth organic acid salt can be easily obtained, for example, by reacting the following alkali metal of an organic acid with chloride of lanthanum in water or an organic solvent such as alcohol or ketone.

The rare earth element used does not have to have a high purity and may contain a small amount of other rare earth elements or elements other than rare earth elements. The rare earth organic acid salt may contain a small amount of lanthanum or an organic acid as an impurity.

The organic acid compounds used are the following general formulas (I) to (VI
It is represented by II).

R ¹ -LH …… (I) (Wherein R ¹ , R ² and R ^{5 to} R ⁸ represent an aliphatic hydrocarbon group or an aromatic hydrocarbon group, R ³ represents an aromatic hydrocarbon group, and R ⁴ represents an aliphatic hydrocarbon group. , R ^{9 to} R ¹² represent an aliphatic hydrocarbon group, an aromatic hydrocarbon group, an alkoxy group or a phenoxy group, L represents an oxygen atom or a sulfur atom, and j, k, l and m are 1 or more and 6 or more. The following integers are shown.) Details of these organic acid compounds are described in JP-A-61-97331. The above general formula (I) represents alcohol, thioalcohol, phenol or thiophenol. Examples of these are methyl alcohol, ethyl alcohol, n-propyl alcohol, iso-propyl alcohol, tert-butyl alcohol, tert-amyl alcohol, n-hexyl alcohol, cyclohexyl alcohol, allyl alcohol, 2-butenyl alcohol, 3- Hexenyl alcohol, 2.5-decadienyl alcohol, benzyl alcohol, phenol, catechol, 1-naphthol, 2-naphthol, 2.6-di-
tert-butylphenol, 2,6-di-tert-butyl-
4-methylphenol, 2,4,6-tri-tert-butylphenol, 4-phenylphenol, ethanethiol, 1-butanethiol, 2-pentanethiol, 2-
Examples include iso-butanethiol, thiophenol, 2-naphthalenethiol, cyclohexanethiol, 3-methylcyclohexanethiol, 2-naphthalenethiol, benzenemethanethiol, 2-naphthalenemethanethiol.

The general formula (II) represents a carboxylic acid or a sulfur congener. Examples of these are isovaleric acid, caprylic acid, octanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, cyclopentanecarboxylic acid, naphthenic acid, ethylhexanoic acid, pivalic acid, versatic acid. (Synthetic acid composed of a mixture of isomers of C10 monocarboxylic acid sold by Shell Chemical), phenylacetic acid, benzoic acid, 2-naphthoic acid, hexanethiol acid, 2,2-dimethylbutanethioic acid, decanthioic acid , Tetradecanoic acid, thiobenzoic acid and the like.

The general formula (III) represents alkylallyl sulfonic acid.
Examples thereof include dodecylbenzenesulfonic acid, tetradecylbenzenesulfonic acid, hexadecylbenzenesulfonic acid, octadecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, n-hexylnaphthalenesulfonic acid and dibutylphenylsulfonic acid.

The general formula (IV) represents a monoalcohol ester of sulfuric acid. Examples of these are sulfuric acid monoester of lauryl alcohol, sulfuric acid monoester of oleyl alcohol,
Examples thereof include sulfuric acid monoesters of stearyl alcohol.

Formula (V) represents a phosphoric acid diester of an ethylene oxide adduct of alcohol or phenol. Examples of these are phosphoric acid diesters of ethylene oxide adducts of dodecyl alcohol, phosphoric acid diesters of ethylene oxide adducts of octyl alcohol, phosphoric acid diesters of ethylene oxide adducts of stearyl alcohol, phosphoric acid diesters of ethylene oxide adducts of oleyl alcohol. Examples thereof include acid diesters, nonylphenol ethylene oxide adduct phosphoric acid esters, and dodecylphenol ethylene oxide adduct phosphoric acid esters.

The general formula (VI) represents a phosphorous acid diester of an ethylene oxide adduct of alcohol or phenol. Examples of these include phosphite diester of ethylene oxide adduct of dodecyl alcohol, phosphite diester of ethylene oxide adduct of stearyl alcohol,
Examples thereof include phosphite diester of ethylene oxide adduct of stearyl alcohol, phosphite diester of ethylene oxide adduct of nonylphenol, and phosphite diester of ethylene oxide adduct of dodecylphenol.

The general formula (VII) represents a pentavalent organic phosphoric acid compound. Examples of this include dibutyl phosphate, dipentyl phosphate, dihexyl phosphate, diheptyl phosphate, dioctyl phosphate,
Bis (1-methylheptyl) phosphate, Bis (2-phosphate)
Ethylhexyl), dilauryl phosphate, dioleyl phosphate, diphenyl phosphate, bis (p-nonylphenyl) phosphate, (butyl) phosphate (2-ethylhexyl), phosphoric acid (1-methylheptyl) (2-ethylhexyl), Phosphoric acid (2-ethylhexyl (p-nonylphenyl), 2
-Ethylhexylphosphonate monobutyl, 2-ethylhexylphosphonate mono-2-ethylhexyl, phenylphosphonate mono-2-ethylhexyl, 2-ethylhexylphosphonate mono-p-nonylphenyl, dibutylphosphinic acid, bis (2-ethylhexyl) phosphinic acid , Bis (1-methylheptyl) phosphinic acid, dilaurylphosphinic acid, dioleylphosphinic acid, diphenylphosphinic acid, bis (p-nonylphenyl) phosphinic acid, butyl (2-ethylhexyl) phosphinic acid (2
-Ethylhexyl (1-methylheptyl) phosphinic acid, (2-ethylhexyl (p-nonylphenyl) phosphinic acid, etc. may be mentioned.

Formula (VIII) represents a trivalent phosphate compound. Examples thereof include bis (2-ethylhexyl) phosphate, bis (1-methylheptyl) phosphate, mono-2-ethylhexyl 2-ethylhexylphosphonate, and bis (2-ethylhexyl) phosphinic acid.

An organomagnesium compound which is another catalyst component forming the present invention is represented by the following general formula (IX).

Mg · R ¹³ · R ¹⁴ ...... (IX) (wherein R ¹³ and R ¹⁴ represent an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and they may be the same or different groups. The organomagnesium may contain a small amount of organoaluminum, organozinc or the like in order to improve its solubility in a hydrocarbon solvent.

Such examples include diethyl magnesium, di-n-
Propyl magnesium, di-isopropyl magnesium, di-n-butyl magnesium, n-butyl-sec-
Butylmagnesium, di-sec-butylmagnesium,
Di-tert-butyl magnesium, di-n-hexyl magnesium, di-n-propyl magnesium, diphenyl magnesium, MAGALA-6E.7.5E (Texas alkyl company)
Etc. are preferred, and more preferred are di-isopropyl magnesium, di-n-butyl magnesium,
Di-sec-butylmagnesium, MAGALA-6E.-7.5E and the like can be mentioned.

The catalyst of the present invention has extremely high activity, and the amount of catalyst used is
The rare earth compound component is preferably 0.01 to 1 mmol, and more preferably 100 g of the conjugated diene monomer to be polymerized.
It is 0.05 to 0.6 mmol. The organomagnesium component is preferably 0.02 to 10 mmol, more preferably 0.1 to 6 mmol, also expressed as the concentration per 100 g of the conjugated diene monomer. Generally, when the amount of the organomagnesium used is too small with respect to a given amount of rare earth compound, not only the polymerization activity is lowered, but also the trans bond content in the obtained conjugated diene polymer becomes low, and The molecular weight distribution will also be broad. On the other hand, when the amount of organomagnesium used is too large, the molecular weight distribution of the obtained conjugated diene polymer is narrowed, but the polymerization activity and the trans bond content are also decreased. In addition, use of an unnecessarily large amount of catalyst not only increases the amount of catalyst residue remaining in the conjugated diene polymer, but is not preferable in terms of economy. That is, the preferable amount of the composite catalyst used in the present invention is represented by the ratio of the rare earth compound (a) which is a constituent component of the catalyst and the organomagnesium (b), and (a) / (b) is 1/0.
The range is 1 to 1/50, more preferably 1 / 0.5 to 1/10.

In the catalyst of the present invention, in addition to the above two components, one or more components selected from organic compounds of lithium, organic aluminum compounds and electron donating compounds are preferably present in a molar ratio of 1/10 or more of the organic magnesium compounds. By doing so, the polymerization activity can be further enhanced. The organic compound of lithium used is represented by the following general formulas (X) to (XV).

R ¹⁵ (Li) _w …… (X) R ¹⁶ (OLi) _x …… (XI) R ¹⁷ (OCH ₂ CH ₂ ) _y OL _i …… (XII) (Wherein R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ represent an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and w, x, y
And z represent an integer of 1 or more and 6 or less. The details of these lithium organic compounds are shown in JP-A-61-97311.

And, as an example of the general formula (X), methyllithium, ethyllithium, n-propyllithium, isopropylthylium, n-butylthylium, sec-butyllithium, t
ert-butyllithium, isoamyllithium, sec-amyllithium-n-hexyllithium, n-octyllithium, allyllithium, benzyllithium, phenyllithium, 1,1-diphenyllithium, tetramethylenedilithium, pentamethylenedilithium, 1 Examples include 2,2-dilithio-1,1,2,2-tetraphenylethane and 1,3-bis (1-lithio-1,3-dimethylpentyl) benzene. Preferred are organic lithium compounds such as n-butyllithium, sec-butyllithium, tert-butyllithium, and 1,3-bis (1-lithio-1,3-dimethylpentyl) benzene.

Examples of general formula (XI) include ethyl alcohol, n-propyl alcohol, iso-propyl alcohol, n-butyl alcohol, iso-butyl alcohol, 2-butyl alcohol, tert-butyl alcohol, n-amyl alcohol, n-hexyl. Alcohol, n-heptyl alcohol, n-octyl alcohol, cyclohexyl alcohol, allyl alcohol, cyclopentyl alcohol, pentyl alcohol, phenol, 1-naphthol, 2,6
-Di-tert-butylphenol, 2,4,6-tri-tert-
Examples thereof include alcohols such as butylphenol, nonylphenol, and 4-phenylphenol, and lithium salts of phenol.

Examples of general formula (XII) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monopropyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether. , Lithium salts such as diethylene glycol monophenyl ether.

Examples of general formula (XIII) include lithium salts such as dimethylaminoethanol, diethylaminoethanol and di-n-propylaminoethanol.

Examples of the general formula (XIV) include lithium salts of secondary amines such as dimethylamine, diethylamine, di-n-propylamine, di-iso-propylamine, di-n-butylamine and di-n-hexylamine. To be

Examples of the general formula (XV) include lithium salts of cyclic imines such as ethyleneimine, triethyleneimine, pyrrolidine, piperidine and hexamethyleneimine.

Particularly preferred organic compounds of lithium are n-butyllithium, sec-butyllithium and iso-amyllithium.

It is possible to change the trans bond content in the obtained conjugated diene polymer depending on the amount of the lithium organic compound coexisting in the catalyst of the present invention. Generally, as the amount of the organic compound of lithium used increases, the polymerization activity increases, while the trans bond content in the obtained conjugated diene polymer decreases. However, when used in an appropriate amount, it is possible to obtain a polymer having a high trans bond content with even higher activity. Therefore, the amount of the organic compound of lithium to be used varies depending on the trans bond content in the target polymer, but when the trans bond content of the present invention is 80% or more, lithium is used. The Li / Mg molar ratio must be 1.5 or less, which is represented by the ratio of the lithium atom in the organic compound, the lithium atom in the organomagnesium compound, and the magnesium atom in the organomagnesium compound. In particular, when trying to obtain a polymer having a trans bond content of 85% or more, it is desirable that the Li / Mg molar ratio is 0.7 or less.

Further, in order to enhance the polymerization activity of the catalyst, an organoaluminum compound that can coexist is represented by the following general formula (XV
It can be represented by I).

AlR ²² R ²³ R ²⁴ ...... (XVI) (wherein R ²² and R ²³ represent hydrogen or an aliphatic hydrocarbon group, and R ²⁴ represents an aliphatic hydrocarbon group.) As such an example, Examples thereof include trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trihexylaluminum, tricycloexylaluminum, diethylaluminum hydride, diisobutylaluminum hydride, ethylaluminum dihydride, isobutylaluminum dihydride. Particularly preferred are triethyl aluminum, triisobutyl aluminum, diethyl aluminum hydride,
It is diisobutylaluminum hydride. When an organoaluminum compound is used, its excessively large amount reduces both the polymerization activity and the trans bond content. Therefore, the amount of the organoaluminum compound used should be kept to an appropriate amount, in which case both the polymerization activity and the trans bond content can be increased. In general, the amount of the organoaluminum compound used is preferably 10 or less, more preferably 1 or less, expressed as Al / Mg molar ratio.

Further, it is possible to coexist with an electron donating compound capable of increasing the polymerization activity of the catalyst. Examples of such compounds include compounds known as so-called Lewis bases, generally ethers or thioethers, and amines. One such example is
Ethers such as dimethyl ether, diethyl ether, diphenyl ether, tetrahydrofuran, anisole, diglyme, dimethylamine, diethylamine, trimethylamine, triethylamine, di-n-butylamine, aniline, diphenylamine, N-ethylaniline, N, N, N ', N' Amines such as tetramethylethylenediamine and dipiperidinoethane, thiophene,
Examples thereof include thioethers such as tetrahydrothiophene and 2,5-dihydrothiophene. Preferably,
Diethyl ether, tetrahydrofuran, triethylamine, N, N, N ', N'-tetramethylethylenediamine. The amount of the electron-donating compound used varies depending on the strength of the compound as a Lewis base, but generally speaking, the strongly basic compound may be used in a small amount as compared with the weakly basic compound. When the above-mentioned electron-donating compound is used in a large amount, it not only decreases the polymerization activity of the composite catalyst, but also decreases the trans bond content in the polymer. The preferable amount of use is indicated by the number of moles per mole of the organomagnesium compound, and is 50 or less, more preferably 5 or less.

The organolithium compounds, organoaluminum compounds, and electron-donating compounds described above may be used alone, or two or more components of these compounds may be used simultaneously. When any of these compounds is used, by using an appropriate amount, a conjugated diene polymer having a high trans bond content can be obtained at a higher conversion rate.

The catalyst in the present invention, in the presence or absence of a conjugated diene monomer, by pre-reacting prior to the polymerization, further increase the polymerization activity, and to obtain a molecular weight distribution of the resulting conjugated diene polymer. It can be narrowed.
At that time, an organic compound of lithium, an organic aluminum compound, and an electron donating compound may coexist in the preliminary reaction system.

This preliminary reaction is preferably carried out at a reaction temperature of 0 to 100 ° C. If the temperature is lower than this, the preliminary reaction is insufficient. On the other hand, if the temperature exceeds 100 ° C., the molecular weight distribution is widened, which is not preferable. A particularly preferred temperature is 20 ° C to 80 ° C. The reaction time is preferably 0.01 to 24 hours. If the reaction time is shorter than this, the preliminary reaction is insufficient, and the reaction time longer than this is unnecessary. Particularly preferable conditions are 0.05 to 5 hours. It is also possible to allow a conjugated diene monomer to be present when carrying out this preliminary reaction,
In that case, the obtained conjugated diene polymer has a narrower molecular weight distribution. The preferred amount of conjugated diene monomer to be used is shown in molar ratio to lanthanum metal atom,
It is 1 to 1000. Below or above this,
The effect of the presence of the conjugated diene monomer is small. Moreover, when the conjugated diene monomer is present in the above molar ratio or more, it becomes difficult to control the temperature in the preliminary reaction due to rapid polymerization of the conjugated diene monomer. A particularly preferred molar ratio is 5 to 200.

Polymerization is carried out using the above catalyst at 0 ° C to 150 ° C, preferably 30
It is carried out at ˜120 ° C., and the polymerization mode may be a batch method or a continuous method. The polymerization is performed by polymerizing butadiene to a trans bond of 80% or more, and the ratio of the high trans polymer to be polymerized in the step (b) in the total composite polymer is 1 to 70% by weight, preferably 3 to 70% by weight. Polymerization is advanced to 60% by weight, more preferably 5 to 50% by weight,
Next, in step (c), an organolithium compound is further added to the above catalyst, and the process proceeds to the step of polymerizing butadiene to a trans bond of 60% or less at a temperature of 50 to 200 ° C. The organolithium compound additionally added is represented by the above general formula (X), and preferred examples thereof include methyllithium, ethyllithium, and n.
-Propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, isoamyl lithium, sec-amyl lithium-n
-Hexyl lithium, n-octyl lithium, allyl lithium, benzyl lithium, phenyl lithium, 1,1-
Diphenyllithium, tetramethylenedilithium, pentamethylenedilithium, 1,2-dilithio-1,1,2,2-tetraphenylethane, 1,3-bis (1-lithio-1,3-dimethylpentyl) benzene, etc. Is mentioned. Preferably,
Organolithium compounds such as n-butyllithium, sec-butyllithium, tert-butyllithium and 1,3-bis (1-lithio-1,3-dimethylpentyl) benzene can be mentioned.

The addition amount thereof is required to be a Li / Mg molar ratio of 2.0 or more, preferably 2.5 or more, which is represented by the ratio of lithium atoms in the organolithium compound to magnesium atoms in the organomagnesium compound. In particular, in order to keep the trans binding amount to 55% or less, 3.0 or more, preferably 4.0 or
It is preferably 5.0 or more. In addition, a Lewis base can be used for the purpose of enhancing the polymerization activity of the catalyst simultaneously with the organolithium compound added thereafter, or enhancing the 1,2 vinyl bond and further lowering the trans bond. Suitable Lewis bases include ethers, thioethers and amines, and examples thereof include ethers such as dimethyl ether, diethyl ether, diphenyl ether, tetrahydrofuran, anisole and diglyme, dimethylamine and diethylamine, Trimethylamine, triethylamine, di-n-
Butylamine, aniline, diphenylamine, N-ethylaniline, N, N, N ', N'-tetramethylethylenediamine, dipiperidinoethane, and other amines, and further thiophene, tetrahydrothiophene, 2,5-dihydrothiophene, etc. The thioethers can be mentioned. Preferred are diethyl ether, tetrahydrofuran, triethylamine and N, N, N ', N'-tetramethylethylenediamine. The amount of the electron-donating compound used varies depending on the strength of the compound as a Lewis base, but generally speaking, the strongly basic compound may be used in a small amount as compared with the weakly basic compound. The preferred amount used is about 0.01 to 50 mol per mol of the organolithium compound. Polymerization was carried out with the above-mentioned organolithium-added catalyst at 30 to 200
It is carried out at a temperature of C, preferably 50 to 150C. At this stage, the monomer mixture prepared in step (a) or the monomer mixture prepared in another composition may be introduced into the polymerization system.

In this case, both the unreacted residual monomer in the step (b) and the monomer introduced in the step (c) are (c)
Polymerized in the process. The monomer polymerized in the step (c) has butadiene and styrene as main components, and other copolymerizable monomers such as isoprene, piperylene, methyl-styrene, and diphenylethylene may be used in combination.
It is necessary for the styrene to polymerize randomly in this step.

The polymerization at this stage is to polymerize the butadiene portion into a trans bond of 60% or less, preferably 55% or less,
The proportion of the low-trans polymer polymerized in step (c) in the total composite polymer is 30 to 99% by weight, preferably 40 to
Polymerization is allowed to proceed to 97% by weight, more preferably 50 to 95% by weight.

After the polymerization reaction reaches a predetermined polymerization rate, a known polymerization terminator may be added to the reaction system to stop the polymerization, and the usual steps of solvent removal and drying in the production of the conjugated diene polymer may be performed.

In the above production method, the total of a block polymer consisting of a high trans resinous polybutadiene block and a low trans rubbery butadiene styrene random copolymer block and a high trans resinous polybutadiene homopolymer and a low trans rubbery butadiene styrene random copolymer The ratio of the number of molecules of the coalesced is controlled by the catalyst composition and the amount ratio of the steps (b) and (c), and the ratio is 1:99 to 85:15.
Is the range.

Further, the weight ratio of the total of the block polymer consisting of the high trans resinous polybutadiene block and the low trans rubbery butadiene styrene copolymer block and the high trans resinous polybutadiene homopolymer and the low trans rubbery butadiene styrene random copolymer is Conditions, that is, catalyst composition and amount ratio in steps (b) and (c), (b)
It can be arbitrarily controlled by the conversion in the step, the amount of additional monomer in the step (c), and the like.

In the above-mentioned production method, the amount of the high-trans resinous polybutadiene homopolymer produced depends on whether the polymerization in the step (b) exceeds a predetermined temperature or the presence of water in the monomer additionally added in the step (c). To increase.

In the above-mentioned production method, the molecular weight of the polymer can be controlled by adjusting the composition or concentration of the catalyst used, and is in the range of about 30,000 to several hundreds of thousands. Further, the molecular weight distribution of the polymer can be controlled by a method of adjusting the composition of the catalyst to be used or the polymerization method. For example, w / n of less than 2 can be easily obtained in ordinary batch polymerization and w / n in continuous polymerization. Can be easily obtained. Known coupling reaction techniques, such as ester compounds, polyepoxy compounds, halogenated hydrocarbon compounds, halogenated silicon compounds and tin halide compounds, etc., coupling agents utilizing the reactive ends of living polymers or polyfunctional compounds such as divinylbenzene. It is also possible, if necessary, to impart a branched structure to the polymers or to broaden the molecular weight distribution by a method of adding a polymerizable monomer to the polymerization system during or after the polymerization.

By this method, a composite polymer having two or more resinous trans polybutadiene blocks in one molecule can be obtained, and this polymer is a thermoplastic elastic body having a resinous trans polybutadiene block as a hard segment.

As the coupling agent used in this method, a bifunctional, trifunctional, tetrafunctional or higher polyfunctional compound is used, and a linear polymer is obtained by the reaction of the bifunctional coupling agent with a living polymer chain. When it is trifunctional or higher, a branched polymer is obtained. Examples of the coupling agent used include dibutyl tin dichloride, dioctyl tin dichloride, diethyl silicon dichloride, dibutyl silicon dibromide, methyl benzoate, butyl tin trichloride, octyl tin chloride, methyl silicon trichloride, and the like. Ethyl silicon trichloride, butyl silicon tribromide, tin tetrachloride, lead tetrachloride, silicon tetrachloride, tetramethoxytin, ethylenebistrichlorosilane, diethyl adipate, dimethyl carbonate, two or more epoxy groups in one molecule or Hydrocarbon-based compounds having ester groups, such as epoxidized soybean oil, liquid polybutadiene having two or more epoxy groups in one molecule, and hydrocarbon compounds having one or more diglycidylamine groups 1 in one molecule , For example, tetraglycidyl-1,3-bisaminomethylcyclohexane, tetraglycidyl diaminodiphe Rumetan, and the like. By utilizing the coupling reaction, the resulting composite polymer is further prevented from cold flow, and when used in rubber applications, the green strength of the unvulcanized product becomes extremely large, which results in work during rubber processing. The sex is greatly improved. Particularly preferably used coupling agents are tin tetrachloride, silicon tetrachloride, tetraglycidyl diaminodiphenylmatan and the like.

Also, known terminal modification techniques, for example, reaction of a living polymer chain with a terminal modifying agent such as trialkyl tin chloride or triallyl tin chloride, similarly in the molecule Compounds having a bond (wherein X represents an oxygen or sulfur atom), N, N-dialkylamino aromatic aldehyde compounds, N, N-dialkylamino aromatic ketone compounds, thiocarbonyl compounds, dithiocarboxylic acid esters, isocyanate compounds It is also possible to use a terminal modification technique by reacting with a terminal modification agent such as a thioisocyanate compound or a carbodiimide compound. The composite polymer obtained by using these terminal modification techniques, for example, in the case of a vulcanized rubber, improves the impact resilience at high temperature while maintaining the wet skid resistance, and further lowers the heat generation property. Improvements have been made, combined with high wear resistance and strength as a composite polymer of the high trans rubber block polymer of the present invention, fuel-saving tires, all-season tires,
It is preferably used for rubber for treads such as high performance tires. Suitable terminal modifiers include tributyltin chloride, triphenyltin chloride, N, N,
N ', N'-tetramethylurea, N-methyl-ε-caprolactam, N-methyl-2-pyrrolidone, N, N'-dimethylethyleneurea, 4,4'-bis (diethylamino) benzophenone, phenylisothiocyanate, Dicyclohexylcarbodiimide and the like.

Furthermore, it is possible to obtain both effects by using the above coupling reaction and the terminal modification technique together.

The double bond of the composite polymer of the present invention can be hydrogenated by a known method. In particular, the composite polymer in which the 1,2-bond portion is selectively hydrogenated has excellent abrasion resistance and heat generation property when used as a vulcanized rubber. In addition, a product obtained by hydrogenating at a high hydrogenation rate in combination with a coupling reaction technique becomes a thermoplastic elastic body having excellent weather resistance.

The composite polymers of the present invention have a wide variety of uses due to their polymer structure and properties. For example, it can be used as a rubber-like polymer for tire treads, carcasses, sidewalls, etc. and exhibits excellent workability, wear resistance, and heat generation.

In addition, it does not show any cold flow property as a toughening agent to improve the buffering property of polystyrene, etc. and has excellent particle size controllability, rigidity and impact resistance balance, and excellent environmental stress crack resistance (ESCR) resistance to oil. It provides polystyrene (HIPS).

Another object of the present invention is to use the above composite polymer,
It is an object of the present invention to provide a rubber composition having excellent processability, excellent strength and abrasion resistance, and a good balance between these properties and wet skid resistance.

That is, the rubber composition of the present invention is a composite rubber alone or a raw material rubber containing at least 20% by weight of the composite polymer, 100 parts by weight, carbon black 10 to 300 parts by weight,
A rubber composition containing 0.1 to 10 parts by weight of a vulcanizing agent.

In the above rubber composition, the raw rubber is selected according to the intended use and purpose of the rubber composition, but in order to take advantage of the features such as processability, strength, abrasion resistance and hardness of the composite polymer of the present invention. Therefore, the raw rubber must contain at least 20% by weight, preferably 25% by weight, of the above composite polymer. As other raw material rubber used together with the composite polymer, natural rubber, synthetic polyisoprene rubber, styrene-butadiene copolymer rubber obtained by an emulsion polymerization method,
Styrene-butadiene copolymer rubber, high cis polybutadiene rubber, low cis polybutadiene rubber, high vinyl polybutadiene rubber, polychloroprene rubber, ethylene-propylene copolymer rubber, butyl rubber, halogenated butyl rubber, acrylonitrile-butadiene obtained by the solution polymerization method. Copolymer rubber, acrylic rubber and the like can be mentioned, and one or more kinds of these raw material rubbers are used depending on the purpose.

Next, in the above rubber composition, 10 to 300 parts by weight of carbon black is used as a reinforcing material with respect to 100 parts by weight of the raw material rubber. If the amount of carbon black is less than 10 parts by weight, the reinforcing performance such as strength and abrasion resistance will be insufficient.
If it exceeds 0 part by weight, heat resistance, elongation, workability, etc. are deteriorated.

The amount of carbon black is preferably 20 to 200 parts by weight. The type of carbon black used is SAF, ISAF, HAF, FEF, GPF, SR having different structures such as particle size, structure, and aggregate distribution depending on the purpose of use of the rubber composition.
F, FT, MT and other classes of carbon black are used. In particular, SAF, ISAF, HAF, etc. with small particle size and high reinforcing property are used for the application of tire tread with high strength and abrasion resistance demand, while on the other hand, for applications requiring heat resistance and compression set strain. As the carbon black, a carbon black having a relatively large particle size is used.

In the above rubber composition, the vulcanizing agent is used in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the raw rubber. A typical vulcanizing agent is sulfur, and in addition, a sulfur-donor compound such as a thiuram compound, a phenol resin, and a peroxide are also used as a vulcanizing agent.

Further, in the above rubber composition, the extender oil for rubber is used in an amount of 1 to 200 parts by weight per 100 parts by weight of the raw rubber, if necessary. Extending oils for rubber improve the processability of rubber compounds,
Also added to improve the dispersibility of carbon black,
Further, it is used for controlling the hardness of the rubber composition obtained with the above carbon black. The extender oil for rubber is selected according to the purpose of use of the rubber composition, and it is preferable to use the aromatic extender oil for rubber in applications where importance is placed on strength and workability, and emphasis is placed on low-temperature performance and heat resistance. For such applications, naphthene-based or paraffin-based extender oils for rubber are suitable. Furthermore, various fatty acid ester type compounds are also used.

Further, in the above rubber composition, various chemicals for rubber are added if necessary. These are vulcanization aids such as stearic acid and zinc white as typical chemicals for rubber,
Sulfenamide-based, thiazole-based, granidine-based, thiuram-based vulcanization accelerators, amine-based and phenol-based antioxidants, and various other chemicals for rubber can be used. The features of the rubber composition of the present invention will be described below.

The composite polymer of the present invention is, as described above, blended by itself,
By vulcanizing, tensile strength, tear strength, mechanical strength such as cut resistance, high hardness wear resistance, balance between wear resistance and wet skid resistance, heat resistance, excellent physical properties such as impact resilience, In addition to a rubber composition having good processing properties such as roll processability and extrusion processability, when other raw material rubbers are used together, the performance characteristics of the other raw material rubbers The strength, abrasion resistance and workability of the obtained rubber composition are improved without significantly deteriorating.

For example, in a rubber composition blended with natural rubber, tensile strength and cut resistance, which have been problems in conventional blend systems of natural rubber and polybutadiene or blend systems of natural rubber and styrene-butadiene copolymer, are greatly improved. While it is possible to improve the wear resistance of the rubber composition of the natural rubber alone, the performance is superior to the natural rubber and polybutadiene systems that have been widely used for treads and sidewalls of various tires. The rubber composition has a wide range of applications.

Further, a rubber composition using the composite polymer of the present invention and a styrene-butadiene copolymer as a raw material rubber is a conventional styrene-containing rubber composition.
Compared with a rubber composition using butadiene copolymer rubber alone or a blend of styrene-butadiene copolymer rubber and polybutadiene rubber as a raw material rubber, wet skid characteristics and low fuel consumption characteristics, which are important performances of tire treads, can be obtained. The rubber composition has improved wear resistance without loss, and is a rubber composition suitable for a tread of a passenger car tire such as a fuel-efficient tire, an all-season tire, and a hyper-performance tire.

Furthermore, the composite polymer of the present invention has a crystalline component, and by applying the hardness of this component, it is possible to obtain a rubber composition having a hardness higher than that of a conventional rubber composition. Thus, a rubber composition having a high hardness of JIS (A) hardness of 75 or more and a good heat resistance and the like can be obtained by using the composite polymer alone or a blend system with other raw material rubbers. It can be used for filler parts, high hardness anti-vibration rubber, high hardness industrial products, etc.

Further, the composite polymer of the present invention can improve the processability of other raw material rubbers by combining it with other raw material rubbers whose workability is not unfavorable. Examples thereof include rubber, polychloroprene rubber, acrylonitrile-butadiene copolymer rubber and the like. In the case of aiming to improve these processability, the ratio of the composite polymer of the present invention in the raw rubber is a relatively small amount, for example, 20 to 30 parts by weight, a balance between physical properties and processability. Is preferred.

The rubber composition of the present invention, together with the raw material rubber and other compounding agents,
Kneaded by a rubber kneader such as an internal mixer or a rubber kneading roll extruder, molded and assembled according to the intended use, and a conventional vulcanizer such as a vulcanizing press vulcanizer at 130 to 200 ° C. After being vulcanized at the temperature of, it is ready for use.

〔Example〕

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

Incidentally, the analysis of the microstructure of polybutadiene was obtained by calculating the butadiene-styrene copolymer by the method of Morello by an infrared spectrophotometer (JASCO A-202 type) by a carbon disulfide solution and by the method of Hampton.

The molecular weight was measured using GPC (Shimadzu Corporation, LC-5A, column: HSG40, 50, 60 each 1 column, column temperature 40 ° C, solvent: tetrahydrofuran, detector: differential refractometer). The average molecular weight of polybutadiene was determined according to a conventional method using a calibration curve previously determined from the relationship between the peak molecular weight and the GPC count.

Glass transition temperature and crystal melting point can be measured by DSC (Seiko Denshi D
SC-20 type) temperature rising rate 10 ° C / min) was used for measurement. Glass transition temperature is the starting point, crystal melting point is the peak temperature (midpoint)
Is.

The high trans resinous polybutadiene homopolymer was quantified by dissolving the composite polymer in an n-hexane-cyclohexane mixed solvent, cooling it to 0 ° C., and centrifuging the precipitated precipitate to obtain crystals.

Example 1 Two stainless steel stirrers and jacketed reactors having an internal volume of 10 liters and a height-to-inside diameter ratio of (L / D) 4 were connected in series, and from the bottom of the first unit 1, A solution of 3-butadiene in n-hexane and lanthanum versatate, dibutylmagnesium and butyllithium as a catalyst were continuously fed, and the internal temperature was kept at 80 ° C to carry out polymerization. The concentration of the monomer mixture was 20% by weight, and the monomer feed rate was 0.67 kg / hr. The amount of catalyst feed is 100 g of monomer
Lanthanum versatate is 0.10 mmol, dibutylmagnesium is 0.50 mmol, and butyllithium is 0.10.
It was set to millimole.

The conversion was measured by sampling from the outlet of the first reactor, and the result was 6.7%. The microstructure of the obtained polymer was 86% trans, 5% vinyl, and 9% cis. Glass transition temperature by DSC is -85 ° C, crystal melting point is + 82 ° C, molecular weight by GPC is w = 120,000, n = 57,000, molecular weight distribution w / n = 2.1, GPC type is gentle 1
It was a mountain.

The polymer solution discharged from the first base was introduced into the bottom of the second base, and from the bottom of the second base, additional 1,3-butadiene, styrene, n
-The monomer mixed liquid consisting of hexane, n-butyllithium and tetramethylethylenediamine were introduced. The concentration of the monomer mixture is 16% by weight, the feed rate of 1,3-butadiene is 0.875 kg / hr, and the feed rate of styrene is 0.
It was 365 kg / hr.

The amount of n-butyllithium introduced at the bottom of the second group was 0.74 mmol per 100 g of all the monomers introduced in the second group. Tetramethylethylenediamine was used in a 3-fold molar amount relative to n-butyllithium introduced in the second group. After the temperature of the second reactor was maintained at 90 ° C and polymerization was performed, 2
To the polymer solution discharged from the base reactor, 2,4-ditertiary-butyl-p-cresol was continuously added at 0.6 phr (parts by weight per 100 parts by weight of rubber), mixed and heated in hot water. The solvent stripped by steam stripping was removed.

The obtained rubber was dried on a hot roll. This is designated as Sample A.

The conversion at the second outlet is 98 for 1,3-butadiene.
It was 5% and styrene was 98.0%. The microstructure of the obtained rubber was measured by the method of Hampton using an infrared spectrophotometer. As a result, the bound styrene was 19% by weight, and the polybutadiene part had a microstructure of 40% trans, 43% vinyl, 17% cis.
The Mooney viscosity is ML _{1 + 4} (100 ° C) 54, the average molecular weight by GPC is w: 230,000, n: 105,000, molecular weight distribution w /
n = 2.2, and the GPC type was a gentle mountain. or,
The block styrene content was 0% based on the total rubber. In addition, the measurement of block styrene was performed by the osmic acid decomposition method (J.Poly.Sci.1,429 (1946).

Isolation styrene by ozonolysis-GP method is 72% by weight based on the total bound styrene, and long-chain block styrene (having a chain of styrene units of 8% or more) based on the total bound styrene.
It is 0.4% by weight, which is a completely random copolymer.

From the above results, the resin-like polybutadiene portion of the trans-86% polymerized in the first group was 23% by weight based on the whole trans-butadiene-based composite polymer, and the low-trans rubber-like styrene-butadiene copolymer polymerized in the second group. The parts are 77% by weight, and the microstructure of the low-trans rubber-like styrene-butadiene copolymer polymerized by the second group is calculated to be 26% trans, 55% vinyl, and 19% cis.

2 g of the obtained composite polymer was dissolved by heating in 100 ml of a mixed solvent of n-hexane / cyclohexane and then cooled to 0 ° C.,
The solution was centrifuged while keeping it at 0 ° C. to separate a precipitate and a solution. When the obtained sediment was vacuum dried and weighed,
It was 0.8% by weight based on the polymer. That is, the high trans resinous polybutadiene homopolymer was 7.2% by weight based on the first polymer (the total amount of the high trans resinous polybutadiene block portion and the high trans resinous polybutadiene homopolymer in the block polymer).

For reference, a high trans resinous polybutadiene homopolymer sampled from the first group and a low trans rubbery butadiene-styrene random copolymer polymerized with n-butyllithium and tetramethylethylenediamine (25 wt% of bound styrene, 0% of block styrene, w = ▲ ▼
10,000, w / n = 2.0, microstructure; trans 26%, vinyl 55%, cis 19%) were blended at 50:50 and fractionated in the same manner. The obtained precipitation was 45% by weight based on the blended polymer. %Met.

When the cold flow of the obtained composite polymer was measured, it did not substantially cold flow.

Transbutadiene-based composite polymer: No cold flow after 3 days Tuffden 2000 (commercial product): Collapses in 2 days.

(A 3 cm × 3 cm × 10 cm (height) rectangular parallelepiped rubber sample was fixed on a table inclined at 30 ° and the sample situation was observed.) Examples 2 to 4 The same method as in Example 1 was performed. . However, the monomer feed rate, composition, catalyst amount, Lewis base content, polymerization temperature, etc. of the first and second groups were changed. The obtained transbutadiene-based composite polymers are referred to as Samples B to D, respectively.
Table 1 shows the analytical values and the like. The obtained samples B to D were used in Example 1
As a result of carrying out a cold flow test in the same manner as above, no cold flow was observed even after 3 days.

Comparative Example 1 161 g of 1,3-
After introducing a 945g cyclohexane mixture containing butadiene and 28g styrene into the reactor, the Ba-Mg-Al initiator (Ba / Mg / Al
= 0.18 / 0.57 / 0.04 Unit mmole / 100g Monomer, US Patent 4,
No. 297,240) was added and polymerization was carried out at 60 ° C. for 1 hour. After sampling a part of it, 1155 g cyclohexane mixture containing 231 g of 1,3-butadiene and cyclohexane solution of Na tertiary amylate and TMEDA (Na / Mg molar ratio = 0.77, TMEDA / Mg molar ratio 0.61). Was added thereto, and polymerization was carried out at 50 ° C. for 1 hour.
Then, methanol was added to stop the reaction, and a polymer was obtained in the same manner as in Example 1. Table 2 shows the analytical values of the obtained polymer and the sample obtained in the middle.

Comparative Example 2 The procedure of Comparative Example 1 was repeated.

However, a Ba-Mg-Al initiator was added, polymerization was carried out at 60 ° C for 5 hours, and Na ternary amylate and TMEDA were added to the mixture.
Polymerization was carried out at 0 ° C. for 1 hour. The obtained polymer is referred to as Sample E. The results are shown in Table 2.

TBSR polymer sampled halfway was the same as in Example 1, n
Crystallization was not possible by the method using a mixed solvent of hexane / cyclohexane. Also, the polymer finally obtained was the same. Further, the cold flow property of the obtained polymer was "defeated in 1 day" evaluated by the method shown in Example 1 and was not preferable.

Comparative Example 3 (Sample F) In the same manner as in Example 1, the first polymer was sampled to obtain a high trans resinous polybutadiene homopolymer (Sample F-1).

Ordinary high vinyl butadiene-styrene random copolymer (ML _{1 + 4} (100 ° C) 55, w = 240,000, w / n: 2.1, using n-butyllithium and tetramethylethylenediamine)
Bonded styrene 26wt%, block styrene 0w%, transformer
26%, vinyl 55%, cis 19%). (Sample F-
2).

23 parts by weight of sample F-1 and 77 parts by weight of sample F-2 are blended to obtain sample F.

Comparative Example 4 (Sample G) In the same manner as in Example 1, the first polymer was sampled to obtain a high trans resinous polybutadiene homopolymer (Sample F-1).

Ordinary high vinyl butadiene-styrene random copolymer using n-butyllithium and tetramethylethylenediamine (ML _{1 +} 460, w = 230,000, w / n = 2.1, bound styrene 35 wt%, block styrene 0%, Trans 26%, vinyl 55%, cis 19%) was obtained (Sample G-2).

10 parts by weight of sample F-1 and 90 parts by weight of sample G-2 are blended to obtain sample G.

Comparative Example 5 (Sample H) Ordinary high vinyl butadiene-styrene random copolymer (ML _{1 + 4} (100 ° C.) 55, w = 250,000, w / n obtained using n-butyllithium and tetramethylethylenediamine)
n = 2.1, bound styrene 19wt%, block styrene 0wt
%, Trans 34%, vinyl 43%, cis 23%) as sample H.

Evaluation Samples A to H were blended in the formulations shown in Table 3 and the vulcanization performance was evaluated. The results are shown in Table 4.

Evaluation method ASTM-D-3403-75 using a pressure kneader with an internal capacity of 300cc
Compounds were obtained by the method B of the standard compounding and mixing procedure of 1., these were vulcanized, and each physical property was measured.

The measurement was performed by the method described below.

(1) Hardness and tensile strength: According to JOIS-K-6301.

(2) Impact resilience: Ryupke method according to JIS-K-6301, but impact resilience at 70 ° C was measured by preheating the sample in an oven at 70 ° C for 1 hour and then quickly taking it out.

(3) Goodrich heat generation Apply a load of 48 using a Goodrich frenxometer.
Pound, displacement 0.225 inch, start 50 ° C, speed 1800r
The test was carried out under the condition of pm, and the temperature rise difference after 20 minutes was shown.

(4) Wet skid resistance Stanley London portable skid tester was used, and the safety walk (made by 3M) was used as the road surface, and the measurement was performed according to the method of ASTM-E-808-74.

(5) Abrasion resistance It was evaluated using a pico abrasion tester, and the larger the value indicated by the index, the better.

Table 3 Compounded raw rubber 100 parts by weight Aromatic oil ^{* 1} 5 parts by weight N-339 carbon black ^{* 2} 45 parts by weight Stearic acid 2 parts by weight Zinc white 5 parts by weight Accelerator CZ ^{* 3} 1 part by weight Sulfur 1.7 parts by weight * 1 Kyodo Petroleum X-140 * 2 Iodine adsorption amount (IA) 90mg / g Dibutylphthalate adsorption amount (DBP) 119ml / 100g * 3 N-cyclohexyl-2-benzothiazylsulfenamide Vulcanization condition: 160 ° C x 20 minutes From the results of Table 4, Samples A to D, which are Examples of the present invention,
It has excellent physical properties and workability as compared with Comparative Examples E to H. Specifically, Sample A, which is the composite polymer of the present invention, is superior in processability, tensile strength, impact resilience, heat generation, and abrasion resistance to Sample F, which is a corresponding polymer blend. The same applies to the comparison between the sample D of the present invention and the corresponding polymer blend sample G. Samples A to D of the present invention are superior to Comparative Examples E to H, particularly in terms of balance between wear resistance and wet skid resistance.

Example 5 and Comparative Examples 6 and 7 Samples A, F and H of 60 parts by weight, natural rubber of 40 parts by weight, a total of 100 parts by weight as a raw rubber, were similarly compounded and evaluated for vulcanization.
The results are shown in Table 5.

From the results of Table 5, Example 5 (Sample A) of the present invention is superior in physical property processability as compared with Comparative Examples 5 (Sample F) and 6 (Sample H). In particular, it is excellent in the balance between abrasion resistance and wet skid resistance, and even when the composite polymer is blended with natural rubber, the excellent features of the composite polymer are exhibited.

Examples 6 to 8 and Comparative Examples 8 to 12 Samples A, D, F, G, H and butadiene-styrene copolymer rubbers were used as raw rubbers, compounded in the formulations shown in Table 3, and vulcanized.
evaluated. Table 6 shows the raw rubber composition and the results.

Examples 6 and 7 (Sample A) are Comparative Example 8 (F) and Comparative Example 9
Compared with (H), the balance between impact resilience and wet skid performance is slightly excellent, and especially the balance between wear resistance and wet skid performance is remarkably excellent.

Example 8 (Sample D) is slightly superior to Comparative Example 10 (G) in lupke impact resilience, and is particularly excellent in balance between wear resistance and wet skid performance.

Example 9 Polymerization was carried out in the same manner as in Example 1 using two polymerization reactors, and then the polymer solution discharged from the second reaction reactor was introduced into the third reaction reactor to obtain tetraglycidyl. After 0.04 phr of 1,3-bisaminomethylcyclohexane was continuously added to carry out the coupling reaction, the same procedure as in Example 1 was repeated.
4-di-tert-butyl-p-cresol is mixed,
A sample was obtained. This is designated as Sample I. It has a Mooney viscosity of ML _{1 + 4} (100 ℃) 89, and an average molecular weight by GPC of w = 30.
The molecular weight distribution w / n = 2.5, and the GPC type had one gentle peak. When the cold flow of the obtained sample I was measured, no cold flow was observed even after 10 days.

Sample I was blended in the same manner as in Example 1, vulcanized and measured for physical properties. The results are shown in Table 7.

Example 10 Polymerization was carried out in the same manner as in Example 2 using two polymerization reactors, and then the polymer solution discharged from the second reaction reactor was introduced into the third reaction reactor to dicyclohexylcarbodiimide. 0.17 phr was added continuously to effect terminal modification,
A sample was obtained in the same manner as in Example 2. This is designated as Sample J. Its Mooney viscosity was ML _{1 + 4} (100 ° C.) 47. Evaluation was performed in the same manner as in Example 9. The results are shown in Table 7.

Example 11 Polymerization was carried out in the same manner as in Example 2 using two polymerization reactors, and then the polymer solution discharged from the second reaction reactor was further introduced into the third reaction reactor and tetrachlorinated. A sample was obtained in the same manner as in Example 2 after continuously adding 0.018 phr of tin and 0.185 phr of tributyltin chloride to simultaneously perform the coupling reaction and the terminal modification. This is designated as Sample K. Its Mooney viscosity is ML _{1 + 4} (100 ° C) 68, and the average molecular weight by GPC is 24.
The molecular weight distribution w / n = 2.5, and the GPC type had one gentle peak. Evaluation was performed in the same manner as in Example 9, and the results are shown in Table 7.
Shown in.

Example 12 Made of stainless steel with an internal volume of 10 l, using a stirrer and a reactor with a jacket, 0.616 kg of 1,3-butadiene, 2.464 kg
Cyclohexane and catalyst were charged and the polymerization was carried out batchwise. The catalyst is lanthanum versatate 0.075 minimol, dibutylmagnesium 0.40 per 100 g of the monomer.
The reaction was carried out at 65 ° C. for 2 hours, using 0.1 mmol of n-butyl lithium. The result of conversion measurement by sampling was 64%, and the microstructure of the polymer was 89% trans, 4% vinyl, and 7% cis. Glass transition temperature by DSC is -87 ℃, crystal melting point +95
℃, GPC molecular weight w = 85,000, molecular weight distribution w /
n = 1.2, and the GPC type had one sharp peak.

In addition to the high trans polybutadiene solution, 1,3-butadiene 0.287 kg, styrene 0.094 kg, cyclohexane 1.
524 kg, 0.40 g of n-butyllithium and 1.6 g of tetramethylethylenediamine were added, polymerization was carried out at an internal temperature of 90 ° C., and after 10 minutes, 0.123 kg of 1,3-butadiene and 0.492 kg of cyclohexane were added over 30 minutes. After continuously adding the mixture, 0.040 phr (part by weight of feed per 100 parts by weight of rubber) of tin tetrachloride was added to carry out the coupling reaction. As a result of measuring the conversion by sampling, it was found that butadiene was 99% and styrene was 98%.

The polymer solution was treated in the same manner as in Example 1 to obtain a polymer. This is designated as sample L. The Mooney viscosity of this is ML _{1 + 4}
(100 ° C.) 62, the molecular weight by GPC was w = 220,000, and the molecular weight distribution w / n was 1.7. The microstructure of the butadiene part is 52% trans, 31% vinyl, 17% cis, the content of bound styrene is 8.5% by weight, the styrene isolated by ozonolysis GPC method is 75% by weight based on the total bound styrene, long chain block. Styrene is 0.2% by weight based on the total bound styrene,
It is a completely random copolymer.

From the above analysis values, the proportion of resin-like high trans polybutadiene in the composite polymer was 35% by weight, and the microstructure of the rubber-like low trans butadiene-styrene copolymer part was trans 32.
%, Vinyl 46%, cis 22%, bound styrene 13% by weight.

When the resinous high-trans polybutadiene homopolymer was measured by fractionation in the same manner as in Example 1, no precipitation was formed and the resinous high-trans polybutadiene homopolymer was hardly formed.

When the cold flow of sample L was measured, no cold flow was observed even after 10 days.

Sample L was blended and vulcanized in the same manner as in Example 9 and the physical properties were measured. The results are shown in Table 7.

Examples 13 to 17 and Comparative Examples 12 to 18 A rubber composition having the composition of the raw rubber shown in Table 8 and having the composition shown in Table 3 as in Example 1 was kneaded and vulcanized, and the physical properties were measured.
The results are shown in Table 8.

From the results shown in Table 8, the rubber compositions of Examples using the composite polymer of the present invention have higher tensile strength than the rubber compositions of Comparative Examples, and the balance between abrasion resistance and wet skid resistance and repulsion. Good balance between elasticity and wet skid resistance.

[Effects of the Invention] As is clear from the above, the transbutadiene-based composite polymer of the present invention is prevented from cold flow,
Further, the rubber composition of the present invention has excellent balance between abrasion resistance and wet skid resistance, and has excellent effects such as improvement in strength and workability, and its industrial value is extremely high.

Claims (2)

[Claims] 1. A glass transition temperature of −80 ° C. or lower and a crystal melting point of
30-130 ℃, trans bond 80% or more, molecular weight 1-20
Resin content polybutadiene block with molecular weight distribution w / n 1.2-4 and bound styrene content 1-50% by weight, trans bond not having crystalline melting point 40% or less, vinyl bond 40-80
%, A block polymer consisting of a rubbery butadiene-styrene random copolymer block having a molecular weight of 2 to 400,000 and a bound styrene content of 1 to 50% by weight, a trans bond having no crystal melting point of 40% or less, and a vinyl bond of 40 to 80 %, Molecular weight 2
~ 400,000 rubber-like butadiene-styrene random copolymer as a main component, the high trans resinous polybutadiene portion containing the resinous block is 1 to 70% by weight of the whole transbutadiene-based composite polymer, and the Mooney viscosity ML. _{1 + 4} (100
C) is 10 to 150, and the molecular weight distribution w / n is 1.2 to 5. 2. A transbutadiene-based composition comprising 100 parts by weight of a raw material rubber containing at least 20% by weight of the transbutadiene-based composite polymer according to claim 1, 10 to 300 parts by weight of carbon black, and 0.1 to 10 parts by weight of a vulcanizing agent. Composite polymer composition.