JP2012197420A - Method for manufacturing rubber composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a rubber composition capable of producing a tire maintaining a high elastic modulus and achieving good driveability.SOLUTION: In the method for manufacturing a rubber composition, the highest temperature attained in the kneading process of the rubber composition including a copolymer of a conjugated diene compound and a non-conjugated olefin is not higher by 20°C than a melting temperature of the non-conjugated olefin moiety in the copolymer.

Description

  The present invention relates to a method for producing a rubber composition that can provide a tire having a high elastic modulus and good steering stability.

  In recent years, as environmental measures and resource saving due to the global warming issue have been emphasized, the demand for improvement in fuel efficiency for automobile tires has increased more than ever. With respect to automobile tires, it is required to contribute to lower fuel consumption of automobiles by reducing the rolling resistance of the tires. In order to reduce the rolling resistance of a tire, it is generally effective to use a rubber material that can give a vulcanized rubber with little hysteresis loss.

  Conventionally, diene rubbers such as natural rubber (NR), polybutadiene (BR), polyisoprene (IR), and styrene-butadiene copolymer rubber have been used as tire rubber materials. These diene rubbers are selected depending on the site used, and are used alone or in a blend of two or more. Among these diene rubbers, high cis-1,4-polybutadiene gives the highest impact resilience, that is, the smallest hysteresis loss vulcanized rubber. Attempts have been made, but it has been difficult to obtain a polymer that has both impact resilience and wear resistance.

  On the other hand, in order to improve the low-temperature resilience and wear resistance by utilizing the characteristics of the polybutadiene rubber having the same high cis content, the high cis content conjugated diene polymer segment having a cis content of 40% or more and the crystallinity A conjugated diene rubber composition using a crystalline block copolymer rubber composed of segments has been proposed (see, for example, Patent Documents 1 and 2).

JP 2000-86857 A JP 2000-154279 A

However, even when such high cis-1,4-polybutadiene or a copolymer thereof is used, the crystallinity varies depending on the production conditions, and a high elastic modulus may not be obtained. It was.
Under such circumstances, an object of the present invention is to provide a method for producing a rubber composition that can provide a tire that maintains a high elastic modulus and has good steering stability.

The present inventor has found that the problems of the present invention can be solved by defining kneading and crosslinking temperatures in the production of a rubber composition containing a copolymer of a conjugated diene compound and a non-conjugated olefin. It came to complete.
That is, the present invention is a method for producing a rubber composition containing a copolymer of a conjugated diene compound and a non-conjugated olefin, the method comprising a kneading step of kneading the rubber composition, and the highest temperature reached in the kneading step Does not exceed the melting temperature of the non-conjugated olefin moiety in the copolymer + 20 ° C.
Moreover, it is a rubber composition obtained by the manufacturing method of the rubber composition containing the copolymer of the said conjugated diene compound and a nonconjugated olefin. Moreover, it is a tire using the said rubber composition.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the rubber composition which can maintain a high elasticity modulus and can provide a favorable steering stability, the rubber composition manufactured by this manufacturing method, and this rubber composition were used. Tires can be provided.

FIG. 1 is a cross-sectional view in the tire radial direction and tread width direction of a tire according to an embodiment of the present invention. FIG. 2 is a diagram showing a ¹³ C-NMR spectrum chart of copolymer A produced according to the production example. FIG. 3 is a diagram showing a DSC curve of copolymer A produced according to the production example.

Hereinafter, the manufacturing method of the rubber composition which concerns on this invention is demonstrated.
<Method for producing rubber composition>
The present invention is a method for producing a rubber composition comprising a copolymer of a conjugated diene compound and a non-conjugated olefin, the method comprising a kneading step for kneading the rubber composition, wherein the highest temperature reached in the kneading step is It is characterized in that the melting temperature of the non-conjugated olefin part in the copolymer does not exceed + 20 ° C.
Here, the melting temperature is the peak temperature of the peak where the endothermic amount is maximum in the melting endothermic curve measured according to the following method.
Specifically, using a differential scanning calorimeter (Perkin Elmer, DSC-7, rapid cooling type), 10 mg of the specimen was previously heated at 220 ° C. for 5 minutes in a nitrogen atmosphere to melt the specimen. Thereafter, the temperature is lowered to 40 ° C. at a rate of 5 ° C./min. Thereafter, the temperature is raised at 5 ° C./min, and in the obtained melting endothermic curve, the peak temperature of the peak having the maximum endotherm is defined as the melting temperature (Tm).

-Kneading step In the method for producing a rubber composition of the present invention, first, a predetermined amount of at least one of various rubber compounding agents other than the copolymer of a conjugated diene compound and a nonconjugated olefin and a vulcanizing agent is prepared, Supply them to a kneader such as a Banbury mixer, intermix, kneader and mix and knead them thoroughly (kneading step), then discharge the blend from the kneader and then vulcanizer, if necessary A vulcanization accelerator or vulcanization aid or another rubber compounding agent is added to produce a final rubber composition used for molding.
What is important here is not to destroy the crystalline structure of the non-conjugated olefin portion in the copolymer in the kneading step.

  Therefore, in the present invention, it is necessary to knead the kneading step at a temperature not higher than the melting temperature of the nonconjugated olefin portion in the copolymer + 20 ° C. or less. Therefore, by controlling the kneading conditions such as the number of revolutions of the kneader, the filling rate, the presence or absence of cooling, the temperature of the blend is a low temperature of the melting temperature of the non-conjugated olefin portion + 20 ° C. or less, preferably the melting temperature + 10 ° C. So that the components are sufficiently mixed and kneaded.

  According to this method, the components can be sufficiently mixed and kneaded without destroying the crystalline structure of the non-conjugated olefin portion, and a rubber composition maintaining a high elastic modulus can be obtained. As a result, sufficient steering stability is obtained when used as a rubber composition for tires.

-Crosslinking process The manufacturing method of the rubber composition of this invention includes the process of bridge | crosslinking the said uncrosslinked rubber composition (especially when using a sulfur compound as a crosslinking agent, it is also called a "vulcanization process"). Can do. That is, the rubber composition in the present invention includes those in an uncrosslinked state and those after crosslinking.
In this step, it is preferable to crosslink at a temperature lower than the melting temperature of the non-conjugated olefin portion in the copolymer + 20 ° C., as in the kneading step.

The crosslinking temperature is such that the temperature of the rubber composition blend during crosslinking is kept below the melting temperature of the non-conjugated olefin portion, preferably below the melting temperature + 20 ° C, more preferably below the melting temperature + 10 ° C. Allow vulcanization to take place.
As the crosslinking time, for example, the uncrosslinked tire can be crosslinked by heat treatment at a temperature of 100 to 140 ° C. until a desired crosslinking density is obtained. As will be described later, when a tire is manufactured, mold vulcanization using a sulfur compound as a crosslinking agent is preferable. There is no restriction | limiting in particular in a vulcanizer, A commercial item can be used conveniently.

<Rubber composition>
Then, the rubber composition manufactured by the manufacturing method of this invention, the rubber product which shape | molded it, and each component which comprises invention are demonstrated concretely.
The rubber composition according to the present invention contains a copolymer of a conjugated diene compound and a non-conjugated olefin, in addition to the copolymer, a rubber component other than the copolymer, a rubber compounding agent, a vulcanizing agent, A vulcanization accelerator, a vulcanization aid, a reinforcing agent, a filler, a softening agent, a crosslinking agent, a processing aid, an antiaging agent, and the like may be included.

<Copolymer of conjugated diene compound and non-conjugated olefin>
Next, a copolymer of a conjugated diene compound and a non-conjugated olefin will be described.
-Constitution of copolymer of conjugated diene compound and non-conjugated olefin Cis 1,4-bond of conjugated diene compound-derived portion (conjugated diene portion) of copolymer of conjugated diene compound and non-conjugated olefin used in the present invention The amount is preferably 50% or more. Furthermore, the cis 1,4-bond amount of the conjugated diene compound-derived moiety (conjugated diene moiety) is preferably more than 92%, more preferably 95% or more. If the amount of cis-1,4 bonds in the conjugated diene compound portion (part derived from the conjugated diene compound) is 50% or more, a low glass transition point (Tg) can be maintained, whereby crack growth resistance and resistance Physical properties such as wear are improved.

  By making the cis 1,4-bond content of the conjugated diene compound-derived portion (conjugated diene portion) more than 92%, it becomes possible to improve crack growth resistance, weather resistance, and heat resistance. Moreover, when the cis 1,4-bond content of the conjugated diene compound-derived portion (conjugated diene portion) is 95% or more, the crack growth resistance, weather resistance, and heat resistance can be further improved.

  The amount of cis-1,4 bonds is the amount in the conjugated diene compound-derived moiety, and is not a ratio relative to the entire copolymer.

  The ratio of the conjugated diene compound in the copolymer of the conjugated diene compound and the non-conjugated olefin is preferably 30 mol% to 98 mol%, more preferably 50 mol% to 98 mol%, and 60 mol% to 98 mol%. Is more preferable, and it is especially preferable that they are 70 mol%-96 mol%. If the proportion of the conjugated diene compound is 30 mol% or more, the compatibility with the diene rubber is good, and if it is 98 mol% or less, the nonconjugated olefin component is sufficiently present, so that sufficient elastic modulus is ensured. Is preferable.

  The non-conjugated olefin is preferably an acyclic olefin. Moreover, it is preferable that carbon number of a nonconjugated olefin is a 2-10 alpha olefin. Since the α-olefin has a double bond at the α-position of the olefin, it can be efficiently copolymerized with the conjugated diene compound. Accordingly, preferred examples of non-conjugated olefins include α-olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, and among these, ethylene, propylene and 1-butene is preferred and ethylene is more preferred. These non-conjugated olefins may be used alone or in combination of two or more. In addition, an olefin refers to the compound which is an aliphatic unsaturated hydrocarbon and has one or more carbon-carbon double bonds.

  The conjugated diene compound preferably has 4 to 12 carbon atoms. Specific examples of the conjugated diene compound include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, and among these, 1,3-butadiene and isoprene are preferable. Moreover, these conjugated diene compounds may be used independently and may be used in combination of 2 or more type.

  The copolymer of the present invention can be prepared by the same mechanism using any of the specific examples of the conjugated diene compound described above.

  The copolymer of the conjugated diene compound and the non-conjugated olefin does not cause a problem of lowering the molecular weight, and the weight average molecular weight (Mw) is not particularly limited. From the viewpoint of application to a polymer structural material, the polystyrene-converted weight average molecular weight (Mw) of the copolymer of the conjugated diene compound and the nonconjugated olefin is preferably 10,000 to 10,000,000. 1,000,000 is more preferable, and 50,000-600,000 is still more preferable. If Mw exceeds 10,000,000, the moldability may be deteriorated.

  The copolymer according to the present invention preferably has a conjugated diene compound-derived portion having a 1,2-adduct portion (including 3,4-adduct portion) content of 5% or less in the conjugated diene compound-derived portion. More preferably, it is 3% or less, More preferably, it is 2.5% or less.

  When the content of the 1,2-adduct portion (including the 3,4-adduct portion) of the conjugated diene compound in the conjugated diene compound-derived portion is 5% or less, the weather resistance and ozone resistance of the copolymer according to the present invention are improved. Further improvement can be achieved. Furthermore, when the content of 1,2 adducts (including 3,4 adducts) in the conjugated diene compound portion is 2.5% or less, the copolymer of the present invention further improves ozone resistance and fatigue resistance. Can be improved.

  The content of the 1,2-adduct portion (including the 3,4-adduct portion) of the conjugated diene compound in the conjugated diene compound-derived portion is an amount in the conjugated diene compound-derived portion, and is not a ratio to the entire copolymer.

  The 1,2-adduct portion (including 3,4-adduct portion) content of the conjugated diene compound portion (including the 3,4-adduct portion) Including) content) has the same meaning as the amount of 1,2-vinyl bonds when the conjugated diene compound is butadiene.

  Further, the molecular weight distribution (Mw / Mn) represented by the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) is preferably 10 or less, and more preferably 6 or less. This is because if the molecular weight distribution exceeds 10, the physical properties are not uniform.

  Here, the average molecular weight and the molecular weight distribution can be determined using polystyrene as a standard substance by gel permeation chromatography (GPC).

The copolymer of the conjugated diene compound and the non-conjugated olefin according to the present invention may be a random copolymer or a block copolymer. Alternatively, a taper copolymer may be used. The taper copolymer is a copolymer in which a random copolymer and a block copolymer are mixed, from a block portion composed of monomer units of a conjugated diene compound and a monomer unit of non-conjugated olefins. And at least one block portion (also referred to as a block structure) and a random portion (also referred to as a random structure) in which monomer units of a conjugated diene compound and a non-conjugated olefin are irregularly arranged. It is a copolymer.
Alternatively, it may be an alternating copolymer in which conjugated diene compounds and non-conjugated olefins are alternately arranged (a molecular chain structure of -ABABABAB-, where A is a conjugated diene compound and B is a non-conjugated olefin). .

The structure of the block copolymer is (AB) _x , A- (BA) _x and B- (AB) _x (where A is a block composed of monomer units of a conjugated diene compound). And B is a block portion composed of monomer units of non-conjugated olefin, and x is an integer of 1 or more. In addition, the block copolymer provided with two or more structures of (AB) or (BA) is called a multiblock copolymer.

  When the copolymer of the conjugated diene compound and the non-conjugated olefin is a block copolymer, the block portion composed of the monomer units of the non-conjugated olefin exhibits static crystallinity. The block part which shows crystallinity can suppress the fall of storage elastic modulus (G ').

-Manufacturing method of the copolymer of a conjugated diene compound and a nonconjugated olefin Next, the manufacturing method of the copolymer based on this invention is demonstrated in detail. However, the manufacturing method described in detail below is merely an example. The copolymer according to the present invention can polymerize a conjugated diene compound and a non-conjugated olefin in the presence of a polymerization catalyst or a polymerization catalyst composition.

  In the method for producing a copolymer of a conjugated diene compound and a non-conjugated olefin, a normal coordination ion polymerization catalyst is used except that a polymerization catalyst described later, or first, second, and third polymerization catalyst compositions are used. Polymerization can be carried out in the same manner as in the method for producing a polymer. The polymerization catalyst or polymerization catalyst composition used in the present invention will be described later.

  As a polymerization method, any method such as a solution polymerization method, a suspension polymerization method, a liquid phase bulk polymerization method, an emulsion polymerization method, a gas phase polymerization method, and a solid phase polymerization method can be used. Moreover, when using a solvent for a polymerization reaction, the solvent used should just be inactive in a polymerization reaction, For example, toluene, cyclohexane, normal hexane, mixtures thereof etc. are mentioned.

  A method for producing a copolymer of a conjugated diene compound and a non-conjugated olefin includes, for example, (1) a polymerization catalyst composition in a polymerization reaction system including a conjugated diene compound as a monomer and a non-conjugated olefin other than the conjugated diene compound. The components of the product may be provided separately and used as a polymerization catalyst composition in the reaction system, or (2) a polymerization catalyst composition prepared in advance may be provided in the polymerization reaction system. Moreover, (2) includes providing a metallocene complex (active species) activated by a cocatalyst. In addition, the usage-amount of the metallocene complex contained in a polymerization catalyst composition has the preferable range of 0.0001-0.01 times mole with respect to the sum total of nonconjugated olefins other than a conjugated diene compound and this conjugated diene compound.

  Moreover, in the manufacturing method of the copolymer of the conjugated diene compound and nonconjugated olefin which concerns on this invention, you may stop superposition | polymerization using polymerization terminators, such as methanol, ethanol, and isopropanol.

  In the production method according to the present invention, the polymerization reaction of the conjugated diene compound and the non-conjugated olefin is preferably performed in an atmosphere of an inert gas, preferably nitrogen gas or argon gas. The polymerization temperature of the polymerization reaction is not particularly limited, but is preferably in the range of −100 ° C. to 200 ° C., for example, and can be about room temperature. If the polymerization temperature is raised, the cis-1,4 selectivity of the polymerization reaction may be lowered. Moreover, since the pressure of the said polymerization reaction fully takes in a conjugated diene compound and a nonconjugated olefin in a polymerization reaction system, the range of 0.1-10.0 MPa is preferable. Further, the reaction time of the polymerization reaction is not particularly limited, and is preferably in the range of 1 second to 10 days, for example, but may be appropriately selected depending on conditions such as the type of monomer to be polymerized, the type of catalyst, and the polymerization temperature. it can.

  In the production method according to the present invention, when the conjugated diene compound is polymerized with a non-conjugated olefin other than the conjugated diene compound, the pressure of the non-conjugated olefin is preferably 0.1 MPa to 10 MPa. When the pressure of the non-conjugated olefin is 0.1 MPa or more, the non-conjugated olefin can be efficiently introduced into the reaction mixture. Moreover, even if the pressure of the non-conjugated olefin is increased too much, the effect of efficiently introducing the non-conjugated olefin reaches a peak, and therefore the pressure of the non-conjugated olefin is preferably 10 MPa or less.

  In the method for producing the copolymer, when the conjugated diene compound is polymerized with a non-conjugated olefin other than the conjugated diene compound, the concentration of the conjugated diene compound at the start of polymerization (mol / l) and the concentration of the non-conjugated olefin (Mol / l) preferably satisfies the relationship of the following formula. By setting the value of the concentration of the non-conjugated olefin / the concentration of the conjugated diene compound to 1 or more, the non-conjugated olefin can be efficiently introduced into the reaction mixture.

Non-conjugated olefin concentration / conjugated diene compound concentration ≧ 1.0
More preferably, it is preferable to satisfy | fill the relationship of a following formula.
Non-conjugated olefin concentration / conjugated diene compound concentration ≧ 1.3
More preferably, it is preferable to satisfy | fill the relationship of a following formula.
Non-conjugated olefin concentration / conjugated diene compound concentration ≧ 1.7

  According to the production method of the present invention, a conjugated diene compound that is a monomer is used in the same manner as in the production method of a polymer using a normal coordination ion polymerization catalyst, except that the polymerization catalyst or the polymerization catalyst composition is used. And non-conjugated olefin can be copolymerized.

-1st polymerization catalyst composition Next, the 1st polymerization catalyst composition used in the manufacturing method of the copolymer of the conjugated diene compound and nonconjugated olefin which concerns on this invention is demonstrated.
As the first polymerization catalyst composition, the following general formula (I):

（式中、Ｍは、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^Rは、それぞれ独立して無置換もしくは置換インデニルを示し、Ｒ^a〜Ｒ^fは、それぞれ独立して炭素数１〜３のアルキル基又は水素原子を示し、Ｌは、中性ルイス塩基を示し、ｗは、０〜３の整数を示す）で表されるメタロセン錯体、及び下記一般式（ＩＩ）：

(In the formula, M represents a lanthanoid element, scandium or yttrium, Cp ^R independently represents unsubstituted or substituted indenyl, and R ^{a to} R ^f each independently represents an alkyl having 1 to 3 carbon atoms. A group or a hydrogen atom, L represents a neutral Lewis base, w represents an integer of 0 to 3), and the following general formula (II):

（式中、Ｍは、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^Rは、それぞれ独立して無置換もしくは置換インデニルを示し、Ｘ'は、水素原子、ハロゲン原子、アルコキシド基、チオラート基、アミド基、シリル基又は炭素数１〜２０の炭化水素基を示し、Ｌは、中性ルイス塩基を示し、ｗは、０〜３の整数を示す）で表されるメタロセン錯体、並びに下記一般式（ＩＩＩ）：

(In the formula, M represents a lanthanoid element, scandium or yttrium, Cp ^R each independently represents an unsubstituted or substituted indenyl group, and X ′ represents a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group. , A silyl group or a hydrocarbon group having 1 to 20 carbon atoms, L represents a neutral Lewis base, and w represents an integer of 0 to 3), and the following general formula (III ):

（式中、Ｍは、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^R'は、無置換もしくは置換シクロペンタジエニル、インデニル又はフルオレニルを示し、Ｘは、水素原子、ハロゲン原子、アルコキシド基、チオラート基、アミド基、シリル基又は炭素数１〜２０の炭化水素基を示し、Ｌは、中性ルイス塩基を示し、ｗは、０〜３の整数を示し、［Ｂ］^-は、非配位性アニオンを示す）で表されるハーフメタロセンカチオン錯体からなる群より選択される少なくとも１種類の錯体を含む重合触媒組成物（以下、第一重合触媒組成物ともいう）が挙げられる。

(In the formula, M represents a lanthanoid element, scandium or yttrium, Cp ^R ′ represents an unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl, and X represents a hydrogen atom, a halogen atom, an alkoxide group or a thiolate group. , An amide group, a silyl group, or a hydrocarbon group having 1 to 20 carbon atoms, L represents a neutral Lewis base, w represents an integer of 0 to 3, and [B] ⁻ represents a non-coordinating group. A polymerization catalyst composition (hereinafter also referred to as a first polymerization catalyst composition) containing at least one complex selected from the group consisting of half metallocene cation complexes represented by

The first polymerization catalyst composition may further contain other components contained in the polymerization catalyst composition containing a normal metallocene complex, such as a promoter. Here, the metallocene complex is a complex compound in which one or more cyclopentadienyl or a derivative thereof is bonded to a central metal. In particular, a metallocene complex having one cyclopentadienyl or a derivative thereof bonded to a central metal may be referred to as a half metallocene complex.
In the polymerization reaction system, the concentration of the complex contained in the first polymerization catalyst composition is preferably in the range of 0.1 to 0.0001 mol / L.

In the metallocene complexes represented by the above general formulas (I) and (II), Cp ^R in the formula is unsubstituted indenyl or substituted indenyl. Cp ^R having an indenyl ring as a basic skeleton can be represented by C ₉ H _7-X R _X or C ₉ H _11-X R _X. Here, X is an integer of 0-7 or 0-11. In addition, each R is preferably independently a hydrocarbyl group or a metalloid group. The hydrocarbyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 8 carbon atoms. Specific examples of the hydrocarbyl group include a methyl group, an ethyl group, a phenyl group, and a benzyl group. On the other hand, examples of metalloid-based metalloids include germyl Ge, stannyl Sn, and silyl Si. The metalloid group preferably has a hydrocarbyl group. The hydrocarbyl group possessed by the metalloid group is the same as the above hydrocarbyl group. Specific examples of the metalloid group include a trimethylsilyl group. Specific examples of the substituted indenyl include 2-phenylindenyl and 2-methylindenyl. Note that the two Cp ^Rs in the general formulas (I) and (II) may be the same as or different from each other.

In the half metallocene cation complex represented by the general formula (III), Cp ^R ′ in the formula is unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl, and among these, unsubstituted or substituted indenyl It is preferable that Cp ^R ′ having a cyclopentadienyl ring as a basic skeleton is represented by C ₅ H _5-X R _X. Here, X is an integer of 0-5. In addition, each R is preferably independently a hydrocarbyl group or a metalloid group. The hydrocarbyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 8 carbon atoms. Specific examples of the hydrocarbyl group include a methyl group, an ethyl group, a phenyl group, and a benzyl group.
On the other hand, examples of metalloid group metalloids include germyl Ge, stannyl Sn, and silyl Si, and the metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group that the metalloid group has is the same as the above hydrocarbyl group. is there. Specific examples of the metalloid group include a trimethylsilyl group. Specific examples of Cp ^R 'having a cyclopentadienyl ring as a basic skeleton include the following.

（式中、Ｍｅはメチル基を示し、Ｒは水素原子、メチル基又はエチル基を示す。）
一般式（ＩＩＩ）において、上記インデニル環を基本骨格とするＣｐ^R'は、一般式（Ｉ）のＣｐ^Rと同様に定義される。好ましい例も同様である。

(In the formula, Me represents a methyl group, and R represents a hydrogen atom, a methyl group, or an ethyl group.)
In the general formula (III), Cp ^R ′ having the indenyl ring as a basic skeleton is defined in the same manner as Cp ^{R in the} general formula (I). The preferable example is also the same.

In the general formula (III), Cp ^R ′ having the fluorenyl ring as a basic skeleton can be represented by C ₁₃ H _9-X R _X or C ₁₃ H _17-X R _X. Here, X is an integer of 0-9 or 0-17. In addition, each R is preferably independently a hydrocarbyl group or a metalloid group. The hydrocarbyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 8 carbon atoms. Specific examples of the hydrocarbyl group include a methyl group, an ethyl group, a phenyl group, and a benzyl group. On the other hand, examples of metalloid-based metalloids include germyl Ge, stannyl Sn, and silyl Si. Moreover, it is preferable that a metalloid group has a hydrocarbyl group, and the hydrocarbyl group which a metalloid group has is the same as said hydrocarbyl group. Specific examples of the metalloid group include a trimethylsilyl group.

  The central metal M in the general formulas (I), (II) and (III) is a lanthanoid element, scandium or yttrium. The lanthanoid elements include 15 elements having atomic numbers 57 to 71, and any of these may be used. Preferred examples of the central metal M include samarium Sm, neodymium Nd, praseodymium Pr, gadolinium Gd, cerium Ce, holmium Ho, scandium Sc, and yttrium Y.

The metallocene complex represented by the general formula (I) contains a silylamide ligand [—N (SiR ₃ ) ₂ ]. The R groups contained in the silylamide ligand (R ^{a to} R ^f in the general formula (I)) are each independently an alkyl group having 1 to 3 carbon atoms or a hydrogen atom. Moreover, it is preferable that at least one of R ^{a to} R ^f is a hydrogen atom. By making at least one of R ^{a to} R ^f a hydrogen atom, the synthesis of the catalyst is facilitated, and the bulk height around silicon is reduced, so that non-conjugated olefin is easily introduced. From the same viewpoint, it is more preferable that at least one of R ^{a to} R ^c is a hydrogen atom and at least one of R ^{d to} R ^f is a hydrogen atom. Furthermore, a methyl group is preferable as the alkyl group.

The metallocene complex represented by the general formula (II) includes a silyl ligand [—SiX ′ ₃ ]. X ′ contained in the silyl ligand [—SiX ′ ₃ ] is a group defined in the same manner as X in the general formula (III) described below, and preferred groups are also the same.

  In the general formula (III), X is a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group, a silyl group, and a hydrocarbon group having 1 to 20 carbon atoms. Here, examples of the alkoxide group include aliphatic alkoxy groups such as a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group; a phenoxy group and 2,6-dioxy -Tert-butylphenoxy group, 2,6-diisopropylphenoxy group, 2,6-dinepentylphenoxy group, 2-tert-butyl-6-isopropylphenoxy group, 2-tert-butyl-6-neopentylphenoxy group, Examples include aryloxide groups such as 2-isopropyl-6-neopentylphenoxy group, and among these, 2,6-di-tert-butylphenoxy group is preferable.

  In the general formula (III), the thiolate group represented by X includes a thiomethoxy group, a thioethoxy group, a thiopropoxy group, a thio-n-butoxy group, a thioisobutoxy group, a thio-sec-butoxy group, and a thio-tert-butoxy group. An aliphatic thiolate group such as thiophenoxy group, 2,6-di-tert-butylthiophenoxy group, 2,6-diisopropylthiophenoxy group, 2,6-dineopentylthiophenoxy group, 2-tert-butyl- Arylthiolate groups such as 6-isopropylthiophenoxy group, 2-tert-butyl-6-thioneopentylphenoxy group, 2-isopropyl-6-thioneopentylphenoxy group, 2,4,6-triisopropylthiophenoxy group Among these, among these, 2,4,6-triisopropylthiopheno Shi group is preferred.

  In the general formula (III), examples of the amide group represented by X include aliphatic amide groups such as a dimethylamide group, a diethylamide group, and a diisopropylamide group; a phenylamide group, a 2,6-di-tert-butylphenylamide group, 2 , 6-diisopropylphenylamide group, 2,6-dineopentylphenylamide group, 2-tert-butyl-6-isopropylphenylamide group, 2-tert-butyl-6-neopentylphenylamide group, 2-isopropyl- Arylamide groups such as 6-neopentylphenylamide group and 2,4,6-tert-butylphenylamide group; bistrialkylsilylamide groups such as bistrimethylsilylamide group. Among these, bistrimethylsilylamide group is preferable.

  In the general formula (III), examples of the silyl group represented by X include trimethylsilyl group, tris (trimethylsilyl) silyl group, bis (trimethylsilyl) methylsilyl group, trimethylsilyl (dimethyl) silyl group, triisopropylsilyl (bistrimethylsilyl) silyl group, and the like. Among these, a tris (trimethylsilyl) silyl group is preferable.

  In the general formula (III), the halogen atom represented by X may be any of a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, but a chlorine atom or a bromine atom is preferred. Moreover, as a C1-C20 hydrocarbon group which X represents, specifically, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert- Linear or branched aliphatic hydrocarbon groups such as butyl group, neopentyl group, hexyl group, octyl group; aromatic hydrocarbon groups such as phenyl group, tolyl group, naphthyl group; aralkyl groups such as benzyl group, etc. Others: Examples include hydrocarbon groups containing silicon atoms such as trimethylsilylmethyl group and bistrimethylsilylmethyl group. Among these, methyl group, ethyl group, isobutyl group, trimethylsilylmethyl group and the like are preferable.

  In the general formula (III), X is preferably a bistrimethylsilylamide group or a hydrocarbon group having 1 to 20 carbon atoms.

In the general formula (III), [B] ^- The non-coordinating anion represented by, for example, a tetravalent boron anion. Specific examples of the tetravalent boron anion include tetraphenyl borate, tetrakis (monofluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis ( Pentafluorophenyl) borate, tetrakis (tetrafluoromethylphenyl) borate, tetra (tolyl) borate, tetra (xylyl) borate, (triphenyl, pentafluorophenyl) borate, [tris (pentafluorophenyl), phenyl] borate, tri Decahydride-7,8-dicarbaoundecaborate and the like can be mentioned, and among these, tetrakis (pentafluorophenyl) borate is preferable.

  The metallocene complex represented by the general formulas (I) and (II) and the half metallocene cation complex represented by the general formula (III) are further 0 to 3, preferably 0 to 1 neutral. Contains Lewis base L. Here, examples of the neutral Lewis base L include tetrahydrofuran, diethyl ether, dimethylaniline, trimethylphosphine, lithium chloride, neutral olefins, neutral diolefins, and the like. Here, when the complex includes a plurality of neutral Lewis bases L, the neutral Lewis bases L may be the same or different.

  Further, the metallocene complex represented by the general formula (I) and the formula (II) and the half metallocene cation complex represented by the general formula (III) may exist as a monomer, It may exist as a body or higher multimer.

  The metallocene complex represented by the general formula (I) includes, for example, a lanthanoid trishalide, scandium trishalide, or yttrium trishalide in a solvent, an indenyl salt (for example, potassium salt or lithium salt) and bis (trialkylsilyl). It can be obtained by reacting with an amide salt (for example, potassium salt or lithium salt). In addition, since reaction temperature should just be about room temperature, it can manufacture on mild conditions. The reaction time is arbitrary, but is about several hours to several tens of hours. The reaction solvent is not particularly limited, but is preferably a solvent that dissolves the raw material and the product. For example, toluene may be used. Below, the reaction example for obtaining the metallocene complex represented by general formula (I) is shown.

（式中、Ｘ”はハライドを示す。）
上記一般式（ＩＩ）で表されるメタロセン錯体は、例えば、溶媒中でランタノイドトリスハライド、スカンジウムトリスハライド又はイットリウムトリスハライドを、インデニルの塩（例えばカリウム塩やリチウム塩）及びシリルの塩（例えばカリウム塩やリチウム塩）と反応させることで得ることができる。なお、反応温度は室温程度にすればよいので、温和な条件で製造することができる。また、反応時間は任意であるが、数時間〜数十時間程度である。反応溶媒は特に限定されないが、原料及び生成物を溶解する溶媒であることが好ましく、例えばトルエンを用いればよい。以下に、一般式（ＩＩ）で表されるメタロセン錯体を得るための反応例を示す。

(In the formula, X ″ represents a halide.)
The metallocene complex represented by the general formula (II) includes, for example, a lanthanide trishalide, scandium trishalide, or yttrium trishalide in a solvent, an indenyl salt (for example, potassium salt or lithium salt), and a silyl salt (for example, potassium). Salt or lithium salt). In addition, since reaction temperature should just be about room temperature, it can manufacture on mild conditions. The reaction time is arbitrary, but is about several hours to several tens of hours. The reaction solvent is not particularly limited, but is preferably a solvent that dissolves the raw material and the product. For example, toluene may be used. Below, the reaction example for obtaining the metallocene complex represented by general formula (II) is shown.

（式中、Ｘ''はハライドを示す。）
上記一般式（ＩＩＩ）で表されるハーフメタロセンカチオン錯体は、例えば、次の反応により得ることができる。

(In the formula, X ″ represents a halide.)
The half metallocene cation complex represented by the general formula (III) can be obtained, for example, by the following reaction.

ここで、一般式（ＩＶ）で表される化合物において、Ｍは、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^R'は、それぞれ独立して無置換もしくは置換シクロペンタジエニル、インデニル又はフルオレニルを示し、Ｘは、水素原子、ハロゲン原子、アルコキシド基、チオラート基、アミド基、シリル基又は炭素数１〜２０の炭化水素基を示し、Ｌは、中性ルイス塩基を示し、ｗは、０〜３の整数を示す。また、一般式［Ａ］⁺［Ｂ］^-で表されるイオン性化合物において、［Ａ］⁺は、カチオンを示し、［Ｂ］^-は、非配位性アニオンを示す。

Here, in the compound represented by the general formula (IV), M represents a lanthanoid element, scandium or yttrium, and Cp ^R ′ independently represents unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl. , X represents a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group, a silyl group, or a hydrocarbon group having 1 to 20 carbon atoms, L represents a neutral Lewis base, and w represents 0 to 3 Indicates an integer. In the ionic compound represented by the general formula [A] ⁺ [B] ⁻ , [A] ⁺ represents a cation, and [B] ⁻ represents a non-coordinating anion.

Examples of the cation represented by [A] ⁺ include a carbonium cation, an oxonium cation, an amine cation, a phosphonium cation, a cycloheptatrienyl cation, and a ferrocenium cation having a transition metal. Examples of the carbonium cation include trisubstituted carbonium cations such as a triphenylcarbonium cation and a tri (substituted phenyl) carbonium cation. The tri (substituted phenyl) carbonyl cation is specifically exemplified by tri (methylphenyl). ) Carbonium cation and the like. Examples of amine cations include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, and tributylammonium cation; N, N-dimethylanilinium cation, N, N-diethylanilinium cation, N, N- Examples thereof include N, N-dialkylanilinium cations such as 2,4,6-pentamethylanilinium cation; dialkylammonium cations such as diisopropylammonium cation and dicyclohexylammonium cation. Examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation. Among these cations, N, N-dialkylanilinium cation or carbonium cation is preferable, and N, N-dialkylanilinium cation is particularly preferable.

The ionic compound represented by the general formula [A] ⁺ [B] ⁻ used for the above reaction is a compound selected and combined from the above non-coordinating anions and cations, which is N, N-dimethylaniline. Preference is given to nium tetrakis (pentafluorophenyl) borate, triphenylcarbonium tetrakis (pentafluorophenyl) borate and the like. In general formula [A] ⁺ [B] ^- ionic compounds represented by is preferably added from 0.1 to 10 mol per mol of the metallocene complex, more preferably it added about 1 molar. When the half metallocene cation complex represented by the general formula (III) is used for the polymerization reaction, the half metallocene cation complex represented by the general formula (III) may be provided as it is in the polymerization reaction system, or the compound represented by the general formula (IV) and the general formula used in the reaction [a] ⁺ [B] ^- provides an ionic compound represented separately into the polymerization reaction system, the general formula in the reaction system (III You may form the half metallocene cation complex represented by this. Further, by using a combination of the metallocene complex represented by the general formula (I) or the formula (II) and the ionic compound represented by the general formula [A] ⁺ [B] ⁻ , A half metallocene cation complex represented by the formula (III) can also be formed.

  The structures of the metallocene complexes represented by the general formulas (I) and (II) and the half metallocene cation complex represented by the general formula (III) are preferably determined by X-ray structural analysis.

  The co-catalyst that can be used in the first polymerization catalyst composition can be arbitrarily selected from components used as a co-catalyst for a polymerization catalyst composition containing a normal metallocene complex. Suitable examples of the cocatalyst include aluminoxanes, organoaluminum compounds, and the above ionic compounds. These promoters may be used alone or in combination of two or more.

  The aluminoxane is preferably an alkylaminoxan, and examples thereof include methylaluminoxane (MAO) and modified methylaluminoxane. As the modified methylaluminoxane, MMAO-3A (manufactured by Tosoh Finechem Co., Ltd.) and the like are preferable. The content of aluminoxane in the first polymerization catalyst composition is such that the element ratio Al / M between the central metal M of the metallocene complex and the aluminum element Al of the aluminoxane is about 10 to 1000, preferably about 100. It is preferable to make it.

  On the other hand, as the organoaluminum compound, the general formula AlRR′R ″ (wherein R and R ′ are each independently a C1 to C10 hydrocarbon group or a hydrogen atom, and R ″ is a C1 to C10 hydrocarbon). Is an organoaluminum compound represented by the following formula: Examples of the organoaluminum compound include trialkylaluminum, dialkylaluminum chloride, alkylaluminum dichloride, and dialkylaluminum hydride. Among these, trialkylaluminum is preferable. Examples of the trialkylaluminum include triethylaluminum and triisobutylaluminum. In addition, it is preferable that it is 2-50 times mole with respect to a metallocene complex, and, as for content of the organoaluminum compound in the said polymerization catalyst composition, it is still more preferable that it is about 10 times mole.

  Further, in the first polymerization catalyst composition, the metallocene complex represented by the general formula (I) and the formula (II) and the half metallocene cation complex represented by the above general formula (III) are respectively suitable cocatalysts. In combination, the amount of cis-1,4 bonds and the molecular weight of the resulting copolymer can be increased.

-2nd polymerization catalyst composition Next, the 2nd polymerization catalyst composition used in the manufacturing method of the copolymer of the conjugated diene compound and nonconjugated olefin which concerns on this invention is demonstrated.
As the second polymerization catalyst composition,
(A) component: a rare earth element compound or a reaction product of the rare earth element compound and a Lewis base, the rare earth element compound or the reaction product having no bond between the rare earth element and carbon,
Component (B): Contains ionic compound (B-1) composed of non-coordinating anion and cation, aluminoxane (B-2), Lewis acid, complex compound of metal halide and Lewis base, and active halogen. A polymerization catalyst composition (hereinafter also referred to as a second polymerization catalyst composition) containing at least one selected from the group consisting of at least one halogen compound (B-3) among organic compounds can be preferably mentioned.
When the second polymerization catalyst composition contains at least one of the ionic compound (B-1) and the halogen compound (B-3), the second polymerization catalyst composition further comprises:
(C) Component: The following general formula (X):
YR ¹ _a R ² _b R ³ _c (X)
(In the formula, Y is a metal selected from Group 1, Group 2, Group 12, and Group 13 of the Periodic Table, and R ¹ and R ² are the same or different and have 1 to 10 carbon atoms. R ³ is a hydrocarbon group or a hydrogen atom, and R ³ is a hydrocarbon group having 1 to 10 carbon atoms, provided that R ³ may be the same as or different from R ¹ or R ^2, and Y is a periodic table. When it is a metal selected from Group 1, a is 1 and b and c are 0, and when Y is a metal selected from Groups 2 and 12 of the Periodic Table, a and b are 1 and c is 0, and when Y is a metal selected from Group 13 of the Periodic Table, a, b and c are 1). Including.

The second polymerization catalyst composition used in the method for producing the copolymer needs to contain the component (A) and the component (B), and the polymerization catalyst composition is the ionic compound (B). -1) and at least one of the above halogen compounds (B-3),
YR ¹ _a R ² _b R ³ _c (X)
(In the formula, Y is a metal selected from Group 1, Group 2, Group 12, and Group 13 of the Periodic Table, and R ¹ and R ² are the same or different and have 1 to 10 carbon atoms. R ³ is a hydrocarbon group or a hydrogen atom, and R ³ is a hydrocarbon group having 1 to 10 carbon atoms, provided that R ³ may be the same as or different from R ¹ or R ^2, and Y is a periodic table. When it is a metal selected from Group 1, a is 1 and b and c are 0, and when Y is a metal selected from Groups 2 and 12 of the Periodic Table, a and b are 1 and c is 0, and when Y is a metal selected from Group 13 of the Periodic Table, a, b and c are 1). It is necessary to include.
Since the ionic compound (B-1) and the halogen compound (B-3) do not have a carbon atom to be supplied to the component (A), the carbon source for the component (A) is the above ( Component C) is required. In addition, even if it is a case where the said polymerization catalyst composition contains the said aluminoxane (B-2), this polymerization catalyst composition can contain the said (C) component. The second polymerization catalyst composition may contain other components, such as a promoter, contained in a normal rare earth element compound-based polymerization catalyst composition.

  The component (A) used in the second polymerization catalyst composition is a rare earth element compound or a reaction product of the rare earth element compound and a Lewis base. Here, the rare earth element compound and a reaction product of the rare earth element compound and a Lewis base are used. Does not have a bond between rare earth elements and carbon. When the rare earth element compound and the reactant do not have a rare earth element-carbon bond, the compound is stable and easy to handle. Here, the rare earth element compound is a compound containing a lanthanoid element or scandium or yttrium composed of the elements of atomic numbers 57 to 71 in the periodic table. Specific examples of the lanthanoid element include lanthanium, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium. In addition, the said (A) component may be used individually by 1 type, and may be used in combination of 2 or more type.

The rare earth element compound is preferably a divalent or trivalent salt or complex compound of a rare earth metal, and one or more coordinations selected from a hydrogen atom, a halogen atom and an organic compound residue. More preferably, the rare earth element compound contains a child. Furthermore, the reaction product of the rare earth element compound or the rare earth element compound and a Lewis base is represented by the following general formula (XI) or (XII):
M ¹¹ X ¹¹ ₂ · L ¹¹ w (XI)
M ¹¹ X ¹¹ ₃ · L ¹¹ w (XII)
(In the formula, M ¹¹ represents a lanthanoid element, scandium or yttrium, and X ¹¹ independently represents a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group, a silyl group, an aldehyde residue, a ketone residue. A group, a carboxylic acid residue, a thiocarboxylic acid residue or a phosphorus compound residue, L ¹¹ represents a Lewis base, and w represents 0 to 3).

  Specific examples of the group (ligand) bonded to the rare earth element of the rare earth element compound include a hydrogen atom; a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, a tert- Aliphatic alkoxy groups such as butoxy group; phenoxy group, 2,6-di-tert-butylphenoxy group, 2,6-diisopropylphenoxy group, 2,6-dineopentylphenoxy group, 2-tert-butyl-6- Isopropylphenoxy group, 2-tert-butyl-6-neopentylphenoxy group, 2-isopropyl-6-neopentylphenoxy group; thiomethoxy group, thioethoxy group, thiopropoxy group, thio-n-butoxy group, thioisobutoxy group, An aliphatic thiolate group such as a thio-sec-butoxy group or a thio-tert-butoxy group; Ofenoxy group, 2,6-di-tert-butylthiophenoxy group, 2,6-diisopropylthiophenoxy group, 2,6-dineopentylthiophenoxy group, 2-tert-butyl-6-isopropylthiophenoxy group, 2 Arylthiolate groups such as -tert-butyl-6-thioneopentylphenoxy, 2-isopropyl-6-thioneopentylphenoxy, 2,4,6-triisopropylthiophenoxy; dimethylamide, diethylamide, diisopropyl Aliphatic amide group such as amide group; phenylamide group, 2,6-di-tert-butylphenylamide group, 2,6-diisopropylphenylamide group, 2,6-dineopentylphenylamide group, 2-tert- Butyl-6-isopropylphenylamide group, 2-ter -Arylamide groups such as butyl-6-neopentylphenylamide group, 2-isopropyl-6-neopentylphenylamide group, 2,4,6-tert-butylphenylamide group; bistrialkylsilyl such as bistrimethylsilylamide group Amide group; silyl group such as trimethylsilyl group, tris (trimethylsilyl) silyl group, bis (trimethylsilyl) methylsilyl group, trimethylsilyl (dimethyl) silyl group, triisopropylsilyl (bistrimethylsilyl) silyl group; fluorine atom, chlorine atom, bromine atom, And halogen atoms such as iodine atom. Furthermore, residues of aldehydes such as salicylaldehyde, 2-hydroxy-1-naphthaldehyde, 2-hydroxy-3-naphthaldehyde; 2′-hydroxyacetophenone, 2′-hydroxybutyrophenone, 2′-hydroxypropiophenone, etc. Hydroxyphenone residues of: acetylacetone, benzoylacetone, propionylacetone, isobutylacetone, valerylacetone, ethylacetylacetone, etc. diketone residues; isovaleric acid, caprylic acid, octanoic acid, lauric acid, myristic acid, palmitic acid, Stearic acid, isostearic acid, oleic acid, linoleic acid, cyclopentanecarboxylic acid, naphthenic acid, ethylhexanoic acid, bivaric acid, versatic acid [trade name of Shell Chemical Co., Ltd., mixture of isomers of C10 monocarboxylic acid Synthetic acids comprised of, carboxylic acid residues such as phenylacetic acid, benzoic acid, 2-naphthoic acid, maleic acid, succinic acid; hexanethioic acid, 2,2-dimethylbutanethioic acid, decanethioic acid, thiobenzoic acid Thiocarboxylic acid residues such as dibutyl phosphate, dipentyl phosphate, dihexyl phosphate, diheptyl phosphate, dioctyl phosphate, bis (2-ethylhexyl phosphate), bis (1-methylheptyl phosphate), dilauryl phosphate Dioleyl phosphate, diphenyl phosphate, bis (p-nonylphenyl) phosphate, bis (polyethylene glycol-p-nonylphenyl) phosphate, (butyl) phosphate (2-ethylhexyl), phosphoric acid (1-methylheptyl) ) (2-ethylhexyl), phosphoric acid esters such as phosphoric acid (2-ethylhexyl) (p-nonylphenyl) Residues; monobutyl 2-ethylhexylphosphonate, mono-2-ethylhexyl 2-ethylhexylphosphonate, mono-2-ethylhexyl phenylphosphonate, mono-p-nonylphenyl 2-ethylhexylphosphonate, mono-2-ethylhexyl phosphonate, Phosphonic acid ester residues such as mono-1-methylheptyl phosphonate, mono-p-nonylphenyl phosphonate, dibutylphosphinic acid, bis (2-ethylhexyl) phosphinic acid, bis (1-methylheptyl) phosphinic acid, di Laurylphosphinic acid, dioleylphosphinic acid, diphenylphosphinic acid, bis (p-nonylphenyl) phosphinic acid, butyl (2-ethylhexyl) phosphinic acid, (2-ethylhexyl) (1-methylheptyl) phosphinic acid, (2-ethylhexyl) Phosphinic acids such as (p-nonylphenyl) phosphinic acid, butylphosphinic acid, 2-ethylhexylphosphinic acid, 1-methylheptylphosphinic acid, oleylphosphinic acid, laurylphosphinic acid, phenylphosphinic acid, p-nonylphenylphosphinic acid Can also be mentioned. In addition, these ligands may be used individually by 1 type, and may be used in combination of 2 or more type.

In the component (A) used in the second polymerization catalyst composition, examples of the Lewis base that reacts with the rare earth element compound include tetrahydrofuran, diethyl ether, dimethylaniline, trimethylphosphine, lithium chloride, neutral olefins, Diolefins and the like. Here, when the rare earth element compound reacts with a plurality of Lewis bases (in the formulas (XI) and (XII), when w is 2 or 3), the Lewis base L ¹¹ is the same or different. It may be.

  The component (B) used in the second polymerization catalyst composition is at least one compound selected from the group consisting of an ionic compound (B-1), an aluminoxane (B-2), and a halogen compound (B-3). is there. In addition, it is preferable that content of the sum total of (B) component in said 2nd polymerization catalyst composition is 0.1-50 times mole with respect to (A) component.

The ionic compound represented by the above (B-1) is composed of a non-coordinating anion and a cation, and reacts with a reaction product of the rare earth element compound or its Lewis base as the component (A) to be cationic. Examples thereof include ionic compounds capable of generating a transition metal compound. Here, as the non-coordinating anion, for example, tetraphenyl borate, tetrakis (monofluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis ( Pentafluorophenyl) borate, tetrakis (tetrafluoromethylphenyl) borate, tetra (tolyl) borate, tetra (xylyl) borate, (triphenyl, pentafluorophenyl) borate, [tris (pentafluorophenyl), phenyl] borate, tri Decahydride-7,8-dicarboundecaborate and the like can be mentioned.
On the other hand, examples of the cation include a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptatrienyl cation, and a ferrocenium cation having a transition metal. Specific examples of the carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation and tri (substituted phenyl) carbonium cation, and more specifically, as tri (substituted phenyl) carbonyl cation, Examples include tri (methylphenyl) carbonium cation, tri (dimethylphenyl) carbonium cation, and the like. Specific examples of ammonium cations include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, and tributylammonium cation (for example, tri (n-butyl) ammonium cation); N, N-dimethylanilinium N, N-dialkylanilinium cation such as cation, N, N-diethylanilinium cation, N, N-2,4,6-pentamethylanilinium cation; dialkylammonium cation such as diisopropylammonium cation and dicyclohexylammonium cation Is mentioned. Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation. Accordingly, the ionic compound is preferably a compound selected and combined from the above-mentioned non-coordinating anions and cations, specifically, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbohydrate. Preferred is nitrotetrakis (pentafluorophenyl) borate. Moreover, these ionic compounds can be used individually by 1 type, or 2 or more types can be mixed and used for them. In addition, it is preferable that it is 0.1-10 times mole with respect to (A) component, and, as for content of the ionic compound in the said 2nd polymerization catalyst composition, it is still more preferable that it is about 1 time mole.

  The aluminoxane represented by the above (B-2) is a compound obtained by bringing an organoaluminum compound and a condensing agent into contact with each other. For example, the repetition represented by the general formula: (—Al (R ′) O—) A chain aluminoxane or cyclic aluminoxane having a unit (wherein R ′ is a hydrocarbon group having 1 to 10 carbon atoms, and some of the hydrocarbon groups may be substituted with a halogen atom and / or an alkoxy group) The degree of polymerization of the unit is preferably 5 or more, and more preferably 10 or more. Here, specific examples of R ′ include a methyl group, an ethyl group, a propyl group, and an isobutyl group. Among these, a methyl group is preferable. Examples of the organoaluminum compound used as an aluminoxane raw material include trialkylaluminums such as trimethylaluminum, triethylaluminum, and triisobutylaluminum, and mixtures thereof, and trimethylaluminum is particularly preferable. For example, an aluminoxane using a mixture of trimethylaluminum and tributylaluminum as a raw material can be preferably used. The aluminoxane content in the second polymerization catalyst composition is such that the element ratio Al / M of the rare earth element M constituting the component (A) and the aluminum element Al of the aluminoxane is about 10 to 1000. It is preferable to do.

  The halogen compound represented by (B-3) is composed of at least one of a Lewis acid, a complex compound of a metal halide and a Lewis base, and an organic compound containing an active halogen, and is, for example, the component (A). By reacting with a rare earth element compound or a reaction product thereof with a Lewis base, a cationic transition metal compound, a halogenated transition metal compound, or a compound in which the transition metal center is deficient in charge can be generated. In addition, it is preferable that content of the sum total of the halogen compound in the said 2nd polymerization catalyst composition is 1-5 times mole with respect to (A) component.

Examples of the Lewis acid include boron-containing halogen compounds such as B (C ₆ F ₅ ) ₃ , Al (C ₆ F _5
3 ) Aluminum-containing halogen compounds such as ₃ can be used, and halogen compounds containing elements belonging to Group III, IV, V, VI or VIII in the periodic table can also be used. Preferably, aluminum halide or organometallic halide is used. Moreover, as a halogen element, chlorine or bromine is preferable. Specific examples of the Lewis acid include methyl aluminum dibromide, methyl aluminum dichloride, ethyl aluminum dibromide, ethyl aluminum dichloride, butyl aluminum dibromide, butyl aluminum dichloride, dimethyl aluminum bromide, dimethyl aluminum chloride, diethyl aluminum bromide, diethyl Aluminum chloride, dibutylaluminum bromide, dibutylaluminum chloride, methylaluminum sesquibromide, methylaluminum sesquichloride, ethylaluminum sesquibromide, ethylaluminum sesquichloride, dibutyltin dichloride, aluminum tribromide, antimony trichloride, antimony pentachloride, phosphorus trichloride , Pentachloride , Tin tetrachloride, titanium tetrachloride, tungsten hexachloride, etc., among which diethylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, diethylaluminum bromide, ethylaluminum sesquibromide, ethylaluminum dibromide preferable.

  The metal halide constituting the complex compound of the above metal halide and Lewis base includes beryllium chloride, beryllium bromide, beryllium iodide, magnesium chloride, magnesium bromide, magnesium iodide, calcium chloride, calcium bromide, iodine. Calcium chloride, barium chloride, barium bromide, barium iodide, zinc chloride, zinc bromide, zinc iodide, cadmium chloride, cadmium bromide, cadmium iodide, mercury chloride, mercury bromide, mercury iodide, manganese chloride, Manganese bromide, manganese iodide, rhenium chloride, rhenium bromide, rhenium iodide, copper chloride, copper iodide, silver chloride, silver bromide, silver iodide, gold chloride, gold iodide, gold bromide, etc. Of these, magnesium chloride, calcium chloride, barium chloride, manganese chloride, zinc chloride, and copper chloride are preferred. , Magnesium chloride, manganese chloride, zinc chloride, copper chloride being particularly preferred.

  Moreover, as a Lewis base which comprises the complex compound of the said metal halide and a Lewis base, a phosphorus compound, a carbonyl compound, a nitrogen compound, an ether compound, alcohol, etc. are preferable. Specifically, tributyl phosphate, tri-2-ethylhexyl phosphate, triphenyl phosphate, tricresyl phosphate, triethylphosphine, tributylphosphine, triphenylphosphine, diethylphosphinoethane, diphenylphosphinoethane, acetylacetone, benzoylacetone , Propionitrile acetone, valeryl acetone, ethyl acetylacetone, methyl acetoacetate, ethyl acetoacetate, phenyl acetoacetate, dimethyl malonate, diethyl malonate, diphenyl malonate, acetic acid, octanoic acid, 2-ethyl-hexanoic acid, olein Acid, stearic acid, benzoic acid, naphthenic acid, versatic acid, triethylamine, N, N-dimethylacetamide, tetrahydrofuran, diphenyl ether, 2-ethyl-hexyl alcohol Examples include oleyl alcohol, stearyl alcohol, phenol, benzyl alcohol, 1-decanol, and lauryl alcohol. Among these, tri-2-ethylhexyl phosphate, tricresyl phosphate, acetylacetone, 2-ethylhexanoic acid, versatic acid, 2 -Ethylhexyl alcohol, 1-decanol and lauryl alcohol are preferred.

  The Lewis base is reacted at a ratio of 0.01 to 30 mol, preferably 0.5 to 10 mol, per mol of the metal halide. When the reaction product with the Lewis base is used, the metal remaining in the polymer can be reduced.

  Examples of the organic compound containing the active halogen include benzyl chloride.

The component (C) used in the second polymerization catalyst composition is represented by the following general formula (X):
YR ¹ _a R ² _b R ³ _c (X)
[Wherein Y is a metal selected from Group 1, Group 2, Group 12 and Group 13 of the Periodic Table, and R ¹ and R ² are the same or different and have 1 to 10 carbon atoms. R ³ is a hydrocarbon group or a hydrogen atom, and R ³ is a hydrocarbon group having 1 to 10 carbon atoms, provided that R ³ may be the same as or different from R ¹ or R ^2, and Y is a periodic table. When it is a metal selected from Group 1, a is 1 and b and c are 0, and when Y is a metal selected from Groups 2 and 12 of the Periodic Table, a and b are 1 and c is 0, and when Y is a metal selected from Group 13 of the Periodic Table, a, b and c are 1]. Yes, the following general formula (Xa):
AlR ¹ R ² R ³ (Xa)
[Wherein, R ¹ and R ² are the same or different and each represents a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom, and R ³ is a hydrocarbon group having 1 to 10 carbon atoms, provided that R ³ represents the above It may be the same as or different from R ¹ or R ² ]. Examples of the organoaluminum compound of the formula (X) include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, tripentylaluminum, Trihexyl aluminum, tricyclohexyl aluminum, trioctyl aluminum; diethyl aluminum hydride, di-n-propyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl aluminum hydride, dihexyl aluminum hydride, diisohexyl hydride Aluminum, dioctyl aluminum hydride, diisooctyl aluminum hydride; ethyl aluminum dihydride, n-propyl aluminum Hydride, include isobutyl aluminum dihydride and the like, among these, triethylaluminum, triisobutylaluminum, hydrogenated diethylaluminum, hydrogenated diisobutylaluminum are preferred. The organoaluminum compound as component (C) described above can be used alone or in combination of two or more. In addition, it is preferable that it is 1-50 times mole with respect to (A) component, and, as for content of the organoaluminum compound in the said 2nd polymerization catalyst composition, it is still more preferable that it is about 10 times mole.

-Polymerization catalyst Next, the polymerization catalyst used in the manufacturing method of the copolymer of the conjugated diene compound and nonconjugated olefin which concerns on this invention is demonstrated.
As a polymerization catalyst, it is for superposition | polymerization with a conjugated diene compound and a nonconjugated olefin, and following formula (A):
R _a MX _b QY _b (A)
(In the formula, each R independently represents unsubstituted or substituted indenyl, the R is coordinated to M, M represents a lanthanoid element, scandium or yttrium, and each X independently represents 1 to 1 carbon atoms. 20 represents a hydrocarbon group, X is μ-coordinated to M and Q, Q represents a group 13 element of the periodic table, and Y independently represents a hydrocarbon group having 1 to 20 carbon atoms or A hydrogen atom, wherein Y is coordinated to Q, and a and b are 2).

  In a preferred example of the metallocene composite catalyst, the following formula (XV):

（式中、Ｍ¹は、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^Rは、それぞれ独立して無置換もしくは置換インデニルを示し、Ｒ^a及びＲ^bは、それぞれ独立して炭素数１〜２０の炭化水素基を示し、該Ｒ^a及びＲ^bは、Ｍ¹及びＡｌにμ配位しており、Ｒ^c及びＲ^dは、それぞれ独立して炭素数１〜２０の炭化水素基又は水素原子を示す）で表されるメタロセン系複合触媒が挙げられる。
上記メタロセン系重合触媒を用いることで、共役ジエン化合物と非共役オレフィンとの共重合体を製造することができる。また、上記メタロセン系複合触媒、例えば予めアルミニウム触媒と複合させてなる触媒を用いることで、共重合体合成時に使用されるアルキルアルミニウムの量を低減したり、無くしたりすることが可能となる。なお、従来の触媒系を用いると、共重合体合成時に大量のアルキルアルミニウムを用いる必要がある。例えば、従来の触媒系では、金属触媒に対して１０当量以上のアルキルアルミニウムを用いる必要があるところ、上記メタロセン系複合触媒であれば、５当量程度のアルキルアルミニウムを加えることで、優れた触媒作用が発揮される。

( ^Wherein M ¹ represents a lanthanoid element, scandium or yttrium, Cp ^R each independently represents an unsubstituted or substituted indenyl group, and R ^a and R ^b each independently have 1 to 20 carbon atoms. R ^a and R ^b are μ-coordinated to M ¹ and Al, and R ^c and R ^d each independently represents a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom. Metallocene-based composite catalysts represented by
By using the metallocene polymerization catalyst, a copolymer of a conjugated diene compound and a non-conjugated olefin can be produced. In addition, by using the metallocene composite catalyst, for example, a catalyst previously combined with an aluminum catalyst, the amount of alkylaluminum used at the time of copolymer synthesis can be reduced or eliminated. If a conventional catalyst system is used, it is necessary to use a large amount of alkylaluminum at the time of copolymer synthesis. For example, in the conventional catalyst system, it is necessary to use 10 equivalents or more of alkylaluminum with respect to the metal catalyst. Is demonstrated.

  In the metallocene composite catalyst, the metal M in the formula (A) is a lanthanoid element, scandium, or yttrium. The lanthanoid elements include 15 elements having atomic numbers 57 to 71, and any of these may be used. Preferred examples of the metal M include samarium Sm, neodymium Nd, praseodymium Pr, gadolinium Gd, cerium Ce, holmium Ho, scandium Sc, and yttrium Y.

  In the formula (A), each R is independently an unsubstituted indenyl or a substituted indenyl, and the R is coordinated to the metal M. Specific examples of the substituted indenyl group include 1,2,3-trimethylindenyl group, heptamethylindenyl group, 1,2,4,5,6,7-hexamethylindenyl group, and the like. It is done.

  In the above formula (A), Q represents a group 13 element in the periodic table, and specific examples include boron, aluminum, gallium, indium, thallium and the like.

  In the above formula (A), each X independently represents a hydrocarbon group having 1 to 20 carbon atoms, and X is μ-coordinated to M and Q. Here, as a C1-C20 hydrocarbon group, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group , Pentadecyl group, hexadecyl group, heptadecyl group, stearyl group and the like. Note that the μ coordination is a coordination mode having a crosslinked structure.

  In the formula (A), each Y independently represents a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom, and the Y is coordinated to Q. Here, as a C1-C20 hydrocarbon group, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group , Pentadecyl group, hexadecyl group, heptadecyl group, stearyl group and the like.

In the above formula (XV), the metal M ¹ is a lanthanoid element, scandium or yttrium. The lanthanoid elements include 15 elements having atomic numbers 57 to 71, and any of these may be used. Preferred examples of the metal M ¹ include samarium Sm, neodymium Nd, praseodymium Pr, gadolinium Gd, cerium Ce, holmium Ho, scandium Sc, and yttrium Y.

In the above formula (XV), Cp ^R is unsubstituted indenyl or substituted indenyl. Cp ^R having an indenyl ring as a basic skeleton can be represented by C ₉ H _7-X R _X or C ₉ H _11-X R _X. Here, X is an integer of 0-7 or 0-11. In addition, each R is preferably independently a hydrocarbyl group or a metalloid group. The hydrocarbyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 8 carbon atoms. Specific examples of the hydrocarbyl group include a methyl group, an ethyl group, a phenyl group, and a benzyl group. On the other hand, examples of metalloid group metalloids include germyl Ge, stannyl Sn, and silyl Si, and the metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group that the metalloid group has is the same as the above hydrocarbyl group. is there. Specific examples of the metalloid group include a trimethylsilyl group. Specific examples of the substituted indenyl include 2-phenylindenyl and 2-methylindenyl. Incidentally, the two Cp ^R in the formula (XV) may each be the same or different from each other.

In the above formula (XV), R ^A and R ^B each independently represent a hydrocarbon group having 1 to 20 carbon atoms, said R ^A and R are coordinated μ to M ¹及A ^l. Here, as a C1-C20 hydrocarbon group, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group , Pentadecyl group, hexadecyl group, heptadecyl group, stearyl group and the like. Note that the μ coordination is a coordination mode having a crosslinked structure.

In the above formula (XV), R ^C and R ^D are each independently a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom. Here, as a C1-C20 hydrocarbon group, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group , Pentadecyl group, hexadecyl group, heptadecyl group, stearyl group and the like.

  The metallocene composite catalyst is, for example, in a solvent in the following formula (XVI):

（式中、Ｍ²は、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^Rは、それぞれ独立して無置換もしくは置換インデニルを示し、Ｒ^E〜Ｒ^Jは、それぞれ独立して炭素数１〜３のアルキル基又は水素原子を示し、Ｌは、中性ルイス塩基を示し、ｗは、０〜３の整数を示す）で表されるメタロセン錯体を、ＡｌＲ^KＲ^LＲ^Mで表される有機アルミニウム化合物と反応させることで得られる。なお、反応温度は室温程度にすればよいので、温和な条件で製造することができる。また、反応時間は任意であるが、数時間〜数十時間程度である。反応溶媒は特に限定されないが、原料及び生成物を溶解する溶媒であることが好ましく、例えばトルエンやヘキサンを用いればよい。なお、上記メタロセン系複合触媒の構造は、¹Ｈ−ＮＭＲやＸ線構造解析により決定することが好ましい。

(In the formula, M ² represents a lanthanoid element, scandium or yttrium, Cp ^R each independently represents an unsubstituted or substituted indenyl group, and R ^{E to} R ^J each independently represents a group having 1 to 3 carbon atoms. an alkyl group or a hydrogen atom, L is a neutral Lewis base, w is, the metallocene complex represented by an integer of 0 to 3), an organoaluminum compound represented by AlR ^K R ^L R ^M It is obtained by reacting with. In addition, since reaction temperature should just be about room temperature, it can manufacture on mild conditions. The reaction time is arbitrary, but is about several hours to several tens of hours. The reaction solvent is not particularly limited, but is preferably a solvent that dissolves the raw material and the product. For example, toluene or hexane may be used. The structure of the metallocene composite catalyst is preferably determined by ¹ H-NMR or X-ray structural analysis.

In the metallocene complex represented by the above formula (XVI), Cp ^R is unsubstituted indenyl or substituted indenyl, and has the same meaning as Cp ^R in the above formula (XV). In the above formula (XVI), the metal M ² is a lanthanoid element, scandium or yttrium,
It is synonymous with the metal M ¹ in the above formula (XV).

The metallocene complex represented by the above formula (XVI) is a silylamide ligand [—N (SiR _3
2 ) Including. The R groups (R ^{E to} R ^J groups) contained in the silylamide ligand are each independently an alkyl group having 1 to 3 carbon atoms or a hydrogen atom. Moreover, it is preferable that at least one of R ^{E to} R ^J is a hydrogen atom. By making at least one of R ^{E to} R ^J a hydrogen atom, the catalyst can be easily synthesized. Furthermore, a methyl group is preferable as the alkyl group.

  The metallocene complex represented by the above formula (XVI) further contains 0 to 3, preferably 0 to 1, neutral Lewis bases L. Here, examples of the neutral Lewis base L include tetrahydrofuran, diethyl ether, dimethylaniline, trimethylphosphine, lithium chloride, neutral olefins, neutral diolefins, and the like. Here, when the complex includes a plurality of neutral Lewis bases L, the neutral Lewis bases L may be the same or different.

  In addition, the metallocene complex represented by the above formula (XVI) may exist as a monomer, or may exist as a dimer or a higher multimer.

On the other hand, the organoaluminum compound used for the production of the metallocene composite catalyst is represented by AlR ^K R ^L R ^M , where R ^K and R ^L are each independently a monovalent carbon atom having 1 to 20 carbon atoms. R ^M is a hydrogen group or a hydrogen atom, and R ^M is a monovalent hydrocarbon group having 1 to 20 carbon atoms, provided that R ^M may be the same as or different from R ^K or R ^L described above. Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group and tetradecyl group. , Pentadecyl group, hexadecyl group, heptadecyl group, stearyl group and the like.

  Specific examples of the organoaluminum compound include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, tripentylaluminum, Hexyl aluminum, tricyclohexyl aluminum, trioctyl aluminum; diethyl aluminum hydride, di-n-propyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl aluminum hydride, dihexyl aluminum hydride, diisohexyl aluminum hydride , Dioctylaluminum hydride, diisooctylaluminum hydride; ethylaluminum dihydride, n-propylaluminium Dihydride, isobutyl aluminum dihydride and the like. Among these, triethylaluminum, triisobutylaluminum, hydrogenated diethylaluminum, hydrogenated diisobutylaluminum are preferred. Moreover, these organoaluminum compounds can be used individually by 1 type, or 2 or more types can be mixed and used for them. In addition, the amount of the organoaluminum compound used for the production of the metallocene composite catalyst is preferably 1 to 50 times mole, more preferably about 10 times mole relative to the metallocene complex.

-3rd polymerization catalyst composition Next, the 3rd polymerization catalyst composition used in the manufacturing method of the copolymer of the conjugated diene compound and nonconjugated olefin which concerns on this invention is demonstrated.
The third polymerization catalyst composition is characterized in that it contains the above metallocene composite catalyst and a boron anion, and further contains other components such as a cocatalyst contained in the polymerization catalyst composition containing a normal metallocene catalyst. Etc. are preferably included. The metallocene composite catalyst and boron anion are also referred to as a two-component catalyst. According to the third polymerization catalyst composition, since the boron anion is further contained in the same manner as the above metallocene composite catalyst, it is possible to arbitrarily control the content of each monomer component in the copolymer. It becomes.

  In the third polymerization catalyst composition, specific examples of the boron anion constituting the two-component catalyst include a tetravalent boron anion. For example, tetraphenylborate, tetrakis (monofluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis (pentafluorophenyl) borate, tetrakis (tetrafluoromethyl) Phenyl) borate, tetra (tolyl) borate, tetra (xylyl) borate, (triphenyl, pentafluorophenyl) borate, [tris (pentafluorophenyl), phenyl] borate, tridecahydride-7,8-dicarboundecaborate Among these, tetrakis (pentafluorophenyl) borate is preferable.

  In addition, the said boron anion can be used as an ionic compound combined with the cation. Examples of the cation include a carbonium cation, an oxonium cation, an amine cation, a phosphonium cation, a cycloheptatrienyl cation, and a ferrocenium cation having a transition metal. Examples of the carbonium cation include trisubstituted carbonium cations such as a triphenylcarbonium cation and a tri (substituted phenyl) carbonium cation. The tri (substituted phenyl) carbonyl cation is specifically exemplified by tri (methylphenyl). ) Carbonium cation and the like. Examples of amine cations include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, and tributylammonium cation; N, N-dimethylanilinium cation, N, N-diethylanilinium cation, N, N- N, N-dialkylanilinium cations such as 2,4,6-pentamethylanilinium cation; dialkylammonium cations such as diisopropylammonium cation and dicyclohexylammonium cation. Examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation. Among these cations, N, N-dialkylanilinium cation or carbonium cation is preferable, and N, N-dialkylanilinium cation is particularly preferable. Therefore, as the ionic compound, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbonium tetrakis (pentafluorophenyl) borate and the like are preferable. In addition, it is preferable to add 0.1-10 times mole with respect to the said metallocene type composite catalyst, and, as for the ionic compound which consists of a boron anion and a cation, it is still more preferable to add about 1 time mole.

  In the third polymerization catalyst composition, it is necessary to use the metallocene composite catalyst and the boron anion, but a reaction system for reacting the metallocene catalyst represented by the formula (XVI) with an organoaluminum compound. If a boron anion is present, the metallocene composite catalyst of the above formula (XV) cannot be synthesized. Therefore, for the preparation of the third polymerization catalyst composition, it is necessary to synthesize the metallocene composite catalyst in advance, isolate and purify the metallocene composite catalyst, and then combine with the boron anion.

Examples of the third polymerization catalyst co-catalyst which can be used in the compositions, for example, other organic aluminum compound represented by AlR ^K R ^L R ^M described above, aluminoxane can be preferably used. The aluminoxane is preferably an alkylaminoxan, and examples thereof include methylaluminoxane (MAO) and modified methylaluminoxane. As the modified methylaluminoxane, MMAO-3A (manufactured by Tosoh Finechem Co., Ltd.) and the like are preferable. These aluminoxanes may be used alone or in combination of two or more.

<Content of copolymer of conjugated diene compound and non-conjugated olefin>
There is no restriction | limiting in particular as content in the rubber component of the copolymer of a conjugated diene compound and a nonconjugated olefin, Although it can select suitably according to the objective, 3 to 95 mass% is preferable. When the content of the copolymer of the conjugated diene compound and the non-conjugated olefin in the rubber component is 3% by mass or more, a sufficient elastic modulus is obtained, and when it is 95% by mass or less, the properties as rubber are obtained. It is preferable because it can be maintained.

<Rubber components other than copolymer>
There is no restriction | limiting in particular as rubber components other than the copolymer of the said conjugated diene compound and nonconjugated olefin, According to the objective, it can select suitably. For example, natural rubber, various butadiene rubber, various styrene-butadiene copolymer rubber, isoprene rubber, butyl rubber, bromide of copolymer of isobutylene and p-methylstyrene, halogenated butyl rubber, acrylonitrile butadiene rubber, chloroprene rubber, ethylene -Propylene copolymer rubber, ethylene-propylene-diene copolymer rubber, styrene-isoprene copolymer rubber, styrene-isoprene-butadiene copolymer rubber, isoprene-butadiene copolymer rubber, chlorosulfonated polyethylene, acrylic rubber , Epichlorohydrin rubber, polysulfide rubber, silicone rubber, fluorine rubber, urethane rubber, and the like. These may be used individually by 1 type and may use 2 or more types together.

<Rubber compounding agent>
As a rubber compounding agent compounded in a copolymer of a conjugated diene compound and a non-conjugated olefin, a vulcanizing agent usually compounded in rubber and various other compounding agents can be used as they are. Examples of the vulcanizing agent include sulfur, a sulfur-based compound, and an organic peroxide, and a vulcanization accelerator or a vulcanization auxiliary can be used in combination as necessary. Preferred examples include a combination of sulfur and a vulcanization accelerator, or a combination of an organic peroxide and a vulcanization aid.

<Vulcanizing agent>
As the vulcanizing agent, any of sulfur, a sulfur compound, and an organic peroxide can be used. Examples of the sulfur compound include sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, and selenium dithiocarbamate.
Among the sulfur and sulfur compounds, sulfur is preferable, and they are usually 0.1 to 20 parts by mass, preferably 0. 0 to 100 parts by mass with respect to 100 parts by mass of a rubber component containing a copolymer of a conjugated diene compound and a nonconjugated olefin. 5 to 5 parts by mass, more preferably 1.0 to 3.0 parts by mass is added.

Examples of the organic peroxide include dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2, 5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, di-t-butylperoxide, di-t-butylperoxy-3,3,5-trimethylcyclohexane, di-t-butylhydroperoxide, etc. Is mentioned. Of these, dicumyl peroxide, di-t-butyl peroxide, and di-t-butylperoxy-3,3,5-trimethylcyclohexane are preferably used. The amount of the organic peroxide used is usually 3 × 10 ^{−3 to} 5 × 10 ⁻² parts by mass, preferably 1 with respect to 100 parts by mass of the rubber component containing the copolymer of the conjugated diene compound and the nonconjugated olefin. A range of × 10 ^{−3 to} 3 × 10 ⁻² parts by mass is desirable.
Examples of the compounding agent other than the vulcanizing agent include a vulcanization accelerator, a vulcanization aid, a reinforcing material, a filler, a softening agent, a processing aid, and an antiaging agent. Moreover, when manufacturing a foaming molding, a foaming agent is added other than an above-described compounding agent, and a foaming adjuvant and a defoaming agent may be added simultaneously as needed. Furthermore, an antioxidant, a heat stabilizer, an antistatic agent, a colorant, a lubricant and the like can be blended within the range of the object of the present invention depending on the molding method and application. Next, typical vulcanizing agents and other various rubber compounding agents will be described.
<Vulcanization accelerator>
When sulfur or a sulfur compound is used as a vulcanizing agent, a combined use of a vulcanization accelerator is preferable, and the following compounds can be given as examples.
(1) N-cyclohexyl-2-benzothiazolsulfenamide, N-oxydiethylene-2-benzothiazolsulfenamide, N, N′-diisopropyl-2-benzothiazolsulfenamide, 2-mercaptobenzothiazo- , Thiazole compounds such as 2- (2,4-dinitrophenyl) mercaptobenzothiazol, 2- (2,6-diethyl-4-morpholinothio) benzothiazol, dibenzothiazyl-disulfide (2) Guanidine compounds such as diphenylguanidine, triphenylguanidine and diorthotolylguanidine (3) Aldehyde amine compounds such as acetaldehyde-aniline condensate and butyraldehyde-aniline condensate (4) Imidazolines such as 2-mercaptoimidazoline Compounds (5) Diethyl Thiourea compounds such as urea and dibutylthiourea (6) Thiuram compounds such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide (7) Dithiocarbamate salts such as zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate and tellurium diethyldithiocarbamate Compound (8) Xanthogen compounds such as zinc dibutylxanthate (9) Zinc flower.
These vulcanization accelerators are 0.1 to 20 parts by mass, preferably 0.2 to 10 parts by mass, with respect to 100 parts by mass of the rubber component containing a copolymer of a conjugated diene compound and a nonconjugated olefin. Preferably, it is added at a ratio of 0.5 to 5 parts by mass.

<Vulcanization aid>
When an organic peroxide is used as the vulcanizing agent, it is preferable to use a vulcanization aid in combination. Examples of the vulcanization aid include sulfur; quinone dioxime compounds such as p-quinone dioxime; (meth) acrylate compounds such as ethylene glycol dimethacrylate and trimethylolpropane trimethacrylate; diallyl phthalate, tri Allyl compounds such as allyl isocyanurate; other maleimide compounds and divinyl benzene. Such a vulcanization auxiliary is added at a ratio of 0.5 to 2 mol, preferably an equivalent mol, with respect to 1 mol of the organic peroxide to be used.

<Reinforcing agent>
Various carpon blacks and finely divided silicic acid can be used as a reinforcing material. Specific examples of the carbon black include carbon blacks such as SRF, GPF, FEF, MAF, HAF, ISAF, SAF, FT, and MT. These carbon blacks may be subjected to surface treatment with a silane coupling agent or the like, and the average particle size thereof is usually 10 to 100 μm, preferably 20 to 80 μm, and the tensile strength of the rubber molded body, It has the effect of increasing mechanical strength such as tear strength and wear resistance.
Carbon black is usually used in a proportion of 20 to 300 parts by mass, preferably 30 to 250 parts by mass, with respect to 100 parts by mass of a rubber component containing a copolymer of a conjugated diene compound and a nonconjugated olefin. It is not limited to. When the blending amount of carbon black is within the above range, the mechanical strength of the molded body can be increased and the weather resistance can be improved.

<Filler>
As the filler, light calcium carbonate, heavy calcium carbonate, talc, clay and the like are used. These fillers are usually blended at a ratio of 200 parts by mass or less, preferably 150 parts by mass or less, with respect to 100 parts by mass of a rubber component containing a copolymer of a conjugated diene compound and a non-conjugated olefin.

<Softener>
As the softener, a softener (oil) usually used for rubber can be used. Specific examples thereof include the following substances.
(1) Petroleum softeners such as process oil, lubricating oil, paraffin, liquid paraffin, petroleum asphalt, and petroleum jelly (2) Coal tar softeners such as coal tar and coal tar pitch (3) Castor oil, linseed oil, rapeseed (4) tall oil (5) sub (6) waxes such as beeswax, carnauba wax, lanolin (7) ricinoleic acid, palmitic acid, barium stearate, calcium stearate, laurin Fatty acids and fatty acid salts such as zinc acid (8) Synthetic polymer materials such as petroleum resins, atactic polypropylene and coumarone indene resins.
These softeners are usually used in a proportion of 100 parts by mass or less, preferably 70 parts by mass or less, based on 100 parts by mass of the rubber component containing a copolymer of a conjugated diene compound and a non-conjugated olefin. When the blending amount of the softening agent is within the above range, the processability of the rubber composition can be improved.

<Processing aid>
The processing aid used for normal rubber | gum processing can be used, The following compound can be mentioned as the example. That is, higher fatty acids such as ricinoleic acid, stearic acid, palmitic acid, lauric acid; higher fatty acid salts such as barium stearate, calcium stearate, zinc stearate; ricinoleic acid ester, stearic acid ester, palmitic acid ester, Higher fatty acid esters such as lauric acid ester. These processing aids are usually blended at a ratio of 10 parts by mass or less, preferably 1 to 5 parts by mass with respect to 100 parts by mass of a rubber component containing a copolymer of a conjugated diene compound and a nonconjugated olefin. .
<Anti-aging agent>
In the present invention, excellent heat resistance and durability are exhibited without any particular addition of an anti-aging agent, but if an appropriate amount is blended, the product life can be further extended. Antiaging agents include, for example, aromatic secondary amine stabilizers such as phenylbutylamine and N, N′-di-2-naphthyl-p-phenylenediamine; dibutylhydroxytoluene, tetrakis [methylene-3 (3,5 Phenolic stabilizers such as -di-t-butyl-4-hydroxyphenyl) cinnamate] methane; bis [2-methyl-4- (3-n-alkylthiopropionyloxy) -5-t-butylphenyl And thioether stabilizers such as sulfide; and dithiocarbamate stabilizers such as nickel dibutyldithiocarbamate.
These anti-aging agents can be used alone or in combination of two or more, and usually 0.1% with respect to 100 parts by mass of a rubber component containing a copolymer of a conjugated diene compound and a non-conjugated olefin. -5 mass parts, Preferably it can mix | blend in the ratio of 0.5-3 mass parts.

<Tire>
Tire structure A tire 100 using the rubber composition according to the present invention will be described with reference to FIG. The tire 100 includes a pair of bead cores 111 and 112, stiffeners 113 and 114, and a carcass ply 121. The stiffeners 113 and 114 extend outward from the bead cores 111 and 112 in the tire radial direction. The carcass ply 121 is folded back at the bead cores 111 and 112 outward in the tread width direction of the stiffeners 113 and 114 to form a horseshoe-shaped tire case shape. On the outer side in the tire radial direction of the carcass ply 121, a belt portion 115 including a plurality of belt layers is disposed.

  A tread portion 118 is disposed outside the belt portion 115 in the tire radial direction. In addition, an inner liner 130 is disposed as an air permeation preventive layer on the inner side in the tire radial direction of the carcass ply 121.

  The tire according to the present invention is not particularly limited as long as the rubber composition and the crosslinked rubber composition according to the present invention are used, and can be appropriately selected according to the purpose. Examples of the application site in the tire of the rubber composition or the crosslinked rubber composition according to the present invention include, but are not limited to, a tread, a base tread, a sidewall, a side reinforcing rubber, a bead filler, an inner liner, and the like. .

-Tire manufacturing method A conventional method can be used as a tire manufacturing method according to the present invention. For example, on a tire molding drum, members usually used for manufacturing a tire such as a carcass layer, a belt layer, and a tread layer made of unvulcanized rubber are sequentially laminated, and the drum is removed to obtain a green tire. Next, the desired tire can be manufactured by heat vulcanizing the green tire according to a conventional method.

<Applications other than tires>
Besides the tire application, the rubber composition or the crosslinked rubber composition according to the present invention can be used for vibration-proof rubber, seismic isolation rubber, belt (conveyor belt), rubber crawler, various hoses, foams, and the like.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.
The analysis method of ethylene-butadiene copolymer (EBR) and the evaluation method of the resin composition are shown below.
<(A) Analytical method of ethylene-butadiene copolymer (EBR)>
・ Copolymer microstructure (1,2-vinyl bond content, cis-1,4 bond content)
The microstructure of the butadiene moiety in the copolymer (1,2-vinyl bond content) was determined from the 1,2-vinyl bond component (5.0 by ¹ H-NMR spectrum (100 ° C., d-tetrachloroethane standard: 6 ppm)). -5.1 ppm) and the integral ratio of the entire butadiene bond component (5-5.6 ppm). Further, the microstructure (cis-1,4 bond amount) of the butadiene moiety in the copolymer is determined based on the ¹³ C-NMR spectrum (100 ° C., d-tetrachloroethane standard: 73.8 ppm). (26.5-27.5 ppm) and the total butadiene bond component (26.5-27.5 ppm + 31.5-32.5 ppm) were obtained from the integral ratio.

-Ethylene content of the copolymer The content (mol%) of the ethylene moiety in the copolymer was determined using a ¹³ C-NMR spectrum (100
Integration of the total ethylene bond component (28.5-30.0 ppm) and the total butadiene bond component (26.5-27.5 ppm + 31.5-32.5 ppm) by [deg.] C, d-tetrachloroethane standard: 73.8 ppm) It was calculated from the ratio.

-Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the copolymer
Gel permeation chromatography [GPC: Tosoh HLC-8121GPC / HT, column: Tosoh GMH _HR- H (S) HT × 2, detector: differential refractometer (RI)], based on monodisperse polystyrene The polystyrene equivalent weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the polymer were determined. The measurement temperature is 140 ° C.

-Block polyethylene melting temperature of copolymer (DSC peak temperature)
Differential scanning calorimetry (DSC) was performed in accordance with JIS K7121-1987, a DSC curve was drawn, and a block polyethylene melting temperature (DSC peak temperature) was measured. In order to avoid the influence of impurities such as single polymer and catalyst residue, the measurement is performed by immersing the copolymer in a large amount of tetrahydrofuran for 48 hours, removing all components dissolved in tetrahydrofuran, and then using the dried rubber component as a sample. did.

-Identification of copolymer The chain distribution was analyzed by applying the ozonolysis-GPC method in the literature ("Proceedings of the Society of Polymer Science, Vol. 42, No. 4, Page 1347"). The gel permeation chromatography was measured based on [GPC: Tosoh HLC-8121GPC / HT, column: Showa Denko GPC HT-803 × 2, detector: differential refractometer (RI), monodisperse polystyrene as a reference. The temperature was measured using 140 ° C.].

<Evaluation Method of Storage Elasticity> Storage Elasticity The storage elastic modulus (G ′) was measured at a temperature of 50 ° C., a frequency of 15 Hz, and a strain of 5% using a viscoelasticity measuring device manufactured by Rheometrics. The measurement results were expressed as an index according to the following formula, with the value of storage elastic modulus (G ′) of Comparative Example 1 described later as 100. The larger the value, the better the storage elastic modulus.
Storage modulus index = {(Storage modulus of test sample) / (Storage modulus of sample of Comparative Example 1)} × 100

<Control of maximum temperature of kneading process / control of vulcanization temperature>
The maximum temperature reached in the kneading process was controlled by the temperature of the Banbury mixer when mixing was started and the rotation speed of the kneading rotor. The vulcanization temperature was controlled by the hot press temperature. The vulcanization time was set based on the maximum torque time of the vibration rheometer test.

Production Example 1 (a) Production of ethylene-butadiene copolymer (EBR) 160 ml of a toluene solution was added to a sufficiently dried 400 ml pressure-resistant glass reactor, and then ethylene was introduced at 0.8 MPa. On the other hand, in a glove box under a nitrogen atmosphere, bis (2-phenylindenyl) gadolinium bis (dimethylsilylamide) [(2-PhC ₉ H ₆ ) ₂ GdN (SiHMe ₂ ) ₂ ] 28.5 μmol in a glass container. , 34.2 μmol of dimethylanilinium tetrakis (pentafluorophenyl) borate [Me ₂ NHPhB (C ₆ F ₅ ) ₄ ] and 1.43 mmol of diisobutylaluminum hydride were dissolved in 8 ml of toluene to obtain a catalyst solution. Thereafter, the catalyst solution was taken out from the glove box, an amount of 28.2 μmol in terms of gadolinium was added to the monomer solution, and polymerization was performed at room temperature for 5 minutes. Thereafter, 100 ml of a toluene solution containing 15.23 g (0.28 mol) of 1,3-butadiene was added while lowering the ethylene introduction pressure at a rate of 0.2 MPa / min, and polymerization was further performed for 90 minutes. After the polymerization, 1 ml of 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) (NS-5) 5% by mass of isopropanol solution was added to stop the reaction, and a copolymer with a large amount of methanol was added. Was separated and vacuum dried at 70 ° C. to obtain a copolymer A (block copolymer). The yield of the obtained copolymer A was 12.50 g.
For the obtained copolymer (a), the microstructure, ethylene content, weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), block polyethylene melting temperature (DSC peak temperature) and chain structure were determined by the above method. Measured and evaluated. The ¹³ C-NMR spectrum chart of copolymer A is shown in FIG. 2, and the DSC curve is shown in FIG.
As the microstructure of the butadiene portion in the copolymer (a), the amount of cis 1,4-bond was 98%, and the amount of 1,2-vinyl bond was 1.2%.
The weight average molecular weight Mw was 350,000, and the molecular weight distribution Mw / Mn was 2.2.
The ethylene content was 7 mol%.
The block polyethylene melting temperature (DSC peak temperature) was 121 ° C., and the chain structure was a block.

Examples 1-4, Comparative Examples 1-3
A copolymer of a conjugated diene compound and a non-conjugated olefin prepared as described above and a diene rubber are blended at an equal weight ratio (50:50), and the components shown in Table 1 are blended according to the blending content. Then, the temperature conditions in the kneading step and the vulcanization step were changed, and Examples 1 to 4 and the rubber compositions of Comparative Examples 1 to 3 were prepared. The storage elastic modulus (G ′) was measured by the above method. The results are shown in Table 1.

In addition, the following were used for each component shown in Table 1.
NR: Natural rubber Carbon black: Tokai Carbon Co., Ltd. Trademark: Seast KH (N339)
Anti-aging agent: N- (1,3-dimethylbutyl) -N′-p-phenylenediamine, manufactured by Ouchi Shinsei Chemical Co., Ltd., knock rack 6C
・ Vulcanization accelerator CZ-G: N-cyclohexyl-2-benzothiazolylsulfenamide, manufactured by Ouchi Shinsei Chemical Co., Ltd., Noxeller CZ-G
・ Vulcanization accelerator DM-P: Dibenzothiazyl disulfide, manufactured by Ouchi Shinsei Chemical Co., Ltd., Noxeller DM-P
・ Silica: Nippon Silica Kogyo Co., Ltd., Trademark: Nipsil AQ
Silane coupling agent: Degussa, trademark Si69

From the results shown in Table 1, the storage elastic moduli of the rubber compositions of Examples 1 to 4 in which the maximum temperature reached in the kneading step does not exceed the melting temperature of the non-conjugated olefin portion in the copolymer A + 20 ° C are compared. It was confirmed that it was better than the rubber compositions of Examples 1 to 3.
Furthermore, the rubber composition produced under the conditions that the temperature of the crosslinking step (vulcanization step) and the maximum temperature reached in the kneading step do not exceed the melting temperature of the non-conjugated olefin portion in the copolymer A + 20 ° C. (that is, It was confirmed that the storage elastic moduli of the rubber compositions of Examples 1 to 3 were further improved.

  Since the rubber composition of the present invention can improve the elastic modulus, it is suitably used for pneumatic tires, anti-vibration rubbers, seismic isolation rubbers, belts (conveyor belts), rubber crawlers, various hoses, foams and the like. .

100 ... tyre, 111,112 ... bead core, 113,114 ... stiffener,
115 ... Belt layer 118 ... Tread part 121 ... Carcass ply 130 ... Inner liner

Claims (15)

A method for producing a rubber composition comprising a copolymer of a conjugated diene compound and a non-conjugated olefin,
A kneading step of kneading the rubber composition;
A method for producing a rubber composition, wherein the maximum temperature reached in the kneading step does not exceed the melting temperature of the non-conjugated olefin portion in the copolymer + 20 ° C.   The method for producing the rubber composition includes a cross-linking step, and both the maximum temperature of the kneading step and the temperature of the cross-linking step do not exceed the melting temperature of the non-conjugated olefin portion in the copolymer + 20 ° C. The method for producing a rubber composition according to claim 1.   The method for producing a rubber composition according to claim 1, wherein the maximum temperature reached in the kneading step does not exceed the melting temperature of the non-conjugated olefin portion in the copolymer + 10 ° C.   The method for producing a rubber composition according to claim 2, wherein the crosslinking step is a vulcanization step using a sulfur compound.   The method for producing a rubber composition according to any one of claims 1 to 4, wherein the copolymer has a conjugated diene content of 30 mol% to 98 mol%.   The method for producing a rubber composition according to any one of claims 1 to 5, wherein the copolymer has a cis 1,4 bond amount of a conjugated diene compound portion of 50% or more.   The method for producing a rubber composition according to any one of claims 1 to 6, wherein the copolymer has a polystyrene-equivalent weight average molecular weight of 10,000 to 10,000,000.   The method for producing a rubber composition according to any one of claims 1 to 7, wherein a molecular weight distribution (Mw / Mn) of the copolymer is 10 or less.   The method for producing a rubber composition according to any one of claims 1 to 8, wherein the non-conjugated olefin is an acyclic olefin.   The method for producing a rubber composition according to claim 1 or 9, wherein the non-conjugated olefin has 2 to 10 carbon atoms.   The method for producing a rubber composition according to claim 9 or 10, wherein the non-conjugated olefin is at least one selected from the group consisting of ethylene, propylene, and 1-butene.   The method for producing a rubber composition according to claim 11, wherein the non-conjugated olefin is ethylene.   The method for producing a rubber composition according to any one of claims 1 to 12, wherein the conjugated diene compound is at least one selected from the group consisting of 1,3-butadiene and isoprene.   A rubber composition obtained by a method for producing a rubber composition comprising a copolymer of a conjugated diene compound and a non-conjugated olefin according to any one of claims 1 to 13.   A tire using a rubber composition obtained by the method for producing a rubber composition containing a copolymer of a conjugated diene compound and a non-conjugated olefin according to any one of claims 1 to 13.

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