JP2013159637A - Rubber composition and tire - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a rubber composition that has excellent abrasion resistance, crack propagation resistance and processability and consequently is preferably useful for tire etc., since conventionally a copolymer of a conjugated diene compound and a nonconjugated olefin and a rubber composition comprising the copolymer to be used for tire are investigated.SOLUTION: A rubber composition comprises a copolymer of a conjugated diene compound and a nonconjugated olefin and a polymer component having a weight-average molecular weight of 2,000-300,000.

Description

  The present invention relates to a rubber composition and a tire.

  Conventionally, a copolymer of a conjugated diene compound and a non-conjugated olefin, and a rubber composition containing the copolymer have been studied. For example, Patent Document 1 discloses a conjugated diene polymerization catalyst containing a group IV transition metal compound of the periodic table having a cyclopentadiene ring structure. As a monomer copolymerizable with this conjugated diene, ethylene is disclosed. Etc. α-olefins are exemplified. Patent Document 2 discloses an olefin polymerization catalyst comprising a transition metal compound such as a titanium compound and a cocatalyst, and discloses a copolymer of an α-olefin and a conjugated diene compound. Patent Document 3 discloses a copolymer of ethylene and butadiene synthesized using ethylene and butadiene as starting materials using a special organometallic complex as a catalyst component. Furthermore, Patent Document 4 discloses a butadiene polymer having a cis content of 92% and an ethylene content of 3% or 9%. However, a rubber composition containing a copolymer of a conjugated diene compound and a non-conjugated olefin is excellent in various physical properties, but generally has a problem of low tack (adhesiveness) and insufficient processability.

JP 2000-154210 A JP 2006-249442 A JP 2006-503141 A JP 2000-86857 A

  An object of the present invention is to provide a rubber composition having excellent wear resistance, crack growth resistance and processability. Another object of the present invention is to provide a tire having excellent wear resistance and crack growth resistance.

  In order to achieve the above object, the gist of the present invention is as follows.

  That is, the rubber composition of the present invention is characterized by comprising a copolymer of a conjugated diene compound and a non-conjugated olefin, and a polymer component having a weight average molecular weight of 2,000 to 300,000. With this configuration, it is possible to provide a rubber composition having excellent wear resistance, crack resistance, and processability.

  In the rubber composition of the present invention, the polymer component is preferably a conjugated diene polymer. By using a conjugated diene polymer as the polymer component, it is possible to further improve the wear resistance, crack resistance, and processability of the resulting rubber composition.

  In the rubber composition of the present invention, it is preferable that a mass ratio between the copolymer and the polymer component is in a range of 10/90 to 90/10. With this configuration, the rubber composition obtained can be excellent in fracture resistance and weather resistance, and can be further improved in workability.

  The rubber composition of the present invention preferably further contains natural rubber. Natural rubber has good compatibility with the copolymer of the conjugated diene compound and the non-conjugated olefin, and further includes a natural rubber, which further improves the crack resistance of the resulting rubber composition. be able to.

  In the rubber composition of the present invention, the cis 1,4-bond amount of the conjugated diene compound-derived portion in the copolymer is preferably more than 50%. When the amount of cis 1,4-bond is more than 50%, the glass transition temperature of the copolymer is lowered, so that the resulting rubber composition can be further improved in crack resistance.

  In the rubber composition of the present invention, the copolymer preferably has a weight average molecular weight of 10,000 to 10,000,000. When the weight average molecular weight of the polymer is 10,000 to 10,000,000, the processability of the resulting rubber composition can be further improved.

  The tire of the present invention comprises a rubber member using any one of the above rubber compositions. The tire is excellent in wear resistance and crack growth resistance.

  According to the present invention, it is possible to provide a rubber composition having excellent wear resistance, crack growth resistance, and processability. Further, according to the present invention, it is possible to provide a tire having both excellent wear resistance and crack resistance.

  Hereinafter, the present invention will be described in detail by exemplifying embodiments thereof. The rubber composition of the present invention comprises a copolymer of a conjugated diene compound and a non-conjugated olefin, and a polymer component having a weight average molecular weight of 2,000 to 300,000. Moreover, the rubber composition of this invention can also contain components, such as another polymer component, a reinforcing filler, and a crosslinking agent, as needed.

(Copolymer of conjugated diene compound and non-conjugated olefin)
The copolymer of the conjugated diene compound and the non-conjugated olefin is not particularly limited, but the cis 1,4-bond amount of the conjugated diene compound-derived portion (conjugated diene portion) is preferably more than 50%. More preferably, it is more than 5%, still more preferably more than 92%. By making the amount of cis 1,4-bond of the conjugated diene compound-derived portion (conjugated diene portion) more than 50%, the rubber composition of the present invention can be further improved in crack resistance. The amount of cis 1,4-bond is the amount in the portion derived from the conjugated diene compound and is not a ratio to the whole copolymer.

  The non-conjugated olefin used as the monomer is a non-conjugated olefin other than the conjugated diene compound, and has excellent heat resistance and reduces the proportion of double bonds in the main chain of the copolymer and controls crystallinity. This makes it possible to increase the degree of design freedom as an elastomer.

  The non-conjugated olefin is preferably an acyclic olefin, and the non-conjugated olefin is preferably an α-olefin having 2 to 10 carbon atoms. Since the α-olefin has a double bond at the α-position of the olefin, copolymerization with the conjugated diene can be performed efficiently. 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.

  In the copolymer of the conjugated diene compound and the non-conjugated olefin, the content of the non-conjugated olefin (part derived from the non-conjugated olefin) is preferably 5 to 95 mol%, and more preferably 5 to 90 mol%. 5 to 80 mol% is more preferable. By setting the content of the non-conjugated olefin to 5 mol% or more, it is excellent in weather resistance, and by setting it to 95 mol% or less, a rubber composition excellent in heat resistance can be obtained without causing layer separation.

  The conjugated diene compound preferably has 4 to 8 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.

  In addition, in the case where a block portion composed of a monomer unit of a non-conjugated olefin is provided, mechanical properties such as breaking strength are improved because static crystallinity is exhibited.

  Such a copolymer does not cause a problem of lowering the molecular weight, and its weight average molecular weight is not particularly limited, but from the viewpoint of application to a polymer structure material, the weight of the copolymer is not limited. The average molecular weight is preferably 10,000 to 10,000,000, more preferably 10,000 to 1,000,000, and still more preferably 2,000 to 600,000. When Mw is 10,000,000 or less, the processability of the rubber composition can be further improved.

  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. When the molecular weight distribution is 10 or less, the physical properties can be made 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).

  In the copolymer of the conjugated diene compound and the non-conjugated olefin of the present invention, it is preferable that the non-conjugated olefin is not continuously arranged.

Next, the manufacturing method of the copolymer of the said conjugated diene compound and a nonconjugated olefin is demonstrated in detail. However, the manufacturing method described in detail below is merely an example.
The conjugated diene compound-nonconjugated olefin copolymer includes a step of polymerizing a conjugated diene compound and a nonconjugated olefin in the presence of the polymerization catalyst or polymerization catalyst composition shown below. 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.

  According to the above production method, except that the polymerization catalyst or the polymerization catalyst composition is used, the monomer conjugated diene compound and the non-conjugated olefin are produced in the same manner as in the production method of the polymer using the normal coordination ion polymerization catalyst. It can be copolymerized.

（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）：

（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）：

（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、該重合触媒組成物は、更に、通常のメタロセン錯体を含む重合触媒組成物に含有される他の成分、例えば助触媒等を含んでいてもよい。ここで、メタロセン錯体は、一つ又は二つ以上のシクロペンタジエニル又はその誘導体が中心金属に結合した錯体化合物であり、特に、中心金属に結合したシクロペンタジエニル又はその誘導体が一つであるメタロセン錯体を、ハーフメタロセン錯体と称することがある。なお、重合反応系において、第一重合触媒組成物に含まれる錯体の濃度は０．１〜０．０００１ｍｏｌ／Ｌの範囲であることが好ましい。 <First polymerization catalyst composition>
The polymerization catalyst composition includes the following general formula (I):

(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):

(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 ):

(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) comprising at least one complex selected from the group consisting of a half metallocene cation complex represented by The product 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, and in particular, one cyclopentadienyl or a derivative thereof bonded to the central metal. A certain metallocene complex may be called 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 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. Note that the two Cp ^Rs in the general formulas (I) and (II) may be the same as or different from each other.

（式中、Ｒは水素原子、メチル基又はエチル基を示す。） 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.

(In the formula, 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), and preferred examples thereof are 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 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.

  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 thiosec-butoxy group, a thiotert-butoxy group and the like Group thiolate group; thiophenoxy group, 2,6-di-tert-butylthiophenoxy group, 2,6-diisopropylthiophenoxy group, 2,6-dineopentylthiophenoxy group, 2-tert-butyl-6-isopropyl Arylthiolate groups such as thiophenoxy group, 2-tert-butyl-6-thioneopentylphenoxy group, 2-isopropyl-6-thioneopentylphenoxy group, 2,4,6-triisopropylthiophenoxy group, etc. Among these, 2,4,6-triisopropylthiophenoxy group 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-tri-tert-butylphenylamide group; and bistrialkylsilylamide groups such as bistrimethylsilylamide group. Among these, bistrimethylsilylamide Groups are preferred.

  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.

  Moreover, 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, a dimer or It may be present as a higher multimer.

（式中、Ｘ''はハライドを示す。） 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.

(In the formula, X ″ represents a halide.)

（式中、Ｘ''はハライドを示す。） The metallocene complex represented by the general formula (II) includes, for example, a lanthanoid trishalide, a scandium trishalide, or a 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.

(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.

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- 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-C10 hydrocarbon group or a hydrogen atom, and R ″ is a C1-C10 An organoaluminum compound represented by (a hydrocarbon group) is preferable. 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 above 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 each used as an appropriate promoter. By combining, the amount of cis-1,4 bonds and the molecular weight of the resulting copolymer can be increased.

<Second polymerization catalyst composition>
In addition, as the polymerization catalyst composition,
Component (a): 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): includes 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 Preferable examples include 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
When the second polymerization catalyst composition contains at least one of an ionic compound (b-1) and a halogen compound (b-3), the polymerization catalyst composition further comprises:
(C) Component: 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 each a hydrocarbon group having 1 to 10 carbon atoms or R ³ is a hydrogen atom, and R ³ is a hydrocarbon group having 1 to 10 carbon atoms, provided that R ¹ , R ² and R ³ may be the same or different from each other, and Y is group 1 of the periodic table 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 selected. 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]. Cost.

  Since the ionic compound (b-1) and the halogen compound (b-3) have no carbon atom to be supplied to the component (a), the carbon source for the component (a) is the above ( c) A component is required. In addition, even if the said polymerization catalyst composition is a case where the said aluminoxane (b-2) is included, 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. In the polymerization reaction system, the concentration of the component (a) contained in the second polymerization catalyst composition is preferably in the range of 0.1 to 0.0001 mol / l.

  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 reaction of the rare earth element compound and the rare earth element compound with a Lewis base is performed. The object does not have a bond between rare earth element 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 each 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, Represents a ketone residue, 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, thio aliphatic thiolate groups such as sec-butoxy group and thio-tert-butoxy group; Noxy 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-tert-butyl Arylamide groups such as ru-6-neopentylphenylamide group, 2-isopropyl-6-neopentylphenylamide group, 2,4,6-tert-butylphenylamide group; bistrialkylsilylamides such as bistrimethylsilylamide group Groups: silyl groups 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, iodine And halogen atoms such as atoms. 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, Residues of phosphonic acid esters such as mono-1-methylheptyl phosphonate and 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. These ligands may be used alone or in combination of two or more.

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 aluminoxane 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 content of the aluminoxane 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. By reacting with a certain 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.

As the Lewis acid, boron-containing halogen compounds such as B (C ₆ F ₅ ) ₃ and aluminum-containing halogen compounds such as Al (C ₆ F ₅ ) ₃ can be used. A halogen compound containing an element belonging to the group V, VI or VIII 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 each a hydrocarbon group having 1 to 10 carbon atoms or R ³ is a hydrogen atom, and R ³ is a hydrocarbon group having 1 to 10 carbon atoms, provided that R ¹ , R ² and R ³ may be the same or different from each other, and Y is group 1 of the periodic table 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 selected. Is 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]. General formula (Xa):
AlR ¹ R ² R ³ (Xa)
[Wherein, R ¹ and R ² are 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 ¹ , R ² , R ³ Are preferably the same or different from each other]. 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 the component (c) described above can be used singly 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 said 2nd polymerization catalyst composition, it is still more preferable that it is about 10 times mole.

<Polymerization catalyst>
The polymerization catalyst is for polymerization of a conjugated diene compound and a non-conjugated olefin, and has the following formula (A):
R _a MX _b QY _b (A)
[In the formula, each R independently represents an unsubstituted or substituted indenyl, the R is coordinated to M, M represents a lanthanoid element, scandium or yttrium; 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].

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

[ ^Wherein , M ¹ represents a lanthanoid element, scandium or yttrium, Cp ^R 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 composite catalysts represented by

<Metalocene composite catalyst>
Hereinafter, the metallocene composite catalyst will be described in detail. The metallocene composite catalyst includes a lanthanoid element, a rare earth element of scandium or yttrium, and a Group 13 element of the periodic table, and has the following formula (A):
R _a MX _b QY _b (A)
[In the formula, each R independently represents an unsubstituted or substituted indenyl, the R is coordinated to M, M represents a lanthanoid element, scandium or yttrium; 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.] 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. If the metallocene composite catalyst is used, an excellent catalytic action can be obtained by adding about 5 equivalents of alkylaluminum. 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.

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

(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, and has the same meaning as the metal M ¹ in the above formula (XV).

The metallocene complex represented by the above formula (XVI) contains a silylamide ligand [—N (SiR ₃ ) ₂ ]. 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.

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

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.

<Third polymerization catalyst composition>
The polymerization catalyst composition may be one containing the metallocene composite catalyst and a boron anion (hereinafter, also referred to as a third polymerization catalyst composition). Furthermore, it is preferable that other components contained in the polymerization catalyst composition containing a normal metallocene-based catalyst, such as a promoter, are 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 metallocene composite catalyst, the content of each monomer component in the copolymer can be arbitrarily controlled. Become.

  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. In addition, these aluminoxanes may be used individually by 1 type, and may be used in combination of 2 or more type.

  In the method for producing a copolymer, as described above, polymerization is carried out in the same manner as in the method for producing a polymer using a normal coordination ion polymerization catalyst, except that the polymerization catalyst or the polymerization catalyst composition is used. be able to. Here, in the copolymer production method, for example, (1) a component of the polymerization catalyst composition is separately provided 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 polymerization catalyst composition may be used 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.

  In the method for producing a copolymer, the polymerization may be stopped using a polymerization terminator such as methanol, ethanol, or isopropanol.

  In the method for producing a copolymer, 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. 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 can be appropriately selected depending on conditions such as the type of monomer to be polymerized, the type of catalyst, and the polymerization temperature.

  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 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) means the following formula:
Non-conjugated olefin concentration / conjugated diene compound concentration ≧ 1.0
It is preferable to satisfy the relationship:
Non-conjugated olefin concentration / conjugated diene compound concentration ≧ 1.3
And more preferably the following formula:
Non-conjugated olefin concentration / conjugated diene compound concentration ≧ 1.7
Satisfy the relationship. 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.

(Weight average molecular weight is 2,000 to 300,000 polymer component)
As the polymer component having a weight average molecular weight of 2,000 to 300,000 used in the present invention, polymers used in ordinary rubber compositions such as isoprene rubber, butadiene rubber, chloroprene rubber and styrene-butadiene copolymer are used. Conjugated diene polymers such as polymer rubber, styrene-isoprene copolymer rubber, styrene-isoprene-butadiene rubber copolymer rubber, acrylonitrile-butadiene rubber, ethylene-propylene copolymer rubber, urethane rubber, silicone rubber , Etc., and having a weight average molecular weight of 2,000 to 300,000. By including such a polymer component, a rubber composition having excellent processability can be obtained. The above-described polymer component usable in the present invention does not include a copolymer of a conjugated diene compound and a non-conjugated olefin. From the viewpoint of crack resistance and processability of the resulting rubber composition, a conjugated diene polymer is preferred. In the present invention, the conjugated diene polymer refers to a homopolymer of a conjugated diene compound or a copolymer using a conjugated diene compound as a monomer (provided that the conjugated diene compound and a non-conjugated olefin are copolymerized). Means a polymer). Among these, butadiene rubber and styrene-butadiene copolymer rubber are particularly preferable from the viewpoint of the effect of the present invention. The styrene-butadiene copolymer rubber is preferably composed of 5 to 80% by mass of styrene (styrene content), and the 1,2-vinyl bond content is preferably 10 to 80%.

  When the weight average molecular weight of the polymer component is less than 2,000, the storage elastic modulus is low and the loss factor is high. For example, when used in a tire, the steering stability is lowered and the loss is high. On the other hand, when it exceeds 300,000, the processability of the resulting rubber composition deteriorates. The weight average molecular weight of the polymer component is preferably 20,000 to 200,000, more preferably 20,000 to 150,000, and most preferably 50,000 to 150,000 from the viewpoint of effects.

  In the present invention, the mass ratio of the copolymer of the conjugated diene compound and the non-conjugated olefin and the polymer component having a weight average molecular weight of 2,000 to 300,000 is within the range of 10/90 to 90/10. It is preferable that it is within a range of 25/75 to 75/25. When the mass ratio is 10/90 or more, the resulting rubber composition has excellent weather resistance, and when it is 90/10 or less, the obtained rubber composition has excellent fracture resistance. , Workability will be better.

(Other polymer components)
Further, in the rubber composition of the present invention, as other polymer components, polymers used in ordinary rubber compositions, such as the components listed above, and the weight average molecular weight is less than 2,000, or More than 300,000 can also be included. Among these, a conjugated diene polymer is preferable, and natural rubber is preferably included. Natural rubber has good compatibility between the conjugated diene compound and the copolymer of the non-conjugated olefin, and by including the natural rubber, the resulting rubber composition can be made more resistant to crack propagation. . As conjugated diene polymers other than natural rubber, isoprene rubber, butadiene rubber, chloroprene rubber, styrene-butadiene copolymer rubber, styrene-isoprene copolymer rubber, styrene-isoprene-butadiene rubber copolymer rubber, Examples include, but are not limited to, acrylonitrile-butadiene rubber.

(Reinforcing filler)
A reinforcing filler can be blended with the rubber composition as necessary. Examples of the reinforcing filler include carbon black and inorganic filler, and at least one selected from carbon black and inorganic filler is preferable. The inorganic filler is not particularly limited and may be appropriately selected depending on the intended purpose.For example, silica, aluminum hydroxide, clay, alumina, talc, mica, kaolin, glass balloon, glass beads, calcium carbonate, Examples thereof include magnesium carbonate, magnesium hydroxide, calcium carbonate, magnesium oxide, titanium oxide, potassium titanate, and barium sulfate. These may be used individually by 1 type and may use 2 or more types together. In addition, when using an inorganic filler, you may use a silane coupling agent suitably.

  There is no restriction | limiting in particular as content of the said reinforcing filler, Although it can select suitably according to the objective, From a viewpoint of the effect of a reinforcing filler, a rubber component (however, a weight average molecular weight is 2,000-300). 5 parts by mass to 200 parts by mass is preferable with respect to 100 parts by mass). If the content of the reinforcing filler is less than 5 parts by mass, the effect of adding the reinforcing filler may not be seen so much, and if it exceeds 200 parts by mass, the rubber filler is mixed with the reinforcing filler. There is a tendency that it does not get caught, and the performance as a rubber composition may be reduced.

(Crosslinking agent)
The rubber composition of the present invention can contain a cross-linking agent appropriately selected according to the purpose. Examples of the crosslinking agent include a sulfur-based crosslinking agent, an organic peroxide-based crosslinking agent, an inorganic crosslinking agent, a polyamine crosslinking agent, a resin crosslinking agent, a sulfur compound-based crosslinking agent, and an oxime-nitrosamine-based crosslinking agent. Sulfur-based crosslinking agents are preferred.

  There is no restriction | limiting in particular as content of the said crosslinking agent, Although it can select suitably according to the objective, 100 mass parts of rubber components (however, a weight average molecular weight is excluding 2,000-300,000 polymer components). On the other hand, 0.1 to 20 parts by mass is preferable from the viewpoint of the effect of the crosslinking agent. When the content of the cross-linking agent is less than 0.1 parts by mass, the cross-linking may not proceed sufficiently. When the content exceeds 20 parts by mass, the cross-linking tends to proceed during kneading, and vulcanization is performed. The physical properties of the material may be impaired.

(Other ingredients)
If necessary, the rubber composition may contain a vulcanization accelerator, a reinforcing agent, a softening agent, a vulcanization aid, a colorant, a flame retardant, a lubricant, a foaming agent, a plasticizer, a processing aid, an antioxidant, and aging. Known agents such as an inhibitor, an anti-scorch agent, an ultraviolet ray inhibitor, an antistatic agent, an anti-coloring agent, and other compounding agents can be used depending on the intended use.

  The rubber composition of the present invention can be produced by kneading these components with, for example, a Banbury mixer, a kneader or the like.

(tire)
The tire of the present invention is not particularly limited as long as it includes a rubber member using the rubber composition of the present invention, and can be appropriately selected according to the purpose. The rubber composition is usually used after vulcanization. The application site of the rubber member using the rubber composition of the present invention is not particularly limited, and examples thereof include treads, sidewalls, side reinforcing rubbers, and bead fillers. Among these, treads and sidewalls are preferable. . As a method for manufacturing the tire, a conventional method can be used. For example, on a tire molding drum, members normally used for manufacturing tires such as carcass, belt, and tread made of unvulcanized rubber and / or cords 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.

  The tire of the present invention thus obtained is excellent in wear resistance and crack growth resistance.

(Applications other than tires)
The rubber composition of the present invention can be used for vibration-proof rubber, seismic isolation rubber, belt (conveyor belt), rubber crawler, various hoses and the like in addition to tire applications.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples.

-Example of production of copolymer of conjugated diene compound and non-conjugated olefin-
After adding 325 mL of a toluene solution containing 13.58 g (0.25 mol) of 1,3-butadiene to a sufficiently dried 400 mL pressure-resistant glass reactor, ethylene was introduced at 0.4 MPa. On the other hand, in a glove box under a nitrogen atmosphere, bis (2-phenylindenyl) gadolinium bis (dimethylsilylamide) [(2-PhC ₉ H ₆ ) 2GdN (SiHMe ₂ ) ₂ ] 18.0 μmol in a glass container, 36.0 μmol of dimethylanilinium tetrakis (pentafluorophenyl) borate (Me ₂ NHPhB (C ₆ F ₅ ) ₄ ) and 0.90 mmol of diisobutylaluminum hydride were charged and dissolved in 10 ml of toluene to obtain a catalyst solution. Thereafter, the catalyst solution was taken out from the glove box, an amount of 17.5 μmol in terms of gadolinium was added to the monomer solution, and polymerization was performed at room temperature for 180 minutes. After the polymerization, 1 mL of 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) (NS-5) 5% by mass 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. The yield of the obtained copolymer A was 12.00 g.

  Regarding the copolymer A obtained as described above, the weight average molecular weight, molecular weight distribution, cis-1,4 bond amount, and ethylene content were measured and evaluated by the following methods.

-Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)
Using gel permeation chromatography [GPC: Tosoh HLC-8121GPC / HT, column: Tosoh GMH _HR- H (S) HT × 2, detector: differential refractometer (RI)], measuring temperature 140 The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) in terms of polystyrene of the polymer were determined on the basis of monodisperse polystyrene at ° C.
The weight average molecular weight (Mw) of the copolymer A was 338,000, and the molecular weight distribution (Mw / Mn) was 1.9.

-Cis-1,4 bond amount The microstructure of the butadiene moiety in the copolymer was measured by ¹ H-NMR spectrum (bond amount of 1,2-vinyl bond) and ¹³ C-NMR spectrum (cis-1,4 bond and It was determined from the integral ratio of the trans-1,4 bond content ratio). The calculated value of cis-1,4 bond amount (%) of copolymer A was 98%.

-Ethylene content The content (mol%) of the ethylene part in the copolymer was determined by the ¹³ C-NMR spectrum (100 ° C, d-tetrachloroethane standard: 73.8 ppm) as a whole of the ethylene-bonded component (28.5- 30.0 ppm) and the integral ratio of the entire butadiene bond component (26.5-27.5 ppm + 31.5-32.5 ppm). The content of the ethylene portion of the copolymer A was 11 mol%.

-Example of production of polymer component having a weight average molecular weight of 2,000 to 300,000-
In an 800 mL pressure-resistant glass container that has been dried and purged with nitrogen, a cyclohexane solution of butadiene (16%) and a cyclohexane solution of styrene (21%) are charged in amounts of 40 g of butadiene monomer and 10 g of styrene monomer. Then, 0.66 mmol of 2,2-ditetrahydrofurylpropane was injected, and 1.32 mmol of n-butyllithium (BuLi) was added thereto, followed by polymerization in a hot water bath at 50 ° C. for 1.5 hours. did. The polymerization conversion was almost 100%. Thereafter, 0.5 mL of a 5 wt% isopropanol solution of 2,6-di-t-butyl-p-cresol (BHT) was further added to the polymerization system to stop the reaction. Then, the styrene-butadiene copolymer rubber (SBR-3) was obtained by drying according to a conventional method.

  Three other types of styrene-butadiene copolymer rubbers (SBR-1, SBR-2, SBR-4) were produced in the same manner except that the amount of n-butyllithium (BuLi) was changed. With respect to the four types of SBR, the weight average molecular weight, styrene amount, and 1,2-vinyl bond amount were measured and evaluated by the following methods. The results are shown in Table 1.

-Weight average molecular weight (Mw)
It measured by the method similar to the copolymer of a conjugated diene compound and a nonconjugated olefin.

-Styrene amount St (% by mass)
The following formula was used for calculation.
Charge amount of styrene monomer (g) / (charge amount of styrene monomer (g) + charge amount of butadiene monomer (g)) × 100

-1,2-vinyl bond amount Vi (%)
^It was determined by ¹ H-NMR spectrum.

(Examples and comparative examples)
Using the copolymer A and SBR1 to SBR4, rubber compositions having the composition shown in Table 2 were prepared according to a conventional method. The obtained unvulcanized rubber composition was appropriately vulcanized and molded, and evaluated for wear resistance, crack resistance, and workability by the following methods.

・ Abrasion resistance (PICO wear resistance)
For a vulcanized rubber obtained by vulcanizing the rubber composition at 160 ° C. for 15 minutes, PICO (pico) abrasion was measured at room temperature in accordance with ASTM-D-2228. did. The results are shown in Table 2. It shows that it is excellent in abrasion resistance, so that an index value is large.

・ Crack Propagation Resistance A 0.5 mm crack was made in the center of a JIS No. 3 test piece obtained by vulcanizing a rubber composition at 160 ° C. for 15 minutes, and repeatedly fatigued at 50 to 100% strain at room temperature. The number of times until it was measured. The value at each strain was determined and the average value was used. Comparative example 1 was taken as 100 and displayed as an index. The results are shown in Table 2. It shows that it is excellent in crack progress resistance, so that an index value is large.

Processability Using a 3-inch roll, a rubber composition was molded at 100 ° C. to prepare a test piece. The surface of the test piece after molding was evaluated according to the following criteria. The results are shown in Table 2.
○: The surface is a glossy smooth surface.
X: Shrinkage is observed after the roll and the surface is rough.

* 1 Process oil * 2 Toast carbon, Seast 9
* 3 New Nippon Rika Co., Ltd., stearic acid 50S
* 4 Nocrack 6C (N- (1,3-dimethylbutyl) -N'-p-phenylenediamine) manufactured by Ouchi Shinsei Chemical Industry
* 5 Nouchira CZ-G (N-cyclohexyl-2-benzothiazolylsulfenamide), manufactured by Ouchi Shinsei Chemical Industry
* 6 Nouchira DM-P (dibenzothiazyl disulfide) manufactured by Ouchi Shinsei Chemical Industry

  As is apparent from the results in Table 2, Examples 1 to 4 including a copolymer of a conjugated diene compound and a non-conjugated olefin and a polymer component having a weight average molecular weight of 2,000 to 300,000 are Compared to Comparative Examples 1 and 2 that do not contain No. 1, the wear resistance and crack resistance were excellent, and the workability was also good, and the effects of the present invention could be confirmed.

  On the other hand, Comparative Example 1 did not contain a polymer component having a weight average molecular weight of 2,000 to 300,000, and was inferior in all of wear resistance, crack resistance, and workability as compared with Examples. In Comparative Example 2, oil was used in place of the polymer component, and the workability was good, but the wear resistance and crack growth resistance were inferior to those of the Examples. It is considered that the reason why the crack resistance is poor when oil is used is that the oil inhibits the crystallinity of the copolymer of the conjugated diene compound and the non-conjugated olefin.

Claims (7)

  A rubber composition comprising a copolymer of a conjugated diene compound and a non-conjugated olefin, and a polymer component having a weight average molecular weight of 2,000 to 300,000.   The rubber composition according to claim 1, wherein the polymer component is a conjugated diene polymer.   The rubber composition according to claim 1 or 2, wherein a mass ratio of the copolymer to the polymer component is in a range of 10/90 to 90/10.   Furthermore, natural rubber is included, The rubber composition in any one of Claims 1-3 characterized by the above-mentioned.   The rubber composition according to any one of claims 1 to 4, wherein the cis 1,4-bond amount of the conjugated diene compound-derived portion in the copolymer is more than 50%.   The rubber composition according to any one of claims 1 to 5, wherein the copolymer has a weight average molecular weight of 10,000 to 10,000,000.   A tire comprising a rubber member using the rubber composition according to claim 1.