JP2012131965A - Copolymer and method for producing the same, and rubber composition, crosslinked rubber composition, and tire - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a copolymer of a conjugated diene compound and a nonconjugated olefin, which copolymer is used for production of a rubber excellent in wettability and low-temperature properties, wherein the 1,2-vinyl bond amount in the conjugated diene compound moiety is ≥10 mol%; a method for producing the copolymer; a rubber composition containing the copolymer; a crosslinked rubber composition obtained by crosslinking the rubber composition; and a tire using the rubber composition or the crosslinked rubber composition.SOLUTION: The copolymer of the conjugated diene compound and the nonconjugated olefin is provided, wherein the 1,2-vinyl bond amount in the conjugated diene compound moiety is ≥10 mol%. The method for producing a copolymer includes a step of polymerizing a conjugated diene compound and a nonconjugated olefin in the presence of a scandium compound or a reaction product of a scandium compound and a Lewis base.

Description

  The present invention relates to a copolymer of a conjugated diene compound and a non-conjugated olefin, a method for producing the copolymer, a rubber composition, a crosslinked rubber composition, and a tire, and in particular, excellent wettability and low temperature characteristics. Used in the production of rubber, a copolymer having a conjugated diene compound portion having a 1,2-vinyl bond content of 10 mol% or more, a method for producing the copolymer, and a rubber composition containing the copolymer , A crosslinked rubber composition obtained by crosslinking the rubber composition, and a tire using the rubber composition or the crosslinked rubber composition.

When two or more types of monomers are polymerized in the same reaction system, a copolymer containing those monomer units as repeating units in one polymer chain is produced. However, the amount of 1,2-vinyl bonds in the conjugated diene compound portion in the copolymer obtained by the polymerization reaction of the conjugated diene compound and the non-conjugated olefin has not been reported.

For example, Japanese Patent Laid-Open No. 2000-154210 (Patent Document 1) discloses a conjugated diene polymerization catalyst containing a Group IV transition metal compound having a cyclopentadiene ring structure, which is co-polymerized with the conjugated diene. As the polymerizable monomer, α-olefin such as ethylene is exemplified, but the amount of 1,2-vinyl bond in the conjugated diene compound portion in the copolymer is as follows.
Not mentioned at all. JP 2006-249442 A (Patent Document 2)
Although a copolymer of an α-olefin and a conjugated diene compound is disclosed, there is no mention of the amount of 1,2-vinyl bonds in the conjugated diene compound portion in the copolymer. In addition, JP-T-2006-503141 (Patent Document 3) discloses a copolymer of ethylene and butadiene synthesized using a special organometallic complex as a catalyst component, but butadiene as a monomer. Is only inserted in the copolymer in the form of trans-1,2-cyclohexane, and the amount of 1,2-vinyl bonds in the conjugated diene compound portion in the copolymer is not mentioned at all. Not. Patent Documents 1 to 3 also describe that rubbers having excellent wettability and low-temperature characteristics are produced using a copolymer in which the amount of 1,2-vinyl bond in the conjugated diene compound portion is 10 mol% or more. There is no suggestion.

  Japanese Patent Application Laid-Open No. 11-228743 (Patent Document 4) discloses an unsaturated elastomer composition comprising an unsaturated olefin copolymer and rubber. Is included in the conjugated diene compound portion of 1,2-vinyl, although the quantitative ratio between the double bond of the side chain derived from the main chain and the double bond of the main chain derived from the 1,4 adduct is mentioned. Japanese Patent Application Laid-Open No. 11-228743 (Patent Document 4) describes and suggests that a rubber having excellent wettability and low-temperature characteristics is produced using a copolymer having a bond amount of 10 mol% or more. Not.

  JP 2000-86857 A (Patent Document 5) discloses that the vinyl content (vinyl bond content) is 6%, the cis content% is 92%, and the ethylene content is 3% or 9%. Butadiene polymers are disclosed. However, Japanese Patent Application Laid-Open No. 2000-86857 discloses the production of a rubber having excellent wettability and low-temperature characteristics using a copolymer having a 1,2-vinyl bond amount of 10 mol% or more in the conjugated diene compound portion. (Patent Document 5) is neither described nor suggested.

  Furthermore, JP 2000-154279 A (Patent Document 6) discloses a conjugated diene rubber composition containing a conjugated diene polymer segment having a cis content% of 40% or more, and in Examples. Discloses a polybutadiene having a 1,2 bond content of 90%. However, for producing a rubber having excellent wettability and low-temperature characteristics using a copolymer having a 1,2-vinyl bond amount of 10 mol% or more in the conjugated diene compound portion, JP-A-2000-154279 (Patent Document 6) is neither described nor suggested.

JP 2000-154210 A JP 2006-249442 A JP-T-2006-503141 JP-A-11-228743 JP 2000-86857 A JP 2000-154279 A

  Accordingly, an object of the present invention is a copolymer of a conjugated diene compound and a non-conjugated olefin, which is used to produce a rubber having excellent wettability and low temperature characteristics, and a conjugated diene compound portion in the copolymer. Copolymer having a 1,2-vinyl bond amount of 10 mol% or more, a method for producing the copolymer, a rubber composition containing the copolymer, and a cross-linking obtained by cross-linking the rubber composition The object is to provide a rubber composition and a tire using the rubber composition or the crosslinked rubber composition.

  As a result of intensive studies to achieve the above object, the inventors of the present invention polymerized a conjugated diene compound and a non-conjugated olefin in the presence of a specific catalyst, whereby one of the conjugated diene compound portions in the copolymer was obtained. The present inventors have found that a copolymer having a 2-vinyl bond content of 10 mol% or more can be obtained, thereby completing the present invention.

  That is, the copolymer of the present invention is a copolymer of a conjugated diene compound and a non-conjugated olefin, and the amount of 1,2-vinyl bonds in the conjugated diene compound portion (the conjugated diene compound-derived portion) is 10 mol% or more. It is characterized by being.

  In the copolymer of the present invention, the amount of cis-1,4 bonds in the conjugated diene compound part (part derived from the conjugated diene compound) is preferably 50 to 90 mol%.

  In another preferred example of the copolymer of the present invention, the content of the non-conjugated olefin moiety (non-conjugated olefin-derived moiety) is more than 0 mol% and 50 mol% or less.

  The copolymer of the present invention has a polystyrene equivalent weight average molecular weight of 10,000 to 10,000,000.

  The copolymer of the present invention preferably has a molecular weight distribution (Mw / Mn) of 10 or less.

  In another preferred embodiment of the copolymer of the present invention, the non-conjugated olefin is an α-olefin.

  In another preferred embodiment of the copolymer of the present invention, the non-conjugated olefin has 2 to 10 carbon atoms. Here, as said nonconjugated olefin, at least 1 type selected from the group which consists of ethylene, propylene, and 1-butene is preferable, and ethylene is still more preferable.

  In another preferred embodiment of the copolymer of the present invention, the conjugated diene compound has 4 to 8 carbon atoms. Here, the conjugated diene compound is preferably at least one selected from the group consisting of 1,3-butadiene and isoprene.

  In addition, the method for producing a copolymer of the present invention includes a step of polymerizing a conjugated diene compound and a non-conjugated olefin in the presence of a scandium compound or a reaction product of a scandium compound and a Lewis base.

（式中、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、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、下記一般式（ＩＩＩ）：

（式中、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、並びに下記一般式（ＩＶ）：
ＳｃＸ''_３・Ｌ'ｗ ・・・ （ＩＶ）
［式中、Ｘ''は、それぞれ独立して、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、炭化水素基、アルデヒド残基、ケトン残基、カルボン酸残基、チオカルボン酸残基又はリン化合物残基を示し、Ｌ'は、ルイス塩基を示し、ｗは、０〜３の整数を示す］で表されるスカンジウム化合物又はスカンジウム化合物とルイス塩基との反応物からなる群より選択される。 In a preferred example of the copolymer of the present invention, the scandium compound or a reaction product of the scandium compound and a Lewis base is represented by the following general formula (I):

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

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

(In the formula, Cp ^R ′ represents unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl, and X represents a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group, a silyl group, or a carbon number of 1-20. of a hydrocarbon group, L is a neutral Lewis base, w is, an integer of 0 to 3, [B] ^- is half metallocene cation complex represented by a non-coordinating anion) And the following general formula (IV):
ScX ″ ₃ · L'w (IV)
[In the formula, each X ″ independently represents a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group, a silyl group, a hydrocarbon group, an aldehyde residue, a ketone residue, a carboxylic acid residue, or a thiocarboxylic acid. An acid residue or a phosphorus compound residue, L ′ represents a Lewis base, and w represents an integer of 0 to 3], or a group comprising a scandium compound or a reaction product of a scandium compound and a Lewis base More selected.

  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.

  The rubber composition of the present invention includes the copolymer of the present invention.

  The rubber composition of the present invention preferably contains 5 to 200 parts by mass of a reinforcing filler and 0.1 to 20 parts by mass of a crosslinking agent with respect to 100 parts by mass of the rubber component.

  The crosslinked rubber composition of the present invention is obtained by crosslinking the rubber composition of the present invention.

  The tire of the present invention is characterized by using the rubber composition of the present invention or the crosslinked rubber composition of the present invention.

  According to the present invention, a copolymer of a conjugated diene compound and a non-conjugated olefin, which is used to produce a rubber having excellent wettability and low temperature characteristics, is a 1,2-vinyl bond in the conjugated diene compound portion. A copolymer having an amount of 10 mol% or more, a method for producing the copolymer, a rubber composition containing the copolymer, a crosslinked rubber composition obtained by crosslinking the rubber composition, and A tire using the rubber composition or the crosslinked rubber composition can be provided.

(Copolymer)
The present invention is described in detail below. The copolymer of the present invention is a copolymer of a conjugated diene compound and a non-conjugated olefin, and the amount of 1,2-vinyl bonds in the conjugated diene compound portion (the conjugated diene compound-derived portion) is 10 mol% or more (conjugated diene compound). The conjugated diene compound has a 1,2 adduct portion (including a 3,4 adduct portion) content of 10 mol% or more in the derived portion.

The copolymer of the present invention has a conjugated diene compound portion having a 1,2-vinyl bond amount of 10 mol% or more (including a 1,2-adduct portion of a conjugated diene compound in a conjugated diene compound-derived portion (including a 3,4-adduct portion). ) Content is 10 mol% or more), the affinity with other rubber components and compounding agents is improved. Moreover, the vinyl group excellent in radical reactivity is arrange | positioned by 10 mol% or more in the principal chain (The 1,2-adduct part (including 3,4 adduct part) content of the conjugated diene compound in the part derived from the conjugated diene compound) 10 mol% or more), it becomes possible to achieve both rubber products in general, particularly low temperature / wet property and other performances.
This copolymer is suitable for, for example, HIPS (high impact polystyrene), ABS (acrylonitrile butadiene styrene resin), a blend by peroxide crosslinking, and the like.
The amount of 1,2-vinyl bond (content of 1,2-adduct portion (including 3,4-adduct portion)) is the amount in the conjugated diene compound-derived portion, and is not a ratio to the whole 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.

In the copolymer of the present invention, the amount of cis-1,4 bonds in the conjugated diene compound portion (the conjugated diene compound-derived portion) is preferably 50 to 90 mol%, and more preferably 70 to 90 mol%. If the amount of cis-1,4 bonds in the conjugated diene compound portion (the conjugated diene compound-derived portion) is within the above range, the glass transition temperature (Tg) is low and the crack growth resistance is good.
The amount of cis-1,4 bonds is the amount in the portion derived from the conjugated diene compound, and is not a ratio relative to the entire copolymer.

  The copolymer of the present invention does not cause a problem of lowering the molecular weight, and its weight average molecular weight (Mw) is not particularly limited, but from the viewpoint of application to a polymer structural material, the copolymer The polystyrene-converted weight average molecular weight (Mw) of the coalescence is preferably 10,000 to 10,000,000, more preferably 10,000 to 1,000,000, and particularly preferably 50,000 to 600,000. 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 5 or less. 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 present invention preferably has a non-conjugated olefin (non-conjugated olefin-derived portion) content of more than 0 mol% and less than 100 mol%. If the content of the non-conjugated olefin (part derived from the non-conjugated olefin) is within the above specified range, mechanical properties such as breaking strength can be improved more reliably. In addition, from the viewpoint of improving mechanical properties such as breaking strength without causing phase separation of the copolymer, the content of the non-conjugated olefin (non-conjugated olefin-derived portion) is more than 0 mol% and 50 mol% or less. More preferably, it is more than 0 mol% and not more than 30 mol%.

  On the other hand, in the copolymer of the present invention, the content of the conjugated diene compound (part derived from the conjugated diene compound) is preferably more than 0 mol% and less than 100 mol%, more preferably 50 mol% or more and less than 100 mol%. Further preferred. If the content of the conjugated diene compound (part derived from the conjugated diene compound) is within the above specified range, the copolymer of the present invention can behave uniformly as an elastomer.

The conjugated diene compound used as the monomer preferably has 4 to 12 carbon atoms, and more preferably 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. 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.

  On the other hand, non-conjugated olefins used as monomers increase the degree of design freedom as an elastomer by reducing the crystallinity by reducing the ratio of double bonds in the main chain of the copolymer and excellent heat resistance. It becomes possible. The olefin is preferably a non-conjugated olefin, preferably an acyclic olefin, and preferably an α-olefin. Furthermore, it is preferable that carbon number of this nonconjugated olefin is 2-10. Therefore, preferred examples of the non-conjugated olefin include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene and the like. Among these, ethylene, propylene and 1 -Butene is more preferred and ethylene is particularly 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.

  Next, the manufacturing method of the copolymer of this invention is demonstrated in detail. However, the manufacturing method described in detail below is merely an example. The method for producing a copolymer of the present invention includes a step of polymerizing a conjugated diene compound and a non-conjugated olefin in the presence of a scandium compound or a reaction product of a scandium compound and a Lewis base. The inventors of the present invention have studied a rare earth element compound or a reaction product of the rare earth element compound and a Lewis base with respect to a catalyst system used for coordination anionic polymerization. As a result, by selecting scandium as the rare earth element, 1,2- It has been found that a copolymer having a vinyl bond amount of 10 mol% or more can be synthesized.

According to the method for producing a copolymer of the present invention, the method is not particularly limited except that a scandium compound or a reaction product of a scandium compound and a Lewis base is used as a catalyst. In the same manner, a conjugated diene compound as a monomer and a non-conjugated olefin can be copolymerized. 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, hexane, cyclohexane, mixtures thereof etc. are mentioned.

The scandium compound is preferably a scandium compound in which scandium is a trivalent salt or complex compound, and contains one or more ligands selected from a hydrogen atom, a halogen atom and an organic compound residue. More preferably it is. Furthermore, the scandium compound or the reaction product of the scandium compound and a Lewis base includes a metallocene complex represented by the general formulas (I) and (II), a half metallocene cation complex represented by the general formula (III), Further, it can be selected from the group consisting of a scandium compound represented by the above general formula (IV) or a reaction product of a scandium compound and a Lewis base.

In the metallocene complexes represented by the general formula (I) and formula (II), Cp ^R in the formula is an unsubstituted indenyl or substituted indenyl. Cp ^R having an indenyl ring as a basic skeleton may 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 above 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 above indenyl ring as the 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 metallocene complex represented by the general formula (I) includes a silylamide ligand [—N (SiR ₃ ) ₂ ]. The R groups (R ^{a to} R ^f in the general formula (I)) 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 ^{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 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. The alkyl group is preferably a methyl 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-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.

（式中、Ｘ'''はハライドを示す。） The metallocene complex represented by the general formula (I) includes, for example, scandium trishalide in a solvent, an indenyl salt (for example, potassium salt or lithium salt) and a bis (trialkylsilyl) amide salt (for example, potassium salt or It can be obtained by reacting with a 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。） In the metallocene complex represented by the general formula (II), for example, scandium trishalide is reacted with an indenyl salt (for example, potassium salt or lithium salt) and a silyl salt (for example, potassium salt or lithium salt) in a solvent. Can be obtained. 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 (V), Cp ^R ′ each independently represents unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl, and X represents a hydrogen atom, a halogen atom or 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. In the ionic compound represented by the general formula [A] ⁺ [B] ⁻ , [A] ⁺ represents a cation, and [B] ⁻ represents a non-coordinating anion.

[A] Examples of the cation represented by ⁺ 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, and is an N, N-dimethylaniline. Preference is given to nium tetrakis (pentafluorophenyl) borate, triphenylcarbonium tetrakis (pentafluorophenyl) borate and the like. Further, the ionic compound represented by the general formula [A] ⁺ [B] ⁻ is preferably added in an amount of 0.1 to 10 times, more preferably about 1 time, with respect to the metallocene complex. 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 a metallocene complex represented by the general formula (I) or the formula (II) and an 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.

  In the scandium compound represented by the above general formula (IV) or a reaction product of a scandium compound and a Lewis base, as a group (ligand) bonded to scandium of the scandium compound, specifically, a hydrogen atom; a methoxy group, Aliphatic alkoxy groups such as ethoxy group, propoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group; phenoxy group, 2,6-di-tert-butylphenoxy group, 2,6-diisopropyl Phenoxy 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 Aliphatic thiolate groups such as thioisobutoxy group, thiosec-butoxy group, thiotert-butoxy group; thiophenoxy group, 2,6-di-tert-butylthiophenoxy group, 2,6-diisopropylthiophenoxy group, 2 , 6-Dineopentylthiophenoxy group, 2-tert-butyl-6-isopropylthiophenoxy group, 2-tert-butyl-6-thioneopentylphenoxy group, 2-isopropyl-6-thioneopentylphenoxy group, 2 Arylthiolate groups such as 1,4,6-triisopropylthiophenoxy group; aliphatic amide groups such as dimethylamide group, diethylamide group, diisopropylamide group; phenylamide group, 2,6-di-tert-butylphenylamide group, 2,6-diisopropylphenylamide group, 2,6-dyne Pentylphenylamide group, 2-tert-butyl-6-isopropylphenylamide group, 2-tert-butyl-6-neopentylphenylamide group, 2-isopropyl-6-neopentylphenylamide group, 2,4,6- arylamide groups such as tert-butylphenylamide group; bistrialkylsilylamide groups such as bistrimethylsilylamide group; trimethylsilyl group, tris (trimethylsilyl) silyl group, bis (trimethylsilyl) methylsilyl group, trimethylsilyl (dimethyl) silyl group, triisopropyl Silyl groups such as silyl (bistrimethylsilyl) silyl group; halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, se linear or branched aliphatic hydrocarbon groups such as c-butyl group, tert-butyl group, neopentyl group, hexyl group and octyl group; aromatic hydrocarbon groups such as phenyl group, tolyl group and naphthyl group; Examples thereof include aralkyl groups such as benzyl group; cyclic hydrocarbon groups such as cyclopentadienyl, indenyl and fluorenyl; hydrocarbon groups containing silicon atoms such as trimethylsilylmethyl group and bistrimethylsilylmethyl group. 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-methyl phosphate) Heptyl), dilauryl phosphate, dioleyl phosphate, diphenyl phosphate, bis (p-nonylphenyl) phosphate, bis (polyethylene glycol-p-nonylphenyl) phosphate, (butyl) phosphate (2-ethylhexyl) ), Phosphoric acid esters (1-methylheptyl) (2-ethylhexyl), phosphoric acid (2-ethylhexyl) (p-nonylphenyl), etc. Residue: monobutyl 2-ethylhexylphosphonate, mono-2-ethylhexyl 2-ethylhexylphosphonate, mono-2-ethylhexyl phenylphosphonate, mono-p-nonyl 2-ethylhexylphosphonate Phosphonic acid ester residues such as phenyl, phosphonic acid mono-2-ethylhexyl, phosphonic acid mono-1-methylheptyl, phosphonic acid mono-p-nonylphenyl, dibutylphosphinic acid, bis (2-ethylhexyl) ) Phosphinic acid, bis (1-methylheptyl) phosphinic acid, dilaurylphosphinic acid, dioleylphosphinic acid, diphenylphosphinic acid, bis (p-nonylphenyl) phosphinic acid, butyl (2-ethylhexyl) phosphinic acid, (2-ethylhexyl) (1-methylheptyl) phosphinic acid, (2-ethylhexyl) L) (p-nonylphenyl) phosphinic acid, butylphosphinic acid, 2-ethylhexylphosphinic acid, 1-methylheptylphosphinic acid, oleylphosphinic acid, laurylphosphinic acid, phenylphosphinic acid, p-nonylphenylphosphinic acid, etc. The residue of phosphinic 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.

  Examples of the Lewis base that reacts with the scandium compound in the scandium compound represented by the general formula (IV) or the reaction product of the scandium compound and the Lewis base include tetrahydrofuran, diethyl ether, dimethylaniline, trimethylphosphine, Examples thereof include lithium chloride, neutral olefins, and neutral diolefins. Here, when the scandium compound reacts with a plurality of Lewis bases (in the formula (IV), when w is 2 or 3), the Lewis bases L ′ may be the same or different.

Further, in the method for producing a copolymer of the present invention, the scandium compound or a reaction product of a scandium compound and a Lewis base (hereinafter also referred to as component (A)) is an ion comprising a non-coordinating anion and a cation. Compound (B-1), aluminoxane (B-2), and a Lewis acid, a complex compound of a metal halide and a Lewis base, and an organic compound containing an active halogen, and at least one halogen compound (B-3). A catalyst system in combination with at least one component (B) selected from the group may be used. In addition, it is preferable that the total usage-amount of (B) component is 0.1-50 times mole with respect to (A) component.

The ionic compound represented by (B-1) is composed of a non-coordinating anion and a cation, and reacts with the scandium compound as the component (A) or a reaction product thereof with a Lewis base to form a cationic transition. Examples thereof include ionic compounds capable of generating metal compounds. 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 such as diisopropylammonium cation and dicyclohexylammonium cation And cations. 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 the usage-amount of the said ionic compound is 0.1-10 times mole with respect to (A) component, and it is still more preferable that it is about 1 times 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 amount of the aluminoxane used is preferably such that the element ratio Al / Sc between scandium Sc constituting the component (A) and the aluminum element Al of the aluminoxane is about 10 to 1000.

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 scandium compound or a reaction product thereof with a Lewis base, a halogenated transition metal compound or a compound having a transition metal center with insufficient charge can be produced. In addition, it is preferable that the total usage-amount of the said halogen compound 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, as well as III, IV, 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, Benzoyl acetone, 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 , Oleic 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.

In addition, when the said (B) component is at least 1 type of an ionic compound (B-1) and a halogen compound (B-3), with respect to the said (A) component and (B) component, (C) component : The following general formula (VI):
YR ¹ _a R ² _b R ³ _c (VI)
[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]. It needs to be combined. Since the ionic compound (B-1) and the halogen compound (B-3) have no carbon atom to be supplied to the component (A), the component (C) is used as a carbon supply source to the component (A). Is required. In addition, even if (B) component is aluminoxane (B-2), (C) component can be combined with (A) component and (B) component. Further, the component (A) may contain other components contained in a normal rare earth element compound catalyst system, such as a promoter.

The component (C) is represented by the following general formula (VII):
AlR ¹ R ² R ³ (VII)
[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 (VII) 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, hydrogenated Diisohexyl aluminum, dioctyl aluminum hydride, diisooctyl aluminum hydride; ethyl aluminum dihydride, n-propyl aluminum Muzi hydride, isobutylaluminum dihydride and the like. Among these, triethylaluminum, triisobutylaluminum, hydrogenated diethylaluminum, hydrogenated diisobutylaluminum are preferred. The organometallic compound as the component (C) described above can be used alone or in combination of two or more. In addition, it is preferable that the usage-amount of the said organometallic compound is 1-50 times mole with respect to (A) component.

  As described above, the method for producing a copolymer of the present invention produces a polymer by a polymerization reaction using a conventional coordination ion polymerization catalyst, except that the catalyst system comprising the component (A) described above is used as a polymerization catalyst. It can be similar to the method. Here, in the method for producing a copolymer of the present invention, for example, (1) a component component of a catalyst system is separately provided in a polymerization reaction system containing a conjugated diene compound and a non-conjugated olefin as monomers, A catalyst system may be used in the reaction system, or (2) a catalyst system prepared in advance may be provided in the polymerization reaction system. In addition, the usage-amount of (A) component has the preferable range of 0.0001-0.01 times mole with respect to the sum total of a conjugated diene compound and a nonconjugated olefin.

In the method for producing a copolymer of the present invention, the polymerization reaction of a conjugated diene compound and an olefin other than the conjugated diene compound 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 0.1-5.0 Mpa is preferable. Further, the reaction time of the above polymerization reaction is not particularly limited, and is preferably in the range of 1 second to 10 days, for example. it can.

(Rubber composition)
The rubber composition of the present invention is not particularly limited as long as it contains the copolymer of the present invention, and can be appropriately selected according to the purpose. However, rubber components other than the copolymer of the present invention, inorganic fillers , Carbon black, a crosslinking agent, and the like are preferable.

<Copolymer>
There is no restriction | limiting in particular as content in the rubber component of the copolymer of this invention, Although it can select suitably according to the objective, 3 mass% or more is preferable.
When the content of the copolymer in the rubber component is less than 3% by mass, the characteristics of the present invention may be small or the characteristics may not be exhibited.

<Rubber component>
The rubber component is not particularly limited and may be appropriately selected depending on the purpose. For example, the copolymer of the present invention, natural rubber, various butadiene rubbers, various styrene-butadiene copolymer rubbers, isoprene rubber, Butyl rubber, isobutylene and p-methylstyrene copolymer bromide, halogenated butyl rubber, acrylonitrile butadiene rubber, chloroprene rubber, ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber, styrene-isoprene copolymer Polymer rubber, styrene-isoprene-butadiene copolymer rubber, isoprene-butadiene copolymer rubber, chlorosulfonated polyethylene, acrylic rubber, epichlorohydrin rubber, polysulfide rubber, silicone rubber, fluorine rubber, urethane rubber, etc. . These may be used individually by 1 type and may use 2 or more types together.

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.
<Inorganic filler>
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, 5 mass parts-200 mass parts are preferable with respect to 100 mass parts of rubber components.
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 reinforcing filler tends not to be mixed. And the performance as a rubber composition may be lowered.

<Crosslinking agent>
There is no restriction | limiting in particular as said crosslinking agent, According to the objective, it can select suitably, For example, a sulfur type crosslinking agent, an organic peroxide type crosslinking agent, an inorganic crosslinking agent, a polyamine crosslinking agent, a resin crosslinking agent, sulfur Compound-based crosslinking agents, oxime-nitrosamine-based crosslinking agents, sulfur and the like can be mentioned. Among them, sulfur-based crosslinking agents are more preferable as the rubber composition for tires.

There is no restriction | limiting in particular as content of the said crosslinking agent, Although it can select suitably according to the objective, 0.1 mass part-20 mass parts are preferable with respect to 100 mass parts of rubber components.
When the content of the cross-linking agent is less than 0.1 parts by mass, the cross-linking hardly proceeds, and when the content exceeds 20 parts by mass, the cross-linking tends to progress during kneading with a part of the cross-linking agent. The physical properties of the sulfide may be impaired.

<Other ingredients>
In addition, it is also possible to use a vulcanization accelerator in combination, and examples of the vulcanization accelerator include guanidine, aldehyde-amine, aldehyde-ammonia, thiazole, sulfenamide, thiourea, thiuram, Dithiocarbamate and xanthate compounds can be used.
If necessary, reinforcing agents, softeners, fillers, vulcanization aids, colorants, flame retardants, lubricants, foaming agents, plasticizers, processing aids, antioxidants, anti-aging agents, scorch prevention agents, Known materials such as ultraviolet ray inhibitors, antistatic agents, anti-coloring agents, and other compounding agents can be used depending on the intended use.

(Crosslinked rubber composition)
The crosslinked rubber composition of the present invention is not particularly limited as long as it is obtained by crosslinking the rubber composition of the present invention, and can be appropriately selected according to the purpose.
The crosslinking conditions are not particularly limited and may be appropriately selected depending on the intended purpose. However, a temperature of 120 ° C. to 200 ° C. and a heating time of 1 minute to 900 minutes are preferable.

(tire)
The tire of the present invention is not particularly limited as long as it uses the rubber composition of the present invention or the crosslinked rubber composition of the present invention, and can be appropriately selected according to the purpose.
Examples of the application site in the tire of the rubber composition of the present invention or the crosslinked rubber composition of the present invention include, but are not limited to, a tread, a base tread, a sidewall, a side reinforcing rubber, and a bead filler. .
As a method for manufacturing the tire, a conventional method can be used. 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)
In addition to tire applications, the rubber composition of the present invention or the crosslinked rubber composition of the present invention may be used for anti-vibration rubber, seismic isolation rubber, belts (conveyor belts), rubber crawlers, various hoses, Moran and the like. it can.

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.

<Synthesis of Sc [N (SiHMe ₂ ) ₂ ] ₃ · (thf) ₂ and (2-MeC ₉ H ₆ ) ₂ Sc {N (SiHMe ₂ ) ₂ }>
Sc [N (SiHMe ₂ ) ₂ ] ₃ · (thf) ₂ and (2-MeC ₉ H ₆ ) ₂ Sc {N (SiHMe ₂ ) ₂ } are available from Dalton Trans. , 2008, 2531-2533. Here, thf means tetrahydrofuran as a coordinating solvent.

<Synthesis of (2-MeC ₉ H ₆ ) ₂ Sc (MeAlMe ₃ )>
Under a nitrogen atmosphere, (2-MeC ₉ H ₆ ) ₂ Sc {N (SiHMe ₂ ) ₂ } (0.37 g, 0.85 mmol) and AlMe ₃ (2.0 mmol, manufactured by Aldrich) in 20 mL of hexane The reaction was allowed to stir at room temperature for 16 hours. Then, after the solvent was distilled off under reduced pressure, the residue was washed several times with hexane, and then hexane was slowly distilled off under reduced pressure to give a yellow powder (2-MeC ₉ H ₆ ) ₂ Sc (MeAlMe ₃ ) (0. 15 g, 45%).

<Synthesis of _{(C 5 Me 4 SiMe 3)} Sc (CH 2 SiMe 3) 2 (thf)>
(C ₅ Me ₄ SiMe ₃ ) Sc (CH ₂ SiMe ₃ ) ₂ (thf) is described in J. Am. Am. Chem. Soc. , 2004, 126 (43) 13910-13911.

Example 1
After adding 300 mL of a toluene solution containing 23.76 g (0.44 mol) of 1,3-butadiene to a sufficiently dried 400 mL pressure-resistant glass reactor, ethylene was introduced at 0.8 MPa. On the other hand, in a glove box under a nitrogen atmosphere, tris bis glass container dimethylsilylamide scandium _{Sc [N (SiHMe 2) 2} ] 3 · (thf) 2 to _{500μmol, Me 2 NHPhB (C 6} F 5) 4, 600 μmol and 10.0 mmol of diisobutylaluminum hydride were charged and dissolved in 25 mL of toluene to obtain a catalyst solution. Thereafter, the catalyst solution was taken out from the glove box, an amount of 440 μmol in terms of scandium was added to the monomer solution, and polymerization was performed at room temperature for 180 minutes. After polymerization, 1 mL of NS-5, 5 mass% isopropanol solution was added to stop the reaction, and the copolymer was separated with a large amount of methanol, followed by vacuum drying at 70 ° C. to obtain copolymer A. The yield of the obtained copolymer A was 37.40 g.

(Example 2)
After adding 200 mL of a toluene solution containing 3.12 g (0.058 mol) of 1,3-butadiene to a sufficiently dried 400 mL pressure-resistant glass reactor, ethylene was introduced at 0.8 MPa. On the other hand, in a glove box under a nitrogen atmosphere, (2-MeC ₉ H ₆ ) ₂ Sc (MeAlMe ₃ ) 21.0 μmol, triphenylcarbonium tetrakis (pentafluorophenyl) borate (Ph ₃ CB (C ₆ F ₅ ) ₄ ) 21.0 μmol and 0.30 mmol of triisobutylaluminum were charged and dissolved in 5 mL of toluene to obtain a catalyst solution. Thereafter, the catalyst solution was taken out from the glove box, added to the monomer solution, and polymerized at 25 ° C. for 90 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 B. The yield of the obtained copolymer B was 9.60 g.

Example 3
The reaction was conducted in the same manner as in Example 2 except that 9.36 g (0.173 mol) of 1,3-butadiene, ethylene pressure of 0.6 MPa, and triisobutylaluminum of 0.25 mmol were used, and the polymerization time was 50 minutes. Copolymer C was obtained in a yield of 9.30 g.

Example 4
The reaction was carried out in the same manner as in Example 2 except that 8.40 g (0.156 mol) of 1,3-butadiene, ethylene pressure 0.8 MPa, triisobutylaluminum 0.61 mmol was used and the polymerization temperature was 35 ° C. for 50 minutes. As a result, the copolymer D was obtained in a yield of 8.10 g.

(Example 5)
After adding 200 mL of a toluene solution containing 10.70 g (0.198 mol) of 1,3-butadiene to a sufficiently dried 400 mL pressure-resistant glass reactor, ethylene was introduced at 0.8 MPa. On the other hand, in a glove box under a nitrogen atmosphere, (C ₅ Me ₄ SiMe ₃ ) Sc (CH ₂ SiMe ₃ ) ₂ (thf) 17.0 μmol, triphenylcarbonium tetrakis (pentafluorophenyl) borate ( Ph ₃ CB (C ₆ F ₅ ) ₄ ) 17.0 μmol and 0.30 mmol of triethylaluminum were charged and dissolved in 5 mL of toluene to obtain a catalyst solution. Thereafter, the catalyst solution was taken out from the glove box, added to the monomer solution, and polymerized at 25 ° C. for 3 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 E. The yield of the obtained copolymer E was 11.30 g.

(Comparative Example 1)
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 ) ₂ GdN (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 dried under vacuum at 70 ° C. to obtain a copolymer F. The yield of the obtained copolymer F was 12.00 g.

(Comparative Example 2)
As in Production Example 1 of JP-A-2000-86857, a toluene solution (Tosoh Akzo Co., Ltd.) containing 26.0 g of toluene and 6.7 mmol of methylaluminosan in a sealed pressure-resistant glass ampoule having an internal volume of 150 ml under a nitrogen atmosphere. Made). The ampoule was kept at the aging temperature (25 ° C.), and a toluene solution of 2-methoxycarbonylmethylcyclopentadienyltrichlorotitanium [MeO (CO) CH ₂ CpTiCl ₃ ] (TiES) 0.0067 mmol was added dropwise, and the aging time (5 minutes) ) Hold. Thereafter, a solution of 2.0 g of butadiene and 6.0 g of toluene was added at −25 ° C., and polymerization was performed at this temperature for 30 minutes. Subsequently, a pressure of 5 kgf / cm ² was applied to the vessel with ethylene, and the reaction was allowed to proceed for about 1 hour. Thereafter, the polymerization reaction was stopped with a small amount of acidic methanol solution, and then the polymerization solution was poured into a large amount of acidic methanol, and the precipitated white solid was collected by filtration and dried to obtain copolymer G.

  For the copolymers A to E of Examples 1 to 5 and the copolymers F and G of Comparative Examples 1 and 2 produced as described above, the microstructure, the ethylene content, the weight average molecular weight (Mw), and the molecular weight Distribution (Mw / Mn) was measured and evaluated by the following method.

(1) Microstructure The microstructure of the butadiene moiety in the copolymer was measured by ¹ H-NMR spectrum (bonding amount of 1,2-vinyl bond) and ¹³ C-NMR spectrum (cis-1,4 bond and trans-1). , 4 bond content ratio). The calculated values of the cis-1,4 bond amount (mol%) and the 1,2-vinyl bond amount (mol%) are shown in Table 1.
(2) Content of ethylene The content (mol%) of the ethylene moiety in the copolymer was determined by ¹³ C-NMR spectrum (100 ° C., d-tetrachloroethane standard: 73.8 ppm) as a whole ethylene-bonded component (28. 5-30.0 ppm) and the total butadiene bond component (26.5-27.5 ppm + 31.5-32.5 ppm). Table 1 shows the ethylene content (mol%).
(3) Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)
Gel permeation chromatography [GPC: Tosoh HLC-8121GPC
/ HT, column: Tosoh GMH _HR- H (S) HT (two in series), detector: differential refractometer (RI)] on the basis of monodisperse polystyrene, the weight average molecular weight of the polymer in terms of polystyrene ( Mw) and molecular weight distribution (Mw / Mn) were determined.

  For Examples 4 and 5 and Comparative Examples 1 and 2, a rubber compound having the compounding formulation shown in Table 2 was prepared, and vulcanized rubber obtained by vulcanization at 160 ° C. for 20 minutes was subjected to low temperature according to the following method. Characteristics, wettability and weather resistance were measured.

* 1: N- (1,3-dimethylbutyl) -N′-p-phenylenediamine, manufactured by Ouchi Shinsei Chemical Co., Ltd., knock rack 6C
* 2: N-cyclohexyl-2-benzothiazolylsulfenamide, manufactured by Ouchi Shinsei Chemical Co., Ltd., Noxeller CZ-G
* 3: Dibenzothiazyl disulfide, manufactured by Ouchi Shinsei Chemical Co., Ltd., Noxeller DM-P

<Low temperature characteristics>
Using a dynamic spectrometer (manufactured by Rheometrics, USA), the elastic modulus G ′ at 0 ° C. was measured under conditions of a tensile dynamic strain of 1% and a frequency of 15 Hz. In Table 3, the index is shown with Comparative Example 1 as 100. The smaller the index value, the better the low-temperature characteristics.

<< wetness >>
In Table 3 in which the slip resistance was measured at room temperature on a concrete road surface wetted with water using a portable wet skid tester, Comparative Example 1 was set as 100 and indicated as an index. A larger index indicates better wettability.

  The copolymer of the present invention can be used for elastomer products in general, particularly for tire members.

Claims (17)

  A copolymer of a conjugated diene compound and a non-conjugated olefin, wherein the conjugated diene compound portion has a 1,2-vinyl bond content of 10 mol% or more.   The copolymer according to claim 1, wherein the cis-1,4 bond content of the conjugated diene compound portion is 50 to 90 mol%.   The copolymer according to claim 1, wherein the content of the non-conjugated olefin moiety is more than 0 mol% and not more than 50 mol%. The copolymer according to claim 1, wherein the polystyrene-equivalent weight average molecular weight is 10,000 to 10,000,000.   The copolymer according to claim 1, wherein the molecular weight distribution (Mw / Mn) is 10 or less.   The copolymer according to claim 1, wherein the non-conjugated olefin is an α-olefin.   The copolymer according to claim 1 or 6, wherein the non-conjugated olefin has 2 to 10 carbon atoms.   The copolymer according to claim 7, wherein the non-conjugated olefin is at least one selected from the group consisting of ethylene, propylene, and 1-butene.   The copolymer according to claim 8, wherein the non-conjugated olefin is ethylene.   The copolymer according to claim 1, wherein the conjugated diene compound has 4 to 8 carbon atoms.   11. The copolymer according to claim 10, wherein the conjugated diene compound is at least one selected from the group consisting of 1,3-butadiene and isoprene.   A method for producing a copolymer, comprising a step of polymerizing a conjugated diene compound and a non-conjugated olefin in the presence of a scandium compound or a reaction product of a scandium compound and a Lewis base. A reaction product of the scandium compound or the scandium compound and a Lewis base is represented by the following general formula (I):

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

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

(In the formula, Cp ^R ′ represents unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl, and X represents a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group, a silyl group, or a carbon number of 1-20. of a hydrocarbon group, L is a neutral Lewis base, w is, an integer of 0 to 3, [B] ^- is half metallocene cation complex represented by a non-coordinating anion) And the following general formula (IV):
ScX ″ ₃ · L'w (IV)
[In the formula, each X ″ independently represents a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group, a silyl group, a hydrocarbon group, an aldehyde residue, a ketone residue, a carboxylic acid residue, or a thiocarboxylic acid. An acid residue or a phosphorus compound residue, L ′ represents a Lewis base, and w represents an integer of 0 to 3], or a group comprising a scandium compound or a reaction product of a scandium compound and a Lewis base The method for producing a copolymer according to claim 12, wherein the copolymer is selected.   A rubber composition comprising the copolymer according to claim 1.   The rubber composition according to claim 14, comprising 5 to 200 parts by mass of a reinforcing filler and 0.1 to 20 parts by mass of a crosslinking agent with respect to 100 parts by mass of the rubber component.   A crosslinked rubber composition obtained by crosslinking the rubber composition according to claim 14.   A tire using the rubber composition according to claim 14 or the crosslinked rubber composition according to claim 16.