JP5917808B2 - Copolymer, rubber composition, crosslinked rubber composition, and tire - Google Patents

Description

  The present invention relates to a copolymer of a conjugated diene compound and a non-conjugated olefin, a rubber composition, a cross-linked rubber composition, and a tire, and in particular, produces a rubber having excellent low heat generation, heat resistance, and ozone resistance. A copolymer of a conjugated diene compound and a non-conjugated olefin, a rubber composition containing the copolymer, a crosslinked rubber composition obtained by crosslinking the rubber composition, and the rubber composition Or a tire using 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 content of 1,2 adducts (including 3,4 adducts) of the conjugated diene compound in the copolymer obtained by the polymerization reaction of the conjugated diene compound and the nonconjugated olefin (part derived from the conjugated diene compound) The 1,2 adduct portion (including the 3,4 adduct portion content) of the conjugated diene compound in the above 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. Examples of polymerizable monomers include α-olefins such as ethylene. Regarding the content of 1,2-adduct parts (including 3,4-adduct parts) of the conjugated diene compound part in the copolymer The rubber composition is excellent in low heat buildup, heat resistance and ozone resistance by making the content of 1,2 adduct (including 3,4 adduct) 5 mol% or less. There is no mention or suggestion of what can be obtained.
Japanese Patent Laid-Open No. 2006-249442 (Patent Document 2) discloses a copolymer of an α-olefin and a conjugated diene compound, but a 1,2 adduct of a conjugated diene compound portion in the copolymer. The content of the part (including the 3,4 adduct part) is not mentioned at all, and the content of the 1,2 adduct part (including the 3,4 adduct part) is 5 mol% or less, thereby reducing heat generation. There is no description or suggestion that a rubber composition excellent in heat resistance, heat resistance and ozone resistance can be obtained.
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 inserted into the copolymer in the form of trans-1,2-cyclohexane, and the 1,2-adduct part (3,4-adduct part) of the conjugated diene compound part in the copolymer is described. The content of 1, 2 adducts (including 3 and 4 adducts) is 5 mol% or less, and is excellent in low heat generation, heat resistance and ozone resistance. There is no description or suggestion that a rubber composition having excellent properties can be obtained.

  Japanese Patent Application Laid-Open No. 11-228743 (Patent Document 4) describes an unsaturated elastomer used for obtaining a vulcanizate having excellent heat resistance and the like and comprising an unsaturated olefin copolymer and rubber. A composition is disclosed, and a quantitative ratio between a double bond of a side chain derived from a 1,2 adduct (including a 3,4 adduct) and a double bond of a main chain derived from a 1,4 adduct Although mentioned, the use of a copolymer having a conjugated diene compound portion having a 1,2 adduct portion (including 3,4 adduct portion) content of 5 mol% or less is disclosed in JP-A-11-228743. (Patent Document 4) is neither described nor suggested. Further, by setting the content of 1,2 adduct portion (including 3,4 adduct portion) to 5 mol% or less, a rubber composition having excellent low heat generation, heat resistance and ozone resistance can be obtained. JP-A-11-228743 (Patent Document 4) neither describes nor suggests.

  JP-A-2000-86857 (Patent Document 5) is used to obtain a rubber composition excellent in low-temperature resilience and the like, and has a vinyl content (vinyl bond content) of 6% and a cis content. A butadiene polymer with a% by volume of 92% and an ethylene content of 3% or 9% is disclosed. However, by using a copolymer in which the content of 1,2-adduct (including 3,4-adduct) in the conjugated diene compound is 5 mol% or less, it is excellent in low heat generation, heat resistance and ozone resistance. Japanese Patent Application Laid-Open No. 2000-86857 (Patent Document 5) neither describes nor suggests obtaining an excellent rubber composition.

  Furthermore, JP 2000-154279 A (Patent Document 6) uses a conjugated diene polymer segment having a cis content of 40% or more, which is used to obtain a rubber composition having excellent low-temperature resilience and the like. Conjugated diene rubber compositions containing a polybutadiene having a 1,2-vinyl bond content of 90% are disclosed in the examples. However, by using a copolymer in which the content of 1,2-adduct (including 3,4-adduct) in the conjugated diene compound is 5 mol% or less, it is excellent in low heat generation, heat resistance and ozone resistance. Japanese Patent Application Laid-Open No. 2000-154279 (Patent Document 6) does not describe or suggest obtaining an excellent rubber composition.

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

  Therefore, an object of the present invention is to produce a rubber having excellent low heat build-up, heat resistance and ozone resistance, and a copolymer of a conjugated diene compound and a non-conjugated olefin, It is in providing the rubber composition containing, the crosslinked rubber composition obtained by bridge | crosslinking this rubber composition, and the tire using the said rubber composition or the said crosslinked rubber composition.

  As a result of intensive studies to achieve the above-mentioned object, the present inventors have polymerized a conjugated diene compound and a non-conjugated olefin in the presence of a specific catalyst, thereby obtaining a 1,2-adduct of a conjugated diene compound-derived moiety. It has been found that a copolymer having a partial content (including a 3,4-adduct portion) of 5 mol% or less can be obtained, and the present invention has been completed.

That is, the copolymer of the present invention is a copolymer of a conjugated diene compound and a non-conjugated olefin, and is a 1,2-adduct portion (3,4-adduct) relative to the total amount of conjugated diene units derived from the conjugated diene compound. The content is 5 mol% or less, including the following general formula (I):
(In the formula, M represents gadolinium , Cp ^R independently represents unsubstituted or substituted indenyl, and R ^{a to} R ^f each independently represents an alkyl group having 1 to 3 carbon atoms or a hydrogen atom. And at least one of R ^{a to} R ^f is a hydrogen atom, L represents a neutral Lewis base, and w represents an integer of 0 to 3). Obtained by polymerizing in the presence of
It is characterized by that.

In the copolymer of the present invention, the amount of cis 1,4-bonds relative to the total amount of conjugated diene units derived from the conjugated diene compound is preferably more than 50 mol%.

In the copolymer of the present invention, the total content of non-conjugated olefin units derived from non-conjugated olefins is preferably more than 0 mol% and 50 mol% or less.

  The copolymer of the present invention preferably 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 the copolymer of the present invention, the non-conjugated olefin is preferably an acyclic olefin.

In the copolymer of the present invention, the non-conjugated olefin preferably has 2 to 10 carbon atoms.

  In the copolymer of the present invention, the non-conjugated olefin is preferably at least one selected from the group consisting of ethylene, propylene and 1-butene, and more preferably ethylene.

  In the copolymer of the present invention, the conjugated diene compound is preferably at least one selected from the group consisting of 1,3-butadiene and isoprene.

  According to the present invention, a copolymer of a conjugated diene compound and a non-conjugated olefin is used to produce a rubber having excellent low heat build-up, excellent crack growth resistance, and excellent ozone resistance. A rubber composition containing a coalescence, 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.

3 is a ¹³ C-NMR spectrum chart of copolymer A. FIG. The DSC curve of the copolymer A is shown. The DSC curve of the copolymer B is shown. The DSC curve of copolymer C is shown. The DSC curve of the copolymer D is shown.

(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 content of 1,2 adduct portion (including 3,4 adduct portion) of the conjugated diene compound-derived portion is 5 mol% or less. It is characterized by being.
The content of the 1,2 adduct portion (including the 3,4 adduct portion) is an amount in the portion derived from the conjugated diene compound, and is not a ratio to the whole copolymer.
In addition, 1, 2 adduct portion (including 3,4 adduct portion) content of conjugated diene compound portion (including 3,4 diadduct portion) 1, 2 adduct portion (3, 4 adduct portion of conjugated diene compound-derived portion) Including) content) has the same meaning as the amount of 1,2-vinyl bonds when the conjugated diene compound is butadiene.

When the copolymer of the present invention has a content of 1,2 adducts (including 3,4 adducts) of the conjugated diene compound-derived part of 5 mol% or less, the copolymer of the present invention has low exothermic properties. , Heat resistance and ozone resistance can be improved. Furthermore, heat resistance can be improved more that the 1,2-adduct part content (a 3, 4-adduct part is included) content of the part derived from a conjugated diene compound is 2.5 mol% or less. The content of 1,2-adduct portion (including 3,4-adduct portion) in the conjugated diene compound-derived portion is more preferably 2 mol% or less.
This copolymer is suitable for, for example, HIPS (high impact polystyrene), ABS (acrylonitrile butadiene styrene resin), a blend by peroxide crosslinking, and the like.

In the copolymer of the present invention, the cis-1,4 bond content of the conjugated diene compound-derived moiety is preferably more than 50 mol%. More preferably, it is 75% or more, more preferably 85% or more, and still more preferably 90% or more. If the cis-1,4 bond content of the conjugated diene compound-derived moiety 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 combined polystyrene equivalent weight average molecular weight (Mw) is preferably 10,000 to 10,000,000, more preferably 10,000 to 1,000,000, and still more 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).

  In the copolymer of the present invention, the content of the non-conjugated olefin-derived moiety is preferably more than 0 mol% and less than 100 mol%. When the content of the non-conjugated olefin-derived portion is within the above specified range, mechanical properties such as breaking strength can be improved more reliably. Further, 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-derived portion is more preferably more than 0 mol% and not more than 50 mol%. .

  On the other hand, in the copolymer of the present invention, the content of the conjugated diene compound-derived moiety is preferably more than 0 mol% and less than 100 mol%, more preferably 50 mol% or more and less than 100 mol%. If the content of the conjugated diene compound-derived moiety 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 have excellent heat resistance and design freedom as elastomers by reducing the crystallinity by reducing the proportion of double bonds in the main chain of the copolymer. It becomes possible to raise. Further, the non-conjugated olefin is preferably an acyclic olefin and is 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 1st manufacturing method of the copolymer of this invention includes the process of superposing | polymerizing a conjugated diene compound and a nonconjugated olefin in presence of the 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, hexane, cyclohexane, mixtures thereof etc. are mentioned.

<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 unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl, and X represents a hydrogen atom, a halogen atom, an alkoxide group or a thiolate group. represents an amide group, a silyl group or a hydrocarbon group having a carbon number of 1 to 20, L is a neutral Lewis base, w is, an integer of 0 to 3, [B] ^- is a non-coordinating 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 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.

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 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) 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) contains 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 a bistrimethylsilylamide group or a carbon number of 1-2.
Zero hydrocarbon groups are preferred.

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

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

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

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

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.

[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.

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 C _{1 to} C ₁₀ hydrocarbon group or a hydrogen atom, and R ″ is C ₁ an organoaluminum compound represented by a hydrocarbon group which the -C ₁₀₎ are preferred. Specific examples of the organoaluminum compound include trialkylaluminum, dialkylaluminum chloride, alkylaluminum dichloride, and dialkylaluminum hydride. Among these, trialkylaluminum is preferable. Furthermore, examples of the trialkylaluminum include triethylaluminum and triisobutylaluminum. In addition, it is preferable that it is 1-50 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,
(A) component: a rare earth element compound or a reaction product of the rare earth element compound and a Lewis base, the rare earth element compound or the reaction product having no bond between the rare earth element and carbon,
Component (B): Contains ionic compound (B-1) composed of non-coordinating anion and cation, aluminoxane (B-2), Lewis acid, complex compound of metal halide and Lewis base, and active halogen. A polymerization catalyst composition (hereinafter also referred to as a second polymerization catalyst composition) containing at least one selected from the group consisting of at least one halogen compound (B-3) among organic compounds can also be suitably mentioned. When the 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 (i):
YR ¹ _a R ² _b R ³ _c (i)
[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 is characterized by including. Since the ionic compound (B-1) and the halogen compound (B-3) do not have a carbon atom to be supplied to the component (A), the carbon source for the component (A) is the above ( Component C) is required. In addition, even if it is a case where the said polymerization catalyst composition contains the said aluminoxane (B-2), this polymerization catalyst composition can contain the said (C) component. Further, the polymerization catalyst composition may contain other components such as a co-catalyst 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)
[Wherein M ¹¹ represents a lanthanoid element, scandium or yttrium, and X ¹¹ independently represents a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group, a silyl group, an aldehyde residue, a ketone residue. Represents a group, a carboxylic acid residue, a thiocarboxylic acid residue or a phosphorus compound residue, L ¹¹ represents a Lewis base, and w represents 0 to 3].

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

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

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

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

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

The halogen compound represented by (B-3) is composed of at least one of a Lewis acid, a complex compound of a metal halide and a Lewis base, and an organic compound containing an active halogen, and is, for example, the component (A). A cationic transition metal compound can be produced by reacting with a rare earth element compound or a reactant thereof with a Lewis base. 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, 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, 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, oleyl Alcohol, stearyl alcohol, phenol,
Examples include benzyl alcohol, 1-decanol, lauryl alcohol, among which tri-2-ethylhexyl phosphate, tricresyl phosphate, acetylacetone, 2-ethylhexanoic acid, versatic acid, 2-ethylhexyl alcohol, 1-decanol, Lauryl alcohol is 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 (i):
YR ¹ _a R ² _b R ³ _c (i)
[Wherein Y is a metal selected from Group 1, Group 2, Group 12 and Group 13 of the Periodic Table, and R ¹ and R ² are the same or different and have 1 to 10 carbon atoms. R ³ is a hydrocarbon group or a hydrogen atom, and R ³ is a hydrocarbon group having 1 to 10 carbon atoms, provided that R ³ may be the same as or different from R ¹ or R ^2, and Y is a periodic table. When it is a metal selected from Group 1, a is 1 and b and c are 0, and when Y is a metal selected from Groups 2 and 12 of the Periodic Table, a and b are 1 and c is 0, and when Y is a metal selected from Group 13 of the Periodic Table, a, b and c are 1]. Yes, the following general formula (X):
AlR ¹¹ R ¹² R ¹³ (X)
[Wherein, R ¹¹ and R ¹² are the same or different and each represents a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom, and R ¹³ is a hydrocarbon group having 1 to 10 carbon atoms, provided that R ¹³ represents the above It may be the same as or different from R ¹¹ or R ¹² ]. 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 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 it is 1-50 times mole with respect to (A) component, and, as for content of the organoaluminum compound in the said 2nd polymerization catalyst composition, it is still more preferable that it is about 10 times mole.

In the first production method of the copolymer of the present invention, as described above, except that the polymerization catalyst composition is used, in the same manner as in the production method of a polymer with a normal coordination ion polymerization catalyst,
Polymerization can be performed. Here, the method for producing a copolymer of the present invention includes, for example, (1) the constitution of a polymerization catalyst composition in a polymerization reaction system containing a conjugated diene compound as a monomer and a non-conjugated olefin other than the conjugated diene compound. The components may be provided separately and used as a polymerization catalyst composition in the reaction system, or (2) a previously prepared polymerization catalyst composition may be provided in the polymerization reaction system. Moreover, (2) includes providing a metallocene complex (active species) activated by a cocatalyst. The amount of metallocene complex contained in the polymerization catalyst composition is
The range of 0.0001 to 0.01-fold mol is preferable with respect to the total of the conjugated diene compound and the non-conjugated olefin other than the conjugated diene compound.

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

In the first method for producing a copolymer of the present invention, the polymerization reaction of the conjugated diene compound and the non-conjugated olefin is preferably performed in an atmosphere of an inert gas, preferably nitrogen gas or argon gas. The polymerization temperature of the polymerization reaction is not particularly limited, but is preferably in the range of −100 ° C. to 200 ° C., for example, and can be about room temperature. If the polymerization temperature is raised, the cis-1,4 selectivity of the polymerization reaction may be lowered. Moreover, since the pressure of the said polymerization reaction fully takes in a conjugated diene compound and a nonconjugated olefin in a polymerization reaction system, the range of 0.1-10 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.

In the first method for producing a copolymer of the present invention, when the conjugated diene compound and the non-conjugated olefin are polymerized, the concentration of the conjugated diene compound (mol / l) and the concentration of the non-conjugated olefin (mol) at the start of the polymerization. / L) is 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.

Further, even if the first polymerization catalyst composition or the second polymerization catalyst composition is not used, that is, when a normal coordination ion polymerization catalyst is used, the monomer into the polymerization reaction system The copolymer of the present invention can be produced by adjusting the charging method. That is, the second production method of the copolymer of the present invention is characterized in that the chain structure of the copolymer is controlled by controlling the introduction of the conjugated diene compound in the presence of the non-conjugated olefin. Can control the arrangement of monomer units in the copolymer. In the present invention, the polymerization reaction system is
It means a place where polymerization of a conjugated diene compound and a non-conjugated olefin is carried out, and specific examples include a reaction vessel.

Here, the charging method of the conjugated diene compound may be either continuous charging or split charging, and further, continuous charging and split charging may be combined. Moreover, continuous input is, for example,
Adding at a constant rate and for a fixed time.

Specifically, the concentration ratio of monomers in the polymerization reaction system can be controlled by dividing or continuously adding the conjugated diene compound to the polymerization reaction system for polymerizing the conjugated diene compound and the non-conjugated olefin. As a result, it is possible to characterize the chain structure (that is, the arrangement of monomer units) in the resulting copolymer. Further, when the conjugated diene compound is added, the presence of the non-conjugated olefin in the polymerization reaction system can suppress the formation of a conjugated diene compound homopolymer. The addition of the conjugated diene compound may be performed after the polymerization of the nonconjugated olefin is started.

For example, when a block copolymer is produced by the above second production method, it is effective to continuously add a conjugated diene compound in the presence of the nonconjugated olefin to the polymerization reaction system in which the polymerization of the nonconjugated olefin has been started in advance. It becomes. In particular, when a multi-block copolymer is produced by the second production method, “a non-conjugated olefin is polymerized in a polymerization reaction system, and then the conjugated diene compound is reacted in the presence of the non-conjugated olefin. It is effective to repeat the operation of “continuous charging into the system” twice or more.

The second production method is not particularly limited as described above, except that the method of charging the monomer into the polymerization reaction system as described above. For example, the solution polymerization method, the suspension polymerization method, the liquid phase bulk polymerization method, Any polymerization method such as an emulsion polymerization method, a gas phase polymerization method, and a solid phase polymerization method can be used. In addition, the second production method is the same as the first production method, except that the method of charging the monomer into the polymerization reaction system as described above, and the conjugated diene compound as a monomer Non-conjugated olefins can be copolymerized.

In the second production method, it is necessary to control the input of the conjugated diene compound. Specifically, it is preferable to control the input amount of the conjugated diene compound and the input frequency of the conjugated diene compound. Examples of the method for controlling the introduction of the conjugated diene compound include a method of controlling by a program such as a computer and a method of controlling by analog using a timer or the like, but are not limited thereto. In addition, as described above, the method for charging the conjugated diene compound is not particularly limited, and examples thereof include continuous charging and divided charging. Here, when the conjugated diene compound is dividedly added, the number of times the conjugated diene compound is added is not particularly limited, but is preferably in the range of 1 to 5 times. If the conjugated diene compound is charged too many times, it may be difficult to distinguish it from a random copolymer.

In the second production method, since it is necessary that the non-conjugated olefin is present in the polymerization reaction system when the conjugated diene compound is charged, the non-conjugated olefin is continuously supplied to the polymerization reaction system. Is preferred. Moreover, the supply method of a nonconjugated olefin is not specifically limited.

(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.
When 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 when it exceeds 200 parts by mass, the reinforcing filler tends not to be mixed. And the performance as a rubber composition may be reduced.

<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 the rubber composition of the present invention or the crosslinked rubber composition of the present invention is used, 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.

Example 1
After adding 160 ml of a toluene solution to a sufficiently dried 400 ml pressure-resistant glass reactor, ethylene was introduced at 0.8 MPa. On the other hand, bis (2-phenylindenyl) gadolinium bis (dimethylsilylamide) [(2-PhC ₉ H ₆ ) ₂ GdN (SiHMe ₂ ) ₂ ] 28.5 μmol in a glass container in a glove box under a nitrogen atmosphere. , 34.2 μmol of dimethylanilinium tetrakis (pentafluorophenyl) borate [Me ₂ NHPhB (C ₆ F ₅ ) ₄ ] and 1.43 mmol of diisobutylaluminum hydride were dissolved in 8 ml of toluene to obtain a catalyst solution. Thereafter, the catalyst solution was taken out from the glove box, an amount of 28.2 μmol in terms of gadolinium was added to the monomer solution, and polymerization was performed at room temperature for 5 minutes. Thereafter, 100 ml of a toluene solution containing 15.23 g (0.28 mol) of 1,3-butadiene was added while lowering the ethylene introduction pressure at a rate of 0.2 MPa / min, and polymerization was further performed for 90 minutes. After the polymerization, 1 ml of 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) (NS-5) 5% by mass of isopropanol solution was added to stop the reaction, and a copolymer with a large amount of methanol was added. Was separated and vacuum dried at 70 ° C. to obtain a copolymer A (block copolymer). The yield of the obtained copolymer A was 12.50 g.

( Reference Example 2)
After adding 700 ml of a toluene solution containing 28.0 g (0.52 mol) of 1,3-butadiene to a sufficiently dry 2 L stainless steel reactor, ethylene was introduced at 0.8 MPa. On the other hand, dimethylaluminum (μ-dimethyl) bis (2-phenylindenyl) neodium [(2-PhC ₉ H ₆ ) ₂ Nd (μ-Me) ₂ AlMe ₂ in a glass container in a glove box under a nitrogen atmosphere. 400.0 μmol, 200.0 μmol of triphenylcarbonium tetrakis (pentafluorophenyl) borate (Ph ₃ CB (C ₆ F ₅ ) ₄ ) were charged and dissolved in 80 ml of toluene to obtain a catalyst solution. Thereafter, the catalyst solution was taken out from the glove box, an amount of 390.0 μmol in terms of neodymium was added to the monomer solution, and polymerization was performed at 60 ° C. for 60 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 the copolymer was separated with a large amount of methanol. And dried in a vacuum at 70 ° C. to obtain a polymer B (random copolymer). The yield of the obtained copolymer B was 17.00 g.

(Example 3)
Ethylene was introduced at 0.8 MPa into a sufficiently dried 400 ml pressure-resistant glass reactor, and then 160 ml of a toluene solution containing 9.14 g (0.17 mol) of 1,3-butadiene was added. On the other hand, bis (2-phenylindenyl) gadolinium bis (dimethylsilylamide) [(2-PhC ₉ H ₆ ) ₂ GdN (SiHMe ₂ ) ₂ ] 28.5 μmol in a glass container in a glove box under a nitrogen atmosphere. , 34.2 μmol of dimethylanilinium tetrakis (pentafluorophenyl) borate [Me ₂ NHPhB (C ₆ F ₅ ) ₄ ] and 1.43 mmol of diisobutylaluminum hydride were dissolved in 8 ml of toluene to obtain a catalyst solution. Thereafter, the catalyst solution was taken out from the glove box, an amount of 28.2 μmol in terms of gadolinium was added to the monomer solution, and polymerization was performed at room temperature for 60 minutes. Thereafter, 60 ml of a toluene solution containing 9.14 g (0.17 mol) of 1,3-butadiene was newly added at a rate of 1.0 ml / min while lowering the ethylene introduction pressure at a rate of 0.1 MPa / min. Thereafter, polymerization was further performed for 60 minutes. After the polymerization, 1 ml of 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) (NS-5) 5% by mass of isopropanol solution was added to stop the reaction, and a copolymer with a large amount of methanol was added. Was separated and vacuum dried at 70 ° C. to obtain a polymer C. The yield of the obtained copolymer C was 16.30 g.

(Comparative Example 1)
Butadiene rubber (BR01, manufactured by JSR) was prepared as a comparative sample.

(Comparative Example 2) Copolymer D was synthesized based on Example 1 of JP-A-2000-86857.

Example were prepared or obtained as described above 1, Reference Example 2, the copolymer A of each of the copolymer of Example 3, B, C, butadiene rubber of Comparative Example 1, the copolymer of Comparative Example 2 For D, the microstructure, ethylene content, weight average molecular weight (Mw), molecular weight distribution (Mw / Mn) and DSC curve were measured and evaluated by the following methods. 1 is a ¹³ C-NMR spectrum chart of the copolymer A, FIG. 2 shows a DSC curve of the copolymer A, and FIG. 3 shows a DSC curve of the copolymer C.
In addition, the vertical axis | shaft of a DSC curve shows a heat flow rate.

(1) Microstructure (1,2-vinyl bond amount (Vi (%)), cis-1,4 bond amount)
The microstructure of the butadiene moiety in the copolymer (1,2-vinyl bond content) was determined by ¹ H-NMR spectrum (100 ° C., d-tetrachloroethane standard: 6 ppm) according to the 1,2-vinyl bond component (5.0 -5.1 ppm) and the total ratio of butadiene bond components (5 to 5.6 ppm), and the microstructure of the butadiene moiety in the copolymer (cis-1,4 bond content) is determined by ¹³ C-NMR spectrum. (100 ° C., d-tetrachloroethane standard: 73.8 ppm) and cis-1,4 bonding component (26.5-27.5 ppm) and total butadiene bonding component (26.5-27.5 ppm + 31.5-32. 5 ppm). Table 1 shows calculated values of 1,2-vinyl bond amount (Vi (%)) and cis-1,4 bond amount (%).
(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 cis-1,4 bond component ( 26.5-27.5 ppm) and the total butadiene bond component (26.5-27.5 ppm + 31.5-32.5 ppm). It was obtained from the integral ratio of.
(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 × 2, detector: differential refractometer (R
I)] with respect to monodisperse polystyrene, the polystyrene equivalent weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the polymer were determined. The measurement temperature is 140 ° C.
(4) DSC curve Differential scanning calorimetry (DSC) was performed in accordance with JIS K 7121-1987, and a DSC curve was drawn. In order to avoid the influence of impurities such as a single polymer and catalyst residue, the measurement was performed by immersing the copolymers A, B, and D in a large amount of tetrahydrofuran for 48 hours, removing all components dissolved in tetrahydrofuran, and then drying. A rubber component was used as a sample. Copolymer C was measured without treatment.

In the ¹³ C-NMR spectrum chart of copolymer A in FIG. 1, a peak derived from the ethylene block portion is observed at 29.4 ppm, and in the DSC curves of copolymers A and D in FIGS. A crystallization temperature derived from a block portion consisting of a monomeric cis unit of 1,3-butadiene at around 10 ° C and a crystallization temperature derived from a block portion consisting of a monomeric unit of ethylene at around 120-130 ° C were observed. it can.
From the above, it can be seen that the copolymers A and D are block copolymers of high cis 1,3-butadiene and ethylene.
The copolymers A and D were analyzed for chain distribution by applying the ozonolysis-GPC method described in the literature ("Science of Polymer Science Vol. 42, No. 4, Page 1347"). The gel permeation chromatography was measured based on [GPC: Tosoh HLC-8121GPC / HT, column: Showa Denko GPC HT-803 × 2, detector: differential refractometer (RI), monodisperse polystyrene as a reference. The temperature was measured using 140 ° C.]. As a result, it was confirmed that the block ethylene component, that is, the polyethylene component having a number average molecular weight (Mn) of 1000 or more was 80% by mass or more and the copolymer A was a block copolymer with respect to the total ethylene component.
In the DSC curve of FIG. 3, only the crystallization temperature derived from the block portion composed of monomeric cis units of 1,3-butadiene was observed by DSC at around −10 ° C. for copolymer B. The crystallization temperature derived from the block part consisting of body units cannot be observed. Further, as a result of analysis of chain distribution by applying the ozonolysis-GPC method, the block ethylene component, that is, the polyethylene component having a number average molecular weight (Mn) of 1000 or more is 10% by mass or less based on the total ethylene component. It was confirmed that the polymer B was a random copolymer.
In the DSC curve of FIG. 4, the copolymer C has a butadiene and ethylene monomer in addition to an endothermic peak of 120 ° C. or more derived from the crystallization temperature of a long-chain block portion composed of an ethylene monomer unit. A broad endothermic peak was observed at 40 ° C. to 120 ° C. indicating that a random portion formed by irregularly arranging units (including low molecular weight blocks) was formed. As a result of analyzing the chain distribution by applying the ozonolysis-GPC method, the block ethylene component, that is, the polyethylene component having a number average molecular weight (Mn) of 1000 or more is 67% by mass, and the copolymer C Was found to be a tapered copolymer of 1,3-butadiene and ethylene.

For Example 1 , Reference Example 2, Example 3 and Comparative Examples 1 and 2, a rubber compound having a compounding formulation shown in Table 2 was prepared, and vulcanized rubber obtained by vulcanizing at 160 ° C. for 20 minutes. According to the following method, low exothermic property, heat resistance, and ozone resistance test 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 exothermicity (index)》
Using a dynamic spectrometer, the measurement was performed under the conditions of a tensile dynamic strain of 3%, a frequency of 15 Hz, and 50 ° C. In Table 3, it represented by the index | exponent which makes the reciprocal number of the comparative example 1 100. It shows that it is excellent in low exothermic property (low loss property), so that an index value is large.

《Heat resistance (index)》
After the sample specimen was thermally deteriorated in an oven at 100 ° C. for 48 hours, the sample was taken out, and a 300% elongation stress (Md 300%) by a tensile test was measured at room temperature in accordance with JIS K 6251. The Md change rate (%) is shown in Table 3 with Md 300% in the tensile test of the sample not subjected to thermal degradation as 100. It shows that heat resistance is so favorable that change rate (%) is small.

<< Ozone resistance (dynamic) >>
The ozone resistance was measured according to JIS K 6259. The strip-shaped test piece was exposed under the conditions of 40 ° C. and ozone concentration of 50 pphm while giving a dynamic elongation of 30%, and the state of the sample after 12 hours (presence of cracks) was judged visually. The results are shown in Table 3.

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

Claims (10)

A copolymer of a conjugated diene compound and a non-conjugated olefin, wherein the content of 1,2 adduct portion (including 3,4 adduct portion) is 5 mol% or less with respect to the total amount of conjugated diene units derived from the conjugated diene compound. Yes,
The following general formula (I):
(In the formula, M represents gadolinium, Cp ^R independently represents unsubstituted or substituted indenyl, and R ^{a to} R ^f each independently represents an alkyl group having 1 to 3 carbon atoms or a hydrogen atom. And at least one of R ^{a to} R ^f is a hydrogen atom, L represents a neutral Lewis base, and w represents an integer of 0 to 3). Obtained by polymerizing in the presence of
A copolymer characterized by the above.   The copolymer according to claim 1, wherein the amount of cis 1,4-bonds relative to the total amount of conjugated diene units derived from the conjugated diene compound exceeds 50 mol%.   The copolymer according to claim 1, wherein the content of the total amount of non-conjugated olefin units derived from the non-conjugated olefin exceeds 0 mol% and is 50 mol% or less.   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 acyclic olefin.   The copolymer according to claim 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 is at least one selected from the group consisting of 1,3-butadiene and isoprene.