JP2012162628A - Copolymer of conjugated diene compound and non-conjugated olefin, rubber composition, crosslinked rubber composition, and tire - Google Patents

Abstract

An object of the present invention is to produce a rubber having excellent wettability, low temperature characteristics, and weather resistance, and a conjugated diene compound containing a cis 1,4 bond in a conjugated diene compound-derived moiety and a non-conjugated olefin. 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 .
In a copolymer of a conjugated diene compound and a non-conjugated olefin, the cis 1,4-bond content of the conjugated diene compound-derived moiety is less than 92%, and the content of the non-conjugated olefin-derived moiety is 10 mol. It is characterized by being less than%.
[Selection figure] None

Description

  The present invention relates to a copolymer of a conjugated diene compound and a non-conjugated olefin, a rubber composition, a crosslinked rubber composition, and a tire, and particularly a rubber excellent in wettability, low temperature characteristics, and weather resistance (ozone resistance). A copolymer of a conjugated diene compound containing a cis 1,4 bond in a conjugated diene compound-derived part (conjugated diene part) and a non-conjugated olefin, a rubber composition containing the copolymer, The present invention relates to a crosslinked rubber composition obtained by crosslinking a rubber composition, and a tire using the rubber composition or the crosslinked rubber composition.

It is well known that coordinated anionic polymerization using a catalyst system typified by a Ziegler-Natta catalyst can homopolymerize olefins and dienes. However, in such a polymerization reaction system, it has been difficult to efficiently copolymerize olefin and diene.
In particular, by applying a copolymer of conjugated diene and non-conjugated olefin to the compounded rubber, the double bond of the conjugated diene compound-derived part (conjugated diene part) in the copolymer is less than that of the conjugated polymer. , Ozone resistance is improved. Further, as one of the required properties other than the ozone resistance required when the rubber composition is applied to various uses (tires, belt conveyors, anti-vibration rubbers, etc.), it is mentioned that the crack growth resistance is improved. .

For example, Patent Document 1 discloses a conjugated diene polymerization catalyst containing a group IV transition metal compound of the periodic table having a cyclopentadiene ring structure. As a monomer copolymerizable with this conjugated diene, ethylene is disclosed. Etc. α-olefins are exemplified. However, the copolymerization of the conjugated diene compound and the non-conjugated olefin is not specifically described. Naturally, there is no description or suggestion of producing a rubber having excellent wettability and low temperature characteristics by setting the cis content and the cis 1,4 bond content to less than 92%. Furthermore, description and suggestion have been made about producing a rubber having a low low-temperature elastic modulus and excellent weather resistance by setting the content of the non-conjugated olefin-derived part (non-conjugated olefin) to less than 10 mol%. Absent.

For example, Patent Document 2 discloses an olefin polymerization catalyst composed of a transition metal compound such as a titanium compound and a co-catalyst, and a copolymer of an α-olefin and a conjugated diene compound. However, it was confirmed that the production and use of the α-olefin, which is a non-conjugated olefin, was only in the range of 66.7 to 99.1 mol%. That is, the specific description about the conjugated diene compound-nonconjugated olefin copolymer in which the content of the nonconjugated olefin-derived portion (nonconjugated olefin) is less than 10 mol%, the cis content and the cis 1,4 bond content are 92% Patent Document 2 neither describes nor suggests producing a rubber having excellent wettability and low-temperature characteristics. Further, Patent Document 2 describes the production of a rubber having a low low-temperature elastic modulus and excellent weather resistance by setting the content of the non-conjugated olefin-derived portion (non-conjugated olefin) to less than 10 mol%. There is no suggestion.

Patent Document 3 discloses a copolymer of ethylene and butadiene synthesized using ethylene and butadiene as starting materials using a special organometallic complex as a catalyst component.
Butadiene, which is a monomer, is inserted into the copolymer in the form of trans-1,2-cyclohexane, and has a structure different from that of the copolymer of the present invention. In addition, the production and use of the ethylene content, which is a non-conjugated olefin, was specifically supported only in the range of 69.6 to 89.0 mol%. Here, the ethylene content was determined by subtracting the molar content of units derived from butadiene whose numerical values are disclosed from 100 mol%. That is, the specific description about the conjugated diene compound-nonconjugated olefin copolymer in which the content of the nonconjugated olefin-derived portion (nonconjugated olefin) is less than 10 mol%, the cis content and the cis 1,4 bond content are 92% Patent Document 3 neither describes nor suggests producing a rubber having excellent wettability by setting the ratio to less than the above. Furthermore, Patent Document 3 describes that a rubber having a low low-temperature elastic modulus and excellent weather resistance can be produced by setting the content of the non-conjugated olefin-derived portion (non-conjugated olefin) to less than 10 mol%. There is no suggestion.

  Patent Document 4 discloses a butadiene polymer having a cis content of 92% and an ethylene content of 3% or 9%. However, Patent Document 4 does not describe or suggest that a rubber having excellent wettability and low-temperature characteristics is produced by setting the cis content and the cis 1,4 bond content to less than 92%.

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

  Accordingly, an object of the present invention is used to produce a rubber having excellent wettability, low temperature characteristics, and weather resistance. The conjugated diene compound-derived moiety (conjugated diene moiety) contains a cis 1,4 bond, and is a conjugated diene. A conjugated diene compound having a cis 1,4-bond content of the compound-derived portion (conjugated diene portion) of less than 92% and a non-conjugated olefin-derived portion (non-conjugated olefin) content of less than 10 mol%; 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 There is.

As a result of intensive studies to achieve the above object, the present inventors polymerized a conjugated diene compound and a non-conjugated olefin in the presence of a specific catalyst, and the resulting conjugated diene compound-non-conjugated olefin copolymer is: It is found that the cis 1,4-bond content of the conjugated diene compound-derived portion (conjugated diene portion) is less than 92%, and the content of the non-conjugated olefin-derived portion (non-conjugated olefin) is less than 10 mol%, The present invention has been completed.

The copolymer of a conjugated diene compound and a non-conjugated olefin of the present invention has a cis 1,4-bond content of a conjugated diene compound-derived portion (conjugated diene portion) of less than 92%, and a non-conjugated olefin-derived portion ( The content of non-conjugated olefin) is less than 10 mol%.
Here, the cis 1,4-bond content means the proportion of 1,4-cis bonds in the conjugated diene unit in the conjugated diene compound-derived portion (conjugated diene compound).

  In such a copolymer, the cis 1,4-bond content of the conjugated diene compound-derived portion (conjugated diene portion) is preferably 50% or more, and more preferably 75% or more.

  By the way, it is preferable that molecular weight distribution (Mw / Mn) is 10 or less.

Preferably, the non-conjugated olefin is an acyclic olefin, more preferably an α-olefin having 2 to 10 carbon atoms, and still more preferably at least one selected from the group consisting of ethylene, propylene and 1-butene. And most preferably ethylene.

And preferably, the conjugated diene compound has 4 to 8 carbon atoms, more preferably at least one selected from the group consisting of 1,3-butadiene and isoprene.

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

The rubber composition of the present invention preferably contains 3% by mass or more of the copolymer in the rubber component.

  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.

  In the copolymer of the conjugated diene compound and the non-conjugated olefin according to the present invention, the cis 1,4-bond content of the conjugated diene compound-derived portion (conjugated diene portion) is less than 92%, and is derived from the non-conjugated olefin. By setting the content of the part (non-conjugated olefin) to less than 10 mol%, it becomes possible to produce a rubber having excellent wettability, low temperature characteristics, and weather resistance.

The present invention is described in detail below.
The copolymer of a conjugated diene compound and a non-conjugated olefin of the present invention has a cis 1,4-bond content of a conjugated diene compound-derived portion (conjugated diene portion) of less than 92%, preferably 50% or more. More preferably, it is 75% or more, and the content of the non-conjugated olefin-derived portion (non-conjugated olefin) is less than 10 mol%, preferably 5.0 mol% to 9.9 mol%.
The cis-1,4 bond content is an amount in the portion derived from the conjugated diene compound, and is not a ratio to the whole copolymer.

By setting the cis 1,4-bond content of the conjugated diene compound-derived part (conjugated diene part) to less than 92%, it is possible to provide a rubber having excellent wettability and low-temperature elastic modulus by reducing crystallinity. It becomes.
By setting the content of the non-conjugated olefin-derived portion (non-conjugated olefin) to less than 10 mol%, it is possible to improve weather resistance and heat resistance without increasing the low temperature elastic modulus. Furthermore, it is preferable in terms of weather resistance and heat resistance that the content of the non-conjugated olefin-derived portion (non-conjugated olefin) is 5.0 mol% to 9.9 mol%.

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

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

The conjugated diene compound preferably has 4 to 8 carbon atoms. Specific examples of the conjugated diene compound include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-
Examples thereof include 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.

In addition, when a block portion composed of a monomer unit of a non-conjugated olefin is provided, it exhibits static crystallinity and can be excellent in mechanical properties such as breaking strength.

Such a copolymer has no 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 structure material, the polystyrene-converted weight average molecular weight (Mw) of this copolymer is preferably 10,000 to 10,000,000. 1,000 to 1,000,000 is more preferable, and 50,000 to 600,000 is more preferable. If Mw exceeds 10,000,000, the moldability may be deteriorated.

Further, a molecular weight distribution (Mw) expressed by a ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn)
Mw / Mn) is preferably 10 or less, and more preferably 6 or less. This is because if the molecular weight distribution exceeds 10, the physical properties are not uniform.
Here, the average molecular weight and molecular weight distribution are determined by gel permeation chromatography (G
PC) polystyrene can be determined as a standard substance.

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

Next, the manufacturing method which can manufacture the copolymer of this invention is demonstrated in detail. However, the manufacturing method described in detail below is merely an example.
The copolymer of the present invention can polymerize a conjugated diene compound and a non-conjugated olefin in the presence of the polymerization catalyst or polymerization catalyst composition described below. As a polymerization method, any method such as a solution polymerization method, a suspension polymerization method, a liquid phase bulk polymerization method, an emulsion polymerization method, a gas phase polymerization method, and a solid phase polymerization method can be used. Moreover, when using a solvent for a polymerization reaction, the solvent used should just be inactive in a polymerization reaction, For example, toluene, cyclohexane, normal hexane, mixtures thereof etc. are mentioned.

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

<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. Represents a group or a hydrogen atom, L represents a neutral Lewis base, and w represents 0.
A metallocene complex represented by 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 ):
( ^Wherein M represents a lanthanoid element, scandium or yttrium, and Cp ^R ′ is
Represents unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl, X is
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. , [B] ⁻ represents a non-coordinating anion) A polymerization catalyst composition containing at least one complex selected from the group consisting of a half metallocene cation complex (hereinafter referred to as a first polymerization catalyst composition). The polymerization catalyst composition may further contain other components contained in the polymerization catalyst composition containing a normal metallocene complex, such as a promoter. Here, the metallocene complex is a complex compound in which one or more cyclopentadienyl or a derivative thereof is bonded to a central metal, 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 0.1 to 0.00.
A range of 01 mol / L is preferred.

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 0-7 or 0
It is an integer of 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,
It is more preferable that it is 0, and it is still more preferable that it is 1-8. 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. As substituted indenyl,
Specifically, 2-phenylindenyl, 2-methylindenyl, etc. are mentioned. Note that the two Cp ^Rs in the general formulas (I) and (II) may be the same as or different from each other.

In the half metallocene cation complex represented by the general formula (III), Cp in the formula
^R ′ is unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl, and among these, unsubstituted or substituted indenyl is preferable. Cp ^R ′ having a cyclopentadienyl ring as a basic skeleton is represented by C ₅ H _5-X R _X. Where X
Is an integer from 0 to 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.
Is more preferably from 1 to 10, more preferably from 1 to 8. 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 metalloids of the metalloid group include germyl Ge, stannyl Sn, silyl Si, and the metalloid group preferably has a hydrocarbyl group,
The hydrocarbyl group of the metalloid group is the same as the above hydrocarbyl group. Specific examples of the metalloid group include a trimethylsilyl group. Specific examples of Cp ^R ′ having a cyclopentadienyl ring as a basic skeleton include the following.
(In the formula, R represents a hydrogen atom, a methyl group or an ethyl group.)

In the general formula (III), Cp ^R ′ having the indenyl ring as a basic skeleton represents
It is similarly defined as Cp ^R in I), and their preferable examples are also the same.

In the general formula (III), Cp ^R ′ having the fluorenyl ring as a basic skeleton is C _13.
It may be represented by H _9-X R _X or C ₁₃ H _17-X R _X. Here, X is 0-9 or 0-17.
Is an integer. In addition, each R is preferably independently a hydrocarbyl group or a metalloid group. The hydrocarbyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 8 carbon atoms. Specific examples of the hydrocarbyl group include a methyl group, an ethyl group, a phenyl group, and a benzyl group. On the other hand, examples of metalloid-based metalloids include germyl Ge, stannyl Sn, silyl Si
Moreover, it is preferable that a metalloid group has a hydrocarbyl group, and the hydrocarbyl group which a metalloid group has is the same as said hydrocarbyl group. Specific examples of the metalloid group include a trimethylsilyl group.

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

The metallocene complex represented by the general formula (I) is a silylamide ligand [—N (SiR ₃ ) ₂
]including. The R group contained in the silylamide ligand (R ^{a to} R ^f in the general formula (I)) is
Each independently represents 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. Furthermore, a methyl group is preferable as the alkyl group.

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

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

In the general formula (III), examples of the thiolate group represented by X include thiomethoxy group, thioethoxy group, thiopropoxy group, thio n-butoxy group, thioisobutoxy group, thiosec-
Aliphatic thiolate groups such as butoxy group and thio-tert-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-
Examples thereof include arylthiolate groups such as isopropyl-6-thioneopentylphenoxy group and 2,4,6-triisopropylthiophenoxy group. Among these, 2,4,6-triisopropylthiophenoxy group is preferable.

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-6-neopentylphenylamide group, 2, Examples include arylamide groups such as 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 is a fluorine atom, a chlorine atom,
Although a bromine atom or an iodine atom may be sufficient, a chlorine atom or a bromine atom is preferable. Also,
Specific examples of the hydrocarbon group having 1 to 20 carbon atoms represented by X include methyl group, 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: Hydrocarbon groups containing silicon atoms such as trimethylsilylmethyl group and bistrimethylsilylmethyl group, and the like. 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
~ 20 hydrocarbon groups are preferred.

In the general formula (III), as the non-coordinating anion represented by [B] ^- , for example,
A tetravalent boron anion is mentioned. 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, tridecahydride-7,
Examples include 8-dicarbaoundecaborate. Among these, tetrakis (pentafluorophenyl) borate is preferable.

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

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

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

The ionic compound represented by the general formula [A] ⁺ [B] ⁻ used for the reaction is a compound selected and combined from the non-coordinating anion and cation, and N, N
-Dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbonium tetrakis (pentafluorophenyl) borate and the like are preferable. The ionic compound represented by the general formula [A] ⁺ [B] ⁻ is 0.1 to 10 with respect to the metallocene complex.
It is preferable to add 1 mol, and it is more preferable to add about 1 mol. The general formula (I
When the half metallocene cation complex represented by II) is used in the polymerization reaction, the general formula (II
The half metallocene cation complex represented by I) may be provided as it is in the polymerization reaction system, or the compound represented by the general formula (IV) used in the above reaction and the general formula [A] ⁺ [B] ⁻ The ionic compound represented may be separately provided in the polymerization reaction system to form a half metallocene cation complex represented by the general formula (III) in the reaction system. In addition, general formula (I) or formula (I
Half metallocene represented by general formula (III) in a reaction system by using a combination of a metallocene complex represented by I) and an ionic compound represented by general formula [A] ⁺ [B] ^- Cationic complexes can also be formed.

Metallocene complexes represented by general formula (I) and formula (II), and the above general formula (III)
It is preferable to determine the structure of the half metallocene cation complex represented 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 aluminoxane content 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 10 to 100.
It is preferable to be about 0, preferably about 100.

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

Further, in the above polymerization catalyst composition, the metallocene complex represented by the general formula (I) and the formula (II) and the half metallocene cation complex represented by the above general formula (III) are each used as an appropriate promoter. By combining, the amount of cis-1,4 bonds and the molecular weight of the resulting copolymer can be increased.

<Second polymerization catalyst composition>
In addition, as the polymerization catalyst composition,
(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 containing at least one selected from the group consisting of at least one halogen compound (B-3) among organic compounds (hereinafter also referred to as a second polymerization catalyst composition) can be preferably exemplified.
When the second polymerization catalyst composition contains at least one of the ionic compound (B-1) and the halogen compound (B-3), the polymerization catalyst composition further comprises:
(C) Component: The following general formula (X):
YR ¹ _a R ² _b R ³ _c (X)
[Wherein Y is a metal selected from Group 1, Group 2, Group 12 and Group 13 of the Periodic Table, and R ¹ and R ² are the same or different and have 1 to 10 carbon atoms. A hydrocarbon group or a hydrogen atom, 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 metal selected from Group 1 of the Periodic Table. In some cases, a is 1.
And b and c are 0 and Y is a metal selected from groups 2 and 12 of the periodic table, a and b are 1 and c is 0, and Y is periodic In the case of a metal selected from Group 13 of the Table, a, b, and c are 1].

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

The component (A) used in the second polymerization catalyst composition is a rare earth element compound or a reaction product of the rare earth element compound and a Lewis base. Here, the 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 rare earth element compound or a reaction product of 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, and se.
aliphatic alkoxy groups such as c-butoxy group and tert-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, thiosec-butoxy group Aliphatic thiolate groups such as thio tert-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, 2,4,6-triisopropylthiophenoxy group Arylthiolate groups such as;
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-dineopentyl Phenylamide group, 2-tert-butyl-6-isopropylphenylamide group, 2-tert-butyl-6-neopentylphenylamide group, 2-isopropyl-6-neopentylphenylamide group, 2,4,6-t
arylamide groups such as ert-butylphenylamide group; bistrialkylsilylamide groups such as bistrimethylsilylamide group; trimethylsilyl group, tris (trimethylsilyl) silyl group, bis (trimethylsilyl) methylsilyl group, trimethylsilyl (dimethyl)
Examples thereof include silyl groups such as silyl group and triisopropylsilyl (bistrimethylsilyl) silyl group; halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom. Furthermore,
Residues of aldehydes such as salicylaldehyde, 2-hydroxy-1-naphthaldehyde, 2-hydroxy-3-naphthaldehyde; hydroxyphenones such as 2′-hydroxyacetophenone, 2′-hydroxybutyrophenone, 2′-hydroxypropiophenone Residues of diketones such as acetylacetone, benzoylacetone, propionylacetone, isobutylacetone, valerylacetone, ethylacetylacetone; 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 [commercial name of Shell Chemical Co., Ltd., composed of isomers of C10 monocarboxylic acid] Synthetic acids], residues of carboxylic acids such as phenylacetic acid, benzoic acid, 2-naphthoic acid, maleic acid, and succinic acid; thiocarboxylic acids such as hexanethioic acid, 2,2-dimethylbutanethioic acid, decanethioic acid, and thiobenzoic acid Acid residue, 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), phosphate (1-methylheptyl) Residues of phosphate esters such as (2-ethylhexyl), phosphoric acid (2-ethylhexyl) (p-nonylphenyl); 2-ethylhexylphosphonate monobutyl, 2-ethylhexylphosphonate mono-2-ethylhexyl, phenylphosphonate mono 2-ethylhexyl, 2-ethylhexylphosphonic acid mono-p-nonylphenyl, phosphonic acid mono-2-ethylhexyl, phosphonic acid mono-1-methylheptyl,
Phosphonic acid ester residues such as mono-p-nonylphenyl phosphonate, 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)
Residue of phosphinic acid such as (p-nonylphenyl) phosphinic acid, butylphosphinic acid, 2-ethylhexylphosphinic acid, 1-methylheptylphosphinic acid, oleylphosphinic acid, laurylphosphinic acid, phenylphosphinic acid, p-nonylphenylphosphinic acid Groups 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), the Lewis base L ¹¹ may be the same or different when w is 2 or 3.

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]
Examples thereof include borates and tridecahydride-7,8-dicarbaoundecaborate.
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 general formula: (—Al (R ′) O—)
A chain aluminoxane or cyclic aluminoxane having a repeating unit represented by the formula:
'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, and the degree of polymerization of the repeating unit is preferably 5 or more, more preferably 10 or more. More preferred). Here, as R ′, specifically, a methyl group,
An ethyl group, a propyl group, an isobutyl group, etc. are mentioned, 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). Reacts with a rare earth element compound or its reactant with a Lewis base,
Cationic transition metal compounds, halogenated transition metal compounds, and compounds in which transition metal centers are insufficiently charged can be generated. In addition, it is preferable that content of the sum total of the halogen compound in the said 2nd polymerization catalyst composition is 1-5 times mole with respect to (A) component.

Examples of the Lewis acid include boron-containing halogen compounds such as B (C ₆ F ₅ ) ₃ , Al (C ₆
F ₅ ) Aluminum-containing halogen compounds such as ₃ can be used, as well as III,
Halogen compounds containing elements belonging to groups IV, 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, benzyl alcohol, 1-decanol, lauryl alcohol, and the like. Among these, tri-2-ethylhexyl phosphate, tricresyl phosphate, acetylacetone,
2-ethylhexanoic acid, versatic acid, 2-ethylhexyl alcohol, 1-decanol and lauryl alcohol are preferred.

The Lewis base is reacted at a ratio of 0.01 to 30 mol, preferably 0.5 to 10 mol, per mol of the metal halide. When the reaction product with the Lewis base is used, the metal remaining in the polymer can be reduced.
Examples of the organic compound containing the active halogen include benzyl chloride.

The component (C) used in the second polymerization catalyst composition is represented by the following general formula (X):
YR ¹ _a R ² _b R ³ _c (X)
[Wherein Y is a metal selected from Group 1, Group 2, Group 12 and Group 13 of the Periodic Table, and R ¹ and R ² are the same or different and have 1 to 10 carbon atoms. A hydrocarbon group or a hydrogen atom, 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 metal selected from Group 1 of the Periodic Table. In some cases, a is 1.
And b and c are 0 and Y is a metal selected from groups 2 and 12 of the periodic table, a and b are 1 and c is 0, and Y is periodic In the case of a metal selected from Table Group 13, a, b and c are 1], and are represented by the following general formula (Xa):
AlR ¹ R ² R ³ (Xa)
[Wherein, R ¹ and R ² are the same or different and each represents a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom, and R ³ is a hydrocarbon group having 1 to 10 carbon atoms, provided that R ³ represents the above It may be the same as or different from R ¹ or R ² ]. Formula (X
) Organoaluminum compounds include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, tripentylaluminum, trihexylaluminum , Tricyclohexyl aluminum, trioctyl aluminum; diethyl aluminum hydride, di-n-propyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl aluminum hydride, dihexyl aluminum hydride, diisohexyl aluminum hydride, hydrogen Dioctylaluminum hydride, diisooctylaluminum hydride; ethylaluminum dihydride, n-
Examples thereof include propylaluminum dihydride and isobutylaluminum dihydride. Among these, triethylaluminum, triisobutylaluminum, diethylaluminum hydride and diisobutylaluminum hydride are preferable. (C
The organoaluminum compound as a component can be used alone or in combination of two or more. In addition, it is preferable that it is 1-50 times mole with respect to (A) component, and, as for content of the organoaluminum compound in the said 2nd polymerization catalyst composition, it is still more preferable that it is about 10 times mole.

<Polymerization catalyst and third polymerization catalyst composition>
The polymerization catalyst is for polymerization of a conjugated diene compound and a non-conjugated olefin, and has the following formula (A):
R _a MX _b QY _b (A)
[In the formula, each R independently represents an unsubstituted or substituted indenyl, the R is coordinated to M, M represents a lanthanoid element, scandium or yttrium; 20 represents a hydrocarbon group, X is μ-coordinated to M and Q, Q represents a group 13 element of the periodic table, and Y independently represents a hydrocarbon group having 1 to 20 carbon atoms or A hydrogen atom, wherein Y is coordinated to Q and a and b are 2].

In a preferred example of the metallocene composite catalyst, the following formula (XV):
[ ^Wherein , M ¹ represents a lanthanoid element, scandium or yttrium, Cp ^R independently represents an unsubstituted or substituted indenyl group, and R ^a and R ^b each independently have 1 to 20 carbon atoms. R ^a and R ^b are μ-coordinated to M ¹ and Al, and R ^c and R ^d each independently represent a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom. Metallocene composite catalysts represented by

The third polymerization catalyst composition includes the metallocene composite catalyst and a boron anion.

<Metalocene composite catalyst>
Hereinafter, the metallocene composite catalyst will be described in detail. The metallocene composite catalyst is
A lanthanoid element, a rare earth element of scandium or yttrium, and a Group 13 element of the periodic table, the following formula (A):
R _a MX _b QY _b (A)
[Wherein, R independently represents unsubstituted or substituted indenyl, R is coordinated to M, M represents a lanthanoid element, scandium or yttrium, and each X independently represents 1 to 1 carbon atoms. 20 represents a hydrocarbon group, X is μ-coordinated to M and Q, Q represents a group 13 element of the periodic table, and Y independently represents a hydrocarbon group having 1 to 20 carbon atoms or A hydrogen atom, wherein Y is coordinated to Q, and a and b are 2.] By using the metallocene polymerization catalyst, a copolymer of a conjugated diene compound and a non-conjugated olefin can be produced. In addition, by using the metallocene composite catalyst, for example, a catalyst previously combined with an aluminum catalyst, the amount of alkylaluminum used at the time of copolymer synthesis can be reduced or eliminated. If a conventional catalyst system is used, it is necessary to use a large amount of alkylaluminum at the time of copolymer synthesis. For example, in the conventional catalyst system, it is necessary to use 10 equivalents or more of alkylaluminum with respect to the metal catalyst. Is demonstrated.

In the metallocene composite catalyst, the metal M in the formula (A) is a lanthanoid element,
Scandium or yttrium. Lanthanoid elements include 1 of atomic numbers 57-71.
5 elements are included, and any of these may be used. Preferred examples of the metal M include samarium Sm, neodymium Nd, praseodymium Pr, gadolinium Gd, cerium Ce, holmium Ho, scandium Sc, and yttrium Y.

In the formula (A), each R is independently an unsubstituted indenyl or a substituted indenyl, and the R is coordinated to the metal M. In addition, as a specific example of the substituted indenyl group,
For example, 1,2,3-trimethylindenyl group, heptamethylindenyl group, 1,2,4
, 5,6,7-hexamethylindenyl group and the like.

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

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

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

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

In the above formula (XV), Cp ^R is 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. Hydrocarbyl group has 1 carbon
It is preferably -20, more preferably 1-10, and even more preferably 1-8. Specific examples of the hydrocarbyl group include a methyl group, an ethyl group, a phenyl group, and a benzyl group. On the other hand, as an example of a metalloid-based metalloid,
Examples thereof 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. Specific examples of the metalloid group include a trimethylsilyl group. Specific examples of the substituted indenyl include 2-phenylindenyl and 2-methylindenyl. Incidentally, the two Cp ^R in the formula (XV) may each be the same or different from each other.

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

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

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

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

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

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

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

On the other hand, the organoaluminum compound used to produce the metallocene composite catalyst is AlR ^K.
Represented by R ^L R ^M, wherein, ^{R K} and ^{R L} are independently a monovalent hydrocarbon group or a hydrogen atom having 1 to 20 carbon atoms, ^{R M} is a monovalent C1-20 Where R is a hydrocarbon group
^M may be the same as or different from the above ^RK or ^RL . Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group and tetradecyl group. , Pentadecyl group, hexadecyl group, heptadecyl group, stearyl group and the like.

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

<Third polymerization catalyst composition>
The polymerization catalyst composition contains the metallocene composite catalyst and a boron anion, and further contains other components such as a cocatalyst contained in the polymerization catalyst composition containing a normal metallocene catalyst. Etc. are preferably included. The metallocene composite catalyst and boron anion are also referred to as a two-component catalyst. According to the third polymerization catalyst composition, since the boron anion is further contained in the same manner as the metallocene composite catalyst, the content of each monomer component in the copolymer can be arbitrarily controlled. It becomes possible.

In the third polymerization catalyst composition, specific examples of the boron anion constituting the two-component catalyst include a tetravalent boron 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, tridecahydride-7,8-dicarbaundecaborate, etc. are mentioned, and among these, tetrakis (pentafluorophenyl) borate is preferable.

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

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

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

In the method for producing a copolymer, as described above, polymerization is carried out in the same manner as in the method for producing a polymer using a normal coordination ion polymerization catalyst, except that the polymerization catalyst or the polymerization catalyst composition is used. be able to. Here, in the method for producing a copolymer, for example, (1) the components of the polymerization catalyst composition are separately contained 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 polymerization catalyst composition may be provided in the reaction system, or (2) a polymerization catalyst composition prepared in advance may be provided in the polymerization reaction system. Moreover, (2) includes providing a metallocene complex (active species) activated by a cocatalyst. In addition, the usage-amount of the metallocene complex contained in a polymerization catalyst composition is 0.000 with respect to the sum total of nonconjugated olefins other than a conjugated diene compound and this conjugated diene compound.
The range of 1-0.01 times mole is preferable.

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

In the method for producing a copolymer, the polymerization reaction of the conjugated diene compound and the non-conjugated olefin is
It is preferably carried out 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. The pressure of the polymerization reaction is 0.1 to 10.0 MP in order to sufficiently incorporate the conjugated diene compound and the non-conjugated olefin into the polymerization reaction system.
A range of a is preferred. Further, the reaction time of the above polymerization reaction is not particularly limited, and for example, 1 second to 1
The range of 0 days is preferable, but can be appropriately selected depending on conditions such as the type of monomer to be polymerized, the type of catalyst, and the polymerization temperature.

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

In the copolymer production method, when the conjugated diene compound is polymerized with a non-conjugated olefin other than the conjugated diene compound, the concentration of the conjugated diene compound at the start of polymerization (mol
/ L) and the concentration (mol / l) of the non-conjugated olefin 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.

(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 rubber filler is mixed with the reinforcing filler. There is a tendency that it does not get caught, and the performance as a rubber composition may be reduced.

<Crosslinking agent>
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 agent 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 and a crosslinking agent in combination. Examples of the vulcanization accelerator include guanidine, aldehyde-amine, aldehyde-ammonia, thiazole, sulfenamide, thiourea, Compounds such as thiuram, dithiocarbamate, xanthate and the like 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.

Example 1
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 0.4 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 room temperature for 120 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 A. The yield of the obtained copolymer A was 17.50 g.

(Example 2)
After adding 120 ml of a toluene solution containing 2.83 g (0.052 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, bis (2-methylindenyl) praseodymium bis (dimethylsilylamide) (2-MeC ₉ H ₆ ) ₂ Pr {N (SiHMe ₂ ) ₂ } is placed in a glass container. 0 μmol, triphenylcarbonium tetrakis (pentafluorophenyl) borate (Ph ₃ CB (C ₆ F ₅ ) ₄ ) 27.0 μmol, and 1.35 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 50 ° 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 copolymer B. The yield of the obtained copolymer B was 1.50 g.

(Example 3)
After adding 120 ml of a toluene solution containing 2.83 g (0.052 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, bis (2-phenylindenyl) praseodymium bis (dimethylsilylamide) (2-PhC ₉ H ₆ ) ₂ Pr {N (SiHMe ₂ ) ₂ } is placed in a glass container. 0 μmol, triphenylcarbonium tetrakis (pentafluorophenyl) borate (Ph ₃ CB (C ₆ F ₅ ) ₄ ) 27.0 μmol, and triisobutylaluminum 1.35 mmol 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 80 ° C. for 135 minutes. After polymerization, 1 ml of 2,2'-methylene-bis (4-ethyl-6-t-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 vacuo at 70 ° C. to obtain polymer C. The yield of the obtained copolymer C was 2.20 g.

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

(Comparative Example 2)
After adding 320 ml of a toluene solution containing 18.28 g (0.34 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, 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 80 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 copolymer D. The yield of the obtained copolymer D was 16.00 g.

  For the copolymers A to D and butadiene rubber (BR01, manufactured by JSR) obtained as described above, the weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), cis-1,4 bond content, ethylene The content rate was measured and evaluated by the following method.

(1) Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)
Using gel permeation chromatography [GPC: Tosoh HLC-8121GPC / HT, column: Tosoh GMH _HR- H (S) HT × 2, detector: differential refractometer (RI)], measuring temperature 140 The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) in terms of polystyrene of the polymer were determined on the basis of monodisperse polystyrene at ° C.
(2) Cis-1,4 bond content 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). Coupling and Trans-1,4
It was determined from the integral ratio of the bond content ratio. The calculated values of cis-1,4 bond amount (%) are shown in Table 3.
(3) 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-bound 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%).

  For Examples 1 to 3 and Comparative Examples 1 and 2, a rubber compound having the compounding recipe shown in Table 1 was prepared, and vulcanized rubber obtained by vulcanizing 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 2, the index is shown with Comparative Example 1 as 100. The smaller the index value, the better the low-temperature characteristics.

<< wetness >>
In Table 2 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.

《Ozone resistance test》
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 visually judged. The results are shown in Table 2.

Claims (14)

In a copolymer of a conjugated diene compound and a non-conjugated olefin,
A conjugated diene compound and a non-conjugated olefin characterized in that the cis 1,4-bond content of the conjugated diene compound-derived moiety is less than 92% and the content of the non-conjugated olefin-derived moiety is less than 10 mol%. Copolymer.   2. The copolymer of a conjugated diene compound and a non-conjugated olefin according to claim 1, wherein the cis 1,4-bond content of the conjugated diene compound-derived moiety is 50% or more.   The copolymer of a conjugated diene compound and a non-conjugated olefin according to claim 2, wherein a cis 1,4-bond content of the conjugated diene compound-derived moiety is 75% or more.   The copolymer of a conjugated diene compound and a non-conjugated olefin according to claim 1, wherein the molecular weight distribution (Mw / Mn) is 10 or less.   The copolymer of a conjugated diene compound and a non-conjugated olefin according to claim 1, wherein the non-conjugated olefin is an acyclic olefin.   The copolymer of a conjugated diene compound and a non-conjugated olefin according to claim 1, wherein the non-conjugated olefin is an α-olefin having 2 to 10 carbon atoms. The copolymer of a conjugated diene compound and a nonconjugated olefin according to claim 5 or 6, wherein the nonconjugated olefin is at least one selected from the group consisting of ethylene, propylene, and 1-butene.   The copolymer of a conjugated diene compound and a non-conjugated olefin according to claim 7, wherein the non-conjugated olefin is ethylene.   2. The copolymer of a conjugated diene compound and a non-conjugated olefin according to claim 1, wherein the conjugated diene compound has 4 to 8 carbon atoms. The copolymer of a conjugated diene compound and a non-conjugated olefin according to claim 9, wherein the conjugated diene compound is at least one selected from the group consisting of 1,3-butadiene and isoprene.   A rubber composition comprising the copolymer according to claim 1.   The rubber composition according to claim 11, 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 11.   A tire comprising the rubber composition according to claim 11 or the crosslinked rubber composition according to claim 13.