JP6025413B2 - Copolymer of conjugated diene compound and non-conjugated olefin, method for producing the copolymer, rubber composition and tire - Google Patents

Description

  The present invention relates to a copolymer of a conjugated diene compound and a non-conjugated olefin that does not use a fossil resource as a starting material, a method for producing the copolymer, a rubber composition, and a tire.

In recent years, a method for refining fuel oil from biological resources (so-called biomass) including plant resources has been proposed due to increasing demands for reducing fossil resource consumption and greenhouse gas emissions (patents) Reference 1). Such a fuel oil is called a biofuel, and since it does not increase the total amount of carbon dioxide emission, it is expected in the future as a substitute for a fuel oil derived from fossil resources. In addition to the field of fuel oil, biomass-derived compounds are often used not only in the fields of home appliances, household goods, and automobiles.
In the field of automobile tires, the consumption of fossil resources, which are raw materials for tires, can be reduced, and by improving tire characteristics such as fuel efficiency and durability, it is possible to contribute to a reduction in environmental burden.
An example of realizing a reduction in fuel consumption of an automobile is to reduce the rolling resistance of a tire. Conventionally, as rubber materials for tires, diene rubbers such as natural rubber (NR), polybutadiene (BR), polyisoprene (IR), styrene-butadiene copolymer rubber are used, and tire types and rubber materials are used. Depending on the site to be used, an appropriate one of these diene rubbers has been selected and used alone or in a blend of two or more.

In order to reduce the rolling resistance of a tire, it is generally effective to use a rubber material from which a vulcanized rubber with little hysteresis loss can be obtained. Among the diene rubbers described above, for example, high cis-1,4-polybutadiene can form a vulcanized rubber having the highest impact resilience, that is, the smallest hysteresis loss.
Therefore, in order to improve the low-temperature resilience and wear resistance by utilizing the characteristics of polybutadiene rubber, a crystalline block copolymer comprising a high cis-containing conjugated diene polymer segment having a cis content of 40% or more and a crystalline segment is used. A conjugated diene rubber composition using a polymer rubber has been proposed (see, for example, Patent Documents 2 and 3).

  In the future, tires using biomass-derived raw materials will become widespread, and for biomass-derived tires, as with tires formed using ordinary raw materials, rolling resistance is reduced, workability, It is required to improve tire characteristics such as wear and weather resistance.

JP 2009-046661 A JP 2000-86857 A JP 2000-154279 A

  The present invention relates to a copolymer of a conjugated diene compound and a non-conjugated olefin that do not use fossil resources as a starting material, and can achieve a balance between workability, wear resistance, and weather resistance, and the copolymer An object of the present invention is to provide a production method, a rubber composition, and a tire.

The present invention
[1] A copolymer obtained by copolymerizing at least a conjugated diene compound and a non-conjugated olefin, and comprising at least a bio-conjugated diene compound component and a bio-non-conjugated olefin component synthesized from biological resources including plant resources A biomass-derived compound having any of the above, and a value of δ13C of the biomass-derived compound is −30 ‰ to −28.5 ‰, or −22 ‰ or more,
[2] The method for producing a copolymer according to [1], wherein a mixture containing the bioconjugated diene compound is generated from a biological resource including plant resources, and the copolymer is produced using the mixture. Manufacturing method,
[3] A rubber composition comprising the butadiene polymer of [1] above,
[4] A tire comprising the rubber composition of [3] above,
I will provide a.

  According to the present invention, a copolymer of a conjugated diene compound and a non-conjugated olefin that does not use a fossil resource as a starting material, the copolymer capable of achieving a good balance of workability, wear resistance, and weather resistance, the copolymer A method for producing a polymer, a rubber composition, and a tire can be provided.

[Copolymer of conjugated diene compound and non-conjugated olefin]
<Copolymer>
The copolymer of a conjugated diene compound and a non-conjugated olefin according to an embodiment of the present invention is a copolymer obtained by copolymerizing at least a conjugated diene compound and a non-conjugated olefin, and includes the conjugated diene compound and the non-conjugated olefin. The olefin includes a biomass-derived compound having at least one of a bioconjugated diene compound component and a biononconjugated olefin component synthesized from a biological resource including a plant resource, and the value of δ13C of the biomass-derived compound is −30 ‰ to -28.5 ‰, or -22 ‰ or more.
One of the conjugated diene compound and the non-conjugated olefin may be synthesized from petroleum resources. That is, the biomass-derived compound may contain only a bioconjugated diene compound component, or may contain both a bioconjugated diene compound component and a bio nonconjugated olefin component.
The copolymer preferably contains 10 to 90% by mass of a conjugated diene compound and 10 to 90% by mass of a nonconjugated olefin.

The weight average molecular weight (Mw) of the copolymer of the conjugated diene compound and the non-conjugated olefin of the present invention does not cause a problem of lowering the molecular weight. From the viewpoint of application to a polymer structure material, the copolymer The Mw is preferably 10,000 or more, and more preferably 1,000,000 or less. This is because if Mw is 10,000 or less, the mechanical strength as a structural material is insufficient, and if Mw exceeds 1,000,000, the moldability is deteriorated.
Further, the molecular weight distribution (Mw / Mn) represented by the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) is preferably 10 or less, and more preferably 6 or less. This is because it becomes easy to generate uniform physical properties. Here, the average molecular weight and the molecular weight distribution can be determined using polystyrene as a standard substance by gel permeation chromatography (GPC).

  In the copolymer of the conjugated diene compound and the non-conjugated olefin of the present invention, the amount of cis-1,4 bonds in the conjugated diene compound portion is preferably 50% or more, and more preferably 70% or more. If the amount of cis-1,4 bonds in the conjugated diene compound portion is 50% or more, high elongation crystallinity and low glass transition point (Tg) can be maintained, thereby improving physical properties such as abrasion resistance. Is done.

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

The structure of the block copolymer is (AB) _x , A- (BA) _x and B- (AB) _x (where A is a block composed of monomer units of a conjugated diene compound). And B is a block portion composed of monomer units of non-conjugated olefin, and x is an integer of 1 or more.
In the case of a block copolymer, the content of the non-conjugated olefin (part derived from the non-conjugated olefin) of the copolymer of the present invention is preferably more than 0 mol% and 50 mol% or less, more than 0 mol% and More preferably, it is 40 mol% or less. If the content of the non-conjugated olefin (the non-conjugated olefin-derived portion) is within the above range, the heat resistance can be effectively improved without causing macro phase separation.
On the other hand, the content of the conjugated diene compound (part derived from the conjugated diene compound) of the copolymer of the present invention is preferably 50 mol% or more and less than 100 mol%, preferably 60 mol% or more and less than 100 mol%. Further preferred. If the content of the conjugated diene compound (part derived from the conjugated diene compound) is within the above range, the copolymer of the present invention has rubber-like elasticity.

<Conjugated diene compound>
The value of δ13C of the conjugated diene compound is −30 ‰ to −28.5 ‰, or −22 ‰ or more. The value of δ13C of the conjugated diene compound is measured by a stable isotope ratio measuring apparatus. δ13C represents the ratio of stable isotopes in the substance. δ13C is the ratio of ¹³ C to ¹² C in the target substance, and ¹³ C / ¹² C is compared to the isotope ratio in the standard sample (fossil of Cretaceous belemnite). This is an index indicating how much the deviation is, and this ratio is represented by ‰ (percentage). It means that the ratio of ¹³ C in a substance is so low that the value (negative value) of (delta) ^13C leaves | separates from zero.
Light isotopes are more diffusive and more reactive than heavy isotopes. For example, in the case of carbon atoms of carbon dioxide in the atmosphere taken into plants by photosynthesis, ¹² C is better than ¹³ C. It has been found that it is easily fixed in plants.
That is, the carbon atoms taken into the plant body have a relatively large amount of ¹² C and a smaller amount of ¹³ C than carbon atoms in the atmosphere. Therefore, the stable isotope ratio (δ13C) of carbon taken into the plant body is lower than the stable isotope ratio of carbon existing in the atmosphere.
This change in isotope ratio is called isotope fractionation and is represented by Δ13C (Δ13C is distinguished from δ13C).
Δ13C = (δ13C in the atmosphere) − (δ13C in the sample)

Therefore, the substance derived from the conjugated diene compound can be identified from the value of δ13C of the conjugated diene compound.
The value of δ13C of the conjugated diene compound is preferably in the range of −21 ‰ to −12 ‰. The value of δ13C of the conjugated diene compound is preferably in the range of −29.5 ‰ to −28.5 ‰. Further, the value of δ13C of the conjugated diene compound is preferably in the range of −30 ‰ to −29 ‰.

  The conjugated diene compound used as a monomer is a compound synthesized from a biological resource including a plant resource, and preferably has 4 to 8 carbon atoms. Specific examples of the conjugated diene compound include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, and the like. These conjugated diene compounds may be used alone or in combination of two or more. Among the conjugated diene compounds described above, 1,3-butadiene and isoprene are preferable, and 1,3-butadiene is particularly preferable.

≪Method for producing biobutadiene monomer≫
(Production method)
A method for synthesizing a biobutadiene monomer using bioethanol synthesized from biological resources (biomass) including plant resources as a starting material will be described. A method for producing a biobutadiene monomer will be described.
First, bioethanol is produced from biomass. By contacting the produced bioethanol with a composite metal oxide containing at least magnesium and silicon as metal elements under heating, a mixture containing a biobutadiene monomer component can be produced. In this production method, the composite metal oxide acts as a catalyst. From the viewpoint of expressing good catalytic activity, the temperature when bioethanol is brought into contact with the composite metal oxide is preferably 350 ° C to 450 ° C.

(Production of bioethanol)
Examples of biological resources that can be used as raw materials for bioethanol include sugarcane, corn, sugar beet, cassava, beet, wood, and algae. Among these resources, it is preferable to use sugarcane, corn, and sugar beet that contain a large amount of sugar or starch from the viewpoint of production efficiency.

(Composite metal oxide)
The composite metal oxide contains at least magnesium and silicon as metal elements. Among these, it is preferable to use a silica-magnesia composite oxide synthesized by a sol-gel method. Usable metal elements include zinc, zirconium, copper, aluminum, calcium, phosphorus, tantalum and the like.

(Production method of composite metal oxide)
Examples of the method for producing the composite metal oxide include a sol-gel method and a method in which silica is mixed with an aqueous solution of a metal salt and supported by evaporation and drying.

(Contact reaction between bioethanol and mixed metal oxide)
For the contact reaction between the composite metal oxide and bioethanol, a generally known reaction method can be used. For example, among the reaction methods disclosed in Japanese Patent Application Laid-Open No. 2009-051760, a reaction method using a fixed bed gas flow type catalytic reaction device is applicable.
The composite metal oxide is filled in the reaction tube, heated as a pretreatment in a carrier gas atmosphere such as nitrogen gas, and then the temperature of the reaction tube is lowered to the reaction temperature. Thereafter, a predetermined amount of carrier gas and bioethanol are introduced. The biobutadiene monomer is separated from the gas produced by the reaction. As a separation method, the generated gas is passed through a cooled condenser to separate heavy impurities such as unreacted bioethanol and water, and then the reaction gas is bubbled into an organic solvent to remove the biobutadiene monomer. It is dissolved in a solvent and recovered as a solution. Light impurities such as ethylene and carrier gas N ₂ are passed through without being dissolved in the organic solvent and discharged from the solvent tank.

<Non-conjugated olefin>
The non-conjugated olefin in the copolymer of the conjugated diene compound and the non-conjugated olefin according to the embodiment of the present invention is synthesized from a biological resource including a plant resource, and the ¹⁴ C decay of the non-conjugated olefin The gram amount value per minute is 0.1 dpm / gC or more. ¹⁴ C decay value per gram per minute is a value measured by accelerator mass spectrometry (AMS) or liquid scintillation counting method (LSC).
Further, the value of Δ14C of the non-conjugated olefin is −75 to −225 ‰. The value of Δ14C of the non-conjugated olefin is a value converted into a ¹⁴ C concentration ( ¹⁴ AN) when it is assumed that the sample carbon is δ13C = −25.0 ‰.
Δ14C can be calculated from the above-described value of δ13C as follows.
δ14C = [( ¹⁴ As− ¹⁴ AR) / ¹⁴ AR] × 1000 (1)
δ13C = [( ¹³ As− ¹³ APDB) / ¹³ APDB] × 1000 (2)
here,
¹⁴ As: ¹⁴ C concentration of sample carbon: ( ¹⁴ C / ¹² C) s or ( ¹⁴ C / ¹³ C) s
¹⁴ AR: ¹⁴ C concentration of standard modern carbon: ( ¹⁴ C / ¹² C) R or ( ¹⁴ C / ¹³ C) R
The ¹⁴ C concentration in the equation (1) is converted based on the following equation based on the measured value of δ13C.
^{14 AN = 14 As × (0.975} / (1 + δ13C / 1000)) 2 ( when using a ¹⁴ C / ¹² C as ¹⁴ As)
Or
^{14 AN = 14 As × (0.975} / (1 + δ13C / 1000)) ( when using ¹⁴ C / ¹³ C as ¹⁴ As)
From the above,
Δ14C = [( ¹⁴ AN− ¹⁴ AR) / ¹⁴ AR] × 1000 (‰)

The value of Δ14C of the non-conjugated olefin is −75 to −225 ‰, which is the same level as Δ14C of carbon in the current atmospheric carbon dioxide, and is included in the organic matter fixed in the existing growing plant body. Means carbon. Since the half-life of radioactive carbon ¹⁴ C is about 5730 years, carbon contained in fossil resources does not include ¹⁴ C. Δ14C of butadiene derived from fossil resources is about −1000 ‰.
Therefore, the butadiene polymer-derived substance can be specified by the Δ14C value of the butadiene polymer, the amount of gram per minute per ¹⁴ C, or the value of δ13C.

The non-conjugated olefin used as a monomer is a non-conjugated olefin other than a conjugated diene compound, and has excellent heat resistance and reduces the proportion of double bonds in the main chain of the copolymer to control crystallinity. This makes it possible to increase the degree of design freedom as an elastomer.
As the non-conjugated olefin, an acyclic olefin is preferable, and an α-olefin having 2 to 10 carbon atoms is preferable. If it is an α-olefin, since it has a double bond at the α-position of the olefin, copolymerization with a conjugated diene compound can be carried out efficiently.
From this viewpoint, preferred examples of the non-conjugated olefin include α-olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, and 1-octene. These non-conjugated olefins may be used alone or in combination of two or more. Among the non-conjugated olefins described above, ethylene, propylene and 1-butene are preferable, and ethylene is particularly preferable.
In addition, an olefin refers to the compound which is an aliphatic unsaturated hydrocarbon and has one or more carbon-carbon double bonds.

≪Method for producing bioethylene monomer≫
(Production method)
Bioethylene monomer can be synthesized using bioethanol synthesized from biological resources (biomass) including plant resources as a starting material. In this production method, biomass is gasified to produce synthesis gas, and this synthesis gas is converted to ethanol to obtain bioethanol. Subsequently, bioethanol can be dehydrated to obtain bioethylene.

≪Method for producing biopropylene monomer≫
(Production method)
After bioethanol synthesized from biological resources (biomass) including plant resources is used as a starting material, biomethanol is converted to ethylene (referred to as bioethylene) by a dehydration reaction, and the bioethylene and produced water are separated. Then, the separated bioethylene is purified by adsorption. Biopropylene can be produced from the obtained bioethylene by a metathesis reaction together with a raw material containing n-butene.

<Other ingredients>
The copolymer according to the embodiment of the present invention is a copolymer with a conjugated diene compound and a non-conjugated olefin, as a third component, a diene compound other than the conjugated diene compound, an aromatic vinyl compound, or the like. Also good. Examples of conjugated diene compounds other than those described above include 2,3-dimethylbutadiene and 2-phenyl-1,3-butadiene. In addition, diolefinic hydrocarbons are suitable as diene compounds other than conjugated diene compounds. Specifically, chloroprene (2-chloro-1,3-butadiene), cyclopentadiene, 2,3-dimethyl-1,3-butadiene and the like can be used.
Examples of the diene compound include ethylidene norbornene (ENB), 1,4-hexadiene (1,4-HD), dicyclopentadiene (DCP), and the like.
Examples of the aromatic vinyl compound include styrene, p-methylstyrene, m-methylstyrene, p-tert-butylstyrene, α-methylstyrene, chloromethylstyrene, vinyltoluene and the like.
Examples of the copolymer obtained by copolymerizing the above compound include an ethylene-butadiene copolymer (EBR), an ethylene-propylene copolymer (EPM), and an ethylene-propylene-diene copolymer (EPDM). Examples include various styrene-butadiene copolymers, styrene-isoprene copolymers, styrene-isoprene-butadiene copolymers, isoprene-butadiene copolymers, and the like.
In addition, as a monomer used when forming the copolymer which concerns on embodiment of this invention, in addition to what was synthesize | combined from the biological origin resources as mentioned above, conventionally well-known petroleum Chemically derived monomers can be used.

[Method for producing copolymer]
In the method for producing a copolymer of a conjugated diene compound and a nonconjugated olefin according to an embodiment of the present invention, a conjugated diene compound and a nonconjugated olefin are polymerized in the presence of a polymerization catalyst or a 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, etc. are mentioned.

  In the method for producing a copolymer of a conjugated diene compound and a non-conjugated olefin, a method for producing a polymer using a normal coordination ion polymerization catalyst can be applied except that the polymerization catalyst or the polymerization catalyst composition is used.

<Production Method (1): First Polymerization Catalyst Composition>
As the first polymerization catalyst composition, a metallocene complex represented by the following general formula (I), a metallocene complex represented by the following general formula (II), and a half metallocene cation complex represented by the following general formula (III) And a polymerization catalyst composition containing at least one complex selected from the group consisting of (hereinafter also referred to as a first polymerization catalyst composition).

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

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

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

(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)

（式中、Ｍは、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^R’は、無置換もしくは置換シクロペンタジエニル、インデニル又はフルオレニルを示し、Ｘは、水素原子、ハロゲン原子、アルコキシド基、チオラート基、アミド基、シリル基又は炭素数１〜２０の炭化水素基を示し、Ｌは、中性ルイス塩基を示し、ｗは、０〜３の整数を示し、［Ｂ］^-は、非配位性アニオンを示す）

(In the formula, M represents a lanthanoid element, scandium or yttrium, Cp ^R ′ represents an unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl, and X represents a hydrogen atom, a halogen atom, an alkoxide group or a thiolate group. , An amide group, a silyl group, or a hydrocarbon group having 1 to 20 carbon atoms, L represents a neutral Lewis base, w represents an integer of 0 to 3, and [B] ⁻ represents a non-coordinating group. Anion)

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

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

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

（式中、Ｒは水素原子、メチル基又はエチル基を示す。）

(In the formula, R represents a hydrogen atom, a methyl group or an ethyl group.)

In the general formula (III), Cp ^R ′ having the indenyl ring as a basic skeleton is defined in the same manner as Cp ^{R in the} general formula (I), and preferred examples thereof are also the same.

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

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

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

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

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

  In the general formula (III), the thiolate group represented by X includes a thiomethoxy group, a thioethoxy group, a thiopropoxy group, a thio n-butoxy group, a thioisobutoxy group, a thiosec-butoxy group, a thiotert-butoxy group and the like Group thiolate group; thiophenoxy group, 2,6-di-tert-butylthiophenoxy group, 2,6-diisopropylthiophenoxy group, 2,6-dineopentylthiophenoxy group, 2-tert-butyl-6-isopropyl Arylthiolate groups such as thiophenoxy group, 2-tert-butyl-6-thioneopentylphenoxy group, 2-isopropyl-6-thioneopentylphenoxy group, 2,4,6-triisopropylthiophenoxy group, etc. Among these, 2,4,6-triisopropylthiophenoxy group Preferred.

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

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

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

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

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

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

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

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

（式中、Ｘ’’はハライドを示す。）

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

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

（式中、Ｘ’’はハライドを示す。）

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

  The half metallocene cation complex represented by the general formula (III) can be obtained, for example, by the following reaction.

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

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

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

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

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

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

  On the other hand, as the organoaluminum compound, the general formula AlRR′R ″ (wherein R and R ′ are each independently a C1-C10 hydrocarbon group or a hydrogen atom, and R ″ is a C1-C10 An organoaluminum compound represented by (a hydrocarbon group) is preferable. Specific examples of the organoaluminum compound include trialkylaluminum, dialkylaluminum chloride, alkylaluminum dichloride, and dialkylaluminum hydride. Among these, trialkylaluminum is preferable. Furthermore, examples of the trialkylaluminum include triethylaluminum and triisobutylaluminum. In addition, it is preferable that it is 1-50 times mole with respect to a metallocene complex, and, as for content of the organoaluminum compound in the said polymerization catalyst composition, it is still more preferable that it is about 10 times mole.

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

<Production Method (2) 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. R ³ is a hydrocarbon group or a hydrogen atom, and R ³ is a hydrocarbon group having 1 to 10 carbon atoms, provided that R ³ may be the same as or different from R ¹ or R ^2, and Y is a periodic table. When it is a metal selected from Group 1, a is 1 and b and c are 0, and when Y is a metal selected from Groups 2 and 12 of the Periodic Table, a, b and c are 1, and when Y is a metal selected from Group 13 of the Periodic Table, a, b and c are 1.]
It is characterized by including the organometallic compound represented by these.

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. R ³ is a hydrocarbon group or a hydrogen atom, and R ³ is a hydrocarbon group having 1 to 10 carbon atoms, provided that R ³ may be the same as or different from R1 or R2, and Y is the first in the periodic table. When the metal is selected from the group, a is 1, and b and c are 0, and when Y is the metal selected from groups 2 and 12 of the periodic table, a and a, b and c are 1 when b is 1 and c is 0 and Y is a metal selected from Group 13 of the Periodic Table]
It is necessary to contain the organometallic compound represented by these.

  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 reaction product of the rare earth element compound or the rare earth element compound and a Lewis base is represented by the following general formula (XI) or (XII):
M ¹¹ X ¹¹ ₂・ L ¹¹ _w ... (XI)
M ¹¹ X ¹¹ ₃・ L ¹¹ _w ... (XII)
[Wherein, M ¹¹ represents a lanthanoid element, scandium or yttrium, and X ¹¹ independently represents a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group, a silyl group, an aldehyde residue, a ketone residue. 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].
Can be represented by:

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

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

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

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

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

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

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

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

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

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

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

The component (C) used in the second polymerization catalyst composition is represented by the following general formula (X):
YR ¹ _a R ² _b R ³ _c (X)
[Wherein Y is a metal selected from Group 1, Group 2, Group 12 and Group 13 of the Periodic Table, and R ¹ and R ² are the same or different and have 1 to 10 carbon atoms. R ³ is a hydrocarbon group or a hydrogen atom, and R ³ is a hydrocarbon group having 1 to 10 carbon atoms, provided that R ³ may be the same as or different from R ¹ or R ^2, and Y is a periodic table. When it is a metal selected from Group 1, a is 1 and b and c are 0, and when Y is a metal selected from Groups 2 and 12 of the Periodic Table, a, b and c are 1, and when Y is a metal selected from Group 13 of the Periodic Table, a, b and c are 1.]
And an organic metal compound 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 ]
It is preferable that it is an organoaluminum compound represented by these.

  Examples of the organoaluminum compound of the formula (X) include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, tripentylaluminum, Trihexyl aluminum, tricyclohexyl aluminum, trioctyl aluminum; diethyl aluminum hydride, di-n-propyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl aluminum hydride, dihexyl aluminum hydride, diisohexyl hydride Aluminum, dioctyl aluminum hydride, diisooctyl aluminum hydride; ethyl aluminum dihydride, n-propyl aluminum Hydride, include isobutyl aluminum dihydride and the like, among these, triethylaluminum, triisobutylaluminum, hydrogenated diethylaluminum, hydrogenated diisobutylaluminum are preferred. The organometallic compound as the component (C) described above can be used alone or in combination of two or more. In addition, it is preferable that content of the organoaluminum compound in the said 2nd polymerization catalyst composition is 1-50 times mole with respect to (A) component.

<Production Method (3): 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 MXQY (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.]
The metallocene type composite catalyst represented by these is mentioned.

  In the suitable example of the said polymerization catalyst, the metallocene type complex catalyst represented by a following formula (3-I) is mentioned.

（式中、Ｍ¹は、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^Rは、それぞれ独立して無置換もしくは置換インデニルを示し、Ｒ^A及びＲ^Bは、それぞれ独立して炭素数１〜２０の炭化水素基を示し、該Ｒ^A及びＲ^Bは、Ｍ¹及びＡｌにμ配位しており、Ｒ^C及びＲ^Dは、それぞれ独立して炭素数１〜２０の炭化水素基又は水素原子を示す）

(In the formula, 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. Show)

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

<Metalocene composite catalyst>
Below, the said polymerization catalyst is demonstrated in detail. The polymerization catalyst has a lanthanoid element, a rare earth element of scandium or yttrium, and a group 13 element of the periodic table, and is represented by the following formula (A).
R _a MX _b QY _b (A)
(In the formula, each R independently represents unsubstituted or substituted indenyl, the R is coordinated to M, M represents a lanthanoid element, scandium or yttrium, and each X independently represents 1 to 1 carbon atoms. 20 represents a hydrocarbon group, X is μ-coordinated to M and Q, Q represents a group 13 element of the periodic table, and Y independently represents a hydrocarbon group having 1 to 20 carbon atoms or A hydrogen atom, 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 above polymerization catalyst, for example, a catalyst previously combined with an aluminum catalyst, it is possible to reduce or eliminate the amount of alkylaluminum used at the time of copolymer synthesis. If a conventional catalyst system is used, it is necessary to use a large amount of alkylaluminum at the time of copolymer synthesis. For example, in the conventional catalyst system, it is necessary to use 10 equivalents or more of alkylaluminum with respect to the metal catalyst. If the metallocene composite catalyst is used, an excellent catalytic action can be obtained by adding about 5 equivalents of alkylaluminum. Is demonstrated.

  In the metallocene composite catalyst, the metal M in the formula (A) is a lanthanoid element, scandium, or yttrium. The lanthanoid elements include 15 elements having atomic numbers 57 to 71, and any of these may be used. Preferable examples of the metal M1 include samarium Sm, neodymium Nd, praseodymium Pr, gadolinium Gd, cerium Ce, holmium Ho, scandium Sc, and yttrium Y.

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

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

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

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

In the above formula (3-I), the metal M ¹ is a lanthanoid element, scandium or yttrium. The lanthanoid elements include 15 elements having atomic numbers 57 to 71, and any of these may be used. Preferred examples of the metal M ¹ include samarium Sm, neodymium Nd, praseodymium Pr, gadolinium Gd, cerium Ce, holmium Ho, scandium Sc, and yttrium Y.

In the above formula (3-I), Cp ^R is unsubstituted indenyl or substituted indenyl. Cp ^R having an indenyl ring as a basic skeleton can be represented by C ₉ H _7-X R _X or C ₉ H _11-X R _X. Here, X is an integer of 0-7 or 0-11. In addition, each R is preferably independently a hydrocarbyl group or a metalloid group. The hydrocarbyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 8 carbon atoms. Specific examples of the hydrocarbyl group include a methyl group, an ethyl group, a phenyl group, and a benzyl group. On the other hand, examples of metalloid group metalloids include germyl Ge, stannyl Sn, and silyl Si, and the metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group that the metalloid group has is the same as the above hydrocarbyl group. is there. Specific examples of the metalloid group include a trimethylsilyl group. Specific examples of the substituted indenyl include 2-phenylindenyl and 2-methylindenyl. In addition, two Cp ^R in the formula (3-I) may be the same or different from each other.

In the above formula (3-I), R ^A and R ^B each independently represent a hydrocarbon group having 1 to 20 carbon atoms, and R ^A and R are μ-coordinated to M ¹ and Al. . 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 said formula (3-I), R <^C> and R ^<D> are respectively independently a C1-C20 hydrocarbon group 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.

Note that the metallocene complex catalysts are, for example, in a solvent, is obtained by a metallocene complex represented by the following formula (3-II), is reacted with an organic aluminum compound represented by AlR ^K R ^L R ^M .

（式中、Ｍ²は、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^Rは、それぞれ独立して無置換もしくは置換インデニルを示し、Ｒ^E〜Ｒ^Jは、それぞれ独立して炭素数１〜３のアルキル基又は水素原子を示し、Ｌは、中性ルイス塩基を示し、ｗは、０〜３の整数を示す）

(In the formula, M ² represents a lanthanoid element, scandium or yttrium, Cp ^R each independently represents an unsubstituted or substituted indenyl group, and R ^{E to} R ^J each independently represents a group having 1 to 3 carbon atoms. An alkyl group or a hydrogen atom, L represents a neutral Lewis base, and w represents an integer of 0 to 3)

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.

In the metallocene complex represented by the above formula (3-II), Cp ^R is unsubstituted indenyl or substituted indenyl, and has the same meaning as Cp ^R in the above formula (3-I). In the above formula (3-II), the metal M ² is a lanthanoid element, scandium or yttrium, and has the same meaning as the metal M ¹ in the above formula (3-I).

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

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

  Moreover, the metallocene complex represented by the above formula (3-II) may exist as a monomer, or may exist as a dimer or a multimer higher than that.

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

  Specific examples of the organoaluminum compound include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, tripentylaluminum, Hexyl aluminum, tricyclohexyl aluminum, trioctyl aluminum; diethyl aluminum hydride, di-n-propyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl aluminum hydride, dihexyl aluminum hydride, diisohexyl aluminum hydride , Dioctylaluminum hydride, diisooctylaluminum hydride; ethylaluminum dihydride, n-propylaluminium Dihydride, isobutyl aluminum dihydride and the like. Among these, triethylaluminum, triisobutylaluminum, hydrogenated diethylaluminum, hydrogenated diisobutylaluminum are preferred. Moreover, these organoaluminum compounds can be used individually by 1 type, or 2 or more types can be mixed and used for them. In addition, the amount of the organoaluminum compound used for the production of the metallocene composite catalyst is preferably 2 to 50 times mol, and more preferably about 3 to 5 times mol for the metallocene complex.

<Third polymerization catalyst composition>
The polymerization catalyst composition (hereinafter also referred to as a third polymerization catalyst composition) includes the metallocene composite catalyst and a boron anion, and further includes a normal metallocene catalyst. It is preferable that other components contained in the composition, such as a promoter, are included. The metallocene composite catalyst and boron anion are also referred to as a two-component catalyst. According to the third polymerization catalyst composition, it is possible to produce a conjugated diene compound-nonconjugated olefin copolymer as in the case of the metallocene composite catalyst. It becomes possible to arbitrarily control the content of the monomer component in the copolymer.

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

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

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

  In the first production method of the conjugated diene compound-nonconjugated olefin copolymer of the present invention, as described above, except for using the metallocene composite catalyst or the third polymerization catalyst composition, the usual method is used. Polymerization can be carried out in the same manner as in the method for producing a polymer using a coordination ion polymerization catalyst. Here, when the method for producing a copolymer of the present invention uses the third polymerization catalyst composition, for example, (1) In a polymerization reaction system containing a conjugated diene compound and a non-conjugated olefin as a monomer, The components of the two-component catalyst are provided separately, and may be used as the third polymerization catalyst composition in the polymerization reaction system. (2) The third polymerization catalyst composition prepared in advance is added to the polymerization reaction system. May be provided. In addition, the usage-amount of the said metallocene type composite catalyst has the preferable range of 0.0001-0.01 times mole with respect to the sum total of a conjugated diene compound and a nonconjugated olefin.

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

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

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

In the method for producing the copolymer, when the conjugated diene compound is polymerized with a non-conjugated olefin other than the conjugated diene compound, the concentration of the conjugated diene compound at the start of polymerization (mol / l) and the concentration of the non-conjugated olefin (Mol / l) means the following formula:
Non-conjugated olefin concentration / conjugated diene compound concentration ≧ 1.0
It is preferable to satisfy the relationship:
Non-conjugated olefin concentration / conjugated diene compound concentration ≧ 1.3
And more preferably the following formula:
Non-conjugated olefin concentration / conjugated diene compound concentration ≧ 1.7
Satisfy the relationship. By setting the value of the concentration of the non-conjugated olefin / the concentration of the conjugated diene compound to 1 or more, the non-conjugated olefin can be efficiently introduced into the reaction mixture.

[Rubber composition]
The rubber composition of the present invention contains a copolymer of the conjugated diene compound of the present invention and a non-conjugated olefin, and further, rubber components other than the copolymer of the present invention, inorganic filler, carbon black, other additives, etc. It is preferable to contain. The copolymer should just contain the butadiene polymer of this invention, and components other than a butadiene polymer can be suitably selected according to the objective.
There is no restriction | limiting in particular in content of the copolymer in the rubber composition of this invention, According to the objective, it can select suitably. The content of the copolymer is preferably 10% by mass or more.

<Rubber components other than copolymer>
There is no restriction | limiting in particular in the rubber component which can be mix | blended with the rubber composition of this invention, According to the objective, it can select suitably.
Examples of the rubber component include the copolymer of the present invention, natural rubber, epoxidized natural rubber, various butadiene rubbers, various styrene-butadiene copolymer rubbers, isoprene rubber, butyl rubber, and a copolymer of isobutylene and p-methylstyrene. Bromide, halogenated butyl rubber, acrylonitrile butadiene rubber, chloroprene rubber, ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber, styrene-isoprene copolymer rubber, styrene-isoprene-butadiene copolymer Examples thereof include rubber, isoprene-butadiene copolymer rubber, chlorosulfonated polyethylene, acrylic rubber, epichlorohydrin rubber, polysulfide rubber, silicone rubber, fluorine rubber, and urethane rubber. These may be used individually by 1 type and may use 2 or more types together.

<Reinforcing filler>
A reinforcing filler can be blended in 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.
There is no restriction | limiting in particular in an inorganic filler, According to the objective, it can select suitably. Examples of inorganic fillers include silica, aluminum hydroxide, clay, alumina, talc, mica, kaolin, glass balloon, glass beads, calcium carbonate, magnesium carbonate, magnesium hydroxide, calcium carbonate, magnesium oxide, titanium oxide, and titanium. Examples include potassium acid 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 in content of a reinforcing filler, According to the objective, it can select suitably. The reinforcing filler is preferably contained in an amount of 5 to 200 parts by mass with respect to 100 parts by mass of the rubber component.
The effect which reinforces a rubber composition as content of a reinforcing filler is 5 mass parts or more is acquired. A rubber component and a reinforcing filler can be mixed as it is 200 mass parts or less, and the performance as a rubber composition can be improved.

<Other additives>
Other additives include vulcanization accelerators. As the vulcanization accelerator, compounds such as guanidine, aldehyde-amine, aldehyde-ammonia, thiazole, sulfenamide, thiourea, thiuram, dithiocarbamate and xanthate can be used.
If necessary, reinforcing agents, softeners, fillers, vulcanization aids, colorants, flame retardants, lubricants, foaming agents, plasticizers, processing aids, antioxidants, anti-aging agents, anti-scorch agents, UV rays Known agents such as an inhibitor, an antistatic agent, an anti-coloring agent and other compounding agents can be used according to the purpose of use.

[Crosslinked rubber composition]
The rubber composition of the present invention may contain a crosslinking agent in addition to the copolymer of the present invention, a rubber component other than the copolymer, an inorganic filler, carbon black, and other additives. The rubber composition can form a crosslinked crosslinked rubber composition.

<Crosslinking agent>
There is no restriction | limiting in particular in the crosslinking agent which can be used for preparation of a crosslinked rubber composition, According to the objective, it can select suitably. For example, sulfur crosslinking agent, organic peroxide crosslinking agent, inorganic crosslinking agent, polyamine crosslinking agent, resin crosslinking agent, sulfur compound crosslinking agent, oxime-nitrosamine crosslinking agent sulfur and the like can be mentioned. Among these, in the case of a rubber composition for tires, it is preferable to use a sulfur-based crosslinking agent.
There is no restriction | limiting in particular in content of a crosslinking agent, According to the objective, it can select suitably. The crosslinking agent is preferably contained in an amount of 0.1 to 20 parts by mass with respect to 100 parts by mass of the rubber component.
If content of a crosslinking agent is 0.1 mass part or more, it can bridge | crosslink so that a predetermined effect may be acquired. If it is 20 mass parts or less, it can prevent that a bridge | crosslinking advances during kneading | mixing, and will not impair the physical property of a vulcanizate.

[tire]
The tire of the present invention includes the rubber composition or the crosslinked rubber composition of the present invention. In the tire of the present invention, components other than the rubber composition or the crosslinked rubber composition can be appropriately selected depending on the purpose.
Examples of the application site of the rubber composition or crosslinked rubber composition of the present invention in a tire include treads, base treads, sidewalls, side reinforcing rubbers, and bead fillers. The application site is not limited to these.
The tire of the present invention can be manufactured using a conventional method. 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.

[Production example of biobutadiene polymer]
<Method for producing catalyst>
A silica-magnesia composite oxide synthesized by a sol-gel method was used as a catalyst. The manufacturing method of this catalyst is as follows. First, Mg (OH) ₂ gel was synthesized by dropping 100 mL of a 14% aqueous ammonia solution into a solution of Mg (NO ₃ ) ₂ .6H ₂ O (64 g) dissolved in 100 mL of distilled water. On the other hand, Si (OH) ₄ gel was synthesized by dropping 12.5 mL of 1.38 M nitric acid and 50 mL of 14% aqueous ammonia into a solution of Si (OC ₂ H ₅ ) ₄ (55 mL) dissolved in 150 mL of ethanol. The obtained Mg (OH) ₂ gel was subjected to suction filtration after washing with distilled water, and the Si (OH) ₄ gel was subjected to suction filtration after washing with ethanol. These two kinds of gels were mixed, and the mixed gel was air-dried, then dried at 80 ° C., 500 ° C., and calcined in an N ₂ atmosphere to produce a silica-magnesia composite oxide catalyst.

<Method for producing biobutadiene monomer>
Bioethanol obtained by fermenting sugarcane, tapioca and corn starches with yeast was used as a starting material.
A biobutadiene monomer was produced by contacting the catalyst produced by the above method with the bioethanol.
As the reaction apparatus, a fixed bed gas flow type catalytic reaction apparatus was used. The manufactured silica-magnesia composite oxide catalyst was filled in a quartz reaction tube, and was subjected to heat treatment at 500 ° C. for 2 hours in a carrier gas atmosphere (N ₂ ; gas flow rate 66 mL / min) as a pretreatment.
After completion of the pretreatment, the temperature of the catalyst tube was lowered to the reaction temperature, and bioethanol gas diluted with N ₂ was introduced. The reaction temperature was 350 ° C. or 450 ° C.
The mixture containing the biobutadiene monomer was recovered by performing the following separation operation on the gas generated by the reaction. First, the product gas was bubbled into hexane, so that the target biobutadiene monomer was dissolved in the solvent. The recovered butadiene solution was purified by drying to further remove impurities such as ethanol, acetaldehyde, diethyl ether, ethoxyethylene, and ethyl acetate. Thereby, 1,3-butadiene was obtained.

[Production example of bioethylene]
100 ml of Sumitomo Chemically Activated Alumina (NKHD24) was charged into the center of a SUS reactor of a pressurized flow device with an outer diameter of 20 mm and a length of 80 cm, and atmospheric pressure nitrogen gas was 200 ml / min from the top of the reactor at 500 ° C. for 2 hours. After distribution, the temperature was lowered to 350 ° C. To this, ethanol derived from Petroplus biomass (ethanol content 92%) was fed from the top of the reactor at a rate of 20 g / h. The outlet line at the bottom of the reactor is connected to a back pressure valve set to 0.5 MPa via a trap made by SUS (capacity 500 ml). During the reaction, the reaction is performed by cooling the SUS trap from the outside with ice. The produced water and the reaction ethanol were collected by the above, and the produced ethylene passed through a back pressure valve in a gaseous state, and then compressed to 5 MPa by a compressor and collected as liquefied ethylene in a liquefied gas container. After 10 hours, the weight of bioethylene collected in the liquefied gas container was 119 g, the conversion was 99% or more, and the yield was 99%.

[Method for producing polymer]
<Example 1>
Using the obtained 1,3-butadiene (biobutadiene), a copolymer A was produced based on the following.
After adding 300 ml of a toluene solution containing 40 g of the obtained 1,3-butadiene (biobutadiene) to a sufficiently dried 1000 ml pressure-resistant glass reactor, ethylene was introduced at 1.0 MPa. Meanwhile, in a glove box under a nitrogen atmosphere, bis (2-phenylindenyl) gadolinium bis (dimethylsilylamide) [(2-PhC ₉ H ₆ ) ₂ GdN (SiHMe ₂ ) ₂ ] 9.6 μmmol is placed in a glass container. Dimethylanilinium tetrakis (pentafluorophenyl) borate [Me ₂ NHPhB (C ₆ F ₅ ) ₄ ] 9.6 μmmol and diisobutylaluminum hydride 0.384 mmol were charged and dissolved in 20 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 60 ° C. for 90 minutes. After the polymerization, 1 ml of 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) (NS-5) 5% by mass of isopropanol solution was added to stop the reaction, and a copolymer with a large amount of methanol was added. Was separated and vacuum-dried at 50 ° C. to obtain a copolymer A. The yield of the obtained copolymer A was 43 g.

<Example 2>
Using the obtained 1,3-butadiene (biobutadiene) and the obtained ethylene (bioethylene), a copolymer B was produced based on the following.
After adding 300 ml of a toluene solution containing 40 g of the obtained 1,3-butadiene (biobutadiene) to a sufficiently dried 1000 ml pressure-resistant glass reactor, the obtained ethylene (bioethylene) was introduced at 1.0 MPa. did. Meanwhile, in a glove box under a nitrogen atmosphere, bis (2-phenylindenyl) gadolinium bis (dimethylsilylamide) [(2-PhC ₉ H ₆ ) ₂ GdN (SiHMe ₂ ) ₂ ] 9.6 μmmol is placed in a glass container. Dimethylanilinium tetrakis (pentafluorophenyl) borate [Me ₂ NHPhB (C ₆ F ₅ ) ₄ ] 9.6 μmmol and diisobutylaluminum hydride 0.384 mmol were charged and dissolved in 20 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 60 ° C. for 90 minutes. After the polymerization, 1 ml of 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) (NS-5) 5% by mass of isopropanol solution was added to stop the reaction, and a copolymer with a large amount of methanol was added. Was separated and vacuum dried at 50 ° C. to obtain a copolymer B. The yield of the obtained copolymer B was 43 g.

<Example 3>
In a well-dried 1500 ml pressure-resistant glass reactor, 300 ml of toluene was added in advance, and in a glove box under a nitrogen atmosphere, bis (2-phenylindenyl) gadolinium bis (dimethylsilylamide) [(2 _{-PhC 9 H 6) 2 GdN (} SiHMe 2) 2] 20μmmol, trityl tetrakis (pentafluorophenyl) borate _{[Ph 3 CB (C 6 F} 5) 4] were charged 30Myummol, and diisobutylaluminum hydride 1.8 mmol, toluene 20ml To obtain a catalyst solution. Thereafter, the catalyst solution was taken out from the glove box, added to a pressure-resistant glass reactor, heated to 60 ° C., and then ethylene was introduced at 1.5 MPa. At the same time, 150 g of 1,3-butadiene (biobutadiene) obtained above was obtained. The toluene solution containing 600 ml was added to the pressure-resistant glass reactor over 120 minutes (5 ml / min) for polymerization. After standing for 10 minutes, 1 ml of 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) (NS-5) 5% by mass isopropanol solution was added to stop the reaction, and a large amount of methanol was added. Then, the copolymer was separated and dried in vacuum at 50 ° C. to obtain copolymer C. The yield of the obtained copolymer C was 171 g.

<Comparative Example 1>
Polymerization was carried out in the same manner as in Example 1 except that commercially available synthetic butadiene derived from petroleum was used in place of the obtained 1,3-butadiene (biobutadiene), yielding 43 g of copolymer D. I got it.

[Evaluation method]
<Microstructure>
The microstructure of the butadiene moiety in the copolymer is determined by ¹ H-NMR spectrum (bonding amount of 1,2-vinyl bond) and ¹³ C-NMR spectrum (containing cis-1,4 bond and trans-1,4 bond). (Quantity ratio). The calculated values of cis-1,4 bond amount (%) are shown in Table 1.

<Content of ethylene>
The content (mol%) of the ethylene moiety in the copolymer was determined from the integration ratio of ¹ H-NMR spectrum and ¹³ C-NMR spectrum. The calculated values are shown in Table 1.

<Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)>
Gel permeation chromatography [GPC: Tosoh HLC-8121GPC / HT, column: Tosoh GMH _HR- H (S) HT × 2, detector: differential refractometer (RI), GPC measurement temperature: 140 ° C.] 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 monodispersed polystyrene. The analytical values are shown in Table 1.

<Measurement of δ13C>
The value of δ13C of butadiene produced using biobutadiene produced from ethanol derived from corn, sugarcane and tapioca was measured with a stable isotope ratio measuring device.

<Measurement of Δ14C>
As a starting material, the value of δ13C of ethylene produced from bioethanol obtained by fermenting sugarcane, tapioca and corn starch in yeast was measured with a stable isotope ratio measuring device, and Δ14C was calculated by the above conversion method. Calculated.

<Measurement of ¹⁴ C decay per gram per minute>
¹⁴ C decay rate per gram of ethylene produced from ethanol derived from corn, sugarcane, tapioca was measured by accelerator mass spectrometry (AMS), liquid scintillation counting (Liquid Scintillation Counting Method) LSC; did.

<Roll processability>
A rubber composition was produced using each of the copolymers A to D obtained in Examples 1 to 3 and Comparative Example 1.
The unvulcanized rubber composition was wound around an 8-inch open roll at 60 ° C., and the winding condition was visually observed to evaluate the roll processability in the following three stages.
A: Adheres to a roll and roll processability is good.
B: Although some bagging occurs, it can be wound around a roll.
C: It is not sticky and does not wind around the roll and cannot be rolled (powder, granular).
<Ozone resistance>
The ozone resistance was measured according to JIS K 6259.
A rubber composition was produced using each of the copolymers A to D obtained in Examples 1 to 3 and Comparative Example 1, and strip-shaped test pieces were prepared. While applying 30% dynamic elongation to the strip-shaped test piece, it was exposed at 40 ° C. and an ozone concentration of 50 ppm, and the state of the sample (presence of cracks) after 24 hours was visually judged.

[Evaluation results]
The rubber composition of Examples 1 and 3 using copolymers A and C of biobutadiene and ordinary ethylene, and the rubber composition of Example 2 using copolymer B of biobutadiene and bioethylene In either case, it was found that a result comparable to a rubber composition using a copolymer D polymerized from commercially available synthetic butadiene derived from petroleum and ethylene was obtained.

Claims (14)

At least conjugated diene compound and a non-conjugated olefin A method of manufacturing a copolymer be that the copolymer using a metallocene catalyst,
The copolymer includes at least one of biomass-derived compounds of the bio-conjugated diene compound component and bio nonconjugated olefin component synthesized from resources from organisms including plant resources,
A method for producing a copolymer , wherein a value of δ13C of the biomass-derived compound is −30 ‰ to −28.5 ‰, or −22 ‰ or more. The copolymer is, as the biomass-derived compound, including the bio-conjugated diene compound component, the production method of the copolymer of claim 1. The copolymer is, as the biomass-derived compound comprises both the bio-conjugated diene compound component and bio nonconjugated olefin components, the production method of the copolymer of claim 1. The copolymer, the disintegrations per minute per gram quantity value of ^{14 C} of the non-conjugated olefin is 0.1dpm / gC above method for producing a copolymer according to any one of claims 1 to 3. The copolymer, the conjugated diene compound 10-90 wt%, comprising said non-conjugated olefin 10 to 90 wt%, the production method of the copolymer according to any one of claims 1 to 4. The copolymer further is obtained by copolymerizing a diene compound, method for producing a copolymer according to any one of claims 1 to 5. The copolymer is further said conjugated diene compound is obtained by copolymerizing a different conjugated diene compounds, the production method of the copolymer according to any one of claims 1 to 6. The copolymer, the ranges of values -21 ‰ ~-12 ‰ of δ13C of conjugated diene compounds, the production method of the copolymer of claim 1. The copolymer, the ranges of values -29.5 ‰ ~-28.5 ‰ in δ13C of conjugated diene compounds, the production method of the copolymer of claim 1. The copolymer, the ranges of values -30 ‰ ~-29 ‰ of δ13C of conjugated diene compounds, the production method of the copolymer of claim 1. The copolymer has a weight average molecular weight in terms of standard polystyrene is 10,000 to 1,000,000, a manufacturing method of the copolymer according to any one of claims 1 to 10. Producing a mixture containing the bioconjugated diene compound component from a biological resource including a plant resource;
The method for producing a copolymer according to any one of claims 1 to 11, wherein the copolymer is produced using the mixture. Using the copolymer obtained by the production method of the copolymer according to any one of claims 1 to 10, a manufacturing method of a rubber composition to produce a rubber composition. A tire manufacturing method for manufacturing a tire using the rubber composition obtained by the rubber composition manufacturing method according to claim 13.