JP5961483B2 - Method for producing copolymer - Google Patents

Description

  The present invention relates to a method for producing a copolymer.

  It is known that a conjugated diene compound-nonconjugated olefin copolymer that can be effectively used as a raw material rubber for rubber products such as tires can be produced by copolymerizing an olefin and a diene under a certain catalyst. . For example, Patent Document 1 describes the copolymerization of ethylene and diene.

  However, the synthesis method described in Patent Document 1 has problems such as low catalyst activity and limited structure of the polymer to be produced.

  In response to this problem, the present applicant has provided a method for producing a copolymer of a conjugated diene compound and a non-conjugated olefin other than the conjugated diene compound (for example, Patent Documents 2 to 4).

JP-T-2006-503141 International Publication No. 2011-016210 Pamphlet International Publication No. 2012/014421 Pamphlet JP 2012-31314 A

In the methods described in Patent Documents 2 to 4, only aromatic hydrocarbons are used as the solvent.
In recent years, it has been demanded to change the solvent used for the polymerization reaction from aromatic hydrocarbons to aliphatic hydrocarbons (non-aromatic hydrocarbons) in order to reduce the environmental burden, and there is room for further improvement in this respect. there were.

  Then, an object of this invention is to provide the manufacturing method of the copolymer which can synthesize | combine the copolymer of a conjugated diene compound and a nonconjugated olefin, when an aliphatic hydrocarbon is used as a solvent.

The method for producing a copolymer according to the present invention is a method for producing a copolymer in which a conjugated diene compound and a non-conjugated olefin are copolymerized, using an aliphatic hydrocarbon as a solvent, and polymerization in the copolymerization The temperature is 80 ° C. or higher.
Provided is a method for producing a copolymer by synthesizing a copolymer of a conjugated diene compound and a non-conjugated olefin when an aliphatic hydrocarbon is used as a solvent by setting the polymerization temperature in the copolymerization to 80 ° C. or higher. It becomes possible.

Hereinafter, in the present specification, the aliphatic hydrocarbon and aromatic hydrocarbon as the solvent may be referred to as “aliphatic hydrocarbon solvent” and “aromatic hydrocarbon solvent”, respectively.
In this specification, the conjugated diene compound refers to a compound having two double bonds separated by one single bond in the molecule.
In the present specification, the non-conjugated olefin means a non-conjugated olefin other than the conjugated diene compound and does not contain styrene. Here, the olefin refers to a compound that is an aliphatic unsaturated hydrocarbon and has one or more carbon-carbon double bonds.
In the present specification, polymerization of a block portion constituting a copolymer using a conjugated diene compound or a non-conjugated olefin is referred to as “block portion polymerization”.
The “ligand” is a group that is coordinated to the central metal of the catalyst, and means, for example, a group represented by A, B, or C in the general formula (1) described later.
In this specification, a metallocene complex refers to a complex compound in which one or more cyclopentadienyl, indenyl, fluorenyl, or a derivative thereof is bonded to a central metal. In this specification, in particular, a metallocene complex having one cyclopentadienyl, indenyl, fluorenyl, or a derivative thereof bonded to a central metal may be referred to as a half metallocene complex.
In the present specification, the reaction system means a place where copolymerization of a conjugated diene compound and a non-conjugated olefin is performed, and specific examples include a reaction vessel and the like.
In the present specification, the amount of cis-1,4 bond means the amount in the conjugated diene compound-derived moiety, and does not mean the ratio to the entire copolymer.

In the method for producing a copolymer according to the present invention, the aliphatic hydrocarbon is preferably at least one of hexane and cyclohexane.
By using at least one of hexane and cyclohexane, the production cost of the copolymer can be reduced, it is easy to handle in the production process, the effect of reducing the environmental load is high, and the recovery of the target copolymer is easy. There is an effect.

In the method for producing a copolymer according to the present invention, the introduction of the non-conjugated olefin into the reaction system is performed simultaneously with the introduction of the conjugated diene compound into the reaction system or more than the introduction of the conjugated diene compound into the reaction system. This is preferably done first.
By making the order of adding the reactants in this way, it is easy to synthesize a copolymer obtained by copolymerizing a conjugated diene compound and a non-conjugated olefin.

In the method for producing a copolymer according to the present invention, the copolymerization is preferably performed in the presence of a catalyst containing a compound having at least one selected from the group consisting of a lanthanoid element, scandium and yttrium.
By using such a catalyst, it is easy to synthesize a copolymer of a conjugated diene compound and a non-conjugated olefin. Moreover, a conjugated diene compound can be copolymerized with a high amount of cis-1,4 bonds.

In the method for producing a copolymer according to the present invention, the non-conjugated olefin is preferably an acyclic olefin.
When the non-conjugated olefin is an acyclic olefin, there are advantages that the non-conjugated olefin is easily copolymerized with the conjugated diene compound and the molecular weight of the copolymer is easily controlled.

In the method for producing a copolymer according to the present invention, the non-conjugated olefin is preferably an α-olefin having 2 to 10 carbon atoms.
Since the α-olefin has a double bond at the α-position of the olefin, copolymerization with the conjugated diene can be performed efficiently. Furthermore, when the carbon number of the non-conjugated olefin is 2 to 10, there is an advantage that the non-conjugated olefin is easily copolymerized with the conjugated diene compound and the molecular weight of the copolymer is easy to control.

In the method for producing a copolymer according to the present invention, the non-conjugated olefin is preferably at least one of ethylene and propylene.
By using such a non-conjugated olefin, the excellent heat resistance and ozone resistance of the copolymer can be obtained, and the design flexibility as an elastomer can be increased.

In the method for producing a copolymer according to the present invention, the conjugated diene compound preferably has 4 to 8 carbon atoms.
Since the conjugated diene compound has 4 to 8 carbon atoms, it has an advantage that the conjugated diene compound is easily copolymerized with the non-conjugated olefin, and the molecular weight of the copolymer is easily controlled.

In the method for producing a copolymer according to the present invention, the conjugated diene compound is preferably at least one of 1,3-butadiene and isoprene.
When the conjugated diene compound is at least one of 1,3-butadiene and isoprene, there is an advantage that the conjugated diene compound is easily copolymerized with the non-conjugated olefin and the molecular weight of the copolymer is easily controlled. In addition, 1,3-butadiene and isoprene have the advantage of being inexpensive and readily available.

In the method for producing a copolymer according to the present invention, the pressure at the time of charging the non-conjugated olefin into the reaction system is preferably 0.1 MPa to 10 MPa.
With such a pressure, the non-conjugated olefin can be efficiently and sufficiently taken into the copolymer.

In the method for producing a copolymer according to the present invention, the concentration of the conjugated diene compound (mol / L) and the concentration of the non-conjugated olefin (mol / L) at the start of the copolymerization are represented by the following formula:
Non-conjugated olefin concentration / conjugated diene compound concentration ≧ 1.0
It is preferable to satisfy the relationship.
By satisfying such a relationship, a non-conjugated olefin can be efficiently introduced into the copolymer.

  ADVANTAGE OF THE INVENTION According to this invention, when an aliphatic hydrocarbon is used as a solvent, it becomes possible to provide the manufacturing method of the copolymer which can synthesize | combine the copolymer of a conjugated diene compound and a nonconjugated olefin.

1 is a GPC elution curve of copolymer A obtained in Example 1. FIG. FIG. 2 is an elution curve of GPC of copolymer B obtained in Example 2. FIG. 3 is an elution curve of GPC of the mixture I obtained in Comparative Example 1. FIG. 4 is an elution curve of GPC of the mixture J obtained in Comparative Example 2.

(Method for producing copolymer)
Hereinafter, an example of a preferred embodiment of a method for producing a copolymer according to the present invention will be described.
The method for producing a copolymer according to the present invention is a method for producing a copolymer in which a conjugated diene compound and a non-conjugated olefin are copolymerized, using an aliphatic hydrocarbon as a solvent, and polymerization in the copolymerization The temperature is 80 ° C. or higher.
Provided is a method for producing a copolymer by synthesizing a copolymer of a conjugated diene compound and a non-conjugated olefin when an aliphatic hydrocarbon is used as a solvent by setting the polymerization temperature in the copolymerization to 80 ° C. or higher. It becomes possible.

<Solvent>
In the method for producing a copolymer according to the present invention, an aliphatic hydrocarbon is used as a solvent.
The aliphatic hydrocarbon as the solvent is preferably at least one selected from linear, branched and cyclic aliphatic hydrocarbons.
Examples of the linear aliphatic hydrocarbon solvent include pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, and icosane.
Examples of the branched aliphatic hydrocarbon solvent include 2,2,4-trimethylpentane (isooctane). A branched aliphatic hydrocarbon solvent has an advantage that the boiling point is lower than that of a linear aliphatic hydrocarbon solvent having the same number of carbon atoms.
Examples of the cyclic aliphatic hydrocarbon solvent include cyclohexane and methylcyclohexane. The cyclic aliphatic hydrocarbon solvent has an advantage that the solubility of the copolymer obtained by the method for producing a copolymer according to the present invention is higher than that of the linear aliphatic hydrocarbon solvent.
The boiling point of the aliphatic hydrocarbon solvent is preferably 65 ° C to 110 ° C. When the boiling point of the aliphatic hydrocarbon solvent is within this range, there is an advantage that the solvent can be easily distilled off and the copolymer of the target product can be easily recovered.

In the method for producing a copolymer according to the present invention, the aliphatic hydrocarbon is preferably at least one of hexane and cyclohexane.
Since hexane and cyclohexane are inexpensive solvents, the production cost of the copolymer can be lowered by using at least one of hexane and cyclohexane.
Further, when at least one of hexane and cyclohexane is used as a solvent, there is an advantage that the solution viscosity is lower than that when toluene which is an aromatic hydrocarbon is used as a solvent, and it is easy to handle in the production process.
Furthermore, since hexane and cyclohexane have lower boiling points than toluene (hexane boiling point: 68.7 ° C, cyclohexane boiling point: 81.4 ° C, toluene boiling point: 110.6 ° C), the solvent should be distilled off. In addition, there is an advantage that the effect of reducing the environmental load is high, and in addition, the recovery of the target copolymer is easy.
In the method for producing a copolymer according to the present invention, the above-described solvents may be used singly or in combination of two or more.

In the method for producing a copolymer according to the present invention, an aromatic hydrocarbon such as toluene used in a conventional polymerization reaction other than an aliphatic hydrocarbon is used as a solvent without departing from the spirit of the present invention. Also good.
Furthermore, in a preferred embodiment of the present invention, it is possible to use only an aliphatic hydrocarbon solvent as a solvent used for copolymerization.

<Polymerization temperature>
In the method for producing a copolymer according to the present invention, the polymerization temperature in the copolymerization is 80 ° C. or higher. If the said polymerization temperature is less than 80 degreeC, a conjugated diene compound and a nonconjugated olefin cannot fully be copolymerized. If the polymerization temperature in the copolymerization is less than 80 ° C., the reason why the copolymer cannot be synthesized is not clear, but the reason is that the insertion (introduction) reaction of the conjugated diene compound does not proceed from the polymerization active terminal of the nonconjugated olefin. The
What is necessary is just to adjust the polymerization temperature in copolymerization at 80 degreeC or more according to the boiling point of the aliphatic hydrocarbon solvent to be used, the kind of nonconjugated olefin, etc.
The polymerization temperature is preferably 80 ° C to 120 ° C, and more preferably 80 ° C to 100 ° C. When the polymerization temperature is within this range, there is an advantage that there are few side reactions such as a polymerization termination reaction.

In the method for producing a copolymer according to the present invention, the polymerization temperature in the copolymerization is 80 ° C. or higher, but the polymerization temperature of the homopolymerization of the conjugated diene compound or the non-conjugated olefin other than the copolymerization is not particularly limited, It can be adjusted as appropriate.
For example, the polymerization temperature for the polymerization of the block portion using a non-conjugated olefin is preferably 20 ° C to 80 ° C. This has the advantage of reducing the rate of polymerization terminal deactivation (polymerization termination reaction).
For example, the polymerization temperature of the block portion polymerization using the conjugated diene compound is preferably 50 ° C to 80 ° C. Thereby, there is an advantage that the rate of polymerization is high to some extent and the ratio of deactivation of the polymerization terminal (polymerization termination reaction) is reduced.

<Conjugated diene compound>
Examples of the conjugated diene compound used as the monomer include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, and the like.
In the method for producing a copolymer according to the present invention, the conjugated diene compound preferably has 4 to 8 carbon atoms. Since the conjugated diene compound has 4 to 8 carbon atoms, it has an advantage that the conjugated diene compound is easily copolymerized with the non-conjugated olefin, and the molecular weight of the copolymer is easily controlled.

In the method for producing a copolymer according to the present invention, the conjugated diene compound is preferably at least one of 1,3-butadiene and isoprene. When the conjugated diene compound is at least one of 1,3-butadiene and isoprene, there is an advantage that the conjugated diene compound is easily copolymerized with the non-conjugated olefin and the molecular weight of the copolymer is easily controlled. In addition, 1,3-butadiene and isoprene have the advantage of being inexpensive and readily available.
A conjugated diene compound may be used individually by 1 type, and may be used in combination of 2 or more type.

<Non-conjugated olefin>
The non-conjugated olefin used as a monomer is designed as an elastomer by imparting excellent heat resistance to the copolymer and reducing the crystallinity by reducing the proportion of double bonds in the main chain of the copolymer. It works to increase the degree of freedom.
As the non-conjugated olefin, both a cyclic olefin and an acyclic olefin can be used.
In the method for producing a copolymer according to the present invention, the non-conjugated olefin is preferably an acyclic olefin. When the non-conjugated olefin is an acyclic olefin, there are advantages that the non-conjugated olefin is easily copolymerized with the conjugated diene compound and the molecular weight of the copolymer is easily controlled.

In the method for producing a copolymer according to the present invention, the non-conjugated olefin is preferably an α-olefin having 2 to 10 carbon atoms. Since the α-olefin has a double bond at the α-position of the olefin, copolymerization with the conjugated diene can be performed efficiently. Furthermore, when the carbon number of the non-conjugated olefin is 2 to 10, there is an advantage that the non-conjugated olefin is easily copolymerized with the conjugated diene compound and the molecular weight of the copolymer is easy to control.
Here, as an alpha olefin, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, etc. are mentioned.

In the method for producing a copolymer according to the present invention, the non-conjugated olefin is preferably at least one of ethylene and propylene.
By using such a non-conjugated olefin, the excellent heat resistance and ozone resistance of the copolymer can be obtained.
Further, the degree of freedom in design as an elastomer can be increased by reducing the proportion of double bonds in the main chain of the copolymer and reducing the crystallinity.
A nonconjugated olefin may be used individually by 1 type, and may be used in combination of 2 or more type.

<Manufacturing process>
The method for producing a copolymer in which a conjugated diene compound and a non-conjugated olefin according to the present invention are copolymerized particularly uses an aliphatic hydrocarbon solvent and the polymerization temperature in the copolymerization is 80 ° C. or more. The polymerization method is not limited and a conventionally known polymerization method can be used.
For example, as a polymerization method, a solution polymerization method, a suspension polymerization method, a liquid phase bulk polymerization method, an emulsion polymerization method, or the like can be used.

In the method for producing a copolymer according to the present invention, the introduction of the non-conjugated olefin into the reaction system is performed simultaneously with the introduction of the conjugated diene compound into the reaction system or more than the introduction of the conjugated diene compound into the reaction system. It is preferably performed first, and more preferably, the introduction of the non-conjugated olefin into the reaction system is performed before the introduction of the conjugated diene compound into the reaction system.
By making the order of introduction of the reactants in this way, it becomes easier to control the concentration ratio of the monomers in the reaction system to suppress the formation of a homopolymer of the conjugated diene compound, and the conjugated diene compound and the non-conjugated olefin It is easy to synthesize a copolymer obtained by polymerizing. This is probably because the conjugated diene compound is easily polymerized but the non-conjugated olefin is difficult to polymerize.
Further, when the introduction of the non-conjugated olefin into the reaction system is performed prior to the introduction of the conjugated diene compound into the reaction system, the introduction of the non-conjugated olefin into the reaction system is performed into the reaction system of the conjugated diene compound. There is an advantage that the yield of the copolymer is improved as compared with the case where it is carried out simultaneously with the introduction of the above.
When the introduction of the non-conjugated olefin into the reaction system and the introduction of the non-conjugated olefin into the reaction system are performed simultaneously with the introduction of the conjugated diene compound into the reaction system, there is an advantage that there is little deactivation such as a termination reaction. .
The method for charging the reactant is not particularly limited, and may be divided or continuously charged.

In the method for producing a copolymer according to the present invention, when a catalyst is used, the catalyst only needs to be present at the time of copolymerization of the conjugated diene compound and the non-conjugated olefin. The order of input is not particularly limited.
Therefore, before introducing the conjugated diene compound or the non-conjugated olefin into the reaction system, the catalyst may be introduced into the reaction system, or at the same time as the conjugated diene compound or the non-conjugated olefin is introduced into the reaction system. It may be thrown into.

In the method for producing a copolymer according to the present invention, the pressure at the time of charging the non-conjugated olefin into the reaction system is preferably 0.1 MPa to 10 MPa.
With such a pressure, the non-conjugated olefin can be efficiently and sufficiently taken into the copolymer.

In the method for producing a copolymer according to the present invention, the concentration of the conjugated diene compound (mol / L) and the concentration of the non-conjugated olefin (mol / L) at the start of the copolymerization are represented by the following formula:
Non-conjugated olefin concentration / conjugated diene compound concentration ≧ 1.0
It is preferable to satisfy the relationship.
Further, when performing the introduction of the non-conjugated olefin into the reaction system simultaneously with the introduction of the conjugated diene compound into the reaction system,
Non-conjugated olefin concentration / conjugated diene compound concentration ≧ 5.0
It is more preferable that
Although the conjugated diene compound is easily polymerized and the non-conjugated olefin is difficult to polymerize, the non-conjugated olefin can be efficiently introduced into the copolymer by satisfying such a relationship.

  In the method for producing a copolymer according to the present invention, the copolymerization is preferably performed in an inert gas atmosphere. Examples of the inert gas include nitrogen or argon.

<Catalyst>
In the method for producing a copolymer according to the present invention, the catalyst is not particularly limited. For example, the polymerization catalyst composition described in Patent Documents 2 to 3 or the metallocene composite catalyst described in Patent Document 4 is used. Thus, a conjugated diene compound and a non-conjugated olefin may be copolymerized.

In the method for producing a copolymer according to the present invention, the copolymerization is preferably performed in the presence of a catalyst containing a compound having at least one selected from the group consisting of a lanthanoid element, scandium and yttrium.
By using such a catalyst, it is easy to synthesize a copolymer of a conjugated diene compound and a non-conjugated olefin.
Moreover, a conjugated diene compound can be polymerized with a high amount of cis-1,4 bonds. In a copolymer obtained by the method for producing a copolymer according to the present invention (hereinafter also simply referred to as “copolymer”), if the amount of cis-1,4 bonds is high, the copolymer is used for a tire. In such a case, high abrasion resistance, crack growth resistance, wet skid resistance, and the like can be imparted to the tire.

  Examples of the lanthanoid element include lanthanium, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium.

In the method for producing a copolymer according to the present invention, in addition to the catalyst containing a compound having at least one selected from the group consisting of the lanthanoid element, scandium and yttrium, a co-catalyst may be included. A good polymerization catalyst composition may be used. As the polymerization catalyst composition, for example, the following first to third polymerization catalyst compositions are preferable.
Hereinafter, the 1st thru | or 3rd polymerization catalyst composition used suitably in this invention is demonstrated.

<< first polymerization catalyst composition >>
As the first 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): an ionic compound (B-1) composed of a non-coordinating anion and a cation, an aluminoxane (B-2), a Lewis acid, a complex compound of a metal halide and a Lewis base, and an organic containing an active halogen At least one selected from the group consisting of at least one halogen compound (B-3) among the compounds;
The polymerization catalyst composition containing is mentioned.
When the first 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 organometallic compound represented by the following general formula (i) is included.
YR ¹ _a R ² _b R ³ _c (i)
(In General Formula (i), 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 have 1 to 10 carbon atoms. A hydrocarbon group or a hydrogen atom, and R ³ is a hydrocarbon group having 1 to 10 carbon atoms, provided that R ¹ , R ² and R ³ may be the same or different, When Y is a metal selected from group 1 of the periodic table, a is 1, b and c are 0, and Y is selected from groups 2 and 12 of the periodic table A and b are 1 and c is 0, and when Y is a metal selected from Group 13 of the Periodic Table, a, b and c are 1 .)

  Hereinafter, the components (A), (B) and (C) will be described.

-(A) component-
The component (A) is a rare earth element compound or a reaction product of the rare earth element compound and a Lewis base. Here, the rare earth element compound and the reaction product of the rare earth element compound and the Lewis base are composed of a rare earth element and carbon. Has no bonds.
Since 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.

The rare earth element compound is a compound containing a lanthanoid element, scandium or yttrium composed of elements having atomic numbers 57 to 71 in the periodic table.
The lanthanoid element is the same as described above.

The rare earth element compound is preferably a divalent or trivalent salt or complex compound of the rare earth metal, and contains one or more ligands selected from a hydrogen atom, a halogen atom and an organic compound residue. More preferably, it is a rare earth element compound.
Furthermore, the rare earth element compound or the reaction product of the rare earth element compound and the Lewis base is preferably a compound represented by the following general formula (ii) or (iii).
MX ₂ · Lw (ii)
MX ₃ · Lw ··· (iii)
(In each of the general formulas (ii) and (iii), M represents a lanthanoid element, scandium or yttrium, and X independently represents a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group, or a silyl group. Represents an aldehyde residue, a ketone residue, a carboxylic acid residue, a thiocarboxylic acid residue or a phosphorus compound residue, L represents a Lewis base, and w represents an integer of 0 to 3.)

In each of the general formulas (ii) and (iii), M represents a lanthanoid element, scandium or yttrium.
The lanthanoid element is the same as described above.

In each of the general formulas (ii) and (iii), X is independently a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group, a silyl group, an aldehyde residue, a ketone residue, or a carboxylic acid residue. Represents a thiocarboxylic acid residue or a phosphorus compound residue.
There is no restriction | limiting in particular as a halogen atom, According to the objective, it can select suitably.
As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, for example. Among these, a chlorine atom and a bromine atom are preferable.

There is no restriction | limiting in particular as an alkoxide group, According to the objective, it can select suitably.
Examples of the alkoxide group include aliphatic alkoxy groups such as methoxy group, ethoxy group, propoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group; phenoxy group, 2,6-di-tert -Butylphenoxy group, 2,6-diisopropylphenoxy group, 2,6-dineopentylphenoxy group, 2-tert-butyl-6-isopropylphenoxy group, 2-tert-butyl-6-neopentylphenoxy group, 2- Aryl oxide groups such as isopropyl-6-neopentylphenoxy group; and the like. Among these, 2,6-di-tert-butylphenoxy group is preferable.

There is no restriction | limiting in particular as a thiolate group, According to the objective, it can select suitably.
Examples of the thiolate group include aliphatic thiolate groups such as a thiomethoxy group, a thioethoxy group, a thiopropoxy group, a thio n-butoxy group, a thioisobutoxy group, a thiosec-butoxy group, and a thiotert-butoxy group; a thiophenoxy group, 2,6-di-tert-butylthiophenoxy group, 2,6-diisopropylthiophenoxy group, 2,6-dineopentylthiophenoxy group, 2-tert-butyl-6-isopropylthiophenoxy group, 2-tert- Arylthiolate groups such as butyl-6-thioneopentylphenoxy group, 2-isopropyl-6-thioneopentylphenoxy group, 2,4,6-triisopropylthiophenoxy group; and the like. Among these, 2,4,6-triisopropylthiophenoxy group is preferable.

There is no restriction | limiting in particular as an amide group, According to the objective, it can select suitably.
Examples of the amide group include aliphatic amide groups such as dimethylamide group, diethylamide group, and diisopropylamide 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-6-neopentylphenylamide group, 2-isopropyl-6-neopentylphenylamide group, And arylamide groups such as 2,4,6-tri-tert-butylphenylamide group; bistrialkylsilylamide groups such as bistrimethylsilylamide group, and the like. Among these, a bistrimethylsilylamide group is preferable.

There is no restriction | limiting in particular as a silyl group, According to the objective, it can select suitably.
Examples of the silyl group 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.

There is no restriction | limiting in particular as an aldehyde residue, According to the objective, it can select suitably.
Examples of the aldehyde residue include salicylaldehyde, 2-hydroxy-1-naphthaldehyde, 2-hydroxy-3-naphthaldehyde, and the like.

There is no restriction | limiting in particular as a ketone residue, According to the objective, it can select suitably.
Examples of the ketone residue include acetylacetone, benzoylacetone, propionylacetone, isobutylacetone, valerylacetone, ethylacetylacetone, and the like.

There is no restriction | limiting in particular as a carboxylic acid residue, According to the objective, it can select suitably.
Examples of carboxylic acid residues include isovaleric acid, caprylic acid, octanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, linoleic acid, cyclopentanecarboxylic acid, naphthenic acid, and ethylhexane. Acid, bivaric acid, versatic acid [trade name, manufactured by Shell Chemical Co., Ltd., synthetic acid composed of a mixture of isomers of C10 monocarboxylic acid], phenylacetic acid, benzoic acid, 2-naphthoic acid, maleic acid, succinic acid Acid, and the like.

There is no restriction | limiting in particular as a thiocarboxylic acid residue, According to the objective, it can select suitably.
Examples of the thiocarboxylic acid residue include hexanethioic acid, 2,2-dimethylbutanethioic acid, decanethioic acid, thiobenzoic acid, and the like.

There is no restriction | limiting in particular as a phosphorus compound residue, According to the objective, it can select suitably.
Examples of phosphorus compound residues include dibutyl phosphate, dipentyl phosphate, dihexyl phosphate, diheptyl phosphate, dioctyl phosphate, bis (2-ethylhexyl) phosphate, bis (1-methylheptyl) phosphate, and phosphoric acid. Dilauryl, dioleyl phosphate, diphenyl phosphate, bis (p-nonylphenyl) phosphate, bis (polyethylene glycol-p-nonylphenyl) phosphate, (butyl) phosphate (2-ethylhexyl), phosphate (1-methyl) Residues of phosphate esters such as heptyl) (2-ethylhexyl), phosphoric acid (2-ethylhexyl) (p-nonylphenyl); 2-ethylhexylphosphonate monobutyl, 2-ethylhexylphosphonate mono-2-ethylhexyl, phenylphosphone Acid mono-2-ethylhexyl, 2-ethylhexylphosphone Residues of phosphonates such as mono-p-nonylphenyl, mono-2-ethylhexyl phosphonate, 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-ethylhexyl) (p-nonylphenyl) phosphinic acid, butylphosphinic acid, 2-ethylhexylphosphinic acid, 1-methylheptylphosphinic acid, oleylphosphinic acid, laurylphosphinic acid, F Alkenyl phosphinic acid, residues of phosphinic acid such as p- nonylphenyl phosphinic acid; and the like.

In each general formula (ii) and (iii), L represents a Lewis base.
Examples of the Lewis base include tetrahydrofuran, diethyl ether, dimethylaniline, trimethylphosphine, lithium chloride, neutral olefins, neutral diolefins, and the like.
When the rare earth element compound reacts with a plurality of Lewis bases, each Lewis base may be the same or different.

(A) A component may be used individually by 1 type and may be used in combination of 2 or more type.
The concentration of the component (A) contained in the first polymerization catalyst composition with respect to the whole composition is preferably 0.1 mol / L to 0.0001 mol / L.

-(B) component-
The component (B) 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).
The total content of the B component in the polymerization catalyst composition is preferably 0.1 to 50 times mol with respect to the component (A).

--Ionic compound (B-1)-
Examples of the ionic compound (B-1) include an ionic compound capable of generating a cationic transition metal compound by reacting with the rare earth element compound as the component (A) or a reaction product of the rare earth element compound with a Lewis base. Can be mentioned.

  Non-coordinating anions include, for example, tetraphenylborate, tetrakis (monofluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis (pentafluorophenyl) ) Borate, tetrakis (tetrafluoromethylphenyl) borate, tetra (tolyl) borate, tetra (xylyl) borate, (triphenyl, pentafluorophenyl) borate, [tris (pentafluorophenyl), phenyl] borate, tridecahydride- 7,8-dicarbound decaborate and the like.

  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.

Examples of the carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation and tri (substituted phenyl) carbonium cation.
Examples of the tri (substituted phenyl) carbonium cation include a tri (methylphenyl) carbonium cation and a tri (dimethylphenyl) carbonium cation.

  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 cation N, N-diethylanilinium cation, N, N-2,4,6-pentamethylanilinium cation and the like N, N-dialkylanilinium cation; diisopropylammonium cation, dicyclohexylammonium cation and the like dialkylammonium cation; etc. Is mentioned.

  Examples of the phosphonium cation include a triarylphosphonium cation such as a triphenylphosphonium cation, a tri (methylphenyl) phosphonium cation, and a tri (dimethylphenyl) phosphonium cation.

Therefore, the ionic compound (B-1) is preferably a compound selected and combined from the above-mentioned non-coordinating anions and cations, specifically, N, N-dimethylanilinium tetrakis (pentafluorophenyl). Borate, triphenylcarbonium tetrakis (pentafluorophenyl) borate, trityltetrakis (pentafluorophenyl) borate ([Ph ₃ C] [B (C ₆ F ₅ ) ₄ ]), tris (pentafluorophenyl) boron [B ( C ₆ F ₅ ) ₃ ], etc. are preferred.
These ionic compounds may be used individually by 1 type, and 2 or more types may be mixed and used for them.

  The content of the ionic compound (B-1) is preferably 0.1-fold to 10-fold mol and more preferably 1-fold mol with respect to component (A).

--Aluminoxane (B-2)-
Aluminoxane (B-2) is a compound obtained by bringing an organoaluminum compound and a condensing agent into contact with each other. Examples thereof include a chain aluminoxane or a cyclic aluminoxane having a repeating unit represented by the following general formula. :
General formula (-Al (R ') O-)
(In the above general formula, R ′ is a hydrocarbon group having 1 to 10 carbon atoms, and some hydrocarbon groups may be substituted with a halogen atom and / or an alkoxy group. 5 or more is preferable, and 10 or more is more preferable.)

  Examples of R ′ include a methyl group, an ethyl group, a propyl group, and an isobutyl group. Among these, a methyl group is preferable.

  Examples of the organoaluminum compound used as a starting material for aluminoxane include trialkylaluminums such as trimethylaluminum, triethylaluminum, 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.

As the aluminoxane, alkylaluminoxanes such as methylaluminoxane (MAO) and modified methylaluminoxane are preferable.
As the modified methylaluminoxane, MMAO-3A (manufactured by Tosoh Finechem) is preferable.

  As for the content of aluminoxane, the element ratio Al / M of the rare earth element M constituting the component (A) and the aluminum element Al of the aluminoxane is preferably about 10 to 1000, more preferably about 100. .

-Halogen compound (B-3)-
The halogen compound (B-3) comprises at least one of (i) a Lewis acid, (ii) a complex compound of a metal halide and a Lewis base, and (iii) an organic compound containing an active halogen.
For example, the halogen compound (B-3) can react with the component (A) to generate a halogenated transition metal compound or a compound having a transition metal center with insufficient charge.
The total content of the halogen compounds is preferably 1 to 5 times the mol of the component (A).

(I) Lewis acid 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. , 4, 5, 6 or a halogen compound containing an element belonging to Group 8 can also be used.
The Lewis acid is preferably an aluminum halide or an organometallic halide. Moreover, as a halogen element contained in these, chlorine or a bromine is preferable.
Examples of the aluminum halide 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, and the like.
Among these, diethylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, diethylaluminum bromide, ethylaluminum sesquibromide, and ethylaluminum dibromide are preferable.
Examples of the organometallic halide include antimony trichloride, antimony pentachloride, phosphorus trichloride, phosphorus pentachloride, tin tetrachloride, titanium tetrachloride, tungsten hexachloride, and the like.

(Ii) Complex compound of metal halide and Lewis base -metal halide-
Examples of the metal halide include beryllium chloride, beryllium bromide, beryllium iodide, magnesium chloride, magnesium bromide, magnesium iodide, calcium chloride, calcium bromide, calcium iodide, barium chloride, barium bromide and iodide. Barium, 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, odor Rhenium iodide, rhenium iodide, copper chloride, copper iodide, silver chloride, silver bromide, silver iodide, gold chloride, gold iodide, gold bromide, and the like.
Among these, magnesium chloride, calcium chloride, barium chloride, manganese chloride, zinc chloride, and copper chloride are preferable, and magnesium chloride, manganese chloride, zinc chloride, and copper chloride are more preferable.

-Lewis base-
Examples of the Lewis base include phosphorus compounds, carbonyl compounds, nitrogen compounds, ether compounds, alcohols and the like.
Specific examples of Lewis bases include 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-ethylhexanoic acid Oleic acid, stearic acid, benzoic acid, naphthenic acid, versatic acid, triethylamine, N, N-dimethylacetamide, tetrahydrofuran, diphenyl ether, 2-ethylhexyl Alcohol, oleyl alcohol, stearyl alcohol, phenol, benzyl alcohol, 1-decanol, lauryl alcohol, and the like.
Among these, tri-2-ethylhexyl phosphate, tricresyl phosphate, acetylacetone, 2-ethylhexanoic acid, versatic acid, 2-ethylhexyl alcohol, 1-decanol, and lauryl alcohol are preferable.

  The Lewis base is reacted at a ratio of 0.01 mol to 30 mol, preferably 0.5 mol 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.

(Iii) Organic Compound Containing Active Halogen Examples of the organic compound containing active halogen include benzyl chloride.

-(C) component-
Component (C) is an organometallic compound represented by the following general formula (i):
YR ¹ _a R ² _b R ³ _c (i)
(In General Formula (i), 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 have 1 to 10 carbon atoms. A hydrocarbon group or a hydrogen atom, and R ³ is a hydrocarbon group having 1 to 10 carbon atoms, provided that R ¹ , R ² and R ³ may be the same or different from each other. And when Y is a metal selected from Group 1 of the Periodic Table, a is 1, and b and c are 0, and Y is from Groups 2 and 12 of the Periodic Table. When it is a selected metal, a and b are 1 and c is 0, and when Y is a metal selected from group 13 of the periodic table, a, b and c are 1)

Since the ionic compound (B-1) and the halogen compound (B-3) have no carbon atom to supply to the component (A), an organic metal is used as a carbon supply source to the component (A). Compound (C) component is required.
In addition, even if it is a case where a 1st polymerization catalyst composition contains an aluminoxane (B-2), a 1st polymerization catalyst composition can contain an organometallic compound (C) component.

The organometallic compound (C) component is preferably an organoaluminum compound represented by the following general formula (X).
AlR ¹¹ R ¹² R ¹³ (X)
(In the general formula (X), R ¹¹ and R ¹² are each a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom, and R ¹³ is a hydrocarbon group having 1 to 10 carbon atoms. ¹¹ , R ¹² and R ¹³ may be the same or different.

-Organoaluminum compound of general formula (X)-
Examples of the organic aluminum compound of the general formula (X) include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, tri Trialkylaluminum such as pentylaluminum, trihexylaluminum, tricyclohexylaluminum, trioctylaluminum; diethylaluminum hydride, di-n-propylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride, dihexylaluminum hydride, diiso Hexyl aluminum hydride, dioctyl aluminum hydride, diisooctane Dialkylaluminum hydrides such as Le aluminum hydride, ethyl aluminum dihydride, n- propyl aluminum dihydride, isobutyl aluminum dihydride; dialkylaluminum chlorides, alkyl aluminum dichloride; and the like.
These organometallic compounds may be used individually by 1 type, and 2 or more types may be mixed and used for them.
Among these, triethylaluminum, triisobutylaluminum, diethylaluminum hydride, and diisobutylaluminum hydride are preferable.
The content of the organoaluminum compound is preferably 1 to 50 times mol and more preferably 10 times mol for the component (A).

  The first polymerization catalyst composition and the second and third polymerization catalyst compositions described below may contain other components contained in the conventional polymerization catalyst composition without departing from the gist of the present invention. . For example, a conjugated diene compound and / or a non-conjugated olefin, which is a monomer previously blended as a polymerization catalyst composition of a type different from the monomer constituting the main chain of the polymer (hereinafter referred to as “blended monomer”). May also be included.).

（一般式（１）中、Ｍは、ランタノイド元素、スカンジウムまたはイットリウムを表し、Ａ、ＢおよびＣは、それぞれ独立して、水素原子、ハロゲン原子、アルコキシド基、チオラート基、アミド基、シリル基、アルデヒド残基、ケトン残基、カルボン酸残基、チオカルボン酸残基、リン化合物残基、無置換もしくは置換シクロペンタジエニル基、無置換もしくは置換インデニル基、または、無置換もしくは置換フルオレニル基を表し、Ａ、ＢおよびＣの少なくとも１つは、上記無置換もしくは置換のシクロペンタジエニル基、インデニル基またはフルオレニル基である。） << Second polymerization catalyst composition >>
Examples of the second polymerization catalyst composition include a polymerization catalyst composition containing a catalyst represented by the following general formula (1):

(In the general formula (1), M represents a lanthanoid element, scandium or yttrium, and A, B and C are each independently a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group, a silyl group, Represents an aldehyde residue, ketone residue, carboxylic acid residue, thiocarboxylic acid residue, phosphorus compound residue, unsubstituted or substituted cyclopentadienyl group, unsubstituted or substituted indenyl group, or unsubstituted or substituted fluorenyl group , A, B and C are the above-mentioned unsubstituted or substituted cyclopentadienyl group, indenyl group or fluorenyl group.)

In the general formula (1), M represents a lanthanoid element, scandium or yttrium. The lanthanoid element is the same as that mentioned in the first polymerization catalyst composition.
In the general formula (1), A, B and C are each independently a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group, a silyl group, an aldehyde residue, a ketone residue, or a carboxylic acid residue. , A thiocarboxylic acid residue, a phosphorus compound residue, an unsubstituted or substituted cyclopentadienyl group, an unsubstituted or substituted indenyl group, or an unsubstituted or substituted fluorenyl group, wherein at least one of A, B and C is The unsubstituted or substituted cyclopentadienyl group, indenyl group or fluorenyl group.
The halogen atom, alkoxide group, thiolate group, amide group, silyl group, aldehyde residue, ketone residue, carboxylic acid residue, thiocarboxylic acid residue and phosphorus compound residue are mentioned in the first polymerization catalyst composition. It is the same as that.

-Cyclopentadienyl group-
An unsubstituted or substituted cyclopentadienyl group has a cyclopentadienyl ring as a basic skeleton and is represented by the formula C ₅ H _5-X R _X.
In the formula, X is an integer of 0 to 5, and each R is independently an aliphatic hydrocarbon group, an aromatic hydrocarbon group or a metalloid group.
The aliphatic hydrocarbon group or the aromatic hydrocarbon group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and particularly preferably 1 to 8 carbon atoms.
Examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a neopentyl group, a hexyl group, and an octyl group. And straight chain or branched aliphatic hydrocarbon groups such as
Examples of the aromatic hydrocarbon group include a phenyl group, a tolyl group, a naphthyl group, and the like; an aralkyl group such as a benzyl group, and the like.

（式中、Ｒは水素原子、メチル基またはエチル基を表す。） Examples of the metalloid-based metalloid include germyl, stannyl, and silyl.
The metalloid group preferably has an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and the aliphatic hydrocarbon group or aromatic hydrocarbon group of the metalloid group is the above-mentioned aliphatic hydrocarbon group of a cyclopentadienyl group. Or it is the same as an aromatic hydrocarbon group.
As a metalloid group, a trimethylsilyl group etc. are mentioned, for example.
Specific examples of the cyclopentadienyl ring as a basic skeleton include the following.

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

（一般式（２）中、Ｒ^１〜Ｒ^５は、それぞれ独立して、水素原子、炭素数１〜２０の脂肪族炭化水素基または芳香族炭化水素基を表し、Ｒ^１〜Ｒ^５のうち、少なくとも２つは、炭素数１〜２０の脂肪族炭化水素基または芳香族炭化水素基である。ただし、一般式（２）において、インデニル基およびフルオレニル基は除く。）
上記一般式（２）で表される置換シクロペンタジエニル基を用いることにより、脂肪族炭化水素を溶媒として用いた場合において、共役ジエン化合物と非共役オレフィンとの共重合体を合成しやすい。 In the method for producing a copolymer according to the present invention, the substituted cyclopentadienyl group that can be A, B, or C in the general formula (1) is preferably represented by the following general formula (2). .

(In General Formula (2), R ^{1 to} R ⁵ each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group, and among R ^{1 to} R ⁵ , , At least two are an aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 20 carbon atoms (excluding the indenyl group and the fluorenyl group in the general formula (2)).
By using the substituted cyclopentadienyl group represented by the general formula (2), it is easy to synthesize a copolymer of a conjugated diene compound and a non-conjugated olefin when an aliphatic hydrocarbon is used as a solvent.

In General Formula (2), R ^{1 to} R ⁵ each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group, and among R ^{1 to} R ⁵ , At least two are an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group.
The aliphatic hydrocarbon group or the aromatic hydrocarbon group is the same as described above.

  Preferred substituted cyclopentadienyl groups represented by the general formula (2) include, for example, dimethylcyclopentadienyl group, tetramethylcyclopentadienyl group, pentamethylcyclopentadienyl group, benzylcyclopentadienyl group Is mentioned.

-Indenyl group-
The unsubstituted or substituted indenyl group has an indenyl ring as a basic skeleton and is represented by the formula C ₉ H _7-X R _X or C ₉ H _11-X R _X.
In the formula, X is an integer of 0 to 7 or 0 to 11, and R is the same as the above cyclopentadienyl group.

  Examples of the substituted indenyl include 1-methyl-2-phenylindenyl, 1-benzyl-2-phenylindenyl, 2-phenylindenyl, 2-methylindenyl, and the like.

（一般式（３）中、Ｒ^６〜Ｒ^８は、それぞれ独立して、水素原子、炭素数１〜２０の脂肪族炭化水素基または芳香族炭化水素基を表し、Ｒ^６〜Ｒ^８のうち、少なくとも２つは、炭素数１〜２０の脂肪族炭化水素基または芳香族炭化水素基であり、Ｘは、それぞれ独立して、水素原子または炭化水素基を表す。ただし、一般式（３）において、フルオレニル基は除く。）
上記一般式（３）で表される置換インデニル基を用いることにより、脂肪族炭化水素を溶媒として用いた場合において、共役ジエン化合物と非共役オレフィンとの共重合体を合成しやすい。 In the method for producing a copolymer according to the present invention, the substituted indenyl group that can be A, B, or C in the general formula (1) is preferably represented by the following general formula (3).

(In General Formula (3), R ^{6 to} R ⁸ each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group, and among R ^{6 to} R ⁸ , , At least two are an aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 20 carbon atoms, and each X independently represents a hydrogen atom or a hydrocarbon group, provided that the general formula (3) Except fluorenyl group.)
By using the substituted indenyl group represented by the general formula (3), it is easy to synthesize a copolymer of a conjugated diene compound and a non-conjugated olefin when an aliphatic hydrocarbon is used as a solvent.

In General Formula (3), R ^{6 to} R ⁸ each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group, and among R ^{6 to} R ⁸ , At least two are an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group.
The aliphatic hydrocarbon group or the aromatic hydrocarbon group is the same as described above.

In general formula (3), X represents a hydrogen atom or a hydrocarbon group each independently.
The hydrocarbon group for X is the same as the aliphatic hydrocarbon group or aromatic hydrocarbon group described above. In addition, the hydrocarbon group of X may be, for example, a hydrocarbon group containing a silicon atom such as a trimethylsilylmethyl group or a bistrimethylsilylmethyl group.

As preferable substituted indenyl group represented by the general formula (3), for example, 1-methyl-2-phenylindenyl (R ⁶ = methyl group, R ⁷ = phenyl group in the general formula (3)), 1-benzyl -2-phenylindenyl (R ⁶ = benzyl group, R ⁷ = phenyl group in general formula (3)) and the like, and 1-benzyl-2-phenylindenyl is particularly preferable.

-Fluorenyl group-
The unsubstituted or substituted fluorenyl group has a fluorenyl ring as a basic skeleton and is represented by the formula C ₁₃ H _9-X R _X or C ₁₃ H _17-X R _X.
In the formula, X is an integer of 0 to 9 or 0 to 17, and R is the same as the above cyclopentadienyl group.

（一般式（４）中、Ｒ^９は、炭素数１〜２０の脂肪族炭化水素基または芳香族炭化水素基を表し、Ｘは、それぞれ独立して、水素原子または炭化水素基を表す。）
上記一般式（４）で表される置換フルオレニル基を用いることにより、脂肪族炭化水素を溶媒として用いた場合において、共役ジエン化合物と非共役オレフィンとの共重合体を合成しやすい。 In the method for producing a copolymer according to the present invention, the substituted fluorenyl group that can be A, B or C in the general formula (1) is preferably one represented by the following general formula (4).

(In General Formula (4), R ⁹ represents an aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 20 carbon atoms, and X independently represents a hydrogen atom or a hydrocarbon group.)
By using the substituted fluorenyl group represented by the general formula (4), it is easy to synthesize a copolymer of a conjugated diene compound and a non-conjugated olefin when an aliphatic hydrocarbon is used as a solvent.

In General Formula (4), R ⁹ represents an aliphatic hydrocarbon group or aromatic hydrocarbon group having 1 to 20 carbon atoms.
The aliphatic hydrocarbon group or the aromatic hydrocarbon group is the same as described above.

In general formula (4), X represents a hydrogen atom or a hydrocarbon group each independently.
The hydrocarbon group for X is the same as that described in formula (3).

  Preferred examples of the substituted fluorenyl group represented by the general formula (4) include a methyl fluorenyl group, an isopropyl fluorenyl group, and a benzyl fluorenyl group.

In the method for producing a copolymer according to the present invention, the substituted cyclopentadienyl group represented by the general formula (2), the substituted indenyl group represented by the general formula (3), or the general formula (4) By using a catalyst containing a compound having a substituted fluorenyl group as a ligand, a copolymer of a conjugated diene compound and a non-conjugated olefin can be easily synthesized when an aliphatic hydrocarbon is used as a solvent.
The reason for this is not clear, but by having a substituent compared to an unsubstituted cyclopentadienyl group, indenyl group or fluorenyl group, a reaction product such as a non-conjugated olefin having a moderate steric hindrance and a general formula (1 It is easy to approach the central metal M and the catalytic action is enhanced, or the presence of a substituent facilitates the transfer of electrons between the catalyst and the reactant, thereby enhancing the catalytic action. As guessed.

In the method for producing a copolymer according to the present invention, at least one of R ^{1 to} R ⁵ in the general formula (2), at least one of R ^{6 to} R ⁸ in the general formula (3), R ⁹ in the general formula (4) is preferably an aromatic hydrocarbon group. This makes it easier to synthesize a copolymer of a conjugated diene compound and a non-conjugated olefin.

In the method for producing a copolymer according to the present invention, at least two of R ^{1 to} R ⁵ in the general formula (2) and at least two of R ^{6 to} R ⁸ in the general formula (3) are An aromatic hydrocarbon group is more preferable. This makes it easier to synthesize a copolymer of a conjugated diene compound and a non-conjugated olefin.
The reason for this is not clear, but at least two of R ^{1 to} R ⁵ in the general formula (2) and at least two of R ^{6 to} R ⁸ in the general formula (3) are bulky fragrances. By having a group hydrocarbon group, reactants such as non-conjugated olefins can easily approach the central metal M in the general formula (1) to improve the catalytic action, or conventionally used aromatic carbonization It is presumed as a factor that the reaction field can maintain a polar state by having a structure close to a hydrogen solvent as a ligand, and the catalytic action is enhanced.

（一般式（Ｉ）中、Ｍは、上記一般式（１）と同様であり、Ｃｐ^Ｒは、それぞれ独立して、無置換または置換インデニル基を表し、Ｒ^ａ〜Ｒ^ｆは、それぞれ独立して、炭素数１〜３のアルキル基または水素原子を表し、Ｌは、中性ルイス塩基を表し、ｗは、０〜３の整数を表す。）；

（一般式（ＩＩ）中、Ｍ、Ｃｐ^Ｒ、Ｌおよびｗは、上記一般式（Ｉ）と同様であり、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、シリル基または炭素数１〜２０の炭化水素基を表す。）；

（一般式（ＩＩＩ）中、Ｍ、Ｌおよびｗは、上記一般式（Ｉ）と同様であり、Ｃｐ^Ｒ’は、無置換もしくは置換シクロペンタジエニル基、無置換もしくは置換インデニル基または無置換もしくは置換フルオレニル基を表し、Ｘは、上記一般式（ＩＩ）のＸ’と同様であり、［Ｂ］⁻は、非配位性アニオンを表す。） -Metallocene complexes and half metallocene cation complexes-
In a preferred embodiment of the method for producing a copolymer according to the present invention, as a catalyst represented by the general formula (1), a metallocene complex represented by the following general formula (I), a general formula (II) You may use the at least 1 sort (s) of complex selected from the group which consists of the metallocene complex represented and the half metallocene cation complex represented by the following general formula (III):

(In the general formula (I), M is the same as in the general formula (1), Cp ^R each independently represents an unsubstituted or substituted indenyl group, and R ^{a to} R ^f are each independently And represents an alkyl group having 1 to 3 carbon atoms or a hydrogen atom, L represents a neutral Lewis base, and w represents an integer of 0 to 3).

(In the general formula (II), M, Cp ^R , L and w are the same as those in the general formula (I), and X ′ is a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group, a silyl group. Or represents a hydrocarbon group having 1 to 20 carbon atoms);

(In the general formula (III), M, L and w are the same as in the general formula (I), and Cp ^{R ′} is an unsubstituted or substituted cyclopentadienyl group, an unsubstituted or substituted indenyl group or an unsubstituted group. Alternatively, it represents a substituted fluorenyl group, X is the same as X ′ in formula (II), and [B] ⁻ represents a non-coordinating anion.)

  The central metal M in the general formulas (I), (II) and (III) is the same as that mentioned in the first polymerization catalyst composition. As the central metal M, samarium Sm, neodymium Nd, praseodymium Pr, gadolinium Gd, cerium Ce, holmium Ho, scandium Sc, and yttrium Y are preferable.

Cp ^R in the general formulas (I) and (II) is each independently an unsubstituted indenyl group or a substituted indenyl group.
The unsubstituted indenyl group and the substituted indenyl group are the same as the unsubstituted indenyl group and the substituted indenyl group in the general formula (1), respectively. The same applies to preferred substituted indenyl groups.

Cp ^{R ′} in the general formula (III) is an unsubstituted cyclopentadienyl group, a substituted cyclopentadienyl group, an unsubstituted indenyl group, a substituted indenyl group, an unsubstituted fluorenyl group, or a substituted fluorenyl group. These are the same as the respective functional groups in the general formula (1). The same applies to the preferred substituted cyclopentadienyl group, substituted indenyl group or substituted fluorenyl group.

The metallocene complex represented by the general formula (I) includes a silylamide ligand [—N (SiR ^{a to} R ^c ) (SiR ^{d to} R ^f )].
R ^{a to} R ^f are each independently an alkyl group having 1 to 3 carbon atoms or a hydrogen atom.
It is preferable that at least one of R ^{a to} R ^f is a hydrogen atom. When at least one of R ^{a to} R ^f is a hydrogen atom, the synthesis of the catalyst is facilitated, and the bulk around silicon is reduced, so that the non-conjugated olefin is easily introduced.
From the same viewpoint, it is 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. Further, the alkyl group is preferably a methyl group.
Specific examples of the metallocene complex represented by the general formula (I) include bis (2-phenylindenyl) gadolinium bis (dimethylsilylamide), bis (1-methyl-2-phenylindenyl) gadolinium bis (dimethylsilyl). Amide), bis (1-benzyl-2-phenylindenyl) gadolinium bis (dimethylsilylamide), bis (1-methyl-2-phenylindenyl) gadolinium bis (dimethylsilylamide), bis (1- Benzyl-2-phenylindenyl) gadolinium bis (dimethylsilylamide) is preferred, and bis (1-benzyl-2-phenylindenyl) gadolinium bis (dimethylsilylamide) is more preferred.

The metallocene complex represented by the general formula (II) includes a silyl ligand [—SiX ′ ₃ ].
X ′ is a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group, a silyl group, or a hydrocarbon group having 1 to 20 carbon atoms.
The halogen atom, alkoxide group, thiolate group, amide group and silyl group as X ′ are the same as the functional groups of A, B and C in the general formula (1).
Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by X ′ include hydrocarbon groups containing silicon atoms such as trimethylsilylmethyl group and bistrimethylsilylmethyl group, in addition to those mentioned for the substituted cyclopentadienyl group. Can be mentioned.
Among these, a methyl group, an ethyl group, an isobutyl group, a trimethylsilylmethyl group, and the like are preferable.
X ′ is preferably a bistrimethylsilylamide group or a hydrocarbon group having 1 to 20 carbon atoms.

  X in the general formula (III) 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. These are the same as X ′ in the general formula (II).

The metallocene complex represented by the general formulas (I) and (II) and the half metallocene cation complex represented by the general formula (III) contain 0 to 3 neutral Lewis bases L.
The neutral Lewis base L is preferably 0 to 1.
Examples of the neutral Lewis base L include tetrahydrofuran, diethyl ether, dimethylaniline, trimethylphosphine, lithium chloride, neutral olefins, neutral diolefins, and the like.

In the general formula (III), [B] ^- The non-coordinating anion represented by, for example, a tetravalent boron anion.
Examples of tetravalent boron anions include tetraphenyl borate, tetrakis (monofluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis (pentafluorophenyl) Borate, tetrakis (tetrafluoromethylphenyl) borate, tetra (tolyl) borate, tetra (xylyl) borate, (triphenyl, pentafluorophenyl) borate, [tris (pentafluorophenyl), phenyl] borate, tridecahydride-7 , 8-dicarbaoundecaborate and the like. 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) may exist as a monomer, and may be a dimer or a larger amount thereof. It may exist as a body.

The second polymerization catalyst composition may further contain other components contained in the polymerization catalyst composition containing a normal metallocene complex, for example, a compounded monomer, a promoter, and the like. The second polymerization catalyst composition preferably contains a cocatalyst.
In the polymerization reaction system, the concentration of the complex contained in the second polymerization catalyst composition with respect to the entire composition is preferably in the range of 0.1 mol / L to 0.0001 mol / L.

-Cocatalyst-
Specific examples of the co-catalyst that can be used in the second polymerization catalyst composition include the ionic compound (B-1), aluminoxane (B-2), and halogen compound (B-3) of the first polymerization catalyst composition. ) Or specific examples of the organometallic compound (component C). The same applies to preferred promoters.
The content of the organoaluminum compound that can be used in the second polymerization catalyst composition is preferably 1-fold mole to 500-fold mole, more preferably 10-fold mole to 150-fold mole relative to the metallocene complex. .

  By combining the metallocene complex represented by the above general formulas (I) and (II) and the half metallocene cation complex represented by the general formula (III) with an appropriate cocatalyst, The molecular weight of the resulting polymer can be increased.

-Preparation method of metallocene complex and half metallocene cation complex-
A conventionally well-known method can be used for the preparation method of the metallocene complex represented by general formula (I) and (II) and the half metallocene cation complex represented by general formula (III). For example, the metallocene complex represented by the general formulas (I) to (III) can be prepared by the method described in Patent Document 2.
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).
Since reaction temperature should just be about room temperature, it can manufacture on mild conditions.
The reaction time may be appropriately adjusted and 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.

（式中、Ｘ”はハライドを表す。） Below, the reaction example for obtaining the metallocene complex represented by general formula (I) is shown.

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

The metallocene complex represented by the general formula (II) includes, for example, a lanthanide trishalide, scandium trishalide, or yttrium trishalide in a solvent, an indenyl salt (for example, potassium salt or lithium salt), and a silyl salt (for example, , Potassium salt or lithium salt).
Since reaction temperature should just be about room temperature, it can manufacture on mild conditions.
The reaction time may be appropriately adjusted and 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.

（式中、Ｘ”はハライドを表す。） Below, the reaction example for obtaining the metallocene complex represented by general formula (II) is shown.

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

（一般式（ＩＶ）中、Ｍ、Ｘ、Ｌおよびｗは、上記一般式（ＩＩＩ）と同様であり、Ｃｐ^Ｒ’は、それぞれ独立して、上記一般式（ＩＩＩ）のＣｐ^Ｒ’と同様であり、一般式［Ａ］^＋［Ｂ］⁻で表されるイオン性化合物において、［Ａ］^＋は、カチオンを表す。［Ｂ］⁻は、非配位性アニオンを表す。） The half metallocene cation complex represented by the general formula (III) can be obtained, for example, by the following reaction.

(In the general formula (IV), M, X, L and w are the same as the above-mentioned general formula (III), Cp ^{R 'is} independently, Cp ^R in the general formula ^(III)' similar to the In the ionic compound represented by the general formula [A] ⁺ [B] ⁻ , [A] ⁺ represents a cation, and [B] ⁻ represents a non-coordinating anion.)

[A] The cation represented by ⁺ is the same as the cation of the ionic compound (B-1) mentioned in the first polymerization catalyst composition.

The ionic compound represented by the general formula [A] ⁺ [B] ⁻ is preferably added in an amount of 0.1 to 10 times by mole to the metallocene complex represented by the general formula (IV). It is more preferable to add mol.
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. in providing an ionic compound represented separately into the polymerization reaction system, the general formula in the reaction system (III) ^- compound represented by formula (IV) and the general formula [a] + ^[B] used The represented half metallocene cation complex may be formed.
In addition, by using a combination of a metallocene complex represented by general formula (I) or general formula (II) and an ionic compound represented by general formula [A] ⁺ [B] ⁻ in the reaction system, A half metallocene cation complex represented by the general formula (III) can also be formed.

  The structures of the metallocene complex catalyst of the general formula (I), the metallocene complex represented by the general formula (II) and the half metallocene cation complex represented by the general formula (III) and the third polymerization catalyst composition described later are: It is preferable to determine by X-ray structural analysis.

<< Third polymerization catalyst composition >>
As the third polymerization catalyst composition, a metallocene composite catalyst represented by the following formula (A) is preferably exemplified:
R ₂ MX ₂ QY ₂ (A)
(In the formula (A), M is the same as in the general formula (1), each R independently represents an unsubstituted or substituted indenyl group, R is coordinated to M, X Each independently represents a hydrocarbon group having 1 to 20 carbon atoms, X is μ-coordinated to M and Q, Q represents a group 13 element in the periodic table, and Y represents Independently represents a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom, and Y is coordinated to Q.)

The metallocene composite catalyst is a compound having a lanthanoid element, a rare earth element of scandium or yttrium, and a group 13 element of the periodic table.
By using these metallocene composite catalysts, for example, a catalyst that is previously combined with an aluminum catalyst, the amount of alkylaluminum that can be used during the synthesis of the copolymer can be reduced or eliminated.

  The metal M in the formula (A) represents a lanthanoid element, scandium or yttrium, and is the same as that mentioned in the first polymerization catalyst composition. Preferable metal M is also the same as in the above general formulas (I) to (III).

R in Formula (A) is each independently an unsubstituted indenyl group or a substituted indenyl group.
Examples of the substituted indenyl group include those listed in the general formula (1), for example, 1,2,3-trimethylindenyl group, heptamethylindenyl group, 1,2,4,5,6,7- A hexamethylindenyl group, and the like.

X in the formula (A) independently represents a hydrocarbon group having 1 to 20 carbon atoms, and X is coordinated to M and Q in μ.
The hydrocarbon group having 1 to 20 carbon atoms of X is the same as the hydrocarbon group having 1 to 20 carbon atoms of X ′ in the general formula (II).
μ coordination refers to a coordination mode having a cross-linked structure.

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

Y in the formula (A) independently represents a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom, and Y is coordinated to Q.
The hydrocarbon group having 1 to 20 carbon atoms of Y is the same as the hydrocarbon group having 1 to 20 carbon atoms of X ′ in the general formula (II).

（一般式（ＸＸ）中、Ｍ^２１は、上記一般式（１）のＭと同様であり、Ｃｐ^Ｒは、上記一般式（Ｉ）と同様であり、Ｒ^２１およびＲ^２２は、それぞれ独立して、炭素数１〜２０の炭化水素基を表し、Ｒ^２１およびＲ^２２は、Ｍ^２１およびＡｌにμ配位しており、Ｒ^２３およびＲ^２４は、それぞれ独立して、炭素数１〜２０の炭化水素基または水素原子を表す。） The third polymerization catalyst composition is more preferably a metallocene composite catalyst represented by the following general formula (XX):

(In General Formula (XX), M ²¹ is the same as M in General Formula (1), Cp ^R is the same as in General Formula (I), and R ²¹ and R ²² are each independently Represents a hydrocarbon group having 1 to 20 carbon atoms, R ²¹ and R ²² are μ-coordinated to M ²¹ and Al, and R ²³ and R ²⁴ each independently represent 1 to 20 carbon atoms. Represents a hydrocarbon group or a hydrogen atom.)

M ²¹ in the general formula (XX) is the same as that described for the first polymerization catalyst composition. Preferred metals ^{M 21} is also the same as the above-mentioned general formula (II).

Cp ^R in the general formula (XX) is the same as ^R in the above formula (A).

R ²¹ and R ^{22 in} general formula (XX) each independently represent a hydrocarbon group having 1 to 20 carbon atoms, and R ²¹ and R ²² are μ-coordinated to M ²¹ and Al.
The hydrocarbon group having 1 to 20 carbon atoms of R ²¹ and R ²² is the same as the hydrocarbon group having 1 to 20 carbon atoms of X ′ in the general formula (II).

R ²³ and R ^{24 in} general formula (XX) are each independently a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom.
The hydrocarbon group having 1 to 20 carbon atoms of R ²³ and R ²⁴ is the same as the hydrocarbon group having 1 to 20 carbon atoms of X ′ in the general formula (II).

The metallocene-based composite catalyst is obtained, for example, by reacting the metallocene complex represented by the general formula (I) with an organoaluminum compound represented by AlR ²⁵ R ²⁶ R ²⁷ in a solvent.
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 organoaluminum compound is represented by AlR ²⁵ R ²⁶ R ²⁷ .
R ²⁵ and R ²⁶ are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom; R ²⁷ is a monovalent hydrocarbon group having 1 to 20 carbon atoms; ²⁷ may be the same as or different from R ²⁵ or R ²⁶ .
Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms are the same as the specific examples of the hydrocarbon group represented by X in the above formula (A).

Specific examples of the organoaluminum compound are the same as the specific examples of the organoaluminum compound of the general formula (X) of the first polymerization catalyst composition.
An organoaluminum compound may be used individually by 1 type, and 2 or more types may be mixed and used for it.
The amount of the organoaluminum compound used for the production of the metallocene composite catalyst is preferably 2 to 50 times mol, more preferably 3 times mol to 5 times mol with respect to the metallocene complex.

  Similarly to the first and second polymerization catalyst compositions, the third polymerization catalyst composition may also contain a compounded monomer.

<Copolymer>
Since the copolymer obtained by the method for producing a copolymer according to the present invention has fewer double bonds derived from the conjugated diene compound than the homopolymer of the conjugated diene compound, weather resistance (ozone resistance) Excellent.

There is no restriction | limiting in particular as content of the said conjugated diene compound origin part in a copolymer, Although it can select suitably according to the objective, 2 mol%-less than 100 mol% are preferable.
By setting the content of the conjugated diene compound-derived portion in the copolymer to 2 mol% or more, processability can be sufficiently ensured.
On the other hand, when the content of the conjugated diene compound-derived portion is less than 100 mol%, a certain amount of non-conjugated olefin is contained, so that improvement in weather resistance (ozone resistance) can be expected.

There is no restriction | limiting in particular as content of the nonconjugated olefin origin part in a copolymer, Although it can select suitably according to the objective, More than 0 mol% and 98 mol% or less are preferable.
The weather resistance can be improved by setting the content of the non-conjugated olefin-derived portion in the copolymer to more than 0 mol%, and the processability is maintained and the crack growth resistance is improved by setting the content to 98 mol% or less. be able to.

The amount of cis-1,4 bond derived from the conjugated diene compound in the copolymer is not particularly limited and may be appropriately selected according to the purpose, but is preferably over 92%, more preferably over 95%. 97% or more is most preferable.
By setting the amount of cis-1,4 bonds in the conjugated diene compound-derived portion to be more than 92%, a low glass transition point (Tg) can be maintained. Thereby, physical properties such as low-temperature characteristics are improved.
By making the amount of cis-1,4 bonds exceed 95%, it becomes possible to improve the crack growth resistance, weather resistance, and heat resistance, and by setting it to 97% or more, crack growth resistance, weather resistance. Further, the heat resistance can be further improved.

The weight average molecular weight (Mw) of the copolymer is not particularly limited, but from the viewpoint of application to a polymer structural material, the polystyrene equivalent weight average molecular weight (Mw) of the copolymer is 10,000 to 10,000. It is preferably 000,000, more preferably 10,000 to 1,000,000, and particularly preferably 50,000 to 600,000.
Mw is 10, from the viewpoint of a region that exhibits a performance difference between a copolymer obtained by the method for producing a copolymer according to the present invention and a mere polymer blend (for example, a blend of polyethylene and polybutadiene). 000 or more is preferable.
Mw is preferably 10,000,000 or less from the viewpoint of obtaining good moldability.

The molecular weight distribution (Mw / Mn) represented by the ratio between the weight average molecular weight (Mw) and the number average molecular weight (Mn) is preferably 10 or less, and 6 or less from the viewpoint of ensuring the homogeneity of physical properties. More preferably.
Here, the average molecular weight and the molecular weight distribution can be determined using polystyrene as a standard substance by gel permeation chromatography (GPC).

The content of the 1,2-adduct portion (including the 3,4-adduct portion) of the conjugated diene compound in the conjugated diene compound-derived portion of the copolymer is not particularly limited and should be appropriately selected according to the purpose. However, from the viewpoint of improving the weather resistance (ozone resistance) of the copolymer, it is preferably 5% or less, more preferably 3% or less, and particularly preferably 2.5% or less.
The content of the 1,2-adduct portion (including the 3,4-adduct portion) is an amount in the portion derived from the conjugated diene compound, and is not a ratio with respect to the entire copolymer.
In addition, when the conjugated diene compound is butadiene, the content of the 1,2-adduct portion (including the 3,4-adduct portion) of the conjugated diene compound in the conjugated diene compound-derived portion is the amount of 1,2-vinyl bond. It has the same meaning.

-Chain structure-
There is no restriction | limiting in particular as a chain structure of a copolymer, According to the objective, it can select suitably.
Examples of the chain structure of the copolymer include a block copolymer, a random copolymer, a taper copolymer, and an alternating copolymer.

--Block copolymer--
The structure of the block copolymer is (A) _x- (B) _x , (A) _x- (B) _x- (A) _x , (B) _x- (A) _x- (B) _x , A- (B-A) _x and B- (A-B) _x (where A is a block part composed of monomer units of non-conjugated olefin, and B is a single unit of the conjugated diene compound. It is a block part composed of a monomer unit, and x is an integer of 1 or more).
In the present invention, a block copolymer having a plurality of (A-B) or (B-A) structures is referred to as a multi-block copolymer.
When the copolymer is a block copolymer, the block portion composed of the monomer of the non-conjugated olefin exhibits static crystallinity, and thus has excellent mechanical properties such as breaking strength.

  For example, when a block copolymer is produced, it is effective to continuously add a conjugated diene compound in the presence of a nonconjugated olefin to a polymerization reaction system in which polymerization of a nonconjugated olefin has been started in advance. In addition, what is necessary is just to repeat manufacture of a block copolymer, when manufacturing a multiblock copolymer.

--Random copolymer--
When the copolymer is a random copolymer, since the arrangement of the monomer units of the non-conjugated olefin is irregular, the crystallization temperature derived from the block portion does not cause phase separation of the copolymer. Not observed. That is, since it becomes possible to introduce a non-conjugated olefin having properties such as heat resistance into the main chain of the copolymer, the heat resistance is improved.

  When producing a random copolymer, the conjugated diene compound and the non-conjugated olefin are introduced once or more into the polymerization reaction system in which the copolymerization of the conjugated diene compound and the non-conjugated olefin is started. It is effective to continuously add a conjugated diene compound to a polymerization reaction system in which a conjugated diene compound is present in the presence of a non-conjugated olefin.

--Tapered copolymer--
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 nonconjugated olefin are irregularly arranged. It is a copolymer.
The structure of the taper copolymer indicates that the composition of the conjugated diene compound component and the non-conjugated olefin component is distributed continuously or discontinuously.
The chain structure of the non-conjugated olefin component preferably does not contain many long-chain (high molecular weight) non-conjugated olefin block components but contains many short-chain (low molecular weight) non-conjugated olefin block components.

  When manufacturing a taper copolymer, it is effective to use both a block copolymer manufacturing method and a random copolymer manufacturing method. Specifically, (1) a conjugated diene compound is continuously added to a polymerization reaction system in which non-conjugated olefin polymerization has been started in the presence of the non-conjugated olefin, and as a result, copolymerized non-conjugated olefin-conjugated diene compound copolymer A method in which a conjugated diene compound is newly added one or more times to a polymerization reaction system including a coal and / or a conjugated diene compound is continuously added, or (2) a conjugated diene compound in the presence of a non-conjugated olefin. Or a conjugated diene compound is continuously added, and as a result, a conjugated diene compound is continuously added to a polymerization reaction system containing a polymerized non-conjugated olefin-conjugated diene compound copolymer. Moreover, it is possible to synthesize a taper copolymer by carrying out copolymerization using both of these methods.

--Alternate copolymer--
The alternating copolymer is a polymer having a structure in which a conjugated diene compound and a non-conjugated olefin are alternately arranged (a molecular chain structure of -ABABABAB- when A is a non-conjugated olefin and B is a conjugated diene compound). It is.

  Here, for the copolymer obtained by the method of the present invention, the differential scanning calorimetry (DSC) and the nuclear magnetic resonance (NMR) are used to confirm the formation of the block copolymer, random copolymer and taper copolymer. Is used as the main measuring means.

Differential scanning calorimetry (DSC) is a measurement method performed in accordance with JIS K 7121-1987.
Specifically, when a glass transition point derived from homopolymerization of a conjugated diene compound or a crystallization temperature derived from homopolymerization of a nonconjugated olefin can be observed by DSC, the copolymer contains a single conjugated diene compound. It shows that a block part consisting of a monomer unit or a block part consisting of a monomer unit of a non-conjugated olefin is formed.
In addition, when the crystallization temperature derived from the homopolymerization of the non-conjugated olefin is not observed by DSC, or a broad peak is observed compared to the peak of the crystallization temperature derived from the homopolymerization of the non-conjugated olefin, In the copolymer, a random portion in which monomer units of a conjugated diene compound and a nonconjugated olefin are irregularly formed is formed.

  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.

In the examination in the examples, the following solvents were dehydrated through a molecular sieve column.
・ Hexane (special grade manufactured by Kanto Chemical Co., Inc.)
・ Cyclohexane (special grade manufactured by Kanto Chemical Co., Inc.)

Example 1
200 mL of hexane was added as a solvent in advance to a sufficiently dried 1000 mL pressure resistant stainless steel reactor.
In a glove box under a nitrogen atmosphere, bis (2-phenylindenyl) gadolinium bis (dimethylsilylamide) [(2-PhC ₉ H ₆ ) ₂ GdN (SiHMe ₂ ) ₂ ] 24 μmmol, trityltetrakis ( 24 μmmol of pentafluorophenyl) borate [Ph ₃ CB (C ₆ F ₅ ) ₄ ] and 1.44 mmol of diisobutylaluminum hydride were charged, and 20 mL of hexane was added to form a catalyst solution.
Next, the catalyst solution was taken out from the glove box, and the catalyst solution was stirred for 15 minutes using an ultrasonic device.
The catalyst solution was added to the pressure resistant stainless steel reactor and heated to 80 ° C.
Next, ethylene was charged into the pressure resistant stainless steel reactor at a pressure of 1.2 MPa, and the polyethylene block portion was polymerized at 80 ° C. for 20 minutes.
Next, 300 mL of a hexane solution containing 40 g of 1,3-butadiene was charged into the pressure-resistant stainless steel reactor over 5 minutes, and copolymerization was further performed at 80 ° C. for 120 minutes.
Next, 1 mL of 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) (NS-5) 5 mass% isopropanol solution was added to the pressure resistant stainless steel reactor to stop the reaction.
Next, the copolymer was separated using a large amount of methanol, and vacuum-dried at 50 ° C. to obtain a copolymer A. The yield of the obtained copolymer A was 39 g.

(Example 2)
200 mL of hexane was added as a solvent in advance to a sufficiently dried 1000 mL pressure resistant stainless steel reactor.
In a glove box under a nitrogen atmosphere, in a glass container, bis (2-phenylindenyl) gadolinium bis (dimethylsilylamide) [(2-PhC ₉ H ₆ ) ₂ GdN (SiHMe ₂ ) ₂ ] 36 μmmol, trityltetrakis ( Pentafluorophenyl) borate [Ph ₃ CB (C ₆ F ₅ ) ₄ ] 36 μmmol and triisobutylaluminum 2.16 mmol were charged, and 40 mL of hexane was added to form a catalyst solution.
Next, the catalyst solution was taken out from the glove box, and the catalyst solution was stirred for 15 minutes using an ultrasonic device.
The catalyst solution was added to the pressure resistant stainless steel reactor and heated to 90 ° C.
Next, at the same time as introducing ethylene into the pressure resistant stainless steel reactor at a pressure of 1.5 MPa, 300 mL of a hexane solution containing 40 g of 1,3-butadiene was added to the pressure resistant stainless steel reactor over 150 minutes (2 mL / min). Copolymerization was performed at 90 ° C.
Next, after standing for 30 minutes, 1 mL of an isopropanol solution of 5% by mass of 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) (NS-5) was added to the pressure resistant stainless steel reactor to react. Stopped.
Next, the copolymer was separated using a large amount of methanol, and vacuum-dried at 50 ° C. to obtain a copolymer B. The yield of the obtained copolymer B was 41 g.

(Example 3)
In Example 1, the polymerization was carried out in the same manner as in Example 1 except that the polymerization temperatures of the polyethylene block portion and the copolymerization of ethylene and 1,3-butadiene were 90 ° C. and 100 ° C., respectively. As a result, copolymer C was obtained in a yield of 40 g.

Example 4
In Example 1, except that the solvent was changed to hexane instead of hexane, and the polymerization temperature of the polymerization of the polyethylene block portion and the copolymerization of ethylene and 1,3-butadiene was 100 ° C. and 110 ° C., respectively. When polymerization was carried out in the same manner as in Example 1, copolymer D was obtained in a yield of 38 g.

(Example 5)
In Example 1, when the polymerization was carried out in the same manner as in Example 1 except that the solvent was changed to hexane and a mixed solvent of hexane and cyclohexane (20: 80% by mass ratio) was obtained, a copolymer was obtained. E was obtained in a yield of 39 g.

(Example 6)
In Example 1, polymerization was performed in the same manner as in Example 1 except that the polymerization temperature of the polyethylene block portion was set to 70 ° C. As a result, copolymer F was obtained in a yield of 40 g.

(Example 7)
200 mL of hexane was added as a solvent in advance to a sufficiently dried 1000 mL pressure resistant stainless steel reactor.
In a glove box under a nitrogen atmosphere, bis (1-benzyl-2-phenylindenyl) gadolinium bis (dimethylsilylamide) [(1-Bn) (2-Ph) C ₉ H ₆ ) ₂ GdN is placed in a glass container. (SiHMe ₂ ) ₂ ] 24 μmmol, trityltetrakis (pentafluorophenyl) borate [Ph ₃ CB (C ₆ F ₅ ) ₄ ] 24 μmmol and diisobutylaluminum hydride 1.44 mmol were charged, and 20 mL of hexane was added to form a catalyst solution.
Next, the catalyst solution was taken out from the glove box, and the catalyst solution was stirred for 15 minutes using an ultrasonic device.
The catalyst solution was added to the pressure resistant stainless steel reactor and heated to 80 ° C.
Next, ethylene was charged into the pressure resistant stainless steel reactor at a pressure of 1.0 MPa, and at the same time, 300 mL of a hexane solution containing 40 g of 1,3-butadiene was charged into the pressure resistant stainless steel reactor over 150 minutes (2 mL / min). Copolymerization was carried out.
Next, after standing for 10 minutes, 1 mL of an isopropanol solution of 5% by mass of 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) (NS-5) was added to the pressure resistant stainless steel reactor to react. Stopped,
Subsequently, the copolymer was separated using a large amount of methanol, and vacuum-dried at 50 ° C. to obtain a copolymer G. The yield of the obtained copolymer G was 150 g.

(Example 8)
200 mL of hexane was added as a solvent in advance to a sufficiently dried 1000 mL pressure resistant stainless steel reactor.
In a glove box under a nitrogen atmosphere, bis (1-methyl-2-phenylindenyl) gadolinium bis (dimethylsilylamide) [(1-Me) (2-Ph) C ₉ H ₆ ) ₂ GdN is placed in a glass container. (SiHMe ₂ ) ₂ ] 40 μmmol, trityltetrakis (pentafluorophenyl) borate [Ph ₃ CB (C ₆ F ₅ ) ₄ ] 40 μmmol and diisobutylaluminum hydride 1.8 mmol were added, and 20 mL of hexane was added to form a catalyst solution.
Next, the catalyst solution was taken out from the glove box, and the catalyst solution was stirred for 15 minutes using an ultrasonic device.
The catalyst solution was added to the pressure resistant stainless steel reactor and heated to 90 ° C.
Next, ethylene was charged into the pressure resistant stainless steel reactor at a pressure of 1.5 MPa, and at the same time, 300 mL of a hexane solution containing 40 g of 1,3-butadiene was charged into the pressure resistant stainless steel reactor over 240 minutes (1.25 mL / min). Copolymerization was carried out.
Next, after standing for 10 minutes, 1 mL of an isopropanol solution of 5% by mass of 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) (NS-5) was added to the pressure resistant stainless steel reactor to react. Stopped,
Subsequently, the copolymer was separated using a large amount of methanol, and vacuum-dried at 50 ° C. to obtain a copolymer H. The yield of the obtained copolymer H was 43 g.

(Comparative Example 1)
In Example 1, except that the polymerization temperature and the copolymerization temperature of the polyethylene block part were respectively set to 70 ° C., polymerization was performed in the same manner as in Example 1, and as a result, a mixture I of polybutadiene and polyethylene was obtained in a yield of 35 g. Obtained.

(Comparative Example 2)
Polymerization was carried out in the same manner as in Example 2 except that the copolymerization temperature was 75 ° C. in Example 2. As a result, 38 g of the mixture J was obtained.

(Characteristic evaluation)
Each characteristic was evaluated about the copolymer obtained by the Example and the mixture obtained by the comparative example with the following method.

<Microstructure (cis-1,4 bond amount)>
The microstructure of the butadiene moiety in the copolymer or mixture was determined from the integral ratio of ¹³ C-NMR spectrum (content ratio of cis-1,4 bond and trans-1,4 bond). The calculated values of cis-1,4 bond amount (%) are shown in Table 1. In addition, in the case of a mixture, it is the value as the whole mixture containing the homopolymer (polybutadiene) of butadiene.

<Content of ethylene>
The content (mol%) of the ethylene moiety in the copolymer or mixture was determined from the integral ratio of ¹³ C-NMR spectrum. The calculated values are shown in Table 1. In addition, in the case of a mixture, it is the value as the whole mixture containing the ethylene homopolymer (polyethylene).

<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 x 2 detectors: differential refractometer (RI), GPC measurement temperature: 160 ° C.) Thus, the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) in terms of polystyrene of the polymer were determined based on monodisperse polystyrene. The analytical values are shown in Table 1. Moreover, the elution curves of the copolymer A of Example 1, the copolymer B of Example 2, the mixture I of Comparative Example 1 and the mixture J of Comparative Example 2 are shown in FIGS.

<Confirmation of ingredients of mixture I and J>
As shown in FIGS. 3 and 4, respectively, for the mixtures I and J, the GPC elution curves of the polymers obtained in Comparative Examples 1 and 2 suggested the possibility of being a mixture of two components having different molecular weights.
100 mg of the polymer obtained in Comparative Examples 1 and 2 was immersed in 50 mL of THF for 2 days, and then the insoluble matter was filtered and dried. When the GPC measurement was performed again, the high molecular weight component disappeared and an elution curve of only the low molecular component was obtained.
Moreover, when the ¹³ C-NMR spectrum was measured about the insoluble content, it was confirmed that the component is polyethylene.
From the above results. The polymer obtained in Comparative Examples 1 and 2 was found to be a mixture of polybutadiene and polyethylene.

<Ozone resistance>
According to JIS K 6259, the ozone resistance of the copolymer obtained in the example and the mixture obtained in the comparative example was measured.
The strip-shaped test piece was exposed at 40 ° C. and an ozone concentration of 50 ppm while giving 30% dynamic elongation, and the condition of the test piece after 12 hours (presence of cracks) was visually judged.

From Table 1, in Examples 1-8 which made the temperature of the copolymerization of ethylene and 1,3-butadiene 80 ° C. or higher, a copolymer of ethylene and 1,3-butadiene could be synthesized.
However, in Comparative Examples 1 and 2 where the copolymerization temperature of ethylene and 1,3-butadiene was less than 80 ° C., only a mixture of polybutadiene and polyethylene was obtained, and a copolymer could not be synthesized.

  The method for producing a polymer according to the present invention can be suitably used in all fields requiring functional rubber, such as production of tire members (particularly, tire tread members).

Claims (9)

A method for producing a copolymer comprising copolymerizing a conjugated diene compound and a non-conjugated olefin,
Using aliphatic hydrocarbons as solvent, and
The polymerization temperature in the copolymerization is 80 ° C. or higher,
Performing the introduction of the non-conjugated olefin into the reaction system simultaneously with the introduction of the conjugated diene compound into the reaction system or prior to the introduction of the conjugated diene compound into the reaction system;
Performing the copolymerization in the presence of a catalyst comprising a compound having at least one selected from the group consisting of a lanthanoid element, scandium and yttrium,
The compound having at least one selected from the group consisting of the lanthanoid element, scandium and yttrium is represented by the following general formula (ii) or (iii)
MX ₂ · Lw (ii)
MX ₃ · Lw (iii)
(In each of the general formulas (ii) and (iii), M represents a lanthanoid element, scandium or yttrium, and X independently represents a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group, or a silyl group. , An aldehyde residue, a ketone residue, a carboxylic acid residue, a thiocarboxylic acid residue, or a phosphorus compound residue, L represents a Lewis base, and w represents an integer of 0 to 3. A process for producing a copolymer, which is a reaction product of an elemental compound or the rare earth element compound and a Lewis base.   The method for producing a copolymer according to claim 1, wherein the aliphatic hydrocarbon is at least one of hexane and cyclohexane.   The method for producing a copolymer according to claim 1, wherein the non-conjugated olefin is an acyclic olefin.   The method for producing a copolymer according to claim 1, wherein the non-conjugated olefin is an α-olefin having 2 to 10 carbon atoms.   The method for producing a copolymer according to claim 1, wherein the non-conjugated olefin is at least one of ethylene and propylene.   The method for producing a copolymer according to claim 1, wherein the conjugated diene compound has 4 to 8 carbon atoms. The method for producing a copolymer according to claim 6 , wherein the conjugated diene compound is at least one of 1,3-butadiene and isoprene.   The method for producing a copolymer according to claim 1, wherein a pressure at the time of charging the non-conjugated olefin into the reaction system is 0.1 MPa to 10 MPa. At the start of the copolymerization, the concentration of the conjugated diene compound (mol / L) and the concentration of the non-conjugated olefin (mol / L) are represented by the following formula:
Non-conjugated olefin concentration / conjugated diene compound concentration ≧ 1.0
The method for producing a copolymer according to claim 1, wherein the relationship is satisfied.

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