JP6729891B2 - Conjugated diene-based copolymer and method for producing the same, rubber composition, crosslinked rubber composition, and tire - Google Patents

Description

The present invention relates to a conjugated diene-based copolymer, a method for producing the same, a rubber composition, a crosslinked rubber composition, and a tire.

The demand for low fuel consumption of automobiles is increasing in connection with the worldwide movement of the carbon dioxide emission regulations accompanying the increasing concern about environmental problems. In order to meet such requirements, reduction in rolling resistance is also required for tire performance. Here, as a method of reducing the rolling resistance of the tire, it is effective to use a rubber composition having a low loss tangent (tan δ) and a low heat buildup as a rubber composition applied to the tread portion of the tire.

On the other hand, as the rubber composition applied to the tread portion, sidewall portion, bead filler and the like of the tire, a rubber composition having a high dynamic storage elastic modulus (E′) is suitable, and therefore, the loss tangent (tan δ) is low. A rubber composition having a high dynamic storage elastic modulus (E') is required. On the other hand, as a means for improving the dynamic storage elastic modulus (E′) of the rubber composition, a method of increasing the amount of carbon black compounded in the rubber composition or N as described in Patent Document 1 is used. , N'-(4,4'-diphenylmethane)-bismaleimide and other techniques for blending a bismaleimide (BMI) having a specific structure, and a reaction with a rubber component such as polyethylene glycol dimaleate as described in Patent Document 2 A technique of blending a compound having both a group and an adsorption group for a filler is known. Further, Patent Document 3 discloses a rubber composition for a clinch apex containing a myrcene polymer in order to improve fuel economy and the like.

However, when the compounding amount of carbon black in the rubber composition is increased, the dynamic storage elastic modulus (E′) of the rubber composition can be improved, but at the same time, the loss tangent (tan δ) of the rubber composition increases. Then, the low exothermic property of the rubber composition is deteriorated, and further, the Mooney viscosity of the rubber composition is increased, resulting in a problem that the processability is deteriorated.

JP, 2002-121326, A JP, 2003-176378, A JP, 2014-145064, A

An object of the present invention is to provide a conjugated diene-based copolymer capable of obtaining a rubber composition having a high dynamic storage elastic modulus (E′) and a small loss tangent (tan δ), and a method for producing the same. Another object of the present invention is to use a rubber composition containing the conjugated diene-based copolymer, a crosslinked rubber composition obtained by crosslinking the rubber composition, and the rubber composition or the crosslinked rubber composition. To provide tires.

As a result of intensive studies by the present inventors, the rubber composition has a structural unit derived from myrcene and a structural unit derived from a conjugated diene, has a specific 1,4-cis content, and It has been found that the above problems can be solved by blending a conjugated diene-based copolymer in which the content of the constituent unit derived from myrcene falls within a specific range.

That is, the present invention relates to the following <1> to <12>.
<1> Having a structural unit derived from myrcene and a structural unit derived from a conjugated diene compound, the 1,4-cis content is 90% or more, and the content of the structural unit derived from myrcene is 10 mass. % Of the conjugated diene-based copolymer.
<2> The conjugated diene-based copolymer according to <1>, in which the content of the constituent unit derived from myrcene is 1% by mass or less.
<3> The conjugated diene-based copolymer according to <1> or <2>, in which the 1,4-cis content of the conjugated diene-based copolymer is 95% or more.
<4> The conjugated diene-based copolymer according to any one of <1> to <3>, in which the structural unit derived from the conjugated diene compound includes a structural unit derived from butadiene.
<5> The conjugated diene-based copolymer according to any one of <1> to <3>, in which the structural unit derived from the conjugated diene compound includes a structural unit derived from isoprene.
<6> The method for producing a conjugated diene-based copolymer according to any one of <1> to <5>, which has a step of simultaneously reacting myrcene and a conjugated diene compound.
<7> Any one of <1> to <5>, which has a step of polymerizing myrcene to obtain a myrcene polymer and a step of reacting the obtained myrcene polymer with a conjugated diene compound in this order. The method for producing a conjugated diene-based copolymer described in 1.
<8> a step of polymerizing myrcene to obtain a myrcene polymer, a step of reacting the obtained myrcene polymer with a conjugated diene compound to obtain a copolymer, and the obtained copolymer and myrcene The method for producing a conjugated diene-based copolymer according to any one of <1> to <5>, which has steps of reacting with each other in this order.
<9> A rubber composition comprising the conjugated diene copolymer according to any one of <1> to <4> and a diene rubber.
<10> The rubber composition according to <9>, which contains 30 parts by mass or more of the conjugated diene polymer with respect to 100 parts by mass of the rubber component containing the conjugated diene copolymer and the diene rubber.
<11> A crosslinked rubber composition obtained by crosslinking the rubber composition according to <9> or <10>.
<12> A tire characterized by using the rubber composition according to <9> or <10> or the crosslinked rubber composition according to <11>.

ADVANTAGE OF THE INVENTION According to this invention, the conjugated diene type copolymer which can obtain the rubber composition with high dynamic storage elastic modulus (E'), and small loss tangent (tan(delta)) and its manufacturing method can be provided. Further, according to the present invention, a rubber composition containing the conjugated diene-based copolymer, a crosslinked rubber composition obtained by crosslinking the rubber composition, and a tire using the rubber composition or the crosslinked rubber composition. Can be provided.

Hereinafter, the present invention will be described in detail based on the embodiments. In addition, in the following description, the description of “A to B” indicating a numerical range indicates a numerical range including A and B which are end points, and is “A or more and B or less” (when A<B), or “ “A or less and B or more” (when A>B).
Moreover, mass% is synonymous with weight%.

[Conjugated diene copolymer]
The conjugated diene-based copolymer of the present invention has a constitutional unit derived from myrcene and a constitutional unit derived from a conjugated diene compound (hereinafter, also referred to as “conjugated diene unit”), and contains 1,4-cis. The amount is 90% or more, and the content of the constituent unit derived from myrcene is less than 10% by mass.
Here, in the present specification, the “conjugated diene unit” means a unit corresponding to a constitutional unit derived from the conjugated diene compound in the conjugated diene copolymer.
Further, in the present specification, the “conjugated diene compound” means a conjugated diene compound excluding myrcene.
And in this specification, a "copolymer" means the polymer formed by superposing|polymerizing two or more types of monomers.

Mirsen is naturally present in large numbers, and much research has been conducted for its application to industrial production. When radical polymerization is performed on myrcene, a branched structure is introduced into the polymer. Therefore, the present inventors conducted studies for the purpose of modifying the polymer.
As a result, it was found that, by copolymerizing a small amount of myrcene with the conjugated diene compound, a conjugated diene copolymer capable of providing a rubber composition having an excellent balance between storage elastic modulus and loss tangent can be obtained, The present invention has been completed.
Although the detailed mechanism of action is unclear, some are presumed to be as follows. That is, by using myrcene as a raw material monomer, it is considered that a branched structure and a crosslinked structure are introduced into the obtained polymer, but it is difficult to control the degree of branching and the degree of crosslinking, and thus, the conventional myrcene is used. When the content of is not less than 10% by mass, a large amount of gel is likely to be generated in the obtained polymer, and such a polymer is inferior in macro-dispersibility, and sufficient performance cannot be obtained. On the other hand, as in the present invention, when a small amount of myrcene is copolymerized, macrodispersibility is maintained, and as a result, an appropriate branched structure and a crosslinked structure are introduced. It was found that the strength is superior to that of the united body.
Furthermore, by setting the 1,4-cis content to 90% or more, the dynamic storage elastic modulus (E′) can be effectively improved.
The rubber composition containing the conjugated diene-based copolymer has a high dynamic storage elastic modulus (E′) (hereinafter, also simply referred to as storage elastic modulus) and a small loss tangent (tan δ). It was found to be a thing.

<Structural units derived from myrcene>
The conjugated diene-based copolymer of the present invention has a constitutional unit derived from myrcene. Myrcene includes α-myrcene (2-methyl-6-methyleneocta-1,7-diene, 2-methyl-6-methyleneocta-1,7-diene) and β-myrcene (7-methyl-3-methylene). Although there are two isomers of octa-1,6-diene and 7-methyl-3-methyleneocta-1,6-diene), naturally occurring β-myrcene is preferable.

The content of the constituent unit derived from myrcene is less than 10% by mass of the conjugated diene-based copolymer. When the content of the constituent unit derived from myrcene is 10% by mass or more, a large amount of the crosslinked structure is introduced, resulting in a large gel amount and poor macrodispersibility. The content of the constituent unit derived from myrcene is preferably 0.01% by mass or more. When the content of the constituent unit derived from myrcene is 0.01% by mass or more, a branched structure is introduced, so that the storage elastic modulus is higher and the loss is higher than that of a diene polymer composed of only a straight chain. A rubber composition having a small tangent can be obtained.
The content of the constituent unit derived from myrcene is preferably 0.01 to 5% by mass of the conjugated diene-based copolymer, more preferably 0.03 to 3% by mass, and 0.1 to 1% by mass. More preferably, it is mass %. When the content of the constituent unit derived from myrcene is within the above range, a sufficient amount of the crosslinked structure and the branched structure are introduced, the loss tangent is reduced, and a high storage elastic modulus is obtained. In addition, it is preferable because it is more excellent in macro dispersibility.
The content of the structural unit derived from myrcene is determined by the content of myrcene with respect to the total amount of the monomers at the time of producing the conjugated diene-based copolymer, provided that all the monomers are consumed. be able to.

<Structural unit derived from conjugated diene compound>
The conjugated diene-based copolymer of the present invention contains a constituent unit derived from a conjugated diene compound.
The conjugated diene compound preferably has 4 to 8 carbon atoms. Specific examples of the conjugated diene compound include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and the like.
In the present invention, the conjugated diene compound contains at least one selected from the group consisting of 1,3-butadiene and isoprene from the viewpoint of effectively improving the storage elastic modulus of the obtained conjugated diene-based copolymer. Is preferred, and it is more preferred that it consists only of at least one monomer selected from the group consisting of 1,3-butadiene and isoprene, and even more preferred that it consists of only 1,3-butadiene. In other words, the conjugated diene unit in the conjugated diene-based copolymer of the present invention preferably contains at least one constitutional unit selected from the group consisting of 1,3-butadiene unit and isoprene unit, and 1,3- It is more preferable that it is composed only of at least one constitutional unit selected from the group consisting of butadiene units and isoprene units, and it is even more preferable that it is composed of only 1,3-butadiene units.

The conjugated diene compounds may be used alone or in combination of two or more. That is, the conjugated diene-based copolymer of the present invention may contain one type of conjugated diene unit alone, or may contain two or more types.
The content of the conjugated diene unit is preferably 50% by mass or more based on the whole conjugated diene copolymer. It is more preferably 70% by mass or more, further preferably 90% by mass or more, further preferably 95% by mass or more, further preferably 98% by mass or more, and 99% by mass or more. Is more preferable. Further, the content of the conjugated diene unit is preferably 99.9% by mass or less based on the whole conjugated diene copolymer.
When the content of the conjugated diene unit is within the above range, a conjugated diene-based copolymer having excellent storage elastic modulus can be obtained, which is preferable.

<Other structural units>
The conjugated diene-based copolymer of the present invention may have other structural units in addition to the structural unit derived from myrcene and the structural unit derived from the conjugated diene compound. Examples of the other structural unit include a structural unit derived from a non-conjugated olefin compound and a structural unit derived from an aromatic vinyl compound.
The non-conjugated olefin compound preferably has 2 to 10 carbon atoms. Specific examples of the non-conjugated olefin compound include α-olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, and 1-octene, vinyl pivalate, and 1-phenylthioethene. Or a hetero atom-substituted alkene compound such as N-vinylpyrrolidone.
In the present invention, the non-conjugated olefin compound is preferably a non-cyclic non-conjugated olefin compound from the viewpoint of further improving the transparency of the conjugated diene-based copolymer, and the non-cyclic non-conjugated olefin compound. Is more preferably an α-olefin, even more preferably an α-olefin containing ethylene, and particularly preferably consisting of ethylene only. In other words, when the conjugated diene-based copolymer of the present invention has a constitutional unit derived from a non-conjugated olefin, it is preferably a constitutional unit derived from an acyclic non-conjugated olefin, and the non-cyclic The unit derived from the non-conjugated olefin is more preferably a constitutional unit derived from an α-olefin, further preferably an α-olefin unit containing an ethylene unit, and particularly preferably only an ethylene unit.
The non-conjugated olefin compounds may be used alone or in combination of two or more. That is, the conjugated diene-based copolymer of the present invention may contain one type of non-conjugated olefin unit alone, or may contain two or more types.

The conjugated diene-based copolymer of the present invention may contain a structural unit derived from an aromatic vinyl compound (hereinafter, also referred to as “aromatic vinyl unit”) as another structural unit. The aromatic vinyl unit is a constitutional unit derived from an aromatic vinyl compound as a monomer. The aromatic vinyl compound preferably has 8 to 10 carbon atoms. Specific examples of the aromatic vinyl compound include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o,p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene and p-ethylstyrene. Is mentioned.
When the conjugated diene-based copolymer of the present invention contains a structural unit derived from an aromatic vinyl compound, from the viewpoint of improving the heat resistance of the resulting conjugated diene-based copolymer, a structural unit derived from styrene is used. It is preferable that the structural units are derived from styrene alone. In other words, when the conjugated diene-based copolymer of the present invention has an aromatic vinyl unit, the aromatic vinyl unit preferably contains a styrene unit, and more preferably consists of only a styrene unit.
The aromatic ring in the aromatic vinyl unit is not included in the main chain of the copolymer unless it is bonded to the adjacent unit.
The aromatic vinyl compounds may be used alone or in combination of two or more. That is, the conjugated diene-based copolymer of the present invention may contain one kind of aromatic vinyl unit or two or more kinds thereof.

The content of the other structural units is preferably 49.9% by mass or less, more preferably 39.9% by mass or less, and 29.9% by mass or less based on the whole conjugated diene copolymer. More preferably, it is even more preferably 19.9% by mass or less, even more preferably 9.9% by mass or less, even more preferably 5% by mass or less, and 1% by mass or less. It is more preferable that the amount is 0.1% by mass or less, and it is even more preferable that no other structural unit is contained.

In addition, the conjugated diene-based copolymer of the present invention has a cis-1,4 content of 90% or more in the entire constitutional units derived from myrcene and the conjugated diene compound. The conjugated diene-based copolymer of the present invention has a high cis-1,4 content even if it has a constitutional unit derived from myrcene. When the cis-1,4 content is 90% or more, the glass transition temperature becomes low, so that the storage modulus of the resin composition or product using the obtained conjugated diene copolymer is effectively improved. You can From the same viewpoint, the conjugated diene-based copolymer of the present invention preferably has a cis-1,4 bond content of 95% or more, and more preferably 98% or more.
On the other hand, the content of vinyl (1,2-vinyl bond, 3,4-vinyl bond, etc.) in the entire conjugated diene-based copolymer is 10% or less, preferably 5% or less. Moreover, the said trans-1,4 content is 10% or less.
The content of each of cis-1,4, trans-1,4-, and vinyl can be determined from the measurement results of ¹ H-NMR and ¹³ C-NMR by the integral ratio.

The conjugated diene-based copolymer of the present invention preferably has a polystyrene reduced weight average molecular weight (Mw) of 10,000 to 10,000,000, more preferably 100,000 to 5,000,000. , 150,000 to 2,500,000 is more preferable. When the Mw of the conjugated diene-based copolymer is 10,000 or more, sufficient mechanical strength can be ensured, and when the Mw is 10,000,000 or less, high workability is obtained. Can be held.
When the conjugated diene polymer of the present invention has a structural unit derived from myrcene and a structural unit derived from butadiene, the conjugated diene polymer has a polystyrene reduced weight average molecular weight of 300,000 to 1,000, 000 is more preferable, and 400,000 to 800,000 is even more preferable.
When the conjugated diene polymer of the present invention has a constitutional unit derived from myrcene and a constitutional unit derived from isoprene, the conjugated diene polymer has a polystyrene reduced weight average molecular weight of 700,000 to 1, It is more preferably 500,000 and even more preferably 900,000 to 1,300,000.
Further, the conjugated diene-based copolymer of the present invention has a molecular weight distribution (Mw/Mn, MWD) represented by the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of 10.0 or less. It is preferably 7.0 or less, more preferably 4.0 or less, and particularly preferably 2.5 or less. When the molecular weight distribution of the conjugated diene-based copolymer is 10.0 or less, sufficient homogeneity can be brought about in the physical properties of the conjugated diene-based copolymer.
The above weight average molecular weight and molecular weight distribution are determined by gel permeation chromatography (GPC) using polystyrene as a standard substance.

The conjugated diene-based copolymer of the present invention has a branching index of preferably 0.98 or less, more preferably 0.95 or less, and further preferably 0.92 or less. The lower limit of the branching index is not particularly limited, but from the viewpoint of production, it is preferably 0.40 or more, more preferably 0.50 or more, and further preferably 0.70 or more. When the branching index is within the above range, the rubber composition containing the branching index has a high dynamic storage elastic modulus (E′) and a small loss tangent (tan δ), which is preferable.
The branching index can be appropriately set depending on the content of myrcene in the conjugated diene-based copolymer.
The branching index is represented by the following formula, where Rg _s is the radius of gyration of the conjugated diene-based copolymer and Rg _L is the radius of gyration of the linear polymer having the same molecular weight.
Branch index=Rg _s /Rg _L
The smaller the branching index, the more developed the branching structure.
Specifically, it is measured by the method described in the examples.

The chain structure of the conjugated diene-based copolymer of the present invention is not particularly limited and may be appropriately selected depending on the purpose. For example, a structural unit derived from myrcene is A, a structural unit derived from a conjugated diene is selected. In the case of B, a block copolymer having a structure such as A _x -B _y (x and y are integers of 1 or more), a random copolymer having a structure in which A and B are randomly arranged, A taper copolymer in which a random copolymer and a block copolymer are mixed, an alternating copolymer having a configuration such as (AB) _w (w is an integer of 1 or more), A _x1- B A triblock copolymer having a configuration such as _y- A _x2 (x1, x2, y is an integer of 1 or more) and the like can be used.
A desired conjugated diene-based copolymer structure can be obtained by appropriately selecting a method for producing a conjugated diene-based copolymer described below. For example, a random copolymer can be obtained by simultaneously polymerizing myrcene and a conjugated diene compound. On the other hand, by polymerizing only the conjugated diene compound and then adding myrcene for further polymerization, a diblock copolymer having a polymer portion composed of the conjugated diene compound and a polymer portion composed of myrcene is obtained. Further, by polymerizing only the conjugated diene compound, and by adding myrcene in the state where the conjugated diene compound (monomer) remains, the polymer part composed of the conjugated diene compound and the myrcene and the conjugated diene compound are It may be a polymer having randomly polymerized portions. Further, after polymerizing only the conjugated diene compound, polymerization is carried out by adding myrcene, and further, by carrying out the polymerization by adding the conjugated diene compound, a polymer portion composed of the conjugated diene compound and a polymer derived from myrcene. A triblock polymer having a part and a polymer part composed of a conjugated diene compound can also be used.
The conjugated diene-based copolymer of the present invention has a structural unit derived from myrcene, and as a result, has a chained structure (branched structure).

[Method for producing conjugated diene-based copolymer]
<Polymerization process>
Next, an example of the method for producing the conjugated diene-based copolymer of the present invention will be described in detail. An example of the method for producing a conjugated diene-based copolymer of the present invention is based on the assumption that myrcene and a conjugated diene compound are used as monomers, and includes at least a polymerization step, and if necessary, A washing step and other steps can be appropriately included.
The polymerization process may be performed in one stage or in multiple stages of two or more stages. The one-step polymerization process is a process in which all types of monomers to be polymerized, that is, myrcene, a conjugated diene compound, and other monomers are simultaneously reacted and polymerized. In the multi-stage polymerization process, a part or all of one or two kinds of monomers are first reacted to form a polymer (first polymerization step), and then the remaining kinds of monomers or the above-mentioned monomers are used. It is a step of polymerizing by carrying out one or more steps (second polymerization step to final polymerization step) of adding and polymerizing the balance of one or two kinds of monomers.
Here, in the production of the conjugated diene-based copolymer of the present invention, (1) a method of simultaneously reacting myrcene and a conjugated diene compound, (2) polymerization of myrcene to obtain a myrcene polymer, and then obtained A method of reacting a myrcene polymer with a conjugated diene compound, (3) After polymerizing myrcene to obtain a myrcene polymer, the resulting myrcene polymer is reacted with a conjugated diene compound to obtain a copolymer. Further, any method such as a method of reacting the obtained copolymer with myrcene may be selected. The above polymerization reaction is preferably carried out in the presence of a polymerization catalyst composition described later.

As the polymerization method, any method such as a solution polymerization method, a suspension polymerization method, a liquid phase bulk polymerization method, an emulsion polymerization method, a gas phase polymerization method or a solid phase polymerization method can be used. When a solvent is used in the polymerization reaction, such a solvent may be one that is inactive in the polymerization reaction, and examples thereof include toluene, cyclohexane, and normal hexane.

In the polymerization step, the polymerization reaction is preferably carried out in an atmosphere of an inert gas, preferably nitrogen gas or argon gas. The polymerization temperature of the above-mentioned polymerization reaction is not particularly limited, but is preferably in the range of −100° C. to 200° C., and may be about room temperature. In addition, if the polymerization temperature is increased, the cis-1,4 bond selectivity of the polymerization reaction may decrease. Further, the pressure of the polymerization reaction is preferably in the range of 0.1 to 10.0 MPa so that the conjugated diene compound can be sufficiently incorporated into the polymerization reaction system. Also, the reaction time of the above-mentioned polymerization reaction is not particularly limited, and for example, a range of 1 second to 10 days is preferable, but it can be appropriately selected depending on conditions such as the type of catalyst and polymerization temperature.

Further, in the step of polymerizing the conjugated diene compound, the polymerization may be stopped by using a polymerization terminator such as methanol, ethanol or 2-propanol.

Here, the above-mentioned myrcene, the conjugated diene compound, and the step of polymerizing the other monomer, the first polymerization catalyst composition shown below, the second polymerization catalyst composition, the third polymerization catalyst composition, or It is preferable to include a step of polymerizing various monomers in the presence of the fourth polymerization catalyst composition.
The first polymerization catalyst composition, the second polymerization catalyst composition, the third polymerization catalyst composition, and the fourth polymerization catalyst composition, which are preferably used in the polymerization step, will be described below.
(First Polymerization Catalyst Composition)
The first polymerization catalyst composition (hereinafter, also referred to as “first polymerization catalyst composition”) will be described.
The first polymerization catalyst composition,
Component (A1): a rare earth element compound or a reaction product of the rare earth element compound and a Lewis base, which does not have a bond between the rare earth element and carbon, and
Component (B1): an ionic compound (B1-1) consisting of a non-coordinating anion and a cation, an aluminoxane (B1-2), a Lewis acid, a complex compound of a metal halide and a Lewis base, and active halogen. A polymerization catalyst composition containing at least one selected from the group consisting of at least one halogen compound (B1-3) among the organic compounds contained.
When the first polymerization catalyst composition contains at least one selected from the group consisting of an ionic compound (B1-1) and a halogen compound (B1-3), the polymerization catalyst composition further comprises:
Component (C1): Formula (I) below:
YR ¹ _a R ² _b R ³ _c ... (I)
(In the formula, Y is a metal selected from Group 1, Group 2, Group 12 and Group 13 of the periodic table, and R ¹ and R ² are hydrocarbon groups having 1 to 10 carbon atoms or hydrogen. And R ³ is a hydrocarbon group having 1 to 10 carbon atoms, R ¹ , R ² and R ³ may be the same or different from each other, and Y is selected from Group 1 of the periodic table. A is 1 and b and c are 0, and when Y is a metal selected from Groups 2 and 12 of the Periodic Table, a and b are 1 And c is 0, and when Y is a metal selected from Group 13 of the periodic table, a, b and c are 1).

Since the ionic compound (B1-1) and the halogen compound (B1-3) do not have carbon atoms for supplying to the component (A1), they are used as a carbon supply source for the component (A1). Component C1) is required. Even when the polymerization catalyst composition contains the aluminoxane (B1-2), the polymerization catalyst composition can contain the component (C1). The first polymerization catalyst composition may also contain other components contained in a usual rare earth element compound-based polymerization catalyst composition, such as a co-catalyst.
In the polymerization reaction system, the concentration of the component (A1) contained in the first polymerization catalyst composition is preferably in the range of 0.1 to 0.0001 mol/l.
Further, the polymerization catalyst composition preferably contains an additive (D1) which can be an anionic ligand.

The component (A1) used in the first polymerization catalyst composition is a rare earth element compound or a reaction product of the rare earth element compound and a Lewis base, and here, the rare earth element compound and the reaction of the rare earth element compound and the Lewis base. The object does not have a bond between a rare earth element and carbon. When the rare earth element compound and the reactant do not have a rare earth element-carbon bond, the compound is stable and easy to handle. Here, the rare earth element compound is a compound containing a rare earth element (M), that is, a lanthanoid element composed of elements with atomic numbers 57 to 71 in the periodic table, or scandium or yttrium.
Specific examples of the lanthanoid element include lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium. In addition, the said (A1) component may be used individually by 1 type, and may be used in combination of 2 or more type.

The rare earth element compound is preferably a salt or complex compound in which the rare earth metal is divalent or trivalent, and one or more coordinations selected from a hydrogen atom, a halogen atom and an organic compound residue. More preferably, it is a rare earth element compound containing a child. Further, the rare earth element compound or a reaction product of the rare earth element compound and a Lewis base is represented by the following formula (II) or formula (III):
M ¹¹ X ¹¹² ₂ L ¹¹ w (II)
M ¹¹ X ¹¹ ₃ L ¹¹ w (III)
(In each formula, M ¹¹ represents a lanthanoid element, scandium or yttrium, and X ¹¹ independently represents a hydrogen atom, a halogen atom, an alkoxy group, a thiolate group, an amino group, a silyl group, an aldehyde residue, It represents a ketone residue, a carboxylic acid residue, a thiocarboxylic acid residue or a phosphorus compound residue, L ¹¹ represents a Lewis base, and w represents 0 to 3).

As the group (ligand) that binds to the rare earth element of the rare earth element compound, a hydrogen atom, a halogen atom, an alkoxy group (a group excluding hydrogen in the hydroxyl group of alcohol, which forms a metal alkoxide), and a thiolate group ( A thiol group of a thiol compound in which a hydrogen atom has been removed, which forms a metal thiolate., an amino group (ammonia, a primary amine, or a secondary amine with one hydrogen atom bonded to the nitrogen atom removed). Group, which forms a metal amide), a silyl group, an aldehyde residue, a ketone residue, a carboxylic acid residue, a thiocarboxylic acid residue or a phosphorus compound residue. Specifically, a hydrogen atom; an aliphatic alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group; a phenoxy group, 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 -Aromatic alkoxy groups such as isopropyl-6-neopentylphenoxy group; thiomethoxy group, thioethoxy group, thiopropoxy group, thion-butoxy group, thioisobutoxy group, thiosec-butoxy group, thiotert-butoxy group, etc. Aliphatic thiolate group; thiophenoxy group, 2,6-di-tert-butylthiophenoxy group, 2,6-diisopropylthiophenoxy group, 2,6-dineopentylthiophenoxy group, 2-tert-butyl-6- Arylthiolate groups such as isopropylthiophenoxy group, 2-tert-butyl-6-thioneopentylphenoxy group, 2-isopropyl-6-thioneopentylphenoxy group, 2,4,6-triisopropylthiophenoxy group; dimethylamino Groups, aliphatic amino groups such as diethylamino group and diisopropylamino group; phenylamino group, 2,6-di-tert-butylphenylamino group, 2,6-diisopropylphenylamino group, 2,6-dineopentylphenylamino Group, 2-tert-butyl-6-isopropylphenylamino group, 2-tert-butyl-6-neopentylphenylamino group, 2-isopropyl-6-neopentylphenylamino group, 2,4,6-tert-butyl Arylamino groups such as phenylamino groups; bistrialkylsilylamino groups such as bistrimethylsilylamino groups; trimethylsilyl groups, tris(trimethylsilyl)silyl groups, bis(trimethylsilyl)methylsilyl groups, trimethylsilyl(dimethyl)silyl groups, triisopropylsilyl(bis A silyl group such as trimethylsilyl)silyl group; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Further, residues of aldehydes such as salicylaldehyde, 2-hydroxy-1-naphthaldehyde, 2-hydroxy-3-naphthaldehyde; 2'-hydroxyacetophenone, 2'-hydroxybutyrophenone, 2'-hydroxypropiophenone, etc. Residues of hydroxyphenone; residues of diketones such as acetylacetone, benzoylacetone, propionylacetone, isobutylacetone, valerylacetone, ethylacetylacetone; isovaleric acid, caprylic acid, octanoic acid, lauric acid, myristic acid, palmitic acid, Stearic acid, isostearic acid, oleic acid, linoleic acid, cyclopentanecarboxylic acid, naphthenic acid, ethylhexanoic acid, pivalic acid, versatic acid [trade name of Shell Chemical Co., Ltd., a mixture of isomers of C10 monocarboxylic acid Constituent synthetic acids], residues of carboxylic acids such as phenylacetic acid, benzoic acid, 2-naphthoic acid, maleic acid, succinic acid; hexanethioic acid, 2,2-dimethylbutanethioic acid, decanthioic acid, thiobenzoic acid, etc. Residue of thiocarboxylic acid; dibutyl phosphate, dipentyl phosphate, dihexyl phosphate, diheptyl phosphate, dioctyl phosphate, bis(2-ethylhexyl) phosphate, bis(1-methylheptyl) phosphate, dilauryl phosphate, Dioleyl phosphate, diphenyl phosphate, bis(p-nonylphenyl) phosphate, bis(polyethylene glycol-p-nonylphenyl) phosphate, (butyl) phosphate (2-ethylhexyl), phosphoric acid (1-methylheptyl) Residues of phosphoric acid esters such as (2-ethylhexyl) and phosphoric acid (2-ethylhexyl) (p-nonylphenyl); monobutyl 2-ethylhexylphosphonate, mono-2-ethylhexyl 2-ethylhexylphosphonate, monophenylphenylphosphonate. Residues of phosphonate esters such as 2-ethylhexyl, 2-ethylhexyl phosphonate mono-p-nonylphenyl, phosphonate mono-2-ethylhexyl, phosphonate mono-1-methylheptyl, and phosphonate mono-p-nonylphenyl Dibutylphosphinic acid, bis(2-ethylhexyl)phosphinic acid, bis(1-methylheptyl)phosphinic acid, dilaurylphosphinic acid, dioleylphosphinic acid, diphenylphosphinic acid, bis(p-nonylphenyl)phosphinic acid, butyl( 2-Ethylhexyl)phosphinic acid, (2-Ethylhexyl)(1-methylheptyl)phosphinic acid, (2-Ethylhexyl) Sil)(p-nonylphenyl)phosphinic acid, butylphosphinic acid, 2-ethylhexylphosphinic acid, 1-methylheptylphosphinic acid, oleylphosphinic acid, laurylphosphinic acid, phenylphosphinic acid, p-nonylphenylphosphinic acid and other phosphinic acids The residue of can also be mentioned. In addition, these ligands may be used individually by 1 type, and may be used in combination of 2 or more type.

In the component (A1) used in the first polymerization catalyst composition, the Lewis base that reacts with the rare earth element compound is, for example, tetrahydrofuran, diethyl ether, dimethylaniline, trimethylphosphine, lithium chloride, neutral olefins, Diolefins and the like. Here, when the rare earth element compound reacts with a plurality of Lewis bases (in the formulas (II) and (III), w is 2 or 3), the Lewis bases L ¹¹ may be the same or different. May be.

The rare earth element compound preferably contains a compound represented by the following formula (IV).
M-(NQ ¹ )(NQ ² )(NQ ³ )... (IV)
(In the formula, M is at least one selected from a lanthanoid element, scandium, and yttrium, and NQ ¹ , NQ ² and NQ ³ are amino groups, which may be the same or different, provided that M -Has an N bond)
That is, the compound represented by the above formula (IV) is characterized by having three MN bonds. Having three MN bonds has the advantage that the bonds are chemically equivalent and therefore the structure is stable and therefore easy to handle.

In the above formula (IV), the amino group represented by NQ (NQ ¹ , NQ ² , and NQ ³ ) is an aliphatic amino group such as dimethylamino group, diethylamino group or diisopropylamino group; phenylamino group, 2,6 -Di-tert-butylphenylamino group, 2,6-diisopropylphenylamino group, 2,6-dineopentylphenylamino group, 2-tert-butyl-6-isopropylphenylamino group, 2-tert-butyl-6 -Arylamino groups such as neopentylphenylamino group, 2-isopropyl-6-neopentylphenylamino group and 2,4,6-tert-butylphenylamino group; any of bistrialkylsilylamino groups such as bistrimethylsilylamino group However, a bistrimethylsilylamino group is preferable.

The component (B1) used in the first polymerization catalyst composition is at least one selected from the group consisting of an ionic compound (B1-1), an aluminoxane (B1-2) and a halogen compound (B1-3). .. The total content of the component (B1) in the first polymerization catalyst composition is preferably 0.1 to 50 times the mol of the component (A1).

The ionic compound (B1-1) is composed of a non-coordinating anion and a cation, and reacts with a rare earth element compound as the component (A1) or a reaction product thereof with a Lewis base to form a cationic transition metal compound. Examples thereof include ionic compounds that can be generated. Here, as the non-coordinating anion, for example, tetraphenyl borate, tetrakis(monofluorophenyl)borate, tetrakis(difluorophenyl)borate, tetrakis(trifluorophenyl)borate, tetrakis(tetrafluorophenyl)borate, tetrakis( Pentafluorophenyl)borate, tetrakis(tetrafluoromethylphenyl)borate, tetra(tolyl)borate, tetra(xylyl)borate, (triphenyl, pentafluorophenyl)borate, [tris(pentafluorophenyl),phenyl]borate, tri Decahydride-7,8-dicarbaundecaborate and the like can be mentioned. On the other hand, examples of the cation include a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptatrienyl cation, and a ferrocenium cation having a transition metal. Specific examples of the carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation and tri(substituted phenyl)carbonium cation, and more specifically, as the tri(substituted phenyl)carbonyl cation, Examples thereof include tri(methylphenyl)carbonium cation and tri(dimethylphenyl)carbonium cation. Specific examples of ammonium cations include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation (eg, tri(n-butyl)ammonium cation); N,N-dimethylanilinium. Cations, N,N-dialkylanilinium cations, N,N-dialkylanilinium cations such as N,N,2,4,6-pentamethylanilinium cations; dialkylammonium cations such as diisopropylammonium cations and dicyclohexylammonium cations Are listed. Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri(methylphenyl)phosphonium cation, and tri(dimethylphenyl)phosphonium cation. Therefore, the ionic compound is preferably a compound selected and combined from the above-mentioned non-coordinating anion and cation, and specifically, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, triphenylcarboate. Preference is given to titanium tetrakis(pentafluorophenyl)borate and the like. These ionic compounds may be used alone or in combination of two or more. The content of the ionic compound (B1-1) in the first polymerization catalyst composition is preferably 0.1 to 10 times mol, and about 1 times mol of the component (A1). Is more preferable.

The aluminoxane (B1-2) is a compound obtained by bringing an organoaluminum compound and a condensing agent into contact with each other, and is, for example, a chain having a repeating unit represented by the formula: (-Al(R')O-). Aluminoxane or cyclic aluminoxane (in the formula, R'is a hydrocarbon group having 1 to 10 carbon atoms, and some hydrocarbon groups may be substituted with at least one selected from the group consisting of a halogen atom and an alkoxy group) The polymerization degree of the repeating unit is preferably 5 or more, and more preferably 10 or more. Here, specific examples of R'include a methyl group, an ethyl group, a propyl group, an isobutyl group and the like, and among these, a methyl group is preferable. Examples of the organoaluminum compound used as a raw material for the aluminoxane include trialkylaluminums such as trimethylaluminum, triethylaluminum, tributylaluminum, triisobutylaluminum, and the like, and trimethylaluminum is particularly preferable. For example, aluminoxane using a mixture of trimethylaluminum and tributylaluminum as a raw material can be preferably used. The content of the aluminoxane (B1-2) in the first polymerization catalyst composition is such that the element ratio Al/M of the aluminum element Al of the aluminoxane to the rare earth element M constituting the component (A1) is 10 to 1. It is preferable to set it to about 000.

The halogen compound (B1-3) is composed of at least one of a Lewis acid, a complex compound of a metal halide and a Lewis base, and an organic compound containing active halogen, and is, for example, a rare earth element compound as the component (A1). Alternatively, it can react with a reaction product thereof with a Lewis base to form a cationic transition metal compound, a halogenated transition metal compound, or a compound in which the transition metal center has an insufficient charge. The total content of the halogen compounds (B1-3) in the first polymerization catalyst composition is preferably 1 to 5 times the mol of the component (A1).

As the Lewis _acid, B _{(C 6} F ₅₎ boron-containing halogen compounds such as _{3, Al (C 6 F 5} ) except that the aluminum-containing halogen compounds such as ₃ can be used, the third group in the periodic table, the A halogen compound containing an element belonging to Group 4, Group 5, Group 6, or Group 8 can also be used. Preferably, an aluminum halide or an organic metal halide is used. Further, chlorine or bromine is preferable as the halogen element. As the Lewis acid, specifically, 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, dibutyl aluminum bromide, dibutyl aluminum chloride, methyl aluminum sesquibromide, methyl aluminum sesquichloride, ethyl aluminum sesquibromide, ethyl aluminum sesquichloride, dibutyltin dichloride, aluminum tribromide, antimony trichloride, antimony pentachloride, phosphorus trichloride , Phosphorus pentachloride, tin tetrachloride, titanium tetrachloride, tungsten hexachloride, and the like. Among these, diethyl aluminum chloride, ethyl aluminum sesquichloride, ethyl aluminum dichloride, diethyl aluminum bromide, ethyl aluminum sesquibromide, ethyl aluminum dichloride. Bromide is particularly preferred.

Examples of the metal halide forming the complex compound of the metal halide and the Lewis base include beryllium chloride, beryllium bromide, beryllium iodide, magnesium chloride, magnesium bromide, magnesium iodide, calcium chloride, calcium bromide, and iodine. Calcium iodide, barium chloride, barium bromide, barium iodide, zinc chloride, zinc bromide, zinc iodide, cadmium chloride, cadmium bromide, cadmium iodide, mercury chloride, mercury bromide, mercury iodide, manganese chloride, Manganese bromide, manganese iodide, rhenium chloride, rhenium bromide, rhenium iodide, copper chloride, copper iodide, silver chloride, silver bromide, silver iodide, gold chloride, gold iodide, gold bromide, etc. Of these, magnesium chloride, calcium chloride, barium chloride, manganese chloride, zinc chloride and copper chloride are preferable, and magnesium chloride, manganese chloride, zinc chloride and copper chloride are particularly preferable.

Further, as the Lewis base constituting the complex compound of the metal halide and the Lewis base, a phosphorus compound, a carbonyl compound, a nitrogen compound, an ether compound, an alcohol and the like are preferable. Specifically, tributyl phosphate, tri-2-ethylhexyl phosphate, triphenyl phosphate, tricresyl phosphate, triethylphosphine, tributylphosphine, triphenylphosphine, diethylphosphinoethane, diphenylphosphinoethane, acetylacetone, benzoylacetone , Propionitrile acetone, valeryl acetone, ethyl acetylacetone, methyl acetoacetate, ethyl acetoacetate, phenyl acetoacetate, dimethyl malonate, diethyl malonate, diphenyl malonate, acetic acid, octanoic acid, 2-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, etc. Of these, tri-2-ethylhexyl phosphate, tricresyl phosphate, acetylacetone, 2-ethylhexanoic acid, versatic acid, 2-ethylhexyl alcohol, 1-decanol, and lauryl alcohol are preferred.

The Lewis base is reacted in a ratio of preferably 0.01 to 30 mol, more preferably 0.5 to 10 mol, per 1 mol of the metal halide. Use of the reaction product with the Lewis base can reduce the amount of metal remaining in the polymer.

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

The component (C1) used in the first polymerization catalyst composition has the following formula (I):
YR ¹ _a R ² _b R ³ _c ... (I)
(In the formula, Y is a metal selected from Group 1, Group 2, Group 12 and Group 13 of the periodic table, and R ¹ and R ² are hydrocarbon groups having 1 to 10 carbon atoms or hydrogen. And R ³ is a hydrocarbon group having 1 to 10 carbon atoms, R ¹ , R ² and R ³ may be the same or different from each other, and Y is selected from Group 1 of the periodic table. A is 1 and b and c are 0, and when Y is a metal selected from Groups 2 and 12 of the Periodic Table, a and b are 1 And c is 0, and when Y is a metal selected from Group 13 of the periodic table, a, b and c are 1), which is an organometallic compound represented by the following formula ( V):
AlR ¹ R ² R ³ ... (V)
(In the formula, R ¹ and R ² are a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom, R ³ is a hydrocarbon group having 1 to 10 carbon atoms, and R ¹ , R ² , and R ³ are respectively It may be the same or different from each other).
Examples of the organoaluminum compound of the formula (V) include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, tripentylaluminum, Trihexyl aluminum, tricyclohexyl aluminum, trioctyl aluminum; diethyl aluminum hydride, di-n-propyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl aluminum hydride, dihexyl aluminum hydride, diisohexyl hydride Aluminum, dioctylaluminum hydride, diisooctylaluminum hydride; ethylaluminum dihydride, n-propylaluminium dihydride, isobutylaluminum dihydride, and the like can be mentioned. Among these, triethylaluminum, triisobutylaluminum, diethylaluminum hydride. Diisobutylaluminum hydride is preferred. The organoaluminum compound as the component (C1) described above may be used alone or in combination of two or more. The content of the organoaluminum compound in the first polymerization catalyst composition is preferably 1 to 50 times mol, and more preferably about 10 times mol, of the component (A1).

Addition of the additive (D1) which can be an anionic ligand has an effect that a conjugated diene-based copolymer having a higher cis-1,4 bond content can be synthesized in high yield. Therefore, it is preferable.
The additive (D1) is not particularly limited as long as it can be exchanged with the amino group of the component (A1), but preferably has an OH group, an NH group or an SH group.

Specific compounds having an OH group include aliphatic alcohols and aromatic alcohols. Specifically, 2-ethyl-1-hexanol, dibutylhydroxytoluene, alkylated phenol, 4,4'-thiobis(6-t-butyl-3-methylphenol), 4,4'-butylidenebis(6-t- Butyl-3-methylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylenebis(4-ethyl-6-t-butylphenol), 2,6-di- t-4-ethylphenol, 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, n-octadecyl-3-(4-hydroxy-3,5-di-t -Butylphenyl)propionate, tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane, dilaurylthiodipropionate, distearylthiodipropionate, dimyristylthio Examples thereof include, but are not limited to, propionate and the like. For example, as a hindered phenol type, triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,3 5-Di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5 -Triazine, pentaerythryl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylenebis[3-(3,5-di-t-) Butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, N,N′-hexamethylenebis(3,5-di-t-butyl) -4-hydroxy-hydrocinnamamide), 3,5-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris(3,5 -Di-t-butyl-4-hydroxybenzyl)benzene, tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, octylated diphenylamine, 2,4-bis[(octylthio)methyl ]-O-Cresol etc. can be mentioned. As the hydrazine-based compound, N,N'-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl]hydrazine can be mentioned.

Examples of those having an NH group include primary amines or secondary amines such as alkylamines and arylamines. Specific examples thereof include dimethylamine, diethylamine, pyrrole, ethanolamine, diethanolamine, dicyclohexylamine, N,N'-dibenzylethylenediamine, bis(2-diphenylphosphinophenyl)amine and the like.

Examples of compounds having an SH group include compounds represented by the following formulas (VI) and (VII), in addition to aliphatic thiols and aromatic thiols.

^(Wherein, R 1, ^{R 2} and ^{R 3} each independently _{-O-C j H 2j + 1} , - _{at) a -O-C m H 2m} + 1 or _{-C n H 2n + 1 - (} O-C k H 2k Represented, j, m and n are each independently an integer of 0 to 12, k and a are each independently an integer of 1 to 12, R ⁴ is a carbon number of 1 to 12, Chain, branched, or cyclic, saturated or unsaturated, alkylene group, cycloalkylene group, cycloalkylalkylene group, cycloalkenylalkylene group, alkenylene group, cycloalkenylene group, cycloalkylalkenylene group, cycloalkenylalkenylene group, arylene group Or an aralkylene group.)
Specific examples of the compound represented by the formula (VI) include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, (mercaptomethyl)dimethylethoxysilane, and mercaptomethyltrimethoxysilane. Are listed.

(Wherein, W is ^-NR 8 -, - O- or ^-CR 9 ^{R 10} - (wherein, ^{R 8} and ^{R 9} are ^{_{-C p H 2p + 1, R}} 10 is _-C q _{H 2q + 1,} p and q are each independently 0-20 integer) is represented by, ^{R 5} and ^{R 6} each independently _{-M-C r H 2r -.} ( where, M is -O- or - CH ₂ −, r is an integer of 1 to 20), and R ⁷ is —O—C _j H _2j+1 , —(O—C _k H _2k −) _a —O—C _m H _2m+1. or represented by _{-C n H 2n + 1, j} , m and n are each independently 0 to 12 integer, k and a are each independently an integer from 1 to 12, ^{R 4} is C 1 -C ~12, linear, branched, or cyclic, saturated or unsaturated, alkylene group, cycloalkylene group, cycloalkylalkylene group, cycloalkenylalkylene group, alkenylene group, cycloalkenylene group, cycloalkylalkenylene group, It is a cycloalkenyl alkenylene group, an arylene group or an aralkylene group.)
Specific examples of those represented by the formula (VII) include 3-mercaptopropyl(ethoxy)-1,3-dioxa-6-methylaza-2-silacyclooctane and 3-mercaptopropyl(ethoxy)-1,3-dioxa-. 6-butylaza-2-silacyclooctane, 3-mercaptopropyl(ethoxy)-1,3-dioxa-6-dodecylaza-2-silacyclooctane and the like can be mentioned.

As the additive (D1), an anionic tridentate ligand precursor represented by the following formula (VIII) can be preferably used.
E ¹ -T ¹ -X-T ² -E ² ... (VIII)
(X represents an anionic electron-donating group containing a coordinating atom selected from Group 15 atoms of the Periodic Table, and E ¹ and E ² are each independently a group 15 atom or Group 16 atom of the Periodic Table. A neutral electron donating group containing a selected coordinating atom is shown, and T ¹ and T ² are respectively a bridging group bridging X and E ¹ and E ^2.

The additive (D1) is preferably added in an amount of 0.01 to 10 mol, and more preferably 0.1 to 1.2 mol, relative to 1 mol of the rare earth element compound. When the added amount is 0.1 mol or more, the polymerization of the monomer proceeds, and the object of the present invention can be achieved. Further, the addition amount is preferably an equivalent amount (1.0 mol) to the rare earth element compound, but an excessive amount may be added. The addition amount of 1.2 mol or less is preferable because the loss of the reagent is small.

In the above formula (VIII), the neutral electron donating groups E ¹ and E ² are groups containing a coordination atom selected from Groups 15 and 16 of the periodic table. Further, E ¹ and E ² may be the same group or different groups. Examples of the coordinating atom include nitrogen N, phosphorus P, oxygen O, sulfur S and the like, but P is preferable.

When the coordinating atom contained in E ¹ and E ² is P, the neutral electron donating group E ¹ or E ² may be a diarylphosphino group such as a diphenylphosphino group or a ditolylphosphino group. A dialkylphosphino group such as a dimethylphosphino group or a diethylphosphino group; an alkylarylphosphino group such as a methylphenylphosphino group, and preferably a diarylphosphino group.

When the coordinating atom contained in E ¹ and E ² is N, the neutral electron donating group E ¹ or E ² may be a dialkyl group such as dimethylamino group, diethylamino group or bis(trimethylsilyl)amino group. Examples include amino groups; diarylamino groups such as diphenylamino groups; alkylarylamino groups such as methylphenyl groups.

When the coordination atom contained in E ¹ and E ² is O, the neutral electron donating group E ¹ or E ² is an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group; Examples thereof include aryloxy groups such as phenoxy group and 2,6-dimethylphenoxy group.

When the coordinating atom contained in E ¹ and E ² is S, the neutral electron-donating group E ¹ or E ² may be an alkylthio group such as methylthio group, ethylthio group, propylthio group or butylthio group; Examples thereof include arylthio groups such as phenylthio group and tolylthio group.

The anionic electron-donating group X is a group containing a coordination atom selected from Group 15 of the periodic table. The coordination atom is preferably phosphorus P or nitrogen N, and more preferably N.

The bridging groups T ¹ and T ² may be any groups capable of bridging X and E ¹ and E ² , and examples thereof include an arylene group which may have a substituent on the aryl ring. Further, T ¹ and T ² may be the same group or different groups.
Examples of the arylene group include a phenylene group, a naphthylene group, a pyridylene group and a thienylene group, and a phenylene group and a naphthylene group are preferable. Further, any group may be substituted on the aryl ring of the arylene group. Examples of the substituent include an alkyl group such as a methyl group and an ethyl group; an aryl group such as a phenyl group and a tolyl group; a halogen group such as fluoro, chloro and bromo; and a silyl group such as a trimethylsilyl group.
As the arylene group, a 1,2-phenylene group is more preferable.

(Second polymerization catalyst composition)
Next, the second polymerization catalyst composition (hereinafter, also referred to as “second polymerization catalyst composition”) will be described. The second polymerization catalyst composition has the following formula (IX):

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

(In the formula, M represents a lanthanoid element, scandium or yttrium, Cp ^R independently represents an unsubstituted or substituted indenyl, and X′ represents a hydrogen atom, a halogen atom, an alkoxy group, a thiolate group, an amino group. , A silyl group or a hydrocarbon group having 1 to 20 carbon atoms, L represents a neutral Lewis base, and w represents an integer of 0 to 3, and a metallocene complex represented by the following formula (XI: ):

(In the formula, M represents a lanthanoid element, scandium or yttrium, Cp ^R′ represents an unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl, and X represents a hydrogen atom, a halogen atom, an alkoxy group or a thiolate group. , An amino group, a silyl group or a hydrocarbon group having 1 to 20 carbon atoms, L represents a neutral Lewis base, w represents an integer of 0 to 3, and [B] ⁻ represents a non-coordinating property. A polymerization catalyst composition containing at least one kind of complex selected from the group consisting of half metallocene cation complexes represented by (indicating an anion).

The second polymerization catalyst composition may further contain other components contained in the polymerization catalyst composition containing a usual metallocene complex, such as a cocatalyst. Here, the metallocene complex is a complex compound in which one or more cyclopentadienyl or a derivative thereof is bound to a central metal, and particularly, one cyclopentadienyl or a derivative thereof bound to a central metal is one. Certain metallocene complexes are sometimes referred to as half metallocene complexes.
In the polymerization reaction system, the concentration of the complex contained in the second polymerization catalyst composition is preferably in the range of 0.1 to 0.0001 mol/L.

In the metallocene complexes represented by the above formulas (IX) and (X), Cp ^R in the formula is unsubstituted indenyl or substituted indenyl. Cp ^R of the indenyl ring as a basic skeleton _may be represented by C _{9 H 7-x R} x or _{C 9 H 11-x R x} . Here, X is an integer of 0 to 7 or 0 to 11. Further, it is preferable that each R is independently a hydrocarbyl group or a metalloid group. The hydrocarbyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and further preferably 1 to 8 carbon atoms. Preferable examples of the hydrocarbyl group include a methyl group, an ethyl group, a phenyl group and a benzyl group. On the other hand, examples of the metalloid of the metalloid group include germyl Ge, stannyl Sn, and silyl Si, and the metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group of the metalloid group is the same as the above hydrocarbyl group. is there. Specific examples of the metalloid group include a trimethylsilyl group and the like. Specific examples of the substituted indenyl include 2-phenylindenyl and 2-methylindenyl. The two Cp ^Rs in formulas (IX) and (X) may be the same or different from each other.

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

(In the formula, R represents a hydrogen atom, a methyl group or an ethyl group.)
In the formula (XI), Cp ^R′ having the above indenyl ring as a basic skeleton is defined in the same manner as Cp ^{R in the} general formula (IX), and preferred examples are also the same.

In the formula (XI), CpR ^′ having the fluorenyl ring as a basic skeleton may be represented by C ₁₃ H _9-x R _x or C ₁₃ H _17-x R _x . Here, X is an integer of 0-9 or 0-17. Further, it is preferable that each R is independently a hydrocarbyl group or a metalloid group. The hydrocarbyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and further preferably 1 to 8 carbon atoms. Preferable examples of the hydrocarbyl group include a methyl group, an ethyl group, a phenyl group and a benzyl group. On the other hand, examples of the metalloid of the metalloid group include germyl Ge, stannyl Sn, and silyl Si, and the metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group of the metalloid group is the same as the above hydrocarbyl group. is there. Specific examples of the metalloid group include a trimethylsilyl group and the like.

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

The metallocene complex represented by the formula (IX) contains a silylamide ligand [—N(SiR ₃ ) ₂ ]. The R groups (R ^{a to} R ^f in formula (IX)) contained in the silylamide ligand are each independently an alkyl group having 1 to 3 carbon atoms or a hydrogen atom. Further, at least one of R ^{a to} R ^f is preferably 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 bulkiness around silicon is reduced, so that a non-conjugated olefin compound or an aromatic vinyl compound is introduced. It is easy to be done. From the same viewpoint, it is more preferable that at least one of R ^{a to} R ^c is a hydrogen atom and at least one of R ^{d to} R ^f is a hydrogen atom. Further, the alkyl group is preferably a methyl group.

The metallocene complex represented by the formula (X) include silyl ligand [-SiX _'3]. X′ contained in the silyl ligand [—SiX′ ₃ ] is a group defined in the same manner as X in formula (XI) described below, and the preferable groups are also the same.

In formula (XI), X is a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkoxy group, a thiolate group, an amino group, a silyl group, and a hydrocarbon group having 1 to 20 carbon atoms. Here, as the alkoxy group, an aliphatic alkoxy group such as methoxy group, ethoxy group, propoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group; phenoxy group, 2,6-dioxy group -Tert-butylphenoxy group, 2,6-diisopropylphenoxy group, 2,6-dineopentylphenoxy group, 2-tert-butyl-6-isopropylphenoxy group, 2-tert-butyl-6-neopentylphenoxy group, An aryloxy group such as a 2-isopropyl-6-neopentylphenoxy group may be mentioned, and among these, a 2,6-di-tert-butylphenoxy group is preferable.

In formula (XI), the thiolate group represented by X is an aliphatic group such as thiomethoxy group, thioethoxy group, thiopropoxy group, thion-butoxy group, thioisobutoxy group, thiosec-butoxy group, and thiotert-butoxy group. Thiolate group; thiophenoxy group, 2,6-di-tert-butylthiophenoxy group, 2,6-diisopropylthiophenoxy group, 2,6-dineopentylthiophenoxy group, 2-tert-butyl-6-isopropylthio group Arylthiolate groups such as phenoxy group, 2-tert-butyl-6-thioneopentylphenoxy group, 2-isopropyl-6-thioneopentylphenoxy group, 2,4,6-triisopropylthiophenoxy group, and the like can be mentioned. Of these, a 2,4,6-triisopropylthiophenoxy group is preferable.

In formula (XI), the amino group represented by X is an aliphatic amino group such as a dimethylamino group, a diethylamino group or a diisopropylamino group; a phenylamino group, 2,6-di-tert-butylphenylamino group, 2, 6-diisopropylphenylamino group, 2,6-dineopentylphenylamino group, 2-tert-butyl-6-isopropylphenylamino group, 2-tert-butyl-6-neopentylphenylamino group, 2-isopropyl-6 An arylamino group such as a neopentylphenylamino group and a 2,4,6-tri-tert-butylphenylamino group; a bistrialkylsilylamino group such as a bistrimethylsilylamino group, and among these, a bistrimethylsilylamino group Is preferred.

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

In formula (XI), the halogen atom represented by X may be any of a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, but a chlorine atom or a bromine atom is preferable. Further, as the hydrocarbon group having 1 to 20 carbon atoms represented by X, specifically, 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- group. Linear or branched aliphatic hydrocarbon groups such as butyl group, neopentyl group, hexyl group, octyl group; aromatic hydrocarbon groups such as phenyl group, tolyl group, naphthyl group; aralkyl groups such as benzyl group And a hydrocarbon group containing a silicon atom such as a trimethylsilylmethyl group and a bistrimethylsilylmethyl group, among which a methyl group, an ethyl group, an isobutyl group, a trimethylsilylmethyl group and the like are preferable.

In formula (XI), X is preferably a bistrimethylsilylamino group or a hydrocarbon group having 1 to 20 carbon atoms.

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

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

Further, the metallocene complex represented by the above formulas (IX) and (X), and the half metallocene cation complex represented by the above formula (XI) may be present as a monomer, a dimer or a dimer thereof. It may exist as the above multimer.

Examples of the metallocene complex represented by the above formula (IX) include a lanthanoid tris halide, scandium tris halide or yttrium tris halide in a solvent, an indenyl salt (for example, potassium salt or lithium salt) and a bis(trialkylsilyl)amine. It can be obtained by reacting with a salt (for example, potassium salt or lithium salt). Since the reaction temperature may be about room temperature, it can be produced under mild conditions. The reaction time is arbitrary, but is several hours to several tens hours. The reaction solvent is not particularly limited, but a solvent that dissolves the raw material and the product is preferable, and for example, toluene may be used. Below, the example of reaction for obtaining the metallocene complex represented by Formula (IX) is shown.

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

The metallocene complex represented by the above formula (X) is, for example, a lanthanoid tris halide, scandium tris halide or yttrium tris halide in a solvent, an indenyl salt (eg potassium salt or lithium salt) and a silyl salt (eg potassium salt). Or a lithium salt). Since the reaction temperature may be about room temperature, it can be produced under mild conditions. The reaction time is arbitrary, but is several hours to several tens hours. The reaction solvent is not particularly limited, but a solvent that dissolves the raw material and the product is preferable, and for example, toluene may be used. Below, the example of reaction for obtaining the metallocene complex represented by Formula (X) is shown.

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

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

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

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

The ionic compound represented by the general formula [A] ⁺ [B] ⁻ used in the above reaction is a compound selected and combined from the above non-coordinating anion and cation, and is N,N-dimethylaniline. Preferred are titanium tetrakis(pentafluorophenyl)borate and triphenylcarbonium tetrakis(pentafluorophenyl)borate. Further, the ionic compound represented by the formula [A] ⁺ [B] ⁻ is preferably added in an amount of 0.1 to 10 times mol, and more preferably about 1 time mol, of the metallocene complex. When the half metallocene cation complex represented by the formula (XI) is used in the polymerization reaction, the half metallocene cation complex represented by the formula (XI) may be provided as it is in the polymerization reaction system, or may be used in the above reaction. The compound represented by the formula (XII) and the ionic compound represented by the formula [A] ⁺ [B] ⁻ to be used are separately provided in the polymerization reaction system, and represented by the formula (XI) in the reaction system. A half metallocene cation complex may be formed. Further, by using the metallocene complex represented by the formula (IX) or (X) and the ionic compound represented by the formula [A] ⁺ [B] ⁻ in combination, the compound represented by the formula (XI) is used in the reaction system. It is also possible to form a half metallocene cation complex represented by

The structures of the metallocene complexes represented by the above formulas (IX) and (X) and the half metallocene cation complex represented by the above formula (XI) are preferably determined by X-ray structural analysis.

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

As the aluminoxane, alkylaminoxane is preferable, and examples thereof include methylaluminoxane (MAO) and modified methylaluminoxane. As the modified methylaluminoxane, MMAO-3A (manufactured by Tosoh Finechem Co., Ltd.) and the like are preferable. The content of aluminoxane in the second polymerization catalyst composition is such that the element ratio Al/M of aluminum element Al of aluminoxane to the central metal M of the metallocene complex is about 10 to 1,000, preferably about 100. It is preferable to do so.

On the other hand, the organoaluminum compound is represented by the general formula AlRR'R'' (wherein R and R'are each independently a hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, or a hydrogen atom, and R' ′ Is a hydrocarbon group having 1 to 10 carbon atoms) is preferable. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a chlorine atom is preferable. Examples of the organoaluminum compound include trialkylaluminum, dialkylaluminum chloride, alkylaluminum dichloride, dialkylaluminum hydride and the like, and of these, trialkylaluminum is preferable. Examples of trialkylaluminum include triethylaluminum and triisobutylaluminum. The content of the organoaluminum compound in the polymerization catalyst composition is preferably 1 to 50 times mol, and more preferably about 10 times mol, of the metallocene complex.

Further, in the polymerization catalyst composition, the metallocene complex represented by the formulas (IX) and (X) and the half metallocene cation complex represented by the formula (XI) are respectively combined with a suitable cocatalyst. Thus, the cis-1,4 bond content and the molecular weight of the obtained polymer can be increased.

(Third Polymerization Catalyst Composition)
Next, the third polymerization catalyst composition (hereinafter, also referred to as “third polymerization catalyst composition”) will be described.
As the third polymerization catalyst composition, a rare earth element-containing compound represented by the following formula (XIII):
_Ra MX _b QY _b ...(XIII)
(In the formula, each R independently represents an unsubstituted or substituted indenyl, the R is coordinated to M, M represents a lanthanoid element, scandium or yttrium, and X independently represents 1 to 1 carbon atoms. 20 is a hydrocarbon group, X is μ-coordinated to M and Q, Q is a Group 13 element of the periodic table, and Y is independently a hydrocarbon group having 1 to 20 carbon atoms or A hydrogen atom, Y is coordinated to Q, and a and b are 2), which is a polymerization catalyst composition containing a metallocene-based composite catalyst.
In a preferable example of the metallocene-based composite catalyst, the following formula (XIV):

(In the formula, M ¹ represents a lanthanoid element, scandium, or yttrium, Cp ^R independently represents an unsubstituted or substituted indenyl, and R ^A and R ^B each independently have 1 to 20 carbon atoms. Represents a hydrocarbon group, R ^A and R ^B are μ-coordinated to M ¹ and Al, and R ^C and R ^D each independently represent a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom. The metallocene-based composite catalyst represented by

A polymer can be produced by using the metallocene-based polymerization catalyst. Further, by using the metallocene-based composite catalyst, for example, a catalyst which is previously combined with an aluminum catalyst, it is possible to reduce or eliminate the amount of alkylaluminum used during the synthesis of the conjugated diene-based copolymer. Become. In addition, when a conventional catalyst system is used, it is necessary to use a large amount of alkylaluminum during the synthesis of the conjugated diene-based copolymer. For example, in the conventional catalyst system, it is necessary to use 10 molar equivalents or more of alkylaluminum with respect to the metal catalyst, but in the case of the metallocene-based composite catalyst, it is excellent to add about 5 molar equivalents of alkylaluminum. The catalytic action is exerted.

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

In the above formula (XIII), R is independently unsubstituted indenyl or substituted indenyl, and the R is coordinated to the metal M. Specific examples of the substituted indenyl include a 1,2,3-trimethylindenyl group, a heptamethylindenyl group, a 1,2,4,5,6,7-hexamethylindenyl group, and the like. ..
In the above formula (XIII), Q represents an element belonging to Group 13 of the periodic table, and specific examples thereof include boron, aluminum, gallium, indium and thallium.

In the above formula (XIII), X's each independently represent a hydrocarbon group having 1 to 20 carbon atoms, and the X's are μ-coordinated to M and Q. Here, as the hydrocarbon group having 1 to 20 carbon atoms, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group , Pentadecyl group, hexadecyl group, heptadecyl group, stearyl group and the like. Note that the μ-coordination is a coordination mode having a cross-linked structure.
In the above formula (XIII), each Y independently represents a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom, and the Y is coordinated to Q. Here, as the hydrocarbon group having 1 to 20 carbon atoms, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group , Pentadecyl group, hexadecyl group, heptadecyl group, stearyl group and the like.

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

In the above formula (XIV), Cp ^R is unsubstituted indenyl or substituted indenyl. Cp ^R of the indenyl ring as a basic skeleton _may be represented by C _{9 H 7-X R} X or _{C 9 H 11-X R X} . Here, X is an integer of 0 to 7 or 0 to 11. Further, it is preferable that each R is independently a hydrocarbyl group or a metalloid group. The hydrocarbyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and further preferably 1 to 8 carbon atoms. Preferable examples of the hydrocarbyl group include a methyl group, an ethyl group, a phenyl group and a benzyl group. On the other hand, examples of the metalloid of the metalloid group include germyl Ge, stannyl Sn, and silyl Si, and the metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group of the metalloid group is the same as the above hydrocarbyl group. is there. Specific examples of the metalloid group include a trimethylsilyl group and the like.
Specific examples of the substituted indenyl include 2-phenylindenyl and 2-methylindenyl. Note that the two Cp ^Rs in formula (XIV) may be the same or different from each other.

In the formula (XIV), R ^A and R ^B each independently represent a hydrocarbon group having 1 to 20 carbon atoms, and the R ^A and R ^B are μ-coordinated to M ¹ and Al. Here, as the hydrocarbon group having 1 to 20 carbon atoms, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group , Pentadecyl group, hexadecyl group, heptadecyl group, stearyl group and the like. Note that the μ-coordination is a coordination mode having a cross-linked structure.
In the above formula (XIV), R ^C and R ^D are each independently a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom. Here, as the hydrocarbon group having 1 to 20 carbon atoms, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group , Pentadecyl group, hexadecyl group, heptadecyl group, stearyl group and the like.
The metallocene-based composite catalyst may be prepared, for example, in a solvent by the following formula (XV):

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

In the metallocene complex represented by the above formula (XV), Cp ^R is unsubstituted indenyl or substituted indenyl and has the same meaning as Cp ^R in the above formula (XIV). In the formula (XV), the metal M ² is a lanthanoid element, scandium or yttrium, and has the same meaning as the metal M ¹ in the formula (XIV).
The metallocene complex represented by the above formula (XV) contains a silylamide ligand [—N(SiR ₃ ) ₂ ]. The R groups (R ^{E to} R ^J groups) contained in the silylamide ligand are each independently an alkyl group having 1 to 3 carbon atoms or a hydrogen atom. Further, it is preferable that at least one of R ^{E to} R ^J is a hydrogen atom. When at least one of R ^{E to} R ^J is a hydrogen atom, the synthesis of the catalyst becomes easy. Further, the alkyl group is preferably a methyl group.

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

Further, the metallocene complex represented by the above formula (XV) may be present as a monomer, or may be present as a dimer or a multimer thereof.

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

Specific examples of the organic aluminum compound include trimethyl aluminum, triethyl aluminum, tri-n-propyl aluminum, triisopropyl aluminum, tri-n-butyl aluminum, triisobutyl aluminum, tri-t-butyl aluminum, tripentyl aluminum, tri. Hexyl aluminum, tricyclohexyl aluminum, trioctyl aluminum; diethyl aluminum hydride, di-n-propyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl aluminum hydride, dihexyl aluminum hydride, diisohexyl aluminum hydride , Dioctylaluminum hydride, diisooctylaluminum hydride; ethylaluminum dihydride, n-propylaluminium dihydride, isobutylaluminum dihydride, and the like. Among these, triethylaluminum, triisobutylaluminum, diethylaluminum hydride, Diisobutylaluminium hydride is preferred. Further, these organoaluminum compounds may be used alone or in combination of two or more. The amount of the organoaluminum compound used for producing the metallocene composite catalyst is preferably 1 to 50 times mol, and more preferably about 10 times mol, of the metallocene complex.

The third polymerization catalyst composition may include the metallocene-based composite catalyst and a boron anion, and further other components contained in the polymerization catalyst composition including a normal metallocene-based catalyst, such as a co-catalyst. It is preferable to include. The metallocene-based composite catalyst and the boron anion are collectively referred to as a two-component catalyst. According to the third polymerization catalyst composition, like the metallocene composite catalyst, since it further contains a boron anion, it is possible to arbitrarily control the content of each monomer component in the polymer. Becomes

In the third polymerization catalyst composition, a tetravalent boron anion is specifically mentioned as the boron anion constituting the two-component catalyst. For example, tetraphenyl borate, tetrakis(monofluorophenyl)borate, tetrakis(difluorophenyl)borate, tetrakis(trifluorophenyl)borate, tetrakis(tetrafluorophenyl)borate, tetrakis(pentafluorophenyl)borate, tetrakis(tetrafluoromethyl) Phenyl)borate, tetra(tolyl)borate, tetra(xylyl)borate, (triphenyl, pentafluorophenyl)borate, [tris(pentafluorophenyl),phenyl]borate, tridecahydride-7,8-dicarbaundecaborate And the like. Among these, tetrakis(pentafluorophenyl)borate is preferable.

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

When a boron anion is present in the reaction system for reacting the metallocene complex represented by the above formula (XV) and the organoaluminum compound, the metallocene composite catalyst of the above formula (XIV) cannot be synthesized. Therefore, to prepare the third polymerization catalyst composition, it is necessary to synthesize the metallocene-based composite catalyst in advance, isolate and purify the metallocene-based composite catalyst, and then combine the metallocene-based composite catalyst with the boron anion.

Examples of the third polymerization catalyst co-catalyst which can be used in the compositions, for example, other organic aluminum compound represented by AlR ^K R ^L R ^M described above, aluminoxane can be preferably used. As the aluminoxane, alkylaminoxane is preferable, and examples thereof include methylaluminoxane (MAO) and modified methylaluminoxane. As the modified methylaluminoxane, MMAO-3A (manufactured by Tosoh Finechem Co., Ltd.) and the like are preferable. In addition, these aluminoxane may be used individually by 1 type, and may be used in combination of 2 or more type.

(Fourth Polymerization Catalyst Composition)
The fourth polymerization catalyst composition contains a rare earth element compound and a compound having a cyclopentadiene skeleton.
The fourth polymerization catalyst composition,
A rare earth element compound (hereinafter, also referred to as “(A2) component”),
A compound selected from the group consisting of a substituted or unsubstituted cyclopentadiene, a substituted or unsubstituted indene (compound having an indenyl group), and a substituted or unsubstituted fluorene (hereinafter, also referred to as “(B2) component”) )When,
Need to include.
This fourth polymerization catalyst composition,
-Organometallic compound (hereinafter, also referred to as "(C2) component")
-Aluminoxane compound (hereinafter, also referred to as "(D2) component")
-Halogen compound (hereinafter also referred to as "(E2) component")
May be further included.

The fourth polymerization catalyst composition preferably has a high solubility in aliphatic hydrocarbons, and is preferably a homogeneous solution in the aliphatic hydrocarbons. Here, examples of the aliphatic hydrocarbon include hexane, cyclohexane, pentane and the like.
And it is preferable that the fourth polymerization catalyst composition does not contain an aromatic hydrocarbon. Here, examples of the aromatic hydrocarbon include benzene, toluene, xylene and the like.
The phrase "does not contain aromatic hydrocarbons" means that the proportion of aromatic hydrocarbons contained in the polymerization catalyst composition is less than 0.1% by mass.

The component (A2) can be a rare earth element-containing compound having a metal-nitrogen bond (MN bond) or a reaction product of the rare earth element-containing compound and a Lewis base.
Examples of the rare earth element-containing compound include scandium, yttrium, and compounds containing a lanthanoid element composed of elements having atomic numbers 57 to 71. The lanthanoid element is specifically lanthanium, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium.
Examples of the Lewis base include tetrahydrofuran, diethyl ether, dimethylaniline, trimethylphosphine, lithium chloride, neutral olefins, neutral diolefins and the like.

Here, the rare earth element-containing compound or the reaction product of the rare earth element-containing compound and the Lewis base preferably does not have a bond between the rare earth element and carbon. When the reaction product of the rare earth element-containing compound and the Lewis base does not have a rare earth element-carbon bond, the reaction product is stable and easy to handle.
In addition, the said (A2) component may be used individually by 1 type, and may be used in combination of 2 or more type.

Here, the component (A2) is represented by the formula (1)
M-(AQ ¹ )(AQ ² )(AQ ³ )... (1)
(In the formula, M represents at least one element selected from the group consisting of scandium, yttrium, and lanthanoid elements; AQ ¹ , AQ ² and AQ ³ may be the same or different. A group, wherein A represents at least one selected from the group consisting of nitrogen, oxygen or sulfur; provided that it has at least one M-A bond)
The compound represented by is preferable.
The lanthanoid element is specifically lanthanium, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holminium, erbium, thulium, ytterbium, lutetium.
According to the above compound, the catalytic activity in the reaction system can be improved, the reaction time can be shortened, and the reaction temperature can be raised.

As M in the above formula (1), gadolinium is particularly preferable from the viewpoint of enhancing catalytic activity and reaction controllability.
When A in the above formula (1) is nitrogen, examples of the functional group represented by AQ ¹ , AQ ² and AQ ³ (that is, NQ ¹ , NQ ² and NQ ³ ) include an amino group and the like. To be And in this case, it has three MN bonds.
Examples of the amino group include aliphatic amino groups such as dimethylamino group, diethylamino group and diisopropylamino group; phenylamino group, 2,6-di-tert-butylphenylamino group, 2,6-diisopropylphenylamino group, 2,6-Dineopentylphenylamino group, 2-tert-butyl-6-isopropylphenylamino group, 2-tert-butyl-6-neopentylphenylamino group, 2-isopropyl-6-neobentylphenyl Amino groups, arylamino groups such as 2,4,6-tert-butylphenylamino group; bistrialkylsilylamino groups such as bistrimethylsilylamino group, and particularly, solubility in aliphatic hydrocarbons and aromatic hydrocarbons. From the viewpoint of, a bistrimethylsilylamino group is preferable. The above amino groups may be used alone or in combination of two or more.

According to the above configuration, the component (A2) can be a compound having three MN bonds, each bond is chemically equivalent, and the structure of the compound is stable, which facilitates handling.
Further, with the above configuration, the catalytic activity in the reaction system can be further improved. Therefore, the reaction time can be further shortened and the reaction temperature can be further raised.

When A is oxygen, the component (A2) represented by the formula (1) is not particularly limited, but for example, the following formula (1a)
(RO) ₃ M... (1a)
Rare earth alcoholate represented by
The following formula (1b)
_{(R-CO 2) 3 M} ··· (1b)
And a rare earth carboxylate represented by. Here, in each of the above formulas (1a) and (1b), R may be the same or different and is an alkyl group having 1 to 10 carbon atoms.
In addition, since it is preferable that the component (A2) does not have a bond between a rare earth element and carbon, the compound (I) or the compound (II) described above can be preferably used.

When A is sulfur, the component (A2) represented by the formula (1) is not particularly limited, but for example, the following formula (1c)
(RS) ₃ M...(1c)
A rare earth alkyl thiolate represented by
The following formula (1d)
_{(R-CS 2) 3 M} ··· (1d)
And the like. Here, in each of the formulas (1c) and (1d), R may be the same or different and represents an alkyl group having 1 to 10 carbon atoms.
In addition, since it is preferable that the component (A2) does not have a bond between a rare earth element and carbon, the compound (1c) or the compound (1d) described above can be preferably used.

The component (B2) is a compound selected from the group consisting of a substituted or unsubstituted cyclopentadiene, a substituted or unsubstituted indene (compound having an indenyl group), and a substituted or unsubstituted fluorene.
The compound as the component (B2) may be used alone or in combination of two or more.

Examples of the substituted cyclopentadiene include pentamethylcyclopentadiene, tetramethylcyclopentadiene, isopropylcyclopentadiene, trimethylsilyl-tetramethylcyclopentadiene and the like.
Examples of the substituted or unsubstituted indene include indene, 2-phenyl-1H-indene, 3-benzyl-1H-indene, 3-methyl-2-phenyl-1H-indene, 3-benzyl-2-phenyl-1H. -Indene, 1-benzyl-1H-indene and the like can be mentioned, and 3-benzyl-1H-indene and 1-benzyl-1H-indene are particularly preferable from the viewpoint of narrowing the molecular weight distribution.
Examples of the substituted fluorene include trimethylsilylfluorene and isopropylfluorene.

According to the above configuration, it is possible to increase the conjugated electrons included in the compound having a cyclopentadiene skeleton, and it is possible to further improve the catalytic activity in the reaction system. Therefore, the reaction time can be further shortened and the reaction temperature can be further raised.

The organometallic compound (component (C2)) has the formula (2)
YR ⁴ _a R ⁵ _b R ⁶ _c (2)
(In the formula, Y is a metal element selected from the group consisting of elements of Group 1, Group 2, Group 12 and Group 13 of the periodic table, and R ⁴ and R ^{5 each} have 1 to 10 carbon atoms. 10 hydrocarbon groups or hydrogen atoms, R ⁶ is a hydrocarbon group having 1 to 10 carbon atoms, provided that R ⁴ , R ⁵ and R ⁶ may be the same or different from each other, and Y Is a Group 1 metal element, a is 1 and b and c are 0, and Y is a Group 2 or Group 12 metal element, a and b are 1 And c is 0, and a, b and c are 1 when Y is a Group 13 metal element)
Is a compound represented by.
Here, from the viewpoint of enhancing the catalytic activity, it is preferable that at least one of R ¹ , R ² and R ³ is different in the formula (2).

Specifically, the component (C2) is represented by the formula (3)
AlR ⁷ R ⁸ R ⁹ (3)
(Wherein, ^{R 7} and ^{R 8} is a hydrocarbon group or a hydrogen atom having 1 to 10 carbon atoms, ^{R 9} is a hydrocarbon group having 1 to 10 carbon ^atoms, R 7, ^{R 8} and ^{R 9} May be the same or different)
It is preferable that the organoaluminum compound represented by
Examples of the organic aluminum compound include trimethyl aluminum, triethyl aluminum, tri-n-propyl aluminum, triisopropyl aluminum, tri-n-butyl aluminum, triisobutyl aluminum, tri-t-butyl aluminum, tripentyl aluminum, trihexyl. Aluminum, tricyclohexyl aluminum, trioctyl aluminum; diethyl aluminum hydride, di-n-propyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl aluminum hydride, dihexyl aluminum hydride, diisohexyl aluminum hydride, Dioctylaluminum hydride, diisooctylaluminum hydride; ethylaluminum dihydride, n-propylaluminium dihydride, isobutylaluminium dihydride and the like can be mentioned, and particularly triethylaluminum, triisobutylaluminum, diethylaluminum hydride, diisobutyl hydride. Aluminum is preferred and more particularly diisobutylaluminium hydride is preferred.
The organoaluminum compounds may be used alone or in combination of two or more.

The aluminoxane compound (component (D2)) is a compound obtained by bringing an organoaluminum compound and a condensing agent into contact with each other.
By using the component (D2), the catalytic activity in the polymerization reaction system can be further improved. Therefore, the reaction time can be further shortened and the reaction temperature can be further raised.

Here, examples of the organoaluminum compound include trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, and a mixture thereof. Particularly, trimethylaluminum and a mixture of trimethylaluminum and tributylaluminum are preferable.
Examples of the condensing agent include water and the like.

As the component (D2), for example, formula (4)
_{^{- (Al (R 10) O}} ) n - ··· (4)
(Wherein, R ¹⁰ is a hydrocarbon group having 1 to 10 carbon atoms, wherein the halogen and / or may be substituted with an alkoxy group in some hydrocarbon group; R ¹⁰ is between the repeating units And may be the same or different; n is 5 or more).
The aluminoxane represented by

The molecular structure of the aluminoxane may be linear or cyclic.
It is preferable that n is 10 or more.
Examples of the hydrocarbon group for R ¹⁰ include a methyl group, an ethyl group, a propyl group and an isobutyl group, with a methyl group being particularly preferred. The above hydrocarbon groups may be used alone or in combination of two or more. As the hydrocarbon group for R, a combination of a methyl group and an isobutyl group is preferable.

The aluminoxane preferably has a high solubility in aliphatic hydrocarbons and a low solubility in aromatic hydrocarbons. For example, aluminoxane commercially available as a hexane solution is preferable.
Here, examples of the aliphatic hydrocarbon include hexane and cyclohexane.

The component (D2) is particularly represented by the formula (5)
_{- (Al (CH 3) x} (i-C 4 H 9) y O) m - ··· (5)
(In the formula, x+y is 1; m is 5 or more)
A modified aluminoxane represented by (hereinafter also referred to as "TMAO") may be used. Examples of TMAO include TMAO341 manufactured by Tosoh Fine Chemical Co., Ltd.

Further, the component (D2) is particularly represented by the formula (6)
_{- (Al (CH 3) 0.7} (i-C 4 H 9) 0.3 O) k - ··· (6)
(In the formula, k is 5 or more)
A modified aluminoxane represented by (hereinafter also referred to as “MMAO”) may be used. Examples of MMAO include product name: MMAO-3A manufactured by Tosoh Fine Chemical Co., Ltd.

Further, the component (D2) is particularly represented by the formula (7)
_{- [(CH 3) AlO]} i - ··· (7)
(In the formula, i is 5 or more)
A modified aluminoxane represented by (hereinafter also referred to as “PMAO”) may be used. Examples of PMAO include product name: TMAO-211 manufactured by Tosoh Fine Chemical Co., Ltd.

The component (D2) is preferably MMAO or TMAO among the above MMAO, TMAO and PMAO from the viewpoint of enhancing the effect of improving the catalytic activity, and is TMAO from the viewpoint of further enhancing the effect of improving the catalytic activity. Is more preferable.

The halogen compound ((E2) component) is a halogen-containing compound that is a Lewis acid (hereinafter, also referred to as “(E2-1) component”), a complex compound of a metal halide and a Lewis base (hereinafter, “(E2-2)”. Component)) and an organic compound containing active halogen (hereinafter, also referred to as “(E2-3) component”).

These compounds react with the component (A2), that is, a compound containing a rare earth element having an MN bond or a reaction product of the compound containing a rare earth element and a Lewis base to give a cationic transition metal compound or a halogenated transition compound. It produces a metal compound and/or a transition metal compound in a state where electrons are deficient in the transition metal center.
By using the component (E2), the cis-1,4-bond content of the conjugated diene-based copolymer can be improved.

As the component (E2-1), for example, a halogen-containing compound containing an element of Group 3, Group 4, Group 5, Group 6, Group 8, Group 13, Group 14 or Group 15 and the like. In particular, an aluminum halide or an organic metal halide is preferable.
Examples of halogen-containing compounds that are Lewis acids include titanium tetrachloride, tungsten hexachloride, tri(pentafluorophenyl)borate, methylaluminum dibromide, methylaluminum dichloride, ethylaluminium dibromide, ethylaluminum dichloride, butylaluminum dibromide. , Butyl aluminum dichloride, dimethyl aluminum bromide, dimethyl aluminum chloride, diethyl aluminum bromide, diethyl aluminum chloride, dibutyl aluminum bromide, dibutyl aluminum chloride, methyl aluminum sesquibromide, methyl aluminum sesquichloride, ethyl aluminum sesquibromide, ethyl aluminum sesquichloride, aluminum Tribromide, tri(pentafluorophenyl)aluminum, dibutyltin dichloride, tin tetrachloride, phosphorus trichloride, phosphorus pentachloride, antimony trichloride, antimony pentachloride and the like can be mentioned, in particular, ethyl aluminum dichloride, ethyl aluminum dibromide, Diethyl aluminum chloride, diethyl aluminum bromide, ethyl aluminum sesquichloride and ethyl aluminum sesquibromide are preferable.
The halogen is preferably chlorine or bromine.
The halogen-containing compound which is the Lewis acid may be used alone or in combination of two or more.

Examples of the metal halide used as the component (E2-2) include beryllium chloride, beryllium bromide, beryllium iodide, magnesium chloride, magnesium bromide, magnesium iodide, calcium chloride, calcium bromide, calcium iodide, Barium chloride, barium bromide, barium iodide, zinc chloride, zinc bromide, zinc iodide, cadmium chloride, cadmium bromide, cadmium iodide, mercury chloride, mercury bromide, mercury iodide, manganese chloride, manganese bromide , Manganese iodide, rhenium chloride, rhenium bromide, rhenium iodide, copper chloride, copper iodide, silver chloride, silver bromide, silver iodide, gold chloride, gold iodide, gold bromide and the like, particularly , Magnesium chloride, calcium chloride, barium chloride, zinc chloride, manganese chloride and copper chloride are preferred, and magnesium chloride, zinc chloride, manganese chloride and copper chloride are more preferred.
The Lewis base used as the component (E2-2) is preferably a phosphorus compound, a carbonyl compound, a nitrogen compound, an ether compound or an alcohol.
For example, tributyl phosphate, tri-2-ethylhexyl phosphate, triphenyl phosphate, tricresyl phosphate, triethylphosphine, tributylphosphine, triphenylphosphine, diethylphosphinoethane, diphenylphosphinoethane, acetylacetone, benzoylacetone, propiopio Nitrile 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, Particularly, tri-2-ethylhexyl phosphate, tricresyl phosphate, acetylacetone, 2-ethylhexanoic acid, versatic acid, 2-ethylhexyl alcohol, 1-decanol, and lauryl alcohol are preferable.
The number of moles of the Lewis base is 0.01 to 30 moles, preferably 0.5 to 10 moles, per 1 mole of the metal halide. The use of the reaction product with the Lewis base can reduce the amount of metal remaining in the polymer.

Examples of the component (E2-3) include benzyl chloride.

Hereinafter, the mass ratio between the components of the fourth polymerization catalyst composition will be described.
Component (B2) (a compound selected from the group consisting of a substituted or unsubstituted cyclopentadiene, a substituted or unsubstituted indene, and a substituted or unsubstituted fluorene) with respect to the component (A2) (rare earth element compound) in moles From the viewpoint of sufficiently obtaining the catalytic activity, the ratio is preferably more than 0, more preferably 0.5 or more, further preferably 1 or more, and from the viewpoint of suppressing the decrease of the catalytic activity, It is preferably 3 or less, more preferably 2.5 or less, and further preferably 2.2 or less.

The molar ratio of the component (C2) (organic metal compound) to the component (A2) is preferably 1 or more, more preferably 5 or more, from the viewpoint of improving the catalytic activity in the reaction system. From the viewpoint of suppressing the decrease in the catalytic activity in (1), it is preferably 50 or less, more preferably 30 or less, and more preferably about 10.

The molar ratio of aluminum in the component (A2) to the rare earth element in the component (A2) is preferably 10 or more, and is 100 or more, from the viewpoint of improving the catalytic activity in the reaction system. Is more preferable, and from the viewpoint of suppressing a decrease in catalytic activity in the reaction system, it is preferably 1,000 or less, and more preferably 800 or less.

The ratio of the component (E2) (halogen compound) to the component (A2) in moles is preferably 0 or more, more preferably 0.5 or more, and 1.0 or more from the viewpoint of improving the catalytic activity. Is more preferable, and from the viewpoint of maintaining the solubility of the component (E2) and suppressing the decrease in catalyst activity, it is preferably 20 or less, and more preferably 10 or less.
Therefore, according to the above range, the effect of improving the cis-1,4-bond content of the conjugated diene-based copolymer can be enhanced.

The fourth polymerization catalyst composition is a non-coordinating anion (eg, tetravalent boron anion) and a cation (eg, carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptatrienyl cation). , A ferrocenium cation having a transition metal) is preferably not included. Here, the ionic compound has a high solubility in aromatic hydrocarbons and a low solubility in hydrocarbons. Therefore, if the polymerization catalyst composition does not contain an ionic compound, the conjugated diene-based copolymer can be produced while further reducing the environmental load and the production cost.
In addition, "the ionic compound is not included" means that the ratio of the ionic compound contained in the polymerization catalyst composition is less than 0.01% by mass.

<Washing process>
The washing step is a step of washing the conjugated diene-based copolymer obtained in the polymerization step. The medium used for washing is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include methanol, ethanol and 2-propanol. A Lewis acid-derived catalyst is used as a polymerization catalyst. In this case, an acid (for example, hydrochloric acid, sulfuric acid, nitric acid) can be added to these solvents before use. The amount of acid added is preferably 15 mol% or less based on the solvent. If the amount is higher than this, the acid may remain in the conjugated diene-based copolymer, which may adversely affect the reaction during kneading and vulcanization.
By this washing step, the amount of catalyst residue in the conjugated diene-based copolymer can be suitably reduced.

[Rubber composition]
The rubber composition of the present invention contains at least the conjugated diene-based copolymer of the present invention, and may further contain a filler, a crosslinking agent, other rubber components, etc., if necessary.
The other rubber component is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include natural rubber (NR), polyisoprene (IR), butadiene rubber (polybutadiene, BR), acrylonitrile-butadiene rubber ( NBR), styrene-butadiene rubber (SBR), chloroprene rubber, ethylene-propylene rubber (EPM), ethylene-propylene-non-conjugated diene rubber (EPDM), polysulfide rubber, silicone rubber, fluororubber, urethane rubber and the like. These may be used alone or in combination of two or more.
Among these, the other rubber component preferably contains at least one rubber component selected from the group consisting of NR, IR, BR, and SBR, and is selected from the group consisting of NR, IR, and BR. It is more preferable to contain at least one type of rubber component described above, and it is more preferable to contain BR.
In the present invention, it is preferable to contain 10 to 100 parts by mass of the conjugated diene polymer of the present invention to 100 parts by mass of the rubber component containing the conjugated diene copolymer and the diene rubber, and 30 to 90 parts by mass. The content is more preferably contained, and further preferably 40 to 80 parts by mass. When the content of the conjugated diene-based copolymer of the present invention is within the above range, a rubber composition having an excellent balance of storage elastic modulus and loss tangent can be obtained.

In addition, a filler may be used in the rubber composition, if necessary, for the purpose of improving its reinforcing property. The blending amount of the filler is not particularly limited and may be appropriately selected depending on the intended purpose, but is 10 to 100 parts by mass with respect to 100 parts by mass of the rubber component containing the conjugated diene-based copolymer of the present invention. Is preferable, 20-80 mass parts is more preferable, and 30-60 mass parts is especially preferable. When the blending amount of the filler is 10 parts by mass or more, the effect of improving the reinforcing property by blending the filler is obtained, and when it is 100 parts by mass or less, the loss tangent (tan δ) is reduced. be able to.

The filler is not particularly limited and includes carbon black, silica, aluminum hydroxide, clay, alumina, talc, mica, kaolin, glass balloons, glass beads, calcium carbonate, magnesium carbonate, magnesium hydroxide, magnesium oxide. , Titanium oxide, potassium titanate, barium sulfate and the like, among which carbon black is preferably used. These may be used alone or in combination of two or more.

The carbon black is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include FEF, GPF, SRF, HAF, N339, IISAF, ISAF and SAF. These may be used alone or in combination of two or more.
The nitrogen adsorption specific surface area (measured in accordance with N ₂ SA, JIS K 6217-2:2001) of the carbon black is not particularly limited and may be appropriately selected according to the purpose. -100 m< ² >/g is preferable and 35-80 m< ² >/g is more preferable. When the nitrogen adsorption specific surface area (N ₂ SA) of the carbon black is 20 m ² /g or more, the durability of the obtained rubber composition is improved, sufficient crack growth resistance is obtained, and 100 m ² When it is not more than /g, good workability can be maintained while avoiding a large decrease in low loss property.

A crosslinking agent can be used in the rubber composition, if necessary. The cross-linking agent is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include sulfur-based cross-linking agents, organic peroxide-based cross-linking agents, inorganic cross-linking agents, polyamine cross-linking agents, resin cross-linking agents, and sulfur. Examples thereof include compound-based crosslinking agents and oxime-nitrosamine-based crosslinking agents. Among these, as the rubber composition for a tire, a sulfur-based crosslinking agent (vulcanizing agent) is more preferable.
The content of the crosslinking agent is appropriately selected depending on the intended purpose without any limitation, but it is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the rubber component. When the content of the cross-linking agent is 0.1 part by mass or more, the cross-linking proceeds suitably, while when it is 20 mass parts or less, the progress of the cross-linking during kneading is suppressed, and the physical properties of the cross-linked product are good. Is obtained, which is preferable.

When the vulcanizing agent is used, a vulcanization accelerator can be used in combination. Examples of the vulcanization accelerator include guadinine-based, aldehyde-amine-based, aldehyde-ammonia-based, thiazole-based, sulfenamide-based, thiourea-based, thiuram-based, dithiocarbamate-based, and xanthate-based compounds. Further, the rubber composition of the present invention, if necessary, a softening agent, a vulcanization aid, a colorant, a flame retardant, a lubricant, a foaming agent, a plasticizer, a processing aid, an antioxidant, an antiaging agent, Known compounds such as anti-scorch agents, anti-UV agents, anti-static agents, anti-coloring agents, and other compounding agents can be used according to the purpose of use.

[Crosslinked rubber composition]
Further, a crosslinked rubber composition can be obtained by crosslinking the rubber composition of the present invention. The conditions for the cross-linking are not particularly limited and may be appropriately selected depending on the intended purpose, but are preferably a temperature of 120 to 200° C. and a heating time of 1 minute to 900 minutes. Such a crosslinked rubber composition has an excellent balance of storage elastic modulus and loss tangent.

[tire]
The tire of the present invention is not particularly limited as long as it uses the rubber composition of the present invention or the crosslinked rubber composition of the present invention, and can be appropriately selected according to the purpose. Since such a tire uses the rubber composition containing the conjugated diene-based copolymer of the present invention, it has low fuel consumption and a high storage elastic modulus. The application site of the rubber composition of the present invention in the tire is not particularly limited and may be appropriately selected depending on the purpose, and examples thereof include a tread, a base tread, a sidewall, a side reinforcing rubber and a bead filler. .. Among these, it is advantageous to use the rubber composition of the present invention in the tread portion from the viewpoint of low fuel consumption.
As a method of manufacturing the tire, a conventional method can be used. For example, a carcass layer comprising at least one selected from the group consisting of an unvulcanized rubber composition and a cord, a belt layer, a tread layer, and the like, which are commonly used in tire production, are sequentially laminated on a tire molding drum, Remove the drum to make a green tire. Then, a desired tire (for example, a pneumatic tire) can be manufactured by heating and vulcanizing this green tire according to a conventional method.

[Applications other than tires]
The rubber composition of the present invention can be used for anti-vibration rubber, seismic isolation rubber, belts such as conveyor belts, rubber crawlers, various hoses, etc., as well as tire applications.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples.

(Example 1-1: Synthesis of polymer A)
In a glove box under a nitrogen atmosphere, in a glass container, tris bistrimethylsilylamide gadolinium _{(Gd [N (SiMe 3)} 2] 3) ((A2) component) 300 [mu] mol, 1-benzyl-indene ((B2) component) 600 [mu] mol , Diisobutylaluminum hydride ((C2) component) 7.5 mmoL, and further MMAO (manufactured by Tosoh Finechem Co., Ltd., product name: MMAO-3A) ((D2) component) in a ratio of aluminum to gadolinium in MMAO. Was added as 250 and then dissolved in 150 mL of hexane. Then, 600 μmoL of diethylaluminum chloride ((E2-1) component) was added to obtain a polymerization catalyst composition.
On the other hand, 480 g of a hexane solution containing 99.9 g of isoprene and 0.1 g of myrcene was added to a sufficiently dried 1 L pressure-resistant glass reactor to prepare a monomer solution.
Then, the polymerization catalyst composition was taken out from the glove box, and an amount of the polymerization catalyst composition containing 16 μmoL of gadolinium was added to the monomer solution. This reaction system was maintained at 50° C. for 240 minutes to carry out a polymerization reaction. Thereafter, 5 mL of an isopropanol solution (5% by mass) of 2,2′-methylene-bis(6-t-butyl-4-ethylphenol) (manufactured by Ouchi Shinko Chemical Industry Co., Ltd., product name: Nocrac NS-5) was added, The polymerization reaction was stopped by adding it to the reaction system. Furthermore, the reaction product was precipitated and separated by adding a large amount of methanol to the reactor, and further vacuum dried at 60° C. to obtain a polymer A (yield: 100.0 g).

(Example 1-2: Synthesis of polymer B)
Polymerization was carried out in the same manner as in Example 1-1 except that the amount of myrcene added was 0.5 g and the amount of isoprene was 99.5 g. As a result, a polymer B was obtained with a yield of 100.0. ..

(Example 1-3: Synthesis of polymer C)
Polymerization was carried out in the same manner as in Example 1-1 except that the amount of added myrcene was 1.0 g and the amount of isoprene was 99.9 g. As a result, a polymer C was obtained with a yield of 100.0 g. ..

(Example 1-4: Synthesis of polymer D)
80 g of a hexane solution containing 1.0 g of myrcene was added to a sufficiently dried 1 L pressure-resistant glass reactor to prepare a monomer solution. Thereafter, an amount of the polymerization catalyst composition containing 16 μmoL of gadolinium was added to the monomer solution. This reaction system was maintained at room temperature for 30 minutes to carry out a polymerization reaction. Then, 400 g of a hexane solution containing 99 g of isoprene was added, and the mixture was maintained at 50° C. for 240 minutes to carry out a polymerization reaction. Thereafter, 5 mL of an isopropanol solution (5% by mass) of 2,2′-methylene-bis(6-t-butyl-4-ethylphenol) (manufactured by Ouchi Shinko Chemical Industry Co., Ltd., product name: Nocrac NS-5) was added, The polymerization reaction was stopped by adding it to the reaction system. Further, a large amount of methanol was added to the reactor to precipitate/separate the reaction product, which was further vacuum dried at 60° C. to obtain a polymer D (yield: 100.0 g).

(Example 1-5: Synthesis of polymer E)
To a sufficiently dried 1 L pressure resistant glass reactor, 480 g of a hexane solution containing 99 g of isoprene was added to obtain a monomer solution. Thereafter, an amount of the polymerization catalyst composition containing 16 μmoL of gadolinium was added to the monomer solution. This reaction system was maintained at 50° C. for 240 minutes to carry out a polymerization reaction. Thereafter, 1.0 g of myrcene was added, and the polymerization reaction was carried out while maintaining the temperature at 50° C. for 30 minutes. Thereafter, 5 mL of an isopropanol solution (5% by mass) of 2,2′-methylene-bis(6-t-butyl-4-ethylphenol) (manufactured by Ouchi Shinko Chemical Industry Co., Ltd., product name: Nocrac NS-5) was added, The polymerization reaction was stopped by adding it to the reaction system. Furthermore, a reaction product was precipitated and separated by adding a large amount of methanol to the reactor, and further dried in vacuum at 60° C. to obtain a polymer E (yield: 100.0 g).

(Example 1-6: Synthesis of polymer F)
80 g of a hexane solution containing 0.5 g of myrcene was added to a sufficiently dried 1 L pressure-resistant glass reactor to prepare a monomer solution. Thereafter, an amount of the polymerization catalyst composition containing 16 μmoL of gadolinium was added to the monomer solution. This reaction system was maintained at room temperature for 30 minutes to carry out a polymerization reaction. Then, 400 g of a hexane solution containing 99 g of isoprene was added, and the reaction system was maintained at 50° C. for 240 minutes to carry out a polymerization reaction. Thereafter, 0.5 g of myrcene was further added, and the mixture was maintained at 50° C. for 30 minutes to carry out a polymerization reaction. Thereafter, 5 mL of an isopropanol solution (5% by mass) of 2,2′-methylene-bis(6-t-butyl-4-ethylphenol) (manufactured by Ouchi Shinko Chemical Industry Co., Ltd., product name: Nocrac NS-5) was added, The polymerization reaction was stopped by adding it to the reaction system. Furthermore, a reaction product was precipitated and separated by adding a large amount of methanol to the reactor, and further vacuum dried at 60° C. to obtain a polymer F (yield: 100.0 g).

(Example 1-7: Synthesis of polymer G)
In a glove box under a nitrogen atmosphere, in a glass container, tris bistrimethylsilylamide gadolinium _{(Gd [N (SiMe 3)} 2] 3) ((A2) component) 250μmoL, 1- benzyl-indene ((B2) component) 500 [mu] mol , Diisobutylaluminum hydride ((C2) component) 75 mmoL, and MMAO (manufactured by Tosoh Finechem Co., Ltd., product name: MMAO-3A) ((D2) component), the ratio of aluminum to gadolinium in MMAO is 375. And was dissolved in 115 mL of hexane. Thereafter, 500 μmoL of diethylaluminum chloride ((E2-1) component) was added to obtain a polymerization catalyst composition.
On the other hand, 400 g of a cyclohexane solution containing 99 g of butadiene and 1.0 g of myrcene was added to a sufficiently dried 1 L pressure-resistant glass reactor to prepare a monomer solution.
Then, the polymerization catalyst composition was taken out of the glove box, and an amount of the polymerization catalyst composition containing gadolinium of 5 μmoL was added to the monomer solution. This reaction system was maintained at 50° C. for 90 minutes to carry out a polymerization reaction. Thereafter, 5 mL of an isopropanol solution (5% by mass) of 2,2′-methylene-bis(6-t-butyl-4-ethylphenol) (manufactured by Ouchi Shinko Chemical Industry Co., Ltd., product name: Nocrac NS-5) was added, The polymerization reaction was stopped by adding it to the reaction system. Furthermore, the reaction product was precipitated and separated by adding a large amount of methanol to the reactor, and further vacuum dried at 60° C. to obtain a polymer G (yield: 100.0 g).

(Example 1-8: Synthesis of polymer H)
Polymerization was carried out in the same manner as in Example 1-7 except that the amount of myrcene added was 0.5 g and the amount of butadiene was 99.5 g. As a result, a polymer H was obtained with a yield of 100.0 g. It was

(Example 1-9: Synthesis of polymer I)
Polymerization was carried out in the same manner as in Example 1-7 except that the amount of added myrcene was 0.1 g and the amount of butadiene was 99.9 g. As a result, a polymer I was obtained with a yield of 100.0 g. It was

(Example 1-10: Synthesis of polymer J)
Polymerization was carried out in the same manner as in Example 1-7 except that the amount of added myrcene was 5.0 g and the amount of butadiene was 95.0 g. As a result, a polymer J was obtained with a yield of 100.0 g. It was

(Comparative Example 1-1: Synthesis of Polymer K)
Polymerization was carried out in the same manner as in Example 1-1 except that myrcene was not added and the amount of isoprene was changed to 100 g. As a result, a polymer K was obtained with a yield of 100.0 g.

(Comparative Example 1-2: Synthesis of polymer L)
Polymerization was carried out in the same manner as in Example 1-7 except that myrcene was not added and the amount of butadiene was changed to 100 g. As a result, a polymer L was obtained in a yield of 100.0 g.

(Comparative Example 1-3: Synthesis of Polymer M)
Polymerization was carried out in the same manner as in Example 1-7 except that the amount of added myrcene was 11.0 g and the amount of butadiene was 89.0 g. As a result, a polymer M was obtained with a yield of 100.0 g. It was

Regarding the copolymers A to M obtained as described above, the microstructure of the copolymer was measured and evaluated by the following method.
<Micro structure>
Integral ratio of ¹ H-NMR spectrum (content of 1,2-vinyl bond) and ¹³ C-NMR spectrum (content ratio of cis-1,4 bond and trans-1,4 bond) of the copolymer, etc. Sought by. Table 1 shows the cis-1,4 bond content (%) in the entire unit derived from the conjugated diene compound.

<Branch index>
The obtained polymer was added to THF so that the polymer concentration in the solution would be 0.4% by mass. After standing for 24 hours, this solution was subjected to ultracentrifugation for 1 hour at a centrifugal acceleration of about 150,000 G using a stainless centrifuge tube to separate soluble and insoluble components in the solution. The supernatant liquid corresponding to the soluble component in the separated solution was collected, diluted 2-fold with THF, and FFF (field flow fraction)-MALS (multi-angle light scattering detector, Multi-Angle Light Scattering). ). AF2000 manufactured by Postnova was used as the FFF device, Dawn Heleos II manufactured by Wyatt Co. was used as the MALS detector, and PN3140 type manufactured by Postnova was used as the RI detector. At this time, the pipes of the apparatus were connected in the order of FFF device-MALS detector-RI detector.
In addition, since the radius of gyration at each point of the elution curve is obtained in the FFF-MALS measurement, a Log-Log plot (conformation plot) of the radius of gyration and the molecular weight is obtained. Assume that the polymers K and L are linear molecules, and evaluate the degree of branching by comparing the conformation plots of the polymers K and L with the conformation plot of each polymer. You can
The gyration radius Rg _{S of} each polymer (A, B, C, D, E, F) at each weight average molecular weight is compared with the gyration radius Rg _L of the polymer K at the same molecular weight, and the branching index=Rg _S / Rg _L. Similarly, comparing the radius of gyration Rg _S in each of the weight-average molecular weight of the polymer (G, H, I, J , M), the rotational radius Rg _L of the polymer L at the same molecular weight, branching index = _Rg S / Rg _L. The smaller this branch index is, the more the branch structure is developed.

<Weight average molecular weight (Mw) and molecular weight distribution (MWD (Mw/Mn))>
By gel permeation chromatography [GPC: Tosoh HLC-8220GPC/HT, column: Tosoh GMHHR-H(S)HT×2, detector: differential refractometer (RI)] based on monodisperse polystyrene, The polystyrene-reduced weight average molecular weight (Mw) and molecular weight distribution (MWD) of the copolymers A to M were determined. The measurement temperature is 40°C.

<Examples 2-1 to 2-4, Comparative example 2-1>
A rubber composition having a formulation shown in Table 2 was prepared, and vulcanized at 160° C. for 30 minutes to obtain a vulcanized composition. tan δ) was measured.

The components used in Table 2 above are as follows.
・IR2200: polyisoprene rubber, trade name "Nipol IR2200", manufactured by Zeon Corporation ・Carbon black: Asahi carbon, trade name "#80"
・Silica: Product name “Nipseal AQ” manufactured by Nippon Silica Industry Co., Ltd.
-WAX: Microcrystalline wax-Anti-aging agent: N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine, manufactured by Ouchi Shinko Chemical Industry Co., Ltd., trade name "Nocrac 6C"
-Vulcanization accelerator: N-cyclohexyl-2-benzothiazolylsulfenamide, manufactured by Ouchi Shinko Chemical Industry Co., Ltd., trade name "NOXCELLER CZ-G"

(Measurement of dynamic storage elastic modulus (E') and loss tangent (tan δ))
The loss tangent (tan δ) of the vulcanized rubber (crosslinked rubber composition) was measured at a frequency of 52 Hz, an initial strain of 10%, a measurement temperature of 60° C. and a dynamic strain of 1% using a spectrometer (dynamic viscoelasticity measurement tester) manufactured by Ueshima Seisakusho. ) And the dynamic storage elastic modulus (E′) were measured, and the value of Comparative Example 2-1 was set to 100 and displayed as an index. The smaller the index value, the lower the loss tangent (tan δ), the lower the loss of the rubber composition, and the larger the dynamic storage elastic modulus (E′), the better the steering stability.
Further, the modulus (M300) was measured according to JIS K6251:2010. M300 was obtained by the stress at the time when the elongation rate reached 300%, and was indexed with the value of Comparative Example 2-1 as 100.

From Table 1 and Table 3, it is possible to obtain a crosslinked rubber composition having an excellent balance of dynamic storage elastic modulus (E′) and loss tangent (tan δ) by using the conjugated diene-based copolymer of Example. I understood.

The present invention provides a conjugated diene-based copolymer that contributes to an improvement in the balance between the dynamic storage elastic modulus (E′) and the loss tangent (tan δ) of a rubber composition or a rubber product such as a tire. You can Further, according to the present invention, it is possible to provide a rubber composition having an excellent balance of storage elastic modulus and loss tangent and a rubber product such as a tire.

Claims (12)

Having a structural unit derived from myrcene and a structural unit derived from a conjugated diene compound,
1,4-cis content is 90% or more,
Ri der less than 10% by weight content of the constituent unit derived from myrcene,
A conjugated diene-based copolymer having a branching index of 0.70 or more and 0.98 or less . The conjugated diene-based copolymer according to claim 1, wherein the content of the constituent unit derived from myrcene is 1% by mass or less. The conjugated diene-based copolymer according to claim 1 or 2, wherein the 1,4-cis content of the conjugated diene-based copolymer is 95% or more. The conjugated diene-based copolymer according to claim 1, wherein the structural unit derived from the conjugated diene compound includes a structural unit derived from butadiene. The conjugated diene-based copolymer according to claim 1, wherein the structural unit derived from the conjugated diene compound includes a structural unit derived from isoprene. The method for producing a conjugated diene-based copolymer according to claim 1, which has a step of simultaneously reacting myrcene and a conjugated diene compound. Polymerizing myrcene to obtain a myrcene polymer, and
The method for producing a conjugated diene-based copolymer according to any one of claims 1 to 5, which has, in this order, a step of reacting the obtained myrcene polymer with a conjugated diene compound. Polymerizing myrcene to obtain a myrcene polymer,
A step of reacting the obtained myrcene polymer with a conjugated diene compound to obtain a copolymer, and
The method for producing a conjugated diene-based copolymer according to any one of claims 1 to 5, which has a step of reacting the obtained copolymer with myrcene in this order. A rubber composition comprising the conjugated diene copolymer according to any one of claims 1 to 4 and a diene rubber. The rubber composition according to claim 9, which comprises 30 parts by mass or more of the conjugated diene polymer with respect to 100 parts by mass of the rubber component containing the conjugated diene copolymer and the diene rubber. A crosslinked rubber composition obtained by crosslinking the rubber composition according to claim 9 or 10. A tire comprising the rubber composition according to claim 9 or 10 or the crosslinked rubber composition according to claim 11.