JPWO2019142501A1 - Rubber composition, tires, conveyor belts, rubber crawlers, anti-vibration devices, seismic isolation devices and hoses - Google Patents

Abstract

Provided is a rubber composition capable of producing a rubber article having high crack growth resistance and high elastic modulus at high temperature. The rubber composition contains a rubber component (a) containing a multiple copolymer (a1) having a conjugated diene unit, a non-conjugated olefin unit, and an aromatic vinyl unit, and a thermosetting resin (b). , Characterized by.

Description

The present invention relates to rubber compositions, tires, conveyor belts, rubber crawlers, vibration isolators, seismic isolation devices and hoses.

In general, rubber articles such as tires, conveyor belts, rubber crawlers, vibration isolators, seismic isolation devices, hoses, etc. are required to have high durability, and in order to meet such requirements, development of highly durable rubber materials Is desired.

As such a rubber material, the present inventors consider that a multi-component copolymer containing a conjugated diene unit, a non-conjugated olefin unit, and an aromatic vinyl unit provides durability such as crack resistance of a rubber article. It has been found that it can be improved (Patent Document 1 below).

International Publication No. 2015/190072

However, as a result of further studies by the present inventors, it was found that the rubber article using the above-mentioned multiple copolymer is not sufficient from the viewpoint of maintaining the elastic modulus at a high temperature, and there is room for improvement as a rubber material. It was.

Therefore, an object of the present invention is to provide a rubber composition capable of producing a rubber article having high crack growth resistance and high elastic modulus at high temperature.
Another object of the present invention is to provide a tire, a conveyor belt, a rubber crawler, a vibration isolator, a seismic isolation device, and a hose, which have high crack growth resistance and high elastic modulus at high temperature.

The gist structure of the present invention for solving the above problems is as follows.

The rubber composition of the present invention comprises a rubber component (a) containing a multi-element copolymer (a1) having a conjugated diene unit, a non-conjugated olefin unit, and an aromatic vinyl unit.
It is characterized by containing a thermosetting resin (b).

The tire of the present invention is characterized by using the above rubber composition.

The conveyor belt of the present invention is characterized in that the above rubber composition is used.

The rubber crawler of the present invention is characterized in that the above rubber composition is used.

The vibration isolator of the present invention is characterized in that the above rubber composition is used.

The seismic isolation device of the present invention is characterized in that the above rubber composition is used.

The hose of the present invention is characterized by using the above rubber composition.

According to the present invention, it is possible to provide a rubber composition capable of producing a rubber article having high crack growth resistance and high elastic modulus at high temperature.
Further, according to the present invention, it is possible to provide a tire, a conveyor belt, a rubber crawler, a vibration isolator, a seismic isolation device and a hose having high crack growth resistance and high elastic modulus at high temperature.

(1) Rubber Composition The rubber composition according to the embodiment of the present invention (hereinafter, may be referred to as "rubber composition of the present embodiment") has a conjugated diene unit, a non-conjugated olefin unit, and an aroma. It contains a rubber component (a) containing a multidimensional copolymer (a1) having a group vinyl unit and a thermosetting resin (b). Further, the rubber composition of the present embodiment may further contain at least one additive (d) selected from a curing agent (c), a softening agent and liquid rubber, and other components, if necessary. it can.
By containing the above-mentioned components, the rubber composition of the present embodiment has a high elastic modulus in a wide temperature range including high temperature while maintaining high crack growth resistance of the rubber article produced by using the above-mentioned components. Can be.
Therefore, according to the rubber composition of the present embodiment, it is possible to produce a rubber article having high crack growth resistance and high elastic modulus at high temperature.

Hereinafter, each component that can be contained in the rubber composition of the present embodiment will be described.

(Rubber component (a))
The rubber component (a) contained in the rubber composition of the present embodiment contains the multiple copolymer (a1). The rubber component (a) may contain other rubber components other than the multiple copolymer (a1).

<Multiple copolymer (a1)>
The multiple copolymer (a1) used in the present invention has a conjugated diene unit, a non-conjugated olefin unit, and an aromatic vinyl unit.
Here, in the present specification, the "conjugated diene unit" means a unit corresponding to a structural unit derived from a conjugated diene compound in a multi-dimensional copolymer, and the "non-conjugated olefin unit" means a multi-dimensional common weight. In the coalescence, it means a unit corresponding to a structural unit derived from a non-conjugated olefin compound, and "aromatic vinyl unit" means a unit corresponding to a structural unit derived from an aromatic vinyl compound in a multi-element copolymer. To do.
Further, in the present specification, the "conjugated diene compound" means a conjugated diene compound, and the "non-conjugated olefin compound" is an aliphatic unsaturated hydrocarbon having one carbon-carbon double bond. The above-mentioned non-conjugated compound is meant, and the "aromatic vinyl compound" means at least an aromatic compound substituted with a vinyl group and is not included in the conjugated diene compound.
In the present specification, the "multidimensional copolymer" means a copolymer obtained by polymerizing three or more kinds of monomers.

<< Conjugated diene unit >>
The multiple copolymer (a1) has a conjugated diene unit. The conjugated diene unit is usually derived from the conjugated diene compound as a monomer. Since the multiple copolymer (a1) can be polymerized using a conjugated diene compound as a monomer, it can be polymerized using a non-conjugated diene compound such as a known EPDM. In comparison, it has excellent cross-linking characteristics and filler reinforcement. Therefore, the multiple copolymer (a1) also has an advantage that the mechanical properties of the rubber composition and the rubber article produced by using the copolymer can be further improved.
The conjugated diene compound may be used alone or in combination of two or more. That is, the multiple copolymer (a1) may have one type of conjugated diene unit alone or two or more types.

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, and 2,3-dimethyl-1,3-butadiene. The conjugated diene compound as a monomer of the multiple copolymer (a1) is at least one of 1,3-butadiene and isoprene from the viewpoint of more effectively improving the crack growth resistance of the rubber composition and the rubber article. , More preferably composed of only 1,3-butadiene and isoprene, and even more preferably composed of only 1,3-butadiene. In other words, the conjugated diene unit in the multiple copolymer (a1) preferably contains at least one of 1,3-butadiene units and isoprene units, and may consist only of 1,3-butadiene units and isoprene units. More preferably, it consists of only 1,3-butadiene units.

The ratio of the conjugated diene unit in the multiple copolymer (a1) is preferably 1 mol% or more, and preferably 50 mol% or less. When the ratio of the conjugated diene unit is 1 mol% or more, a rubber composition and a rubber article having excellent elongation can be obtained, and when it is 50 mol% or less, the weather resistance of the rubber article is well maintained. Can be done. From the same viewpoint, the ratio of the conjugated diene unit in the multiple copolymer (a1) is more preferably 3 mol% or more, more preferably 40 mol% or less, and further preferably 30 mol% or less. It is more preferably 20 mol% or less, and particularly preferably 15 mol% or less.

<< Non-conjugated olefin unit >>
The multipolymer (a1) has a non-conjugated olefin unit. The non-conjugated olefin unit is usually derived from the non-conjugated olefin compound as a monomer.
The non-conjugated olefin compound may be used alone or in combination of two or more. That is, the multiple copolymer (a1) may have one type of non-conjugated olefin unit alone, or may have two or more types.

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 bivariate and 1-phenylthioethane. Alternatively, a heteroatomic substituted alkene compound such as N-vinylpyrrolidone can be mentioned. The non-conjugated olefin compound as a monomer of the multiple copolymer (a1) does not have a cyclic structure from the viewpoint of forming a crystal structure in the multiple copolymer (a1) that effectively enhances crack resistance. It is more preferable, it is more preferably α-olefin, further preferably it contains ethylene, and even more preferably it is composed of ethylene alone. In other words, the non-conjugated olefin unit in the multiple copolymer (a1) preferably does not have a cyclic structure, is more preferably an α-olefin unit, further preferably contains an ethylene unit, and only the ethylene unit. It is more preferable to consist of.

The proportion of the non-conjugated olefin unit in the multiple copolymer (a1) is preferably 40 mol% or more, and preferably 97 mol% or less. When the ratio of the non-conjugated olefin unit is 40 mol% or more, the ratio of the conjugated diene unit and the aromatic vinyl unit becomes excessively high, resulting in deterioration of weather resistance and fracture resistance (particularly breaking strength (Tb)). Deterioration can be suppressed. Further, when the ratio of the non-conjugated olefin unit is 97 mol% or less, the ratio of the conjugated diene unit and the aromatic vinyl unit becomes excessively low, resulting in deterioration of crack growth resistance due to network non-formation and with other members. It is possible to suppress the deterioration of the co-crossing property of. From the same viewpoint, the proportion of the non-conjugated olefin unit in the multiple copolymer (a1) is more preferably 45 mol% or more, further preferably 55 mol% or more, still more preferably 65 mol% or more. Further, it is more preferably 95 mol% or less, and further preferably 90 mol% or less.

<< Aromatic vinyl unit >>
The multiple copolymer (a1) has an aromatic vinyl unit. The aromatic vinyl unit is usually derived from an aromatic vinyl compound as a monomer.
The aromatic vinyl compound may be used alone or in combination of two or more. That is, the multiple copolymer (a1) may have one type of aromatic vinyl unit alone, or may have two or more types of aromatic vinyl units.

The aromatic vinyl compound preferably has a vinyl group directly bonded to the aromatic ring and 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, p-ethylstyrene and the like. Can be mentioned. The aromatic vinyl compound as a monomer of the multiple copolymer (a1) may contain styrene from the viewpoint of forming a crystal structure in the multiple copolymer (a1) that effectively enhances crack resistance. It is preferably composed only of styrene. In other words, the aromatic vinyl unit in the multiple copolymer (a1) preferably contains a styrene unit, and more preferably consists of only a styrene unit.

The ratio of the aromatic vinyl unit in the multiple copolymer (a1) is preferably 2 mol% or more, and preferably 35 mol% or less. When the ratio of the aromatic vinyl unit is 2 mol% or more, the fracture resistance at high temperature can be improved, and when it is 35 mol% or less, deterioration of fuel efficiency can be suppressed. From the same viewpoint, the ratio of the aromatic vinyl unit in the multiple copolymer (a1) is more preferably 3 mol% or more, more preferably 30 mol% or less, and more preferably 25 mol% or less. More preferably, it is 14 mol% or less.

The number of types of monomers of the multiple copolymer (a1) is not particularly limited as long as the multiple copolymer (a1) has a conjugated diene unit, a non-conjugated olefin unit, and an aromatic vinyl unit. .. The multiple copolymer (a1) may have other structural units other than the conjugated diene unit, the non-conjugated olefin unit, and the aromatic vinyl unit. However, the ratio of the other structural units in the multiple copolymer (a1) is preferably 30 mol% or less, more preferably 20 mol% or less, and 10 mol% or less from the viewpoint of obtaining a desired effect. It is more preferable to have 0 mol%, that is, it is further preferable to have no other constituent units.

The multipolymer (a1) has at least one conjugated diene unit, one non-conjugated olefin unit, and one aromatic vinyl unit. From the viewpoint of obtaining the desired effect, the multiple copolymer (a1) is polymerized using at least one kind of conjugated diene compound, one kind of non-conjugated olefin compound, and one kind of aromatic vinyl compound as a monomer. It is preferably a copolymer.
The multiple copolymer (a1) is more preferably a ternary copolymer consisting of only one kind of conjugated diene unit, one kind of non-conjugated olefin unit, and one kind of aromatic vinyl unit, and 1,3-. More preferably, it is a ternary copolymer consisting of only butadiene units, ethylene units, and styrene units. Here, it is assumed that "a kind of conjugated diene unit" includes conjugated diene units having different binding modes.

In the multiple copolymer (a1), the proportion of the conjugated diene unit is 1 to 50 mol%, the proportion of the non-conjugated olefin unit is 40 to 97 mol%, and the proportion of the aromatic vinyl unit is 2 to 35 mol. It is preferably%. In this case, the crack growth resistance and the elastic modulus at high temperature can be further improved.

It is preferable that the main chain of the multiple copolymer (a1) has only an acyclic structure. Thereby, the crack growth resistance can be further improved. In addition, NMR is used as a main measuring means for confirming whether or not the main chain of the copolymer has a cyclic structure. Specifically, when a peak derived from the cyclic structure existing in the main chain (for example, a peak appearing at 10 to 24 ppm for a three-membered ring to a five-membered ring) is not observed, the main chain of the copolymer is determined. It is shown that it consists only of a non-cyclic structure.

The multi-element copolymer (a1) preferably has a melting point of 30 to 130 ° C. as measured by a differential scanning calorimeter (DSC). When the melting point is 30 ° C. or higher, a rubber composition having high crack growth resistance and high elastic modulus can be produced in a temperature range in which crystals are present. Further, when the melting point is 130 ° C. or lower, the non-conjugated olefin unit having high crystallinity is easily melted when the rubber composition is kneaded, and the workability can be improved.
The melting point of the multi-dimensional copolymer (a1) can be measured using a differential scanning calorimeter according to JIS K 7121-1987.

The multi-element copolymer (a1) preferably has an endothermic peak energy of 10 to 150 J / g at 0 to 120 ° C. measured by DSC. When the energy of the endothermic peak is 10 J / g or more, the rigidity of the rubber article can be further increased. Further, when the energy of the endothermic peak is 150 J / g or less, deterioration of crack resistance can be suppressed, and workability can be improved when the rubber composition is kneaded.
The energy of the endothermic peak of the multi-dimensional copolymer (a1) can be measured using a differential scanning calorimeter according to JIS K 7121-1987.

The multidimensional copolymer (a1) preferably has a glass transition temperature of 0 ° C. or lower as measured by DSC. When the glass transition temperature is 0 ° C. or lower, a rubber composition having good fuel efficiency can be produced.
The glass transition temperature of the multi-dimensional copolymer (a1) can be measured using a differential scanning calorimeter according to JIS K 7121-1987.

The multi-dimensional copolymer (a1) preferably has a crystallinity of 0.5 to 50%. When the crystallinity is 0.5% or more, the rigidity of the rubber article can be further increased. Further, when the crystallinity is 50% or less, deterioration of crack resistance can be suppressed, and workability can be improved when the rubber composition is kneaded.
The crystallinity of the multi-dimensional copolymer (a1) is specifically determined by the crystal melting energy of polyethylene composed of 100% crystal components and the multi-dimensional copolymer measured by DSC in accordance with JIS K 7121-1987. It can be calculated from the ratio with the melting peak energy of.

The weight average molecular weight (Mw) of the multiple copolymer (a1) is preferably 10,000 or more, and preferably 10,000,000 or less. When the Mw of the multiple copolymer (a1) is 10,000 or more, sufficient mechanical strength as a rubber material and a rubber article can be ensured, and when it is 10,000,000 or less. , High workability can be maintained. From the same viewpoint, the Mw of the multipolymer (a1) is more preferably 100,000 or more, further preferably 150,000 or more, and 9,000,000 or less. More preferably, it is 8,000,000 or less.

The number average molecular weight (Mn) of the multiple copolymer (a1) is preferably 10,000 or more, and preferably 10,000,000 or less. When the Mn of the multiple copolymer (a1) is 10,000 or more, sufficient mechanical strength as a rubber material and a rubber article can be ensured, and when it is 10,000,000 or less. , High workability can be maintained. From the same viewpoint, the Mn of the multiple copolymer (a1) is more preferably 50,000 or more, further preferably 100,000 or more, and 9,000,000 or less. More preferably, it is 8,000,000 or less.

The molecular weight distribution (Mw / Mn) of the multiple copolymer (a1) is preferably 1.00 or more, and preferably 4.00 or less. When the molecular weight distribution of the multiple copolymer (a1) is 4.00 or less, sufficient homogeneity can be brought about in the physical properties of the multiple copolymer. From the same viewpoint, the molecular weight distribution of the multiple copolymer (a1) is more preferably 3.50 or less, and further preferably 3.00 or less. Further, the molecular weight distribution of the multi-dimensional copolymer (a1) is more preferably 1.50 or more, and further preferably 1.80 or more.
The above-mentioned weight average molecular weight, number average molecular weight and molecular weight distribution can be determined by gel permeation chromatography (GPC) using polystyrene as a standard substance.

<< Manufacturing method of multiple copolymer >>
The multiple copolymer (a1) is produced, for example, by using at least a conjugated diene compound, a non-conjugated olefin compound and an aromatic vinyl compound as monomers and carrying out a step (polymerization step) of copolymerizing them. can do. Further, in the production of the multi-element copolymer (a1), in addition to the above-mentioned polymerization step, other steps such as a coupling step and a washing step can be further carried out, if necessary. Here, in the production of the multi-element copolymer (a1), in the presence of a polymerization catalyst, it is possible to add only a non-conjugated olefin compound and an aromatic vinyl compound without adding a conjugated diene compound and polymerize them. preferable. In particular, when the polymerization catalyst composition described later is used, the conjugated diene compound is more reactive than the non-conjugated olefin compound and the aromatic vinyl compound. Therefore, in the presence of the conjugated diene compound, the non-conjugated olefin compound and / Alternatively, it tends to be difficult to polymerize the aromatic vinyl compound. Further, it tends to be difficult due to the characteristics of the catalyst to first polymerize the conjugated diene compound and then additionally polymerize the non-conjugated olefin compound and the aromatic vinyl compound.

In the polymerization step, any polymerization method such as a solution polymerization method, a suspension polymerization method, a liquid phase massive polymerization method, an emulsion polymerization method, a gas phase polymerization method, and a solid phase polymerization method can be used. When a solvent is used in the polymerization reaction, the solvent may be any solvent 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 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, when the polymerization temperature is raised, the selectivity of cis-1,4 bond in the conjugated diene unit may decrease. The pressure of the polymerization reaction is preferably in the range of 0.1 to 10.0 MPa in order to sufficiently incorporate the conjugated diene compound into the polymerization reaction system. The reaction time of the polymerization reaction can be appropriately selected depending on the conditions such as the type of polymerization catalyst and the polymerization temperature, but is preferably in the range of 1 second to 10 days, for example.
Further, in the polymerization step, the polymerization reaction may be stopped by using a polymerization terminator such as methanol, ethanol or isopropanol.

The polymerization step may be carried out in one step or in multiple steps of two or more steps. The one-step polymerization step is all kinds of monomers to be polymerized, namely conjugated diene compounds, non-conjugated olefin compounds, aromatic vinyl compounds, and other monomers, preferably conjugated diene compounds, non-conjugated. This is a step of polymerizing an olefin compound and an aromatic vinyl compound by reacting them all at once. In the multi-step polymerization step, 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 are formed. This is a step of polymerizing by performing one or more steps (second polymerization step to final polymerization step) in which the remainder of the one or two kinds of monomers is added and polymerized. In particular, in the production of a multi-element copolymer, it is preferable to carry out the polymerization step in multiple stages.

In the polymerization step, a first monomer raw material containing at least an aromatic vinyl compound and a polymerization catalyst are mixed to obtain a polymerization mixture (first step), and a conjugated diene compound and non-conjugated to the above polymerization mixture. It is preferable to carry out a step (second step) of introducing a second monomer raw material containing at least one selected from the group consisting of an olefin compound and an aromatic vinyl compound. Further, it is more preferable that the first monomer raw material does not contain a conjugated diene compound and the second monomer raw material contains a conjugated diene compound.

The first monomer raw material used in the first step may contain a non-conjugated olefin compound together with the aromatic vinyl compound. In addition, the first monomer raw material may contain the entire amount of the aromatic vinyl compound used, or may contain only a part thereof. Further, the non-conjugated olefin compound is contained in at least one of the first monomer raw material and the second monomer raw material.

The first step is preferably carried out in the reactor under the atmosphere of an inert gas, preferably nitrogen gas or argon gas. The temperature (reaction temperature) in the first step is not particularly limited, but is preferably in the range of -100 ° C to 200 ° C, and may be about room temperature. The pressure in the first step is not particularly limited, but is preferably in the range of 0.1 to 10.0 MPa in order to sufficiently incorporate the aromatic vinyl compound into the polymerization reaction system. The time (reaction time) spent in the first step can be appropriately selected depending on the conditions such as the type of polymerization catalyst and the reaction temperature. For example, when the reaction temperature is 25 to 80 ° C., it is 5 minutes. The range of ~ 500 minutes is preferable.

In the first step, as the polymerization method for obtaining the polymerization mixture, any method such as a solution polymerization method, a suspension polymerization method, a liquid phase massive polymerization method, an emulsion polymerization method, a gas phase polymerization method, and a solid phase polymerization method can be used. Can be used. When a solvent is used in the polymerization reaction, the solvent may be any solvent inactive in the polymerization reaction, and examples thereof include toluene, cyclohexanone, and normal hexane.

The second monomer raw material used in the second step is only a conjugated diene compound, only a conjugated diene compound and a non-conjugated olefin compound, only a conjugated diene compound and an aromatic vinyl compound, or a conjugated diene compound. It is preferably a non-conjugated olefin compound and an aromatic vinyl compound. When the second monomer raw material contains at least one selected from the group consisting of a non-conjugated olefin compound and an aromatic vinyl compound in addition to the conjugated diene compound, these monomer raw materials are used as a solvent or the like in advance. It may be introduced into the polymerization mixture after being mixed with the compound, or each monomer raw material may be introduced from a single state. Further, each monomer raw material may be added at the same time or sequentially. In the second step, the method of introducing the second monomer raw material into the polymerization mixture is not particularly limited, but the flow rate of each monomer raw material is controlled and continuously added to the polymerization mixture. It is preferable to do (so-called monomer ring). Here, when a monomer raw material that is a gas under the conditions of the polymerization reaction system (for example, ethylene as a non-conjugated olefin compound under the conditions of room temperature and normal pressure) is used, the polymerization reaction system is carried out at a predetermined pressure. Can be introduced in.

The second step is preferably carried out in the reactor under the atmosphere of an inert gas, preferably nitrogen gas or argon gas. The temperature (reaction temperature) in the second step is not particularly limited, but is preferably in the range of -100 ° C to 200 ° C, and may be about room temperature. When the reaction temperature is raised, the selectivity of cis-1,4 bond in the conjugated diene unit may decrease. The pressure in the second step is not particularly limited, but is preferably in the range of 0.1 to 10.0 MPa in order to sufficiently incorporate a monomer such as a conjugated diene compound into the polymerization reaction system. The time (reaction time) spent in the second step can be appropriately selected depending on the conditions such as the type of polymerization catalyst and the reaction temperature, but is preferably in the range of 0.1 hour to 10 days, for example.
Further, in the second step, the polymerization reaction may be stopped by using a polymerization terminator such as methanol, ethanol or isopropanol.

The coupling step is a step of carrying out a reaction (coupling reaction) in which at least a part (for example, a terminal) of the polymer chain of the multiple copolymer obtained in the polymerization step is modified with a coupling agent or the like. .. The coupling step is preferably performed when the polymerization reaction reaches 100%. By performing the coupling step, the number average molecular weight (Mn) of the multipolymer can be increased.

The coupling agent used in the coupling reaction is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a tin-containing compound such as bis (-1-octadecyl maleate) diocteltin (lv); 4, Examples thereof include isocyanate compounds such as 4'-diphenylmethane diisocyanate; alkoxysilane compounds such as glycidylpropyltrimethoxysilane. These may be used individually by 1 type, or may be used in combination of 2 or more type. Among these, bis (-1-octadecyl maleate) dioctelsin (IV) is preferable from the viewpoint of improving reaction efficiency and reducing gel formation.

The washing step is a step of washing the multi-dimensional copolymer obtained in the polymerization step or the coupling step. By performing the washing step, the amount of catalyst residue in the multi-component copolymer can be suitably reduced. The medium used for cleaning is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include solvents such as methanol, ethanol and isopropanol. Further, when a catalyst derived from Lewis acid is used as the polymerization catalyst, an acid (for example, hydrochloric acid, sulfuric acid, nitric acid, etc.) can be added to the above-mentioned solvent. The amount of the acid to be added should be 15 mol% or less with respect to the solvent from the viewpoint of preventing the acid from remaining in the multipolymer and adversely affecting the reaction during kneading and vulcanization. preferable.

Here, the above-mentioned polymerization step may be carried out in the presence of the first polymerization catalyst composition, the second polymerization catalyst composition, the third polymerization catalyst composition, or the fourth polymerization catalyst composition shown below. preferable. Hereinafter, the first polymerization catalyst composition, the second polymerization catalyst composition, the third polymerization catalyst composition, and the fourth polymerization catalyst composition will be described.

-First polymerization catalyst composition-
The first polymerization catalyst composition (hereinafter, also referred to as “first polymerization catalyst composition”) will be described.
As the first polymerization catalyst composition,
(A1) Component: 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 the rare earth element compound or reaction product.
Component (B1): Contains an ionic compound (B1-1) composed 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 an active halogen. Examples thereof include a polymerization catalyst composition containing at least one selected from the group consisting of at least one halogen compound (B1-3) among organic compounds.
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): The following general 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 monovalent hydrocarbons having 1 to 10 carbon atoms. It is a group or a hydrogen atom, R ³ is a monovalent 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 the periodic table. When the metal is selected from the first group of the table, a is 1 and b and c are 0, and when Y is the metal selected from the second and twelfth groups of the periodic table. , A and b are 1 and c is 0, and a, b and c are 1 when Y is a metal selected from Group 13 of the Periodic Table). including.

Since the ionic compound (B1-1) and the halogen compound (B1-3) do not have carbon atoms for supplying the component (A1), the above (A1) can be used as a carbon supply source for the component (A1). C1) Ingredients are required. Even when the polymerization catalyst composition contains the aluminoxane (B1-2), the polymerization catalyst composition can contain the component (C1). Further, the first polymerization catalyst composition may contain other components contained in a normal rare earth element compound-based polymerization catalyst composition, for example, a co-catalyst and the like.
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) that 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, a reaction of the rare earth element compound and the rare earth element compound with a Lewis base. The compound 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 rare earth element (M), that is, a compound containing a lanthanoid element composed of elements having 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. The component (A1) may be used alone or in combination of two or more.

Further, the rare earth element compound is preferably a divalent or trivalent salt or complex compound of the rare earth metal, and has one or more coordinations selected from hydrogen atom, halogen atom and organic compound residue. More preferably, it is a rare earth element compound containing children. Further, the rare earth element compound or the reaction product of the rare earth element compound and the Lewis base is described in the following general formula (II) or general formula (III):
M ¹¹ X ¹¹ 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 is an independent hydrogen atom, halogen atom, alkoxy group, thiolate group, amino group, silyl group, aldehyde residue, respectively. It is preferably represented by a ketone residue, a carboxylic acid residue, a thiocarboxylic acid residue or a phosphorus compound residue, where L ¹¹ indicates a Lewis base and w indicates 0 to 3).

As a group (ligand) bonded to the rare earth element of the above rare earth element compound, a hydrogen atom, a halogen atom, an alkoxy group (a group excluding hydrogen from the hydroxyl group of the alcohol and forming a metal alkoxide), a thiolate group ( A hydrogen-free group of the thiol group of a thiol compound, which forms a metal thiolate), an amino group (ammonia, a primary amine, or a hydrogen atom bonded to a nitrogen atom of a secondary amine was removed. It is a group and forms a metal amide.), silyl groups, aldehyde residues, ketone residues, carboxylic acid residues, thiocarboxylic acid residues or phosphorus compound residues. Specifically, hydrogen atom; 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-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-neopentylthiophenoxy group, 2-isopropyl-6-neopentylthiophenoxy group, 2,4,6-triisopropylthiophenoxy group; dimethylamino An aliphatic amino group such as a group, diethylamino group, 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-tri-tert -Arylamino group such as butylphenylamino group; bistrialkylsilylamino group such as bistrimethylsilylamino group; trimethylsilyl group, tris (trimethylsilyl) silyl group, bis (trimethylsilyl) methylsilyl group, trimethylsilyl (dimethyl) silyl group, triisopropylsilyl (Bistrimethylsilyl) A silyl group such as a silyl group; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom can be mentioned. Furthermore, residues of aldehydes such as salicylaldehyde, 2-hydroxy-1-naphthaldehyde, 2-hydroxy-3-naphthaldehyde; 2'-hydroxyacetophenone, 2'-hydroxybutyrophenone, 2'-hydroxypropiophenone and the like. Residues of hydroxyphenone; Residues of diketones such as acetylacetone, benzoylacetone, propionylacetone, isobutylacetone, valerylacetone, ethylacetylacetone;isovaleric acid, capric acid, octanoic acid, lauric acid, myristic acid, palmitic acid, Stealic acid, isostearic acid, oleic acid, phosphoric acid, cyclopentanecarboxylic acid, naphthenic acid, ethylhexanoic acid, pivalic acid, versaticic acid [trade name manufactured by Shell Chemical Co., Ltd., from a mixture of C10 monocarboxylic acid isomers Synthetic acids composed], residues of carboxylic acids such as phenylacetic acid, benzoic acid, 2-naphthoic acid, maleic acid, succinic acid; hexanethioic acid, 2,2-dimethylbutanthioic acid, decantioic acid, thiobenzoic acid, etc. Residues of thiocarboxylic acid; dibutyl phosphate, dipentyl phosphate, dihexyl phosphate, diheptyl phosphate, dioctyl phosphate, bis (2-ethylhexyl) phosphate, bis (1-methylheptyl) phosphate, dilauryl phosphate, Dioleyl Phosphonate, Diphenyl Phosphonate, Bis Phosphonate (p-Nonylphenyl), Bis Phosphonate (Polyethylene Glycol-p-Nonylphenyl), Phosphonate (Butyl) (2-Ethylhexyl), Phosphonate (1-Methylheptyl) Residues of phosphoesters such as (2-ethylhexyl), phosphate (2-ethylhexyl) (p-nonylphenyl); monobutyl 2-ethylhexylphosphonate, mono-2-ethylhexylphosphonate, mono-2-ethylhexyl phenylphosphonate Residues of phosphonic acid esters such as -2-ethylhexyl, 2-ethylhexylphosphonate mono-p-nonylphenyl, mono-2-ethylhexyl phosphonate, mono-1-methylheptyl phosphonate, mono-p-nonylphenyl phosphonate Dibutylphosphonic acid, bis (2-ethylhexyl) phosphinic acid, bis (1-methylheptyl) phosphinic acid, dilaurylphosphonic acid, diorail phosphonate, diphenylphosphonate, bis (p-nonylphenyl) phosphinic acid, butyl ( 2-Ethylhexyl) phosphonic acid, (2-ethylhexyl) (1-methylheptyl) phosphonate, (2-ethylhexyl) Syl) (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 Residues can also be mentioned.
In addition, these groups (ligands) may be used individually by 1 type, and may be used in combination of 2 or more types.

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

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

In the above general formula (IV), the amino group represented by NQ (NQ ¹ , NQ ² , and NQ ³ ) 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- Arylamino groups such as 6-neopentylphenylamino group, 2-isopropyl-6-neopentylphenylamino group, 2,4,6-tri-tert-butylphenylamino group; bistrialkylsilylamino such as bistrimethylsilylamino group Any of the groups may be used, but 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 which is a component of (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 produced.
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 (trill) borate, tetra (kisilyl) borate, (triphenyl, pentafluorophenyl) borate, [tris (pentafluorophenyl), phenyl] borate, tri Decahydride-7,8-dicarbound decaborate and the like.
On the other hand, examples of the cation include a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptatrienyl cation, a ferrosenium cation having a transition metal, and the like. Specific examples of the carbonium cation include tri-substituted carbonium cations such as triphenyl carbonium cation and tri (substituted phenyl) carbonium cation, and more specifically, as the tri (substituted phenyl) carbonyl cation, Examples thereof include a tri (methylphenyl) carbocation cation and a tri (dimethylphenyl) carbocation cation. Specific examples of ammonium cations include trialkylammonary cations such as trimethylammonium cations, triethylammonary cations, tripropylammonium cations, and tributylammonary cations (eg, tri (n-butyl) ammonium cations); N, N-dimethylanilinium. N, N-dialkylanilinium cations such as cations, N, N-diethylanilinium cations, N, N, 2,4,6-pentamethylanilinium cations; dialkylammonium cations such as diisopropylammonium cations and dicyclohexylammonium cations, etc. Can be mentioned. Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation.
Therefore, as the ionic compound (B1-1), a compound selected and combined from the above-mentioned non-coordinating anions and cations is preferable, and specifically, N, N-dimethylanilinium tetrakis (pentafluorophenyl). Borate, triphenylcarbonium tetrakis (pentafluorophenyl) borate and the like are preferable. In addition, these ionic compounds (B1-1) can 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, more preferably about 1 times mol, with respect to the component (A1). Is more preferable.

The aluminoxane (B1-2) is a compound obtained by contacting an organic aluminum compound with a condensing agent, and is, for example, a chain having a repeating unit represented by the general formula: (-Al (R') O-). Aluminoxane or cyclic aluminoxane (in the formula, R'is a monovalent hydrocarbon group having 1 to 10 carbon atoms, and some hydrocarbon groups are at least one selected from the group consisting of halogen atoms and alkoxy groups. It may be substituted, and the degree of polymerization of the repeating unit is preferably 5 or more, more preferably 10 or more). Here, as R', a methyl group, an ethyl group, a propyl group, an isobutyl group and the like are specifically mentioned, and among these, a methyl group is preferable. Examples of the organoaluminum compound used as a raw material for aluminoxane include trialkylaluminum such as trimethylaluminum, triethylaluminum, tributylaluminum and triisobutylaluminum, and a mixture thereof, 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 aluminoxane (B1-2) in the first polymerization catalyst composition is such that the element ratio Al / M of the aluminum element Al of aluminoxane to the rare earth element M constituting the component (A1) is 10 to 1, It is preferable that the value is about 000.

The halogen compound (B1-3) comprises at least one of an organic compound containing Lewis acid, a complex compound of a metal halide and a Lewis base, and an active halogen, and is, for example, a rare earth element compound or a rare earth element compound which is a component of (A1). By reacting with the reaction product with the Lewis base, a cationic transition metal compound, a halide transition metal compound, or a compound in which the transition metal center is insufficiently charged can be produced. The total content of the halogen compound (B1-3) in the first polymerization catalyst composition is preferably 1 to 5 times mol with respect to the component (A1).

As the Lewis acid, a boron-containing halogen compound such as B (C ₆ F ₅ ) _{3 and} an aluminum-containing halogen compound such as Al (C ₆ F ₅ ) ₃ can be used, and Group 3 and Group 3 in the periodic table. Halogen compounds containing elements belonging to Group 4, Group 5, Group 6 or Group 8 can also be used. Preferred are aluminum halides or organometallic halides. Further, as the halogen element, chlorine or bromine is preferable.
Specific examples of the Lewis acid include methylaluminum dibromide, methylaluminum dichloride, ethylaluminum dibromide, ethylaluminum dichloride, butylaluminum dibromide, butylaluminum dichloride, dimethylaluminum bromide, dimethylaluminum chloride, diethylaluminum bromide, and diethyl. Aluminum chloride, dibutylaluminum bromide, dibutylaluminum chloride, methylaluminum sesquibromide, methylaluminum sesquichloride, ethylaluminum sesquibromide, ethylaluminum sesquichloride, dibutyltin dichloride, aluminum tribromide, antimony trichloride, antimone pentachloride, phosphorus trichloride , Phosphorus pentachloride, tin tetrachloride, titanium tetrachloride, tungsten hexachloride, etc. Among these, diethylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, diethylaluminum bromide, ethylaluminum sesquibromide, ethylaluminum di. Chlorides are particularly preferred.

Examples of the metal halide constituting 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 chloride, barium chloride, barium bromide, barium iodide, zinc chloride, zinc bromide, zinc iodide, cadmium chloride, cadmium bromide, cadmium iodide, mercury chloride, mercury bromide, mercury iodide, manganese chloride, Manganese bromide, manganese iodide, renium chloride, renium bromide, renium iodide, copper chloride, copper bromide, copper iodide, silver chloride, silver bromide, silver iodide, gold chloride, gold iodide, bromide Gold and the like are mentioned, and among these, magnesium chloride, calcium chloride, barium chloride, manganese chloride, zinc chloride and copper chloride are preferable, and magnesium chloride, manganese chloride, zinc chloride and copper chloride are 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, tricredil phosphate, triethylphosphine, tributylphosphine, triphenylphosphine, diethylphosphinoetan, diphenylphosphinoetan, acetylacetone, benzoylacetone. , Propionyl acetone, valeryl acetone, ethyl acetyl acetone, methyl acetoacetate, ethyl acetoacetate, phenyl acetoacetate, dimethyl malonate, diethyl malonate, diphenyl malonate, acetic acid, octanic acid, 2-ethylhexanoic acid, oleic acid, stea Acids, benzoic acid, naphthenic acid, versatic acid, triethylamine, N, N-dimethylacetoamide, tetrahydrofuran, diphenyl ether, 2-ethylhexyl alcohol, oleyl alcohol, stearyl alcohol, phenol, benzyl alcohol, 1-decanol, lauryl alcohol and the like can be mentioned. Of these, tri-2-ethylhexyl phosphate, tricredyl phosphate, acetylacetone, 2-ethylhexanoic acid, versatic acid, 2-ethylhexyl alcohol, 1-decanol, and lauryl alcohol are preferable.

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

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

The component (C1) used in the first polymerization catalyst composition has the following general 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 monovalent hydrocarbons having 1 to 10 carbon atoms. It is a group or a hydrogen atom, R ³ is a monovalent 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 the periodic table. When the metal is selected from the first group of the table, a is 1 and b and c are 0, and when Y is the metal selected from the second and twelfth groups of the periodic table. , A and b are 1 and c is 0, and a, b and c are 1 when Y is a metal selected from Group 13 of the Periodic Table). The following general formula (V):
AlR ¹ R ² R ³ ... (V)
(In the formula, R ¹ and R ² are monovalent hydrocarbon groups or hydrogen atoms having 1 to 10 carbon atoms, R 3 is a monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ¹ and R ^{2 are used.} , R ³ may be the same or different from each other), preferably an organoaluminum compound.

Examples of the organic aluminum compound represented by the general formula (V) include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, and tri-t-butylaluminum. 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, hydrogen Diisohexyl aluminum chemicals, dioctyl aluminum hydrides, diisooctyl aluminum hydrides; ethyl aluminum dihydrides, n-propyl aluminum dihydrides, isobutylaluminum dihydrides, etc., among these, triethylaluminum, triisobutylaluminum, etc. Diethylaluminum hydride and diisobutylaluminum hydride are preferred. The organometallic compound as the component (C1) described above may be used alone or in combination of two or more.
The content of the organometallic compound in the first polymerization catalyst composition is preferably 1 to 50 times mol, more preferably about 10 times mol, with respect to the component (A1).

The addition of the additive (D1), which can be an anionic ligand, is preferable because it has the effect of enabling the synthesis of a multipolymer with a higher cis-1,4 bond content in a high yield. ..

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 any of an OH group, an NH group, and an SH group.

Specific examples of the compound have 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-Butyl-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, di Examples include, but are not limited to, myristyl thiodipropionate. For example, as hindered phenol-based ones, 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-di-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 and the like can be mentioned. In addition, examples of the hydrazine system include N, N'-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine.

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

Examples of those having an SH group include aliphatic thiols, aromatic thiols and the like, as well as compounds represented by the following general formulas (VI) and (VII).

（式中、Ｒ¹、Ｒ²及びＲ³はそれぞれ独立して−Ｏ−Ｃ_jＨ_2j+1、−（Ｏ−Ｃ_kＨ_2k−）_a−Ｏ−Ｃ_mＨ_2m+1又は−Ｃ_nＨ_2n+1で表され、ｊ、ｍ及びｎは、それぞれ独立して０〜１２の整数であり、ｋ及びａは、それぞれ独立して１〜１２の整数であり、Ｒ⁴は、炭素数１〜１２であって、直鎖、分岐、若しくは環状の、飽和若しくは不飽和の、アルキレン基、シクロアルキレン基、シクロアルキルアルキレン基、シクロアルケニルアルキレン基、アルケニレン基、シクロアルケニレン基、シクロアルキルアルケニレン基、シクロアルケニルアルケニレン基、アリーレン基又はアラルキレン基である。）
一般式（ＶＩ）で示されるものの具体例としては、３−メルカプトプロピルトリメトキシシラン、３−メルカプトプロピルトリエトキシシラン、３−メルカプトプロピルメチルジメトキシシラン、（メルカプトメチル）ジメチルエトキシシラン、メルカプトメチルトリメトキシシラン等が挙げられる。

(In the equation, R ¹ , R ² and R ³ are independently _{−OC j} H _{2j + 1} , − ( _{OC k} H _2k −) _a −OC _m H _{2m + 1} or −C. represented by _n H _{2n + 1} , j, m and n are independently integers 0 to 12, k and a are independently integers 1 to 12, and R ⁴ is carbon. Numbers 1-12, linear, branched, or cyclic, saturated or unsaturated, alkylene group, cycloalkylene group, cycloalkylalkylene group, cycloalkenylalkylene group, alkenylene group, cycloalkenylene group, cycloalkylalkenylene Group, cycloalkenyl alkenylene group, arylene group or aralkylene group.)
Specific examples of those represented by the general formula (VI) include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, (mercaptomethyl) dimethylethoxysilane, and mercaptomethyltrimethoxy. Examples include silane.

（式中、Ｗは、−ＮＲ⁸−、−Ｏ−又は−ＣＲ⁹Ｒ¹⁰−（ここで、Ｒ⁸及びＲ⁹は−Ｃ_pＨ_2p+1であり、Ｒ¹⁰は、−Ｃ_qＨ_2q+1であり、ｐ及びｑは、それぞれ独立して０〜２０の整数である。）で表され、Ｒ⁵及びＲ⁶は、それぞれ独立して−Ｍ−Ｃ_rＨ_2r−（ここで、Ｍは−Ｏ−又は−ＣＨ₂−であり、ｒは１〜２０の整数である。）で表され、Ｒ⁷は、−Ｏ−Ｃ_jＨ_2j+1、−（Ｏ−Ｃ_kＨ_2k−）_a−Ｏ−Ｃ_mＨ_2m+1又は−Ｃ_nＨ_2n+1で表され、ｊ、ｍ及びｎは、それぞれ独立して０〜１２の整数であり、ｋ及びａは、それぞれ独立して１〜１２の整数であり、Ｒ⁴は、炭素数１〜１２であって、直鎖、分岐、若しくは環状の、飽和若しくは不飽和の、アルキレン基、シクロアルキレン基、シクロアルキルアルキレン基、シクロアルケニルアルキレン基、アルケニレン基、シクロアルケニレン基、シクロアルキルアルケニレン基、シクロアルケニルアルケニレン基、アリーレン基又はアラルキレン基である。）

(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 _{It is 2q + 1} , and p and q are independently represented by integers 0 to 20.), And R ⁵ and R ⁶ are independently _{−MC r} H _2r − (where, respectively). , M is −O− or −CH ₂₋ , and r is an integer of 1 to 20), and R ⁷ is _{−OC j} H _{2j + 1} , − (OC _k H. _2k −) _a −O−C _m H _{2m + 1} or −C _n H _{2n + 1} , j, m and n are independently integers from 0 to 12, and k and a are respectively. Independently an integer of 1-12, R ⁴ has 1-12 carbon atoms and is a linear, 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 aralkylene group.)

Specific examples of those represented by the general formula (VII) are 3-mercaptopropyl (ethoxy) -1,3-dioxa-6-methylaza-2-silacyclooctane and 3-mercaptopropyl (ethoxy) -1,3-. Examples thereof include dioxa-6-butylaza-2-silacyclooctane and 3-mercaptopropyl (ethoxy) -1,3-dioxa-6-dodecylaza-2-silacyclooctane.

Further, as the additive (D1), an anionic tridentate ligand precursor represented by the following general formula (VIII) can be preferably used.
E ^1- T ^1- X-T ^2- E ² ... (VIII)
(In the equation, X represents an anionic electron donating group containing a coordination atom selected from the group 15 atoms of the periodic table, and E ¹ and E ² are independent of the group 15 of the periodic table. And a neutral electron donating group containing a coordination atom selected from Group 16 atoms, where T ¹ and T ² indicate a bridging group that bridges X with E ¹ and E ² , respectively).

The additive (D1) is preferably added in an amount of 0.01 to 10 mol, more preferably 0.1 to 1.2 mol, based on 1 mol of the rare earth element compound. When the addition amount is 0.1 mol or more, the polymerization reaction of the monomer proceeds sufficiently. The amount added is preferably equivalent to that of the rare earth element compound (1.0 mol), but an excessive amount may be added. When the addition amount is 1.2 mol or less, the loss of the reagent is small, which is preferable.

In the above general 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 coordination atom include nitrogen N, phosphorus P, oxygen O, and sulfur S, 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 is a diarylphosphino group such as a diphenylphosphino group or a ditrilphosphino group. A dialkylphosphino group such as a dimethylphosphino group or a diethylphosphino group; an alkylarylphosphino group such as a methylphenylphosphino group is exemplified, and a diarylphosphino group is preferable.

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

When the coordinating 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, or a butoxy group; Examples thereof include an aryloxy group such as a phenoxy group and a 2,6-dimethylphenoxy group.

When the coordination atom contained in E ¹ and E ² is S, the neutral electron donating group E ¹ or E ² is an alkyl thio group such as a methyl thio group, an ethyl thio group, a propyl thio group, or a butyl thio group; Examples thereof include arylthio groups such as phenylthio groups and trilthio groups.

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

The cross-linking groups T ¹ and T ² may be any group capable of cross-linking X with E ¹ and E ^2, and an arylene group which may have a substituent on the aryl ring is exemplified. 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 trill 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 preferably exemplified.

-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 includes the following general formula (IX):

（式中、Ｍは、ランタノイド元素、スカンジウム又はイットリウムを示し、ＣｐＲは、それぞれ独立して無置換若しくは置換インデニルを示し、Ｒ^a〜Ｒは、それぞれ独立して炭素数１〜３のアルキル基又は水素原子を示し、Ｌは、中性ルイス塩基を示し、ｗは、０〜３の整数を示す。）で表されるメタロセン錯体、及び下記一般式（Ｘ）：

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

（式中、Ｍは、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^Rは、それぞれ独立して無置換若しくは置換インデニルを示し、Ｘ’は、水素原子、ハロゲン原子、アルコキシ基、チオラート基、アミノ基、シリル基又は炭素数１〜２０の一価の炭化水素基を示し、Ｌは、中性ルイス塩基を示し、ｗは、０〜３の整数を示す。）で表されるメタロセン錯体、並びに下記一般式（ＸＩ）：

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

（式中、Ｍは、ランタノイド元素、スカンジウム又はイットリウムを示し、ＣｐＲ’は、無置換若しくは置換シクロペンタジエニル、インデニル又はフルオレニルを示し、Ｘは、水素原子、ハロゲン原子、アルコキシ基、チオラート基、アミノ基、シリル基又は炭素数１〜２０の一価の炭化水素基を示し、Ｌは、中性ルイス塩基を示し、ｗは、０〜３の整数を示し、［Ｂ］−は、非配位性アニオンを示す。）で表されるハーフメタロセンカチオン錯体よりなる群から選択される少なくとも１種類の錯体を含む重合触媒組成物が挙げられる。
第二重合触媒組成物は、更に、通常のメタロセン錯体を含む重合触媒組成物に含有される他の成分、例えば、助触媒等を含んでいてもよい。ここで、メタロセン錯体は、１つ又は２つ以上のシクロペンタジエニル又はその誘導体が中心金属に結合した錯体化合物であり、特に、中心金属に結合したシクロペンタジエニル又はその誘導体が１つであるメタロセン錯体を、ハーフメタロセン錯体と称することがある。
なお、重合反応系において、第二重合触媒組成物に含まれる錯体の濃度は０．１〜０．０００１ｍｏｌ／Ｌの範囲であることが好ましい。

(In the formula, M represents a lanthanoid element, scandium or yttrium, CpR'represents an unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl, and X is a hydrogen atom, a halogen atom, an alkoxy group, a thiolate group, It represents an amino group, a silyl group or a monovalent hydrocarbon group having 1 to 20 carbon atoms, L represents a neutral Lewis base, w represents an integer of 0 to 3, and [B]-is non-coordinating. Examples thereof include a polymerization catalyst composition containing at least one complex selected from the group consisting of half metallocene cation complexes represented by (showing a position anion).
The second polymerization catalyst composition may further contain other components contained in the polymerization catalyst composition containing a normal metallocene complex, for example, a co-catalyst and the like. Here, the metallocene complex is a complex compound in which one or more cyclopentadienyl or a derivative thereof is bonded to a central metal, and in particular, one cyclopentadienyl or a derivative thereof is bonded to the central metal. A certain metallocene complex may be referred to as a half metallocene complex.
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 general formulas (IX) and (X), Cp ^R in the formula is unsubstituted indenyl or substituted indenyl. Cp ^R with an indenyl ring as the basic skeleton can be represented by C ₉ H _7-x R _x or C ₉ H _11-x R _x . Here, X is an integer of 0 to 7 or 0 to 11. Further, it is preferable that R is independently a hydrocarbyl group or a metalloid group. The number of carbon atoms of the hydrocarbyl group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 8. Specific preferred 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 gelmil Ge, stanyl 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, 2-methylindenyl and the like. The two Cp ^Rs in the general formulas (IX) and (X) may be the same or different from each other.

In the half-metallocene cation complex represented by the general formula (XI), Cp R ^'is in the formula, an unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl, among these, unsubstituted or substituted indenyl Is preferable.

In the general formula (XI), 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 to 5. Further, it is preferable that R is independently a hydrocarbyl group or a metalloid group. The number of carbon atoms of the hydrocarbyl group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 8. Specific preferred 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 gelmil Ge, stanyl 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. A cyclopentadienyl ring as Cp R ^'having a basic skeleton, specifically, are exemplified as follows.

（式中、Ｒは水素原子、メチル基又はエチル基を示す。）

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

In the general formula (XI), Cp R ^'is the basic skeleton of the above indenyl ring, is similarly defined as Cp ^R in the general formula (IX) and (X), and preferred examples are also the same.

In the general formula (XI), Cp ^{R 'having} a basic skeleton of the above fluorenyl ring 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 R is independently a hydrocarbyl group or a metalloid group. The number of carbon atoms of the hydrocarbyl group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 8. Specific preferred 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 gelmil Ge, stanyl 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 the general formulas (IX), (X) and (XI) is a lanthanoid element, scandium or yttrium. The lanthanoid element includes 15 elements having atomic numbers 57 to 71, and any of these may be used. Preferable examples of the central metal M include samarium Sm, neodymium Nd, praseodymium Pr, gadolinium Gd, cerium Ce, holmium Ho, scandium Sc and yttrium Y.

The metallocene complex represented by the general formula (IX) contains a silylamide ligand [-N (SiR ₃ ) ₂ ]. The R groups ( ^{Ra to} R ^f in the general formula (IX)) contained in the silylamide ligand are independently alkyl groups having 1 to 3 carbon atoms or hydrogen atoms. Further, it is preferable that at least one of R ^{a to} R ^f is a hydrogen atom. By making at least one of R ^{a to} R ^f a hydrogen atom, the synthesis of the catalyst becomes easy and the bulkiness around silicon becomes low, so that a non-conjugated olefin compound or an aromatic vinyl compound is introduced. It becomes 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, as the alkyl group, a methyl group is preferable.

The metallocene complex represented by the general formula (X) include silyl ligand [-SiX _'3]. 'X contained in _[3 silyl ligand -SiX]' is X as well as being defined group of the general formula (XI) to be described below, is the same preferable groups.

In the general 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 monovalent hydrocarbon group having 1 to 20 carbon atoms. Here, the halogen atom represented by X may be any of a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, but a chlorine atom or a bromine atom is preferable.

In the general formula (XI), the alkoxy group represented by X includes 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 Examples thereof include aryloxy groups such as −neopentylphenoxy group and 2-isopropyl-6-neopentylphenoxy group, and among these, 2,6-di-tert-butylphenoxy group is preferable.

In the general formula (XI), examples of the thiolate group represented by X include fats such as thiomethoxy group, thioethoxy group, thiopropoxy group, thion-butoxy group, thioisobutoxy group, thiosec-butoxy group and thiotert-butoxy group. Group thiolate groups; thiophenoxy group, 2,6-di-tert-butylthiophenoxy group, 2,6-diisopropylthiophenoxy group, 2,6-dineopentylthiophenoxy group, 2-tert-butyl-6-isopropyl Examples thereof include arylthiolate groups such as a thiophenoxy group, a 2-tert-butyl-6-neopentylthiophenoxy group, a 2-isopropyl-6-neopentylthiophenoxy group and a 2,4,6-triisopropylthiophenoxy group. Of these, 2,4,6-triisopropylthiophenoxy groups are preferred.

In the general 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, a 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- Arylamino groups such as 6-neopentylphenylamino group and 2,4,6-tri-tert-butylphenylamino group; bistrialkylsilylamino groups such as bistrimethylsilylamino group are mentioned, and among these, bistrimethylsilylamino Groups are preferred.

In the general 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. Among these, a tris (trimethylsilyl) silyl group is preferable.

Further, in the general formula (XI), as the monovalent 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, and the like. Linear or branched aliphatic hydrocarbon groups such as isobutyl group, sec-butyl group, tert-butyl group, neopentyl group, hexyl group and octyl group; aromatic hydrocarbon groups such as phenyl group, trill group and naphthyl group. In addition to an aralkyl group such as a benzyl group; a hydrocarbon group containing a silicon atom such as a trimethylsilylmethyl group and a bistrimethylsilylmethyl group can be mentioned. Among these, a methyl group, an ethyl group, an isobutyl group and a trimethylsilylmethyl group can be mentioned. Etc. are preferable.

In the general formula (XI), as X, a bistrimethylsilylamino group or a monovalent hydrocarbon group having 1 to 20 carbon atoms is preferable.

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

The metallocene complex represented by the general formulas (IX) and (X) and the half metallocene cation complex represented by the general formula (XI) are further 0 to 3, preferably 0 to 1 neutral Lewis. Contains base L. Here, examples of the neutral Lewis base L include tetrahydrofuran, diethyl ether, dimethylaniline, trimethylphosphine, lithium chloride, neutral olefins, neutral diolefins and the like. Here, when the complex 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 general formulas (IX) and (X) and the half metallocene cation complex represented by the general formula (XI) may exist as a monomer and are dimers. Or it may exist as a multimer of more than that.

The metallocene complex represented by the above general formula (IX) is, for example, a lanthanoid trishalide, a scandium trishalide or an ittrium trishalide in a solvent, an indenyl salt (for example, a potassium salt or a lithium salt) and a bis (trialkylsilyl). It can be obtained by reacting with an amine salt (for example, a 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 about several hours to several tens of hours. The reaction solvent is not particularly limited, but is preferably a solvent that dissolves the raw material and the product, and for example, toluene may be used. An example of the reaction for obtaining the metallocene complex represented by the general formula (IX) is shown below.

（式中、Ｘ’’はハライドを示す。）

(In the formula, X'' indicates a halide.)

The metallocene complex represented by the general formula (X) is, for example, a lanthanoid trishalide, a scandium trishalide or an yttrium trishalide in a solvent, an indenyl salt (for example, a potassium salt or a lithium salt) and a silyl salt (for example, potassium). It can be obtained by reacting with a 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 about several hours to several tens of hours. The reaction solvent is not particularly limited, but is preferably a solvent that dissolves the raw material and the product, and for example, toluene may be used. An example of the reaction for obtaining the metallocene complex represented by the general formula (X) is shown below.

（式中、Ｘ’’はハライドを示す。）

(In the formula, X'' indicates a halide.)

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

In this case, the compound represented by the general formula (XII), M is a lanthanoid element, scandium or yttrium, Cp R ^'are each independently an unsubstituted 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 monovalent hydrocarbon group having 1 to 20 carbon atoms, L represents a neutral Lewis base, and w represents a neutral Lewis base. Indicates an integer from 0 to 3. Further, the formula [A] ⁺ [B] ^- in the ionic compound represented by, [A] ⁺ represents a cation, [B] ^- it is 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, a ferrosenium cation having a transition metal, and the like. Examples of the carbocation cation include a tri-substituted carbonium cation such as a triphenyl carbonium cation and a tri (substituted phenyl) carbonium cation, and the tri (substituted phenyl) carbonyl cation is specifically a tri (methylphenyl) cation. ) Carbonyl cation and the like. Examples of the amine cation include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, and tributylammonium cation; N, N-dimethylanilinium cation, N, N-diethylanilinium cation, N, N, N, N-dialkylanilinium cations such as 2,4,6-pentamethylanilinium cations; dialkylammonium cations such as diisopropylammonium cations and dicyclohexylammonium cations can be mentioned. 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 carbocation cations are preferable, and N, N-dialkylanilinium cations are particularly preferable.

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

The structures of the metallocene complex represented by the general formulas (IX) and (X) and the half metallocene cation complex represented by the general 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 co-catalysts in the polymerization catalyst composition containing a normal metallocene complex. Preferred examples of the co-catalyst include aluminoxane, organoaluminum compounds, and the above-mentioned ionic compounds. These co-catalysts may be used alone or in combination of two or more.

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

On the other hand, as the organic aluminum compound, the general formula AlRR'R'' (in the formula, R and R'are independently monovalent hydrocarbon groups having 1 to 10 carbon atoms, halogen atoms, or hydrogen atoms. , R'' is a monovalent hydrocarbon group having 1 to 10 carbon atoms), and an organic aluminum compound represented by the above 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 among these, trialkylaluminum is preferable. Further, examples of the trialkylaluminum include triethylaluminum and triisobutylaluminum. The content of the organoaluminum compound in the above-mentioned polymerization catalyst composition is preferably 1 to 50 times mol, more preferably about 10 times mol, with respect to the metallocene complex.

Further, in the polymerization catalyst composition, the metallocene complex represented by the general formulas (IX) and (X) and the half metallocene cation complex represented by the general formula (XI) are used as appropriate cocatalysts, respectively. By combining them, 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, as a rare earth element-containing compound, the following general formula (XIII):
R _a MX _b QY _b ... (XIII)
(In the formula, 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. It represents 20 monovalent hydrocarbon groups, X is μ-coordinated to M and Q, Q is a Group 13 element of the Periodic Table, and Y is independently one of 1 to 20 carbon atoms. Examples thereof include a polymerization catalyst composition containing a metallocene-based composite catalyst representing a valent hydrocarbon group or hydrogen atom, in which Y is coordinated to Q, and a and b are 2).

In a preferred example of the metallocene-based composite catalyst, the following general formula (XIV):

（式中、Ｍ¹は、ランタノイド元素、スカンジウム又はイットリウムを示し、ＣｐＲは、それぞれ独立して無置換若しくは置換インデニルを示し、Ｒ^A及びＲ^Bは、それぞれ独立して炭素数１〜２０の一価の炭化水素基を示し、該Ｒ^A及びＲ^Bは、Ｍ¹及びＡｌにμ配位しており、Ｒ^C及びＲ^Dは、それぞれ独立して炭素数１〜２０の一価の炭化水素基又は水素原子を示す）で表されるメタロセン系複合触媒が挙げられる。

(Wherein, M ¹ is a lanthanoid element, scandium or yttrium, CpR is independently a non-substituted or substituted indenyl, R ^A and R ^B are, one independently carbon atoms 1 to 20 indicates the valency of the hydrocarbon group, the R ^a and R ^B are coordinated μ to M ¹ and Al, R ^C and R ^D are each independently a monovalent hydrocarbon having 1 to 20 carbon atoms Examples thereof include metallocene-based composite catalysts represented by (indicating a group or a hydrogen atom).

By using the above-mentioned metallocene-based composite catalyst, a multidimensional copolymer can be produced. Further, by using the above-mentioned metallocene-based composite catalyst, for example, a catalyst that is previously combined with an aluminum catalyst, it is possible to reduce or eliminate the amount of alkylaluminum used in the synthesis of multiple copolymers. If a conventional catalyst system is used, it is necessary to use a large amount of alkylaluminum at the time of synthesizing the multiple copolymer. For example, in the conventional catalyst system, it is necessary to use alkylaluminum of 10 molar equivalents or more with respect to the metal catalyst, but in the case of the metallocene-based composite catalyst, adding alkylaluminum of about 5 molar equivalents is excellent. Catalytic action is exhibited.

In the metallocene-based composite catalyst, the metal M in the general formula (XIII) is a lanthanoid element, scandium or yttrium. The lanthanoid element includes 15 elements having atomic numbers 57 to 71, and any of these may be used. Preferable 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 general formula (XIII), R is an unsubstituted indenyl or a substituted indenyl, respectively, and the R is coordinated to the metal M. Specific examples of the substituted indenyl include 1,2,3-trimethylindenyl group, heptamethylindenyl group, 1,2,4,5,6,7-hexamethylindenyl group and the like. ..
In the above general formula (XIII), Q represents an element of Group 13 of the periodic table, and specific examples thereof include boron, aluminum, gallium, indium, and thallium.

In the above general formula (XIII), X independently represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, and X is μ-coordinated to M and Q. Here, as the monovalent hydrocarbon group having 1 to 20 carbon atoms, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a dodecyl group and a tridecyl group. , Tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, stearyl group and the like. The μ coordination is a coordination mode having a crosslinked structure.

In the above general formula (XIII), Y independently represents a monovalent hydrocarbon group or a hydrogen atom having 1 to 20 carbon atoms, and Y is coordinated with Q. Here, as the monovalent hydrocarbon group having 1 to 20 carbon atoms, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a dodecyl group and a tridecyl group. , Tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, stearyl group and the like.

In the above general formula (XIV), the metal M ¹ is a lanthanoid element, scandium or yttrium. The lanthanoid element includes 15 elements having 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 ittrium Y.

In the above general formula (XIV), Cp ^R is an unsubstituted indenyl or a 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 R is independently a hydrocarbyl group or a metalloid group. The number of carbon atoms of the hydrocarbyl group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 8. Specific preferred 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 gelmil Ge, stanyl 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, 2-methylindenyl and the like. The two Cp ^Rs in the general formula (XIV) may be the same or different from each other.

In the general formula (XIV), R ^A and R ^B are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms, said R ^A and R ^B, M ¹ and μ coordinated to Al doing. Here, the monovalent hydrocarbon group having 1 to 20 carbon atoms includes a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a dodecyl group and a tridecyl group. , Tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, stearyl group and the like. The μ coordination is a coordination mode having a crosslinked structure.
In the above general formula (XIV), ^RC and ^RD are independently monovalent hydrocarbon groups or hydrogen atoms having 1 to 20 carbon atoms. Here, the monovalent hydrocarbon group having 1 to 20 carbon atoms includes a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a dodecyl group and a tridecyl group. , Tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, stearyl group and the like.
The metallocene-based composite catalyst is, for example, in a solvent having the following general formula (XV):

（式中、Ｍ²は、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^Rは、それぞれ独立して無置換若しくは置換インデニルを示し、Ｒ^E〜Ｒ^Jは、それぞれ独立して炭素数１〜３のアルキル基又は水素原子を示し、Ｌは、中性ルイス塩基を示し、ｗは、０〜３の整数を示す）で表されるメタロセン錯体を、ＡｌＲ^KＲ^LＲ^Mで表される有機アルミニウム化合物と反応させることで得られる。なお、反応温度は室温程度にすればよいので、温和な条件で製造することができる。また、反応時間は任意であるが、数時間〜数十時間程度である。反応溶媒は特に限定されないが、原料及び生成物を溶解する溶媒であることが好ましく、例えばトルエンやヘキサンを用いればよい。なお、上記メタロセン系複合触媒の構造は、１Ｈ−ＮＭＲやＸ線構造解析により決定することが好ましい。

(In the formula, M ² represents a lanthanoid element, scandium or yttrium, Cp ^R independently represents an unsubstituted or substituted indenyl, and R ^{E to} R ^J each independently have 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 is 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 about several hours to several tens of hours. The reaction solvent is not particularly limited, but is preferably a solvent that dissolves the raw material and the product, and for example, toluene or hexane may be used. The structure of the metallocene-based composite catalyst is preferably determined by 1H-NMR or X-ray structure analysis.

In the metallocene complex represented by the general formula (XV), Cp ^R is an unsubstituted indenyl or a substituted indenyl, and is synonymous with Cp ^R in the general formula (XIV). Further, in the above general 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 above general formula (XIV).

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

The metallocene complex represented by the above general formula (XV) further contains 0 to 3, preferably 0 to 1 neutral Lewis bases L. Here, examples of the neutral Lewis base L include tetrahydrofuran, diethyl ether, dimethylaniline, trimethylphosphine, lithium chloride, neutral olefins, neutral diolefins and the like. Here, when the complex 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 general formula (XV) may exist as a monomer, or may exist as a dimer or a multimer of more than that.

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 hydrogen group or a hydrogen atom, R ^M is a monovalent hydrocarbon group having 1 to 20 carbon atoms, provided that, R ^M may be the same or different and the R ^K or R ^L. The monovalent hydrocarbon group having 1 to 20 carbon atoms includes a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a dodecyl group, a tridecyl group and a tetradecyl group. , Pentadecyl group, hexadecyl group, heptadecyl group, stearyl group and the like.

Specific examples of the organic aluminum compound include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, tripentylaluminum, and tri. Hexyl aluminum, tricyclohexyl aluminum, trioctyl aluminum; diethylaluminum hydride, di-n-propyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl aluminum hydride, dihexyl aluminum hydride, diisohexyl aluminum hydride , Dioctyl aluminum hydride, Diisooctyl aluminum hydride; ethylaluminum dihydride, n-propylaluminum dihydride, isobutylaluminum dihydride, etc. Among these, triethylaluminum, triisobutylaluminum, diethylaluminum hydride, etc. Diisobutylaluminum 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-based composite catalyst is preferably 1 to 50 times mol, more preferably about 10 times mol, with respect to the metallocene complex.

The third polymerization catalyst composition may contain the metallocene-based composite catalyst and a boron anion, and other components contained in the polymerization catalyst composition containing a normal metallocene-based catalyst, such as a co-catalyst, etc. Is preferably included. 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, similarly to the metallocene-based composite catalyst, since it further contains a boron anion, the content of each monomer component in the polymer can be arbitrarily controlled. It becomes.

Specific examples of the boron anion constituting the two-component catalyst in the third polymerization catalyst composition include tetravalent boron anion. For example, tetraphenyl borate, tetrakis (monofluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis (pentafluorophenyl) borate, tetrakis (tetrafluoromethyl). Phenyl) borate, tetra (trill) borate, tetra (kisilyl) borate, (triphenyl, pentafluorophenyl) borate, [tris (pentafluorophenyl), phenyl] borate, tridecahydride-7,8-dicarbundecaborate Etc., and among these, tetrakis (pentafluorophenyl) borate is preferable.

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

If a boron anion is present in the reaction system for reacting the metallocene complex represented by the general formula (XV) with the organoaluminum compound, the metallocene-based composite catalyst of the general formula (XIV) can be synthesized. Can not. Therefore, in order 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 it with a boron anion.

As the co-catalyst that can be used in the third polymerization catalyst composition, for example, in addition to the above-mentioned organoaluminum compound represented by AlRKRLRM, aluminoxane and the like are preferably mentioned. As the aluminoxane, an alkylaluminoxane is preferable, and examples thereof include methylaluminoxane (MAO) and modified methylaluminoxane. Further, as the modified methylaluminoxane, MMAO-3A (manufactured by Tosoh Finechem Co., Ltd.) or the like is preferable. In addition, these aluminoxans may be used individually by 1 type, and may be used in combination of 2 or more types.

− 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 is
-Rare earth element compounds (hereinafter, also referred to as "(A2) component") and
-A compound selected from the group consisting of substituted or unsubstituted cyclopentadiene, substituted or unsubstituted indene (compound having an indenyl group), and substituted or unsubstituted fluorene (hereinafter, also referred to as "(B2) component"). When,
Is required to include.
This fourth polymerization catalyst composition is
-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 high solubility in an aliphatic hydrocarbon, and preferably becomes a homogeneous solution in the aliphatic hydrocarbon. Here, examples of the aliphatic hydrocarbon include hexane, cyclohexane, pentane and the like.
The fourth polymerization catalyst composition preferably does not contain aromatic hydrocarbons. Here, examples of the aromatic hydrocarbon include benzene, toluene, xylene and the like.
In addition, "does not contain aromatic hydrocarbons" means that the ratio of aromatic hydrocarbons contained in a 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 a compound containing a lanthanoid element composed of scandium, yttrium, or an element having an atomic number of 57 to 71. Specific examples of the lanthanoid element are lanthanium, cerium, placeodimium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, forminium, erbium, thulium, ytterbium, and lutetium.
Examples of the Lewis base include tetrahydrofuran, diethyl ether, dimethylaniline, trimethylphosphine, lithium chloride, neutral olefins, neutral diolefins and the like.

Here, it is preferable that the rare earth element-containing compound or the reaction product of the rare earth element-containing compound and the Lewis base 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.
The component (A2) may be used alone or in combination of two or more.

Here, the component (A2) is represented by the general formula (XVI).
M- (AQ ¹ ) (AQ ² ) (AQ ³ ) ... (XVI)
(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, respectively. A group, where A represents at least one selected from the group consisting of nitrogen, oxygen or sulfur; however, it has at least one MA bond).
It is preferably a compound represented by.
Specifically, the lanthanoid element is lanthanium, cerium, placeodimium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, forminium, erbium, thulium, ytterbium, and 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 general formula (XVI), gadolinium is particularly preferable from the viewpoint of enhancing catalytic activity and reaction controllability.
When A in the above general formula (XVI) is nitrogen, the functional group represented by AQ ¹ , AQ ² , and AQ ³ (that is, NQ ¹ , NQ ² , and NQ ³ ) includes an amino group and the like. Can be mentioned. And in this case, it has three MN bonds.
Examples of the amino group include an aliphatic amino group such as a dimethylamino group, a diethylamino group and a diisopropylamino group; a phenylamino group, a 2,6-di-tert-butylphenylamino group and a 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, Arylamino groups such as 2,4,6-tri-tert-butylphenylamino group; bistrialkylsilylamino groups such as bistrimethylsilylamino group, and in particular, solubility in aliphatic hydrocarbons and aromatic hydrocarbons. From the viewpoint, a bistrimethylsilylamino group is preferable. The amino group 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, the bonds are chemically equivalent, and the structure of the compound is stable, so that handling is easy.
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 increased.

When A in the general formula (XVI) is oxygen, the component (A2) represented by the general formula (XVI) is not particularly limited, but for example, the following general formula (XVII).
(RO) ₃ M ... (XVII)
Rare earth element represented by,
The following general formula (XVIII)
(R-CO ₂ ) ₃ M ... (XVIII)
Examples thereof include rare earth carboxylates represented by. Here, in the above general formulas (XVII) and (XVIII), R may be the same or different, and is an alkyl group having 1 to 10 carbon atoms.
Since it is preferable that the component (A2) does not have a bond between a rare earth element and carbon, the compound represented by the above-mentioned general formula (XVII) or the compound represented by the general formula (XVIII) is preferably used. Can be used.

When A in the general formula (XVI) is sulfur, the component (A2) represented by the general formula (XVI) is not particularly limited, but for example, the following general formula (XIX)
(RS) ₃ M ... (XIX)
Rare earth alkylthiolate represented by,
The following general formula (XX)
(R-CS ₂ ) ₃ M ... (XX)
Examples thereof include compounds represented by. Here, in the above general formulas (XIX) and (XX), R may be the same or different, and is an alkyl group having 1 to 10 carbon atoms.
Since it is preferable that the component (A2) does not have a bond between a rare earth element and carbon, the above-mentioned compound (XIX) or compound (XX) can be preferably used.

The component (B2) is a compound selected from the group consisting of substituted or unsubstituted cyclopentadiene, substituted or unsubstituted indene (compound having an indenyl group), and substituted or unsubstituted fluorene.
The compound of 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-inden, 3-benzyl-1H-inden, 3-methyl-2-phenyl-1H-inden, and 3-benzyl-2-phenyl-1H. Examples thereof include −indene and 1-benzyl-1H-indene, and 3-benzyl-1H-indene and 1-benzyl-1H-indene are particularly preferable from the viewpoint of reducing the molecular weight distribution.
Examples of the substituted fluorene include trimethylsilylfluorene and isopropylfluorene.

According to the above configuration, the conjugated electrons contained in the compound having a cyclopentadiene skeleton can be increased, and 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 increased.

The organometallic compound (component (C2)) has a general formula (XXI):
YR ⁴ _a R ⁵ _b R ⁶ _c・ ・ ・ (XXI)
(In the formula, Y is a metal element selected from the group consisting of the elements of Group 1, Group 2, Group 12 and Group 13 of the periodic table, and R4 and R5 have 1 to 10 carbon atoms. a hydrocarbon group or a hydrogen atom a monovalent, R6 is a monovalent 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, When Y is a group 1 metal element, a is 1 and b and c are 0, and when Y is a group 2 or 12 metal element, a and b is 1 and c is 0, and when Y is a metal element of Group 13, a, b and c are 1).
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 general formula (XXI).

Specifically, the component (C2) is represented by the general formula (XXII) :.
AlR ⁷ R ⁸ R ⁹ ... (XXII)
(In the formula, R ⁷ and R ⁸ are monovalent hydrocarbon groups or hydrogen atoms having 1 to 10 carbon atoms, R ⁹ is a monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ⁷ , R ⁸ and R ⁹ may be the same or different), and are preferably organoaluminum compounds.

Examples of the organic aluminum compound include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, tripentylaluminum, and trihexyl. Aluminum, tricyclohexylaluminum, trioctylaluminum; diethylaluminum hydride, di-n-propylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride, dihexyl aluminum hydride, diisohexyl aluminum hydride, Dioctyl aluminum hydride, diisooctyl aluminum hydride; ethylaluminum dihydride, n-propylaluminum dihydride, isobutylaluminum dihydride, etc. include triethylaluminum, triisobutylaluminum, diethylaluminum hydride, and diisobutylaluminum hydride. Preferably, hydride diisobutylaluminum is more preferred.
The above-mentioned organoaluminum compound may be used alone or in combination of two or more.

The aluminoxane compound (component (D2)) is a compound obtained by contacting an organoaluminum compound with a condensing agent.
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 increased.

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

As the component (D2), for example, the general formula (XXIII):
− (Al (R ¹⁰ ) O) _n − ··· (XXIII)
(In the formula, R ¹⁰ is a monovalent hydrocarbon group having 1 to 10 carbon atoms, where some of the hydrocarbon groups may be substituted with halogen and / or alkoxy groups; R ¹⁰ is Alkoxyxane represented by (n is 5 or more) can be mentioned, which may be the same or different between the repeating units.
The molecular structure of the aluminoxane may be linear or cyclic.

N in the general formula (XXIII) is preferably 10 or more.
Further, examples of the hydrocarbon group of R ^{10 in} the general formula (XXIII) include a methyl group, an ethyl group, a propyl group, an isobutyl group and the like, and a methyl group is particularly preferable. The above hydrocarbon groups may be used alone or in combination of two or more. As the hydrocarbon group of R ¹⁰ , a combination of a methyl group and an isobutyl group is preferable.

The aluminoxane preferably has high solubility in aliphatic hydrocarbons, and preferably has 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 composed of the general formula (XXIV):
− (Al (CH ₃ ) _x (i−C ₄ H ₉ ) _y O) _m − ··· (XXIV)
It may be a modified aluminoxane (hereinafter, also referred to as “TMAO”) represented by (in the formula, x + y is 1; m is 5 or more). Examples of TMAO include product name: TMAO341 manufactured by Tosoh Finechem Co., Ltd.

The component (D2) is particularly composed of the general formula (XXV) :.
− (Al (CH ₃ ) _0.7 (i−C ₄ H ₉ ) _0.3 O) _k − ··· (XXV)
It may be a modified aluminoxane (hereinafter, also referred to as “MMAO”) represented by (k is 5 or more in the formula). Examples of MMAO include product name: MMAO-3A manufactured by Tosoh Finechem Co., Ltd.

Further, the component (D2) is particularly composed of the general formula (XXVI) :.
− [(CH ₃ ) AlO] _i − ・ ・ ・ (XXVI)
It may be a modified aluminoxane (hereinafter, also referred to as “PMAO”) represented by (i is 5 or more in the formula). Examples of PMAO include product name: TMAO-211 manufactured by Tosoh Finechem 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 (hereinafter, also referred to as “(E2-1) component”) which is a Lewis acid, or a complex compound of a metal halide and a Lewis base (hereinafter, “(E2-2) component”. ) Component) and an organic compound containing an active halogen (hereinafter, also referred to as “(E2-3) component”), which is at least one compound selected from the group.

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

Examples of the component (E2-1) include halogen-containing compounds containing elements of Group 3, Group 4, Group 5, Group 6, Group 8, Group 13, Group 14, or Group 15. In particular, aluminum halides or organic metal halides are preferable.
Examples of the halogen-containing compound which is Lewis acid include titanium tetrachloride, tungsten hexachloride, tri (pentafluorophenyl) borate, methylaluminum dibromide, methylaluminum dichloride, ethylaluminum dibromide, ethylaluminum dichloride, and butylaluminum dibromide. , Butylaluminum dichloride, dimethylaluminum bromide, dimethylaluminum chloride, diethylaluminum bromide, diethylaluminum chloride, dibutylaluminum bromide, dibutylaluminum chloride, methylaluminum sesquibromide, methylaluminum sesquichloride, ethylaluminum sesquibromide, ethylaluminum sesquichloride, aluminum Examples thereof include tribromide, tri (pentafluorophenyl) aluminum, dibutyltin dichloride, tin tetrachloride, phosphorus trichloride, phosphorus pentachloride, antimony trichloride, antimone pentachloride, etc., and in particular, ethylaluminum dichloride, ethylaluminum dibromide, etc. Diethylaluminum chloride, diethylaluminum bromide, ethylaluminum sesquichloride, ethylaluminum sesquibromide are preferred.
As the halogen, chlorine or bromine is preferable.
The halogen-containing compound which is Lewis acid may be used alone or in combination of two or more.

Examples of the metal halide used for the component (E2-2) include beryllium chloride, beryllium bromide, beryllium iodide, magnesium chloride, magnesium bromide, magnesium iodide, calcium chloride, calcium bromide, calcium iodide, and the like. 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, renium chloride, renium bromide, renium iodide, copper chloride, copper bromide, copper iodide, silver chloride, silver bromide, silver iodide, gold chloride, gold iodide, gold bromide, etc. Magnesium chloride, calcium chloride, barium chloride, zinc chloride, manganese chloride, and copper chloride are preferable, and magnesium chloride, zinc chloride, manganese chloride, and copper chloride are more preferable.
As the Lewis base used in the component (E2-2), a phosphorus compound, a carbonyl compound, a nitrogen compound, an ether compound, and an alcohol are preferable.
For example, tributyl phosphate, tri-2-ethylhexyl phosphate, triphenyl phosphate, tricredil phosphate, triethylphosphine, tributylphosphine, triphenylphosphine, diethylphosphinoetan, diphenylphosphinoetan, acetylacetone, benzoylacetone, propionylacetone. , Valeryl acetone, ethyl acetyl acetone, 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 Acids, naphthenic acid, versatic acid, triethylamine, N, N-dimethylacetoamide, tetrahydrofuran, diphenyl ether, 2-ethylhexyl alcohol, oleyl alcohol, stearyl alcohol, phenol, benzyl alcohol, 1-decanol, lauryl alcohol and the like can be mentioned in particular. Tri-2-ethylhexyl phosphate, tricresyl phosphate, acetylacetone, 2-ethylhexanoic acid, versatic acid, 2-ethylhexyl alcohol, 1-decanol and lauryl alcohol are preferred.
The number of moles of the Lewis base is preferably 0.01 to 30 mol, more preferably 0.5 to 10 mol, with respect to 1 mol of the metal halide. The reaction with the Lewis base can be used to reduce the amount of metal remaining in the polymer.
The complex compound ((E2-2) component) of the metal halide and the Lewis base may be used alone or in combination of two or more.

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

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

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

The ratio of aluminum in the component (D2) (aluminoxane) to the rare earth element in the component (A2) is preferably 10 or more, preferably 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 molars is preferably 0 or more, more preferably 0.5 or more, and 1.0 or more, from the viewpoint of improving the catalytic activity. It is more preferably 20 or less, and more preferably 10 or less, from the viewpoint of maintaining the solubility of the component (E2) and suppressing the decrease in catalytic activity.
Therefore, according to the above range, the effect of improving the cis-1,4-bond content of the conjugated diene polymer can be enhanced.

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

In the rubber composition of the present embodiment, the proportion of the multiple copolymer (a1) in the rubber component (a) is preferably 10 to 100% by mass. When the above ratio is 10% by mass or more, the crack growth resistance can be sufficiently improved. From the same viewpoint, the ratio of the multiple copolymer (a1) in the rubber component (a) is more preferably 30% by mass or more, and more preferably 70% by mass or more.

<Other rubber components>
The other rubber components are not particularly limited, and are, for example, natural rubber, isoprene rubber, butadiene rubber (BR), styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), chloroprene rubber, ethylene-propylene rubber ( EPM), ethylene-propylene-diene rubber (EPDM), polysulfide rubber, silicone rubber, fluororubber, urethane rubber and the like can be mentioned. These may be unmodified or modified. These other rubber components may be used alone or in combination of two or more.

(Thermosetting resin (b))
The rubber composition of the present embodiment contains a thermosetting resin (b). When the rubber composition contains the thermosetting resin (b), the hardness of the rubber composition can be improved and the elastic modulus at a high temperature can be increased.

The thermosetting resin is not particularly limited as long as it is a resin that can be cured by heating. For example, a phenol resin, a cresol-modified phenol resin, an oil-modified phenol resin (for example, cashew oil-modified phenol resin, tall oil-modified phenol resin, etc.) ), Alkylphenol resin, cresol resin, oil-modified cresol resin and the like. The thermosetting resin may be used alone or in combination of two or more.
Among these, the thermosetting resin (b) preferably contains a phenol resin or a cresol resin from the viewpoint of further increasing the elastic modulus at a high temperature, and also contains a cashew oil-modified phenol resin or a tall oil-modified phenol resin. It is also preferable.

（式中、ｎは１〜９の整数である）で示される。Here, the phenol resin is a condensate of phenols and aldehydes such as formaldehyde, acetaldehyde, and furfural. The cashew oil-modified phenolic resin is the above-mentioned phenolic resin modified with cashew oil. Specifically, the following formula:

(In the formula, n is an integer of 1 to 9).

（式中、Ｒ及びＲ’は、それぞれ独立して、フェノール樹脂に相当する部分であり、Ｒ¹及びＲ²は、それぞれ独立して、炭素数１〜１５のアルキレン基であり、Ｒ³は、炭素数１〜１５のアルキル基である）で示される。
また、トール油変性フェノール樹脂の具体例としては、下式：

（式中、Ｒ及びＲ’は、上記と同様である）で示される樹脂が挙げられる。The tall oil-modified phenolic resin is obtained by modifying the above-mentioned phenolic resin with tall oil. Specifically, the following formula:

(In the formula, R and R'are independent portions corresponding to the phenol resin, R ¹ and R ² are independently alkylene groups having 1 to 15 carbon atoms, and R ³ is. , It is an alkyl group having 1 to 15 carbon atoms).
Further, as a specific example of the tall oil-modified phenol resin, the following formula:

Examples thereof include resins represented by (in the formula, R and R'are the same as above).

The content of the thermosetting resin (b) in the rubber composition of the present embodiment is preferably 5 to 50 parts by mass with respect to 100 parts by mass of the rubber component (a). When the content is 5 parts by mass or more, the elastic modulus at high temperature can be more reliably improved, and when the content is 50 parts by mass or less, the durability due to excessively high hardness and durability and Deterioration of workability can be suppressed. From the same viewpoint, the content of the thermosetting resin (b) with respect to 100 parts by mass of the rubber component (a) is more preferably 6 parts by mass or more, and more preferably 30 parts by mass or less. It is more preferably 20 parts by mass or less.

(Curing agent (c))
The rubber composition of the present embodiment preferably further contains the curing agent (c). When the rubber composition contains the curing agent (c), the thermosetting resin (b) can be effectively cured and the elastic modulus at a high temperature can be further improved.

The curing agent may be any one having an action of curing a thermosetting resin, and examples thereof include hexamethoxymethylmelamine, hexamethylenetetramine, melamine, and methylolmelamine. The curing agent may be used alone or in combination of two or more.
Among these, the curing agent (c) preferably contains hexamethoxymethylmelamine from the viewpoint of further increasing the elastic modulus at high temperature.

The content of the curing agent (c) in the rubber composition of the present embodiment is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the rubber component (a). When the content is 0.1 part by mass or more, the effect of improving the elastic modulus can be more sufficiently obtained, and when it is 10 parts by mass or less, the hardness becomes excessively high. Deterioration of durability and workability can be suppressed. From the same viewpoint, the content of the curing agent (c) with respect to 100 parts by mass of the rubber component (a) is more preferably 0.3 parts by mass or more, and more preferably 5 parts by mass or less.

(Additive (d) selected from softener and liquid rubber)
The rubber composition of the present embodiment preferably contains an additive (d) selected from a softening agent and a liquid rubber. When the rubber composition contains the above additive (d), workability can be further improved. As the additive (d), only the softening agent may be used, only the liquid rubber may be used, or both the softening agent and the liquid rubber may be used.
The "liquid rubber" refers to rubber that exhibits a liquid state at 24 ° C. Further, in the present specification, "liquid rubber" is not included in the above-mentioned rubber component.

Examples of the softener include naphthenic oils, paraffinic oils, aromatic oils and the like. The softener may be used alone or in combination of two or more.
Examples of the liquid rubber include hydrogenated isoprene rubber, hydrogenated butadiene rubber, liquid ethylene / propylene / diene copolymer, liquid ethylene / propylene copolymer, liquid butadiene / styrene / random copolymer and the like. The liquid rubber may be used alone or in combination of two or more.

The solubility parameter (SP value) of the additive (d) is preferably 4 or less. When the SP value of the additive (d) is 4 or less, the compatibility with the multipolymer (a1) is increased, and the additive (d) is suppressed from being locally present and becoming a fracture nuclei. It is possible to improve workability while further improving crack resistance.
Here, the SP value of the additive (d) means a solubility parameter calculated using Hansen's mathematical formula.

The content of the additive (d) in the rubber composition of the present embodiment is preferably 3 to 150 parts by mass with respect to 100 parts by mass of the rubber component (a). When the content is 3 parts by mass or more, workability can be further improved, and when the content is 150 parts by mass or less, various effects of using the multiple copolymer (a1) are more sufficient. Can be enjoyed by.

(Other ingredients)
Further, the rubber composition of the present embodiment is, if necessary, a filler, a cross-linking agent (including a vulcanizing agent such as sulfur), and a cross-linking accelerator (vulcanization accelerator) as long as the effects of the present invention are not impaired. ), Cross-linking accelerator (vulcanization accelerator), anti-aging agent, zinc oxide (ZnO), waxes, antioxidants, foaming agents, plasticizers, lubricants, tackifiers, petroleum resins, UV absorbers , Dispersants, compatibilizers, homogenizing agents and the like can be appropriately contained.

Examples of the filler include silica, carbon black, aluminum oxide, clay, alumina, talc, mica, kaolin, glass balloon, glass beads, calcium carbonate, magnesium carbonate, magnesium hydroxide, calcium carbonate, magnesium oxide, titanium oxide, and the like. Examples thereof include potassium titanate and barium sulfate. The filler may be used alone or in combination of two or more. Among these, it is preferable to contain one or more selected from silica and carbon black.

The carbon black is not particularly limited, and examples thereof include SAF, ISAF, HAF, FF, FEF, GPF, SRF, CF, FT, and MT grade carbon black. One type of carbon black may be used alone, or two or more types may be used in combination.
The silica is not particularly limited, and examples thereof include wet silica, dry silica, colloidal silica and the like. Silica may be used alone or in combination of two or more. When the rubber composition of the present embodiment contains silica as a filler, it is preferable that the rubber composition further contains a silane coupling agent in order to improve the blending effect of the silica.

The content of the filler in the rubber composition of the present embodiment is preferably 10 to 100 parts by mass with respect to 100 parts by mass of the rubber component (a). When the content is 10 parts by mass or more, the effect of improving the crack growth resistance can be obtained, and when the content is 100 parts by mass or less, deterioration of the crack growth resistance can be sufficiently suppressed. it can.

(Manufacturing of rubber composition)
The method for producing the rubber composition of the present embodiment is not particularly limited, and for example, the rubber composition of the present embodiment can be obtained by blending and kneading each of the above-mentioned components according to a conventional method. In addition, at the time of blending and kneading, all the components may be blended and kneaded at one time, or each component may be blended and kneaded in multiple stages such as two steps or three steps. For kneading, a kneading machine such as a roll, an internal mixer, or a Banbury rotor can be used. Further, when molding the rubber composition into a sheet shape, a strip shape, or the like, a known molding machine such as an extrusion molding machine or a press machine can be used.

Moreover, the rubber composition of this embodiment may be produced by cross-linking. The crosslinking conditions are not particularly limited, and usually a temperature of 140 to 180 ° C. and a time of 5 to 120 minutes can be adopted.

The rubber composition of the present embodiment can be used for various rubber articles such as tires, conveyor belts, rubber crawlers, vibration isolators, seismic isolation devices and hoses, which will be described later.

(2) Tire The tire of the present invention is characterized by using the above-mentioned rubber composition. Since the tire of the present invention uses the above-mentioned rubber composition, it has high crack growth resistance and high elastic modulus at high temperature.
In one embodiment, the tire comprises parts such as treads, base treads, sidewalls, belt coated rubbers, ply coated rubbers, side reinforcing rubbers and bead fillers. Then, in one embodiment, the above-mentioned rubber composition can be used for at least one of the above-mentioned sites. In particular, the rubber composition described above can be suitably used for treads and bead fillers.
As a method for manufacturing the tire, a conventional method can be used. For example, members used for normal tire manufacturing such as a carcass layer, a belt layer, and a tread layer made of an unvulcanized rubber composition and / or a cord are sequentially laminated on a tire molding drum, and the drum is removed to form a green tire. To do. Then, by heating and vulcanizing this green tire according to a conventional method, a desired tire (for example, a pneumatic tire) can be manufactured.

(3) Conveyor Belt The conveyor belt of the present invention is characterized by using the above rubber composition. Since the conveyor belt of the present invention uses the rubber composition described above, it has high crack growth resistance and high elastic modulus at high temperatures.
In one embodiment, the conveyor belt has a surface rubber (bottom cover rubber) on the inner peripheral side that comes into contact with a drive pulley, a driven pulley, a shape-retaining rotor, etc., and a reinforcing material under the reinforcing material made of a steel cord or the like. A surface layer rubber (top cover rubber) on the outer peripheral side that comes into contact with the transported article is provided on the upper side of the above. Then, in one embodiment, the above-mentioned rubber composition can be used for at least one of the above-mentioned sites.
In the conveyor belt of the present invention, for example, a reinforcing material is sandwiched between the sheets made of the above-mentioned rubber composition, and then the rubber composition is heat-bonded and vulcanized to bond and coat the rubber composition on the reinforcing material. By doing so, it can be manufactured.

(4) Rubber Crawler The rubber crawler of the present invention is characterized in that the above rubber composition is used. Since the rubber crawler of the present invention uses the above-mentioned rubber composition, it has high crack growth resistance and high elastic modulus at high temperature.
In one embodiment, the rubber crawler comprises a steel cord, an intermediate rubber layer covering the steel cord, a core metal arranged on the intermediate rubber layer, and a main body rubber surrounding the intermediate rubber layer and the core metal. It has a layer and has a plurality of lugs on the ground contact surface side of the main body rubber layer. Then, in one embodiment, the above-mentioned rubber composition can be used for at least one of the above-mentioned sites. In particular, since it is excellent in crack growth resistance, the above-mentioned rubber composition can be suitably used for the main body rubber layer, particularly for the lug.

(5) Anti-vibration device The anti-vibration device of the present invention is characterized by using the above rubber composition. Since the vibration isolator of the present invention uses the rubber composition described above, it has high crack growth resistance and high elastic modulus at high temperature.
The type of anti-vibration device is not particularly limited, and for example, engine mount, torsional damper, rubber bush, strut mount, bound bumper, helper rubber, member mount, stabilizer bush, air spring, center support, and rubber-filled propeller shaft. , Anti-vibration lever, companion damper, damping rubber, idler arm bush, steering column bush, coupling rubber, body mount, muffler support, dynamic damper, piping rubber, etc.

(6) Seismic Isolation Device The seismic isolation device of the present invention is characterized by using the above rubber composition. Since the seismic isolation device of the present invention uses the above-mentioned rubber composition, it has high crack growth resistance and high elastic modulus at high temperature.
In one embodiment, the seismic isolation device includes a laminated body in which soft layers and hard layers are alternately laminated, and a plug that is press-fitted into a hollow portion formed in the center of the laminated body. Then, in one embodiment, the rubber composition described above can be used for at least one of the soft layer and the plug.

(7) Hose The hose of the present invention is characterized in that the above rubber composition is used. Since the hose of the present invention uses the above-mentioned rubber composition, it has high crack growth resistance and high elastic modulus at high temperature.
In one embodiment, the hose is located between the inner rubber layer (inner tube rubber) located radially inside, the outer rubber layer located radially outer, and, if necessary, between the inner rubber layer and the outer rubber layer. It is provided with a reinforcing layer located at. Then, in one embodiment, the above-mentioned rubber composition can be used for at least one of the inner surface rubber layer and the outer surface rubber layer. The rubber composition described above can also be used for a hose composed of a single rubber layer.

Hereinafter, the present invention will be described in more detail with reference to examples, but these examples are for the purpose of exemplifying the present invention and do not limit the present invention in any way.

<Manufacturing of copolymer A (multi-polymer)>
160 g of styrene and 600 mL of toluene as aromatic vinyl compounds were added to a sufficiently dried 1,000 mL pressure resistant stainless steel reactor.
On the other hand, in a glove box under a nitrogen atmosphere, a mono (bis (1,3-tert-butyldimethylsilyl) indenyl) bis (bis (dimethylsilyl) amide) gadolinium complex (1,3-[(t)) was placed in a glass container. −Bu) Me ₂ Si] ₂ C ₉ H ₅ Gd [N (SiHMe ₂ ) ₂ ] ₂ ) 0.25 mmol, dimethylanilinium tetrakis (pentafluorophenyl) borate [Me ₂ NHPhB (C ₆ F ₅ ) ₄ ] 0 .275 mmol and 1.1 mmol of diisobutylaluminum hydride were charged, and 40 mL of toluene was added to obtain a catalytic solution.
The obtained catalyst solution was added to the above-mentioned pressure-resistant stainless steel reactor and heated to 70 ° C.
Next, ethylene as a non-conjugated olefin compound was charged into the above-mentioned pressure-resistant stainless reactor at a pressure of 1.5 MPa, and 80 mL of a toluene solution containing 20 g of 1,3-butadiene as a conjugated diene compound was charged over 8 hours. Then, copolymerization was carried out at 70 ° C. for a total of 8.5 hours.
Then, 1 mL of a 5% by mass isopropanol solution of 2,2'-methylene-bis (4-ethyl-6-t-butylphenol) (NS-5) was added to the pressure resistant stainless steel reactor to stop the polymerization reaction.
Next, the copolymer was separated using a large amount of methanol and vacuum dried at 50 ° C. to obtain a copolymer A (multipolymer).

Regarding the obtained copolymer A, gel permeation chromatography [GPC: HLC-8121 GPC / HT manufactured by Tosoh, column: GMHHR-H (S) HT × 2 manufactured by Tosoh, detector: differential refractive index meter (RI). ], The polystyrene-equivalent number average molecular weight (Mn), weight average molecular weight (Mw), and molecular weight distribution (Mw / Mn) at a measurement temperature of 40 ° C. were determined using the monodisperse polystyrene as a reference. As a result, the number average molecular weight (Mn) was 163,000, the weight average molecular weight (Mw) was 399,000, and the molecular weight distribution (Mw / Mn) was 2.4.
Further, regarding the obtained copolymer A, the ratio of ethylene units, styrene units, and butadiene units (mol%) was determined from the integral ratio of each peak in the ¹ H-NMR spectrum (100 ° C., d-tetrachloroethane standard: 6 ppm). Asked. As a result, the proportion of ethylene units was 85 mol%, the proportion of styrene units was 7 mol%, and the proportion of butadiene units was 8 mol%.
Further, regarding the obtained copolymer A, a differential scanning calorimeter (DSC, manufactured by TA Instruments Japan, "DSCQ2000") conforming to JIS K 7121-1987 was used to determine the melting point and glass transition temperature. The energy of the endothermic peak at 0-120 ° C. was measured. Regarding the measurement of the energy of the endothermic peak, specifically, the temperature is raised from −150 ° C. to 150 ° C. at a heating rate of 10 ° C./min, and the endothermic peak at 0 to 120 ° C. at that time (1st run). The energy of the endothermic peak was measured by determining (enthalpy relaxation). As a result, the melting point was 63 ° C., the glass transition temperature was −28 ° C., and the energy of the endothermic peak was 35.6 J / g.
Further, the crystallinity was calculated from the ratio of the crystal melting energy of polyethylene composed of 100% crystal components to the melting peak energy of the copolymer A measured by DSC, and was calculated to be 12.1%.
Furthermore, in the ¹³ C-NMR spectrum chart of the copolymer A, no peak was observed at 10 to 24 ppm, confirming that the main chain of the copolymer A had only an acyclic structure.

<Manufacturing of copolymer B (binary copolymer)>
After adding 2,000 g of a toluene solution containing 120 g (2.22 mol) of 1,3-butadiene to a sufficiently dried 4 L stainless steel reactor, ethylene was introduced at 1.72 MPa.
On the other hand, in a glove box under a nitrogen atmosphere, into a glass vessel bis (2-phenyl indenyl) gadolinium bis (dimethylsilyl _{amide) [(2-PhC 9 H} 6) 2 GdN (SiHMe 2) 2] 28.5μmol , Dimethylanilinium tetrakis (pentafluorophenyl) borate [Me ₂ NHPhB (C ₆ F ₅ ) ₄ ] 28.5 μmol, and 2.00 mmol of diisobutylaluminum hydride were charged and dissolved in 40 ml of toluene to prepare a catalytic solution.
The obtained catalyst solution was added to the above-mentioned stainless steel reactor in an amount of 25.0 μmol in terms of gadolinium, and polymerization was carried out at 50 ° C. for 90 minutes.
Then, 5 ml of an isopropanol solution of 2,2'-methylene-bis (4-ethyl-6-t-butylphenol) (NS-5) in an amount of 5% by mass was added to terminate the reaction.
Next, the copolymer was separated using a large amount of methanol and vacuum dried at 70 ° C. to obtain a copolymer B (binary copolymer).

For the obtained copolymer B, the number average molecular weight (Mn), the weight average molecular weight (Mw), and the molecular weight distribution (Mw / Mn) were determined in the same manner as in the copolymer A. As a result, the number average molecular weight (Mn) was 121,000, the weight average molecular weight (Mw) was 473,000, and the molecular weight distribution (Mw / Mn) was 3.88.
Further, for the obtained copolymer B, the ratios (mol%) of ethylene units, styrene units, and butadiene units were determined in the same manner as in the copolymer A. As a result, the proportion of ethylene units was 43 mol%, the proportion of styrene units was 0 mol%, and the proportion of butadiene units was 57 mol%.
Further, for the obtained copolymer B, the melting point, the glass transition temperature, and the energy of the endothermic peak at 0 to 120 ° C. were measured in the same manner as in the copolymer A. As a result, the melting point was 120 ° C., the glass transition temperature was −103 ° C., and the energy of the endothermic peak was 48.5 J / g.
Further, the crystallinity was calculated from the ratio of the crystal melting energy of polyethylene composed of 100% crystal components to the melting peak energy of copolymer B measured by DSC, and was calculated to be 16.5%.

<Preparation and evaluation of rubber composition>
The rubber compositions of Comparative Examples 1, 3 and 4 and Examples 1 and 2 were produced using a normal Bunbury mixer according to the formulation shown in Table 1. According to the formulation shown in Tables 1 and 2, rubber compositions of Examples other than Comparative Examples 1, 3 and 4 and Examples 1 and 2 are produced using a normal Bunbury mixer. Using the rubber compositions of Comparative Examples 1, 3 and 4 and Examples 1 and 2, the high-temperature elastic modulus and crack growth resistance were evaluated by the following methods. Further, the high temperature elastic modulus and the crack growth resistance are evaluated by the following methods using the rubber compositions of Examples other than Comparative Examples 1, 3 and 4 and Examples 1 and 2. The results are shown in Tables 1 and 2.

(1) High-temperature elastic modulus After vulcanizing the rubber compositions of Comparative Examples 1, 3 and 4 and Examples 1 and 2 at 160 ° C. for 20 minutes, a dynamic shear viscoelasticity measuring device (manufactured by Leometrics) was used. The storage elastic modulus (E') was measured under the conditions of a temperature of 130 ° C., a dynamic strain of 1.0%, and a frequency of 15 Hz. After vulcanizing the rubber compositions of Comparative Examples 1, 3 and 4 and Examples other than Examples 1 and 2 at 160 ° C. for 20 minutes, a dynamic shear viscoelasticity measuring device (manufactured by Leometrics) was used and the temperature was 130. The storage elastic modulus (E') is measured under the conditions of ° C., dynamic strain 1.0%, and frequency 15 Hz.
In the example using carbon black shown in Table 1, the index is displayed when Comparative Example 1 is 100, and in the example using silica shown in Table 2, Comparative Example 6 is set to 100 and the measured value is an index. To be. The larger the index value, the higher the elastic modulus at high temperature.

(2) Crack growth resistance A JIS No. 3 test piece is prepared from the rubber compositions of each Example and Comparative Example. Next, a 0.5 mm crack is formed in the center of the test piece, repeated fatigue is applied at room temperature with a constant strain of 0 to 100%, and the number of times until the test piece is cut is measured. In the example using carbon black shown in Table 1, the index is displayed when Comparative Example 1 is 100, and in the example using silica shown in Table 2, Comparative Example 6 is set to 100 and the measured value is an index. To be. The larger the index value, the better the crack growth resistance.

* 1 Carbon black: HAF carbon, manufactured by Asahi Carbon Co., Ltd., product name "# 70"
* 2 Silica: Made by Toso Silica Co., Ltd., Product name "Nipseal AQ (registered trademark)"
* 3 Silane coupling agent: Bis (3-trietoxysilylpropyl) disulfide, manufactured by Evonik, trade name "Si75 (registered trademark)", average sulfur chain length: 2.35
* 4 Thermosetting resin A: Sumitomo Bakelite, tall oil-modified phenolic resin * 5 Thermosetting resin B: Sumitomo Bakelite, phenolic resin * 6 Hardener: Hexamethoxymethylmelamine * 7 Softener: Process oil * 8 Aging Inhibitor 6PPD: N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd., trade name "Nocrack 6C (registered trademark)"
* 9 Wax: Made by Seiko Kagaku Co., Ltd., trade name "Santite (registered trademark)"
* 10 Vulcanization accelerator MBTS: Di-2-benzothiazolyl disulfide, manufactured by Sanshin Chemical Industry Co., Ltd., trade name "Sun Cellar DM"
* 11 Vulcanization accelerator TBBS: N-tert-butyl-2-benzothiazolyl sulfeneamide, manufactured by Sanshin Chemical Industry Co., Ltd., trade name "Suncellor NS"
* 12 Vulcanization accelerator DPG: 1,3-diphenylguanidine, manufactured by Sanshin Chemical Industry Co., Ltd., trade name "Sunseller D"

From Tables 1 and 2, it can be seen that by using the rubber compositions of Examples according to the present invention, rubber articles having high crack growth resistance and high elastic modulus at high temperatures can be produced.

According to the present invention, it is possible to provide a rubber composition capable of producing a rubber article having high crack growth resistance and high elastic modulus at high temperature.
Further, according to the present invention, it is possible to provide a tire, a conveyor belt, a rubber crawler, a vibration isolator, a seismic isolation device and a hose having high crack growth resistance and high elastic modulus at high temperature.

Claims (25)

A rubber component (a) containing a multiple copolymer (a1) having a conjugated diene unit, a non-conjugated olefin unit, and an aromatic vinyl unit,
A rubber composition containing a thermosetting resin (b). The multiple copolymer (a1) is
The ratio of the conjugated diene unit is 1 to 50 mol%.
The proportion of the non-conjugated olefin unit is 40 to 97 mol%, and the proportion of the aromatic vinyl unit is 2 to 35 mol%.
The rubber composition according to claim 1. The rubber composition according to claim 1 or 2, wherein the content of the thermosetting resin (b) is 5 to 50 parts by mass with respect to 100 parts by mass of the rubber component (a). The rubber composition according to any one of claims 1 to 3, wherein the thermosetting resin (b) contains a phenol resin or a cresol resin. The rubber composition according to any one of claims 1 to 4, wherein the thermosetting resin (b) contains a cashew oil-modified phenolic resin or a tall oil-modified phenolic resin. The rubber composition according to any one of claims 1 to 5, further comprising a curing agent (c). The rubber composition according to claim 6, wherein the curing agent (c) contains hexamethoxymethylmelamine. The rubber composition according to claim 6 or 7, wherein the content of the curing agent (c) is 0.1 to 10 parts by mass with respect to 100 parts by mass of the rubber component (a). Further, it contains at least one additive (d) selected from a softener and a liquid rubber, and contains.
The rubber composition according to any one of claims 1 to 8, wherein the content of the additive (d) is 3 to 150 parts by mass with respect to 100 parts by mass of the rubber component (a). The rubber composition according to any one of claims 1 to 9, wherein the multiple copolymer (a1) has only a non-cyclic structure in the main chain. The rubber composition according to any one of claims 1 to 10, wherein the multiple copolymer (a1) has a melting point of 30 to 130 ° C. as measured by a differential scanning calorimeter (DSC). The rubber according to any one of claims 1 to 11, wherein the multiple copolymer (a1) has an endothermic peak energy of 10 to 150 J / g measured by a differential scanning calorimeter (DSC) at 0 to 120 ° C. Composition. The rubber composition according to any one of claims 1 to 12, wherein the multiple copolymer (a1) has a glass transition temperature of 0 ° C. or lower as measured by a differential scanning calorimeter (DSC). The rubber composition according to any one of claims 1 to 13, wherein the multiple copolymer (a1) has a crystallinity of 0.5 to 50%. The rubber composition according to any one of claims 1 to 14, wherein the non-conjugated olefin unit does not have a cyclic structure. The rubber composition according to any one of claims 1 to 15, wherein the non-conjugated olefin unit comprises only an ethylene unit. The rubber composition according to any one of claims 1 to 16, wherein the aromatic vinyl unit contains a styrene unit. The rubber composition according to any one of claims 1 to 17, wherein the conjugated diene unit contains at least one of 1,3-butadiene unit and isoprene unit. The rubber composition according to any one of claims 1 to 18, wherein the ratio of the multiple copolymer (a1) in the rubber component (a) is 10 to 100% by mass. A tire using the rubber composition according to any one of claims 1 to 19. A conveyor belt according to any one of claims 1 to 19, wherein the rubber composition is used. A rubber crawler using the rubber composition according to any one of claims 1 to 19. An anti-vibration device according to any one of claims 1 to 19, wherein the rubber composition is used. A seismic isolation device according to any one of claims 1 to 19, wherein the rubber composition is used. A hose using the rubber composition according to any one of claims 1 to 19.