WO2019163835A1

WO2019163835A1 - Rubber composition, tire, conveyor belt, rubber crawler, vibration isolation device, seismic isolation device, and hose

Info

Publication number: WO2019163835A1
Application number: PCT/JP2019/006358
Authority: WO
Inventors: 俊介佐治; 祥子犬束; 健二中谷; 駿種村; 靖宏庄田
Original assignee: 株式会社ブリヂストン
Priority date: 2018-02-22
Filing date: 2019-02-20
Publication date: 2019-08-29
Also published as: JPWO2019163835A1

Abstract

The present invention addresses the problem of providing a rubber composition that strikes a high degree of balance among wear resistance, crack growth resistance, and workability. The rubber composition is characterized by comprising, as a rubber component (a): a multicomponent copolymer (a1) including a conjugated diene unit, a non-conjugated olefin unit, and an aromatic vinyl unit and having an endothermic peak energy of 10-150 J/g as measured using a differential scanning calorimeter (DSC) at 0-120°C; and a conjugated diene rubber (a2) other than the multicomponent copolymer (a1), wherein the contained amount of the multicomponent copolymer (a1) in the rubber component (a) is not less than 5 mass% but less than 50 mass%, the conjugated diene rubber (a2) forms a continuous phase, and the multicomponent copolymer (a1) forms a dispersed phase.

Description

Rubber composition, tire, conveyor belt, rubber crawler, vibration isolator, seismic isolator and hose

The present invention relates to a rubber composition, a tire, a conveyor belt, a rubber crawler, a vibration isolator, a seismic isolation device, and a hose.

In recent years, in order to improve the durability of rubber products such as tires, conveyor belts, rubber crawlers, vibration isolators, seismic isolation devices, hoses, etc., rubber compositions having excellent wear resistance and crack growth resistance have been required. Yes.
In response to such a requirement, the present inventors use a multi-component copolymer containing a conjugated diene unit, a non-conjugated olefin unit, and an aromatic vinyl unit as a rubber component of a rubber composition. It has been found that the wear resistance and crack growth resistance of the rubber composition are improved (Patent Document 1 below).

International Publication No. 2015/190072

However, as a result of further investigation by the present inventors, the rubber composition containing the multi-component copolymer has a high viscosity in an unvulcanized state, and further improvement is necessary from the viewpoint of workability (viscosity reduction). I found out.

Accordingly, an object of the present invention is to solve the above-mentioned problems of the prior art and to provide a rubber composition in which wear resistance, crack growth resistance, and workability are highly balanced.
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 excellent in wear resistance and crack growth resistance.

The gist configuration of the present invention for solving the above-described problems is as follows.

The rubber composition of the present invention contains, as a rubber component (a), a conjugated diene unit, a non-conjugated olefin unit, and an aromatic vinyl unit, and a differential scanning calorimeter (DSC) at 0 to 120 ° C. A multi-component copolymer (a1) having an endothermic peak energy measured in 10 to 150 J / g, and a conjugated diene rubber (a2) other than the multi-component copolymer (a1),
The content of the multi-component copolymer (a1) in the rubber component (a) is 5% by mass or more and less than 50% by mass,
The conjugated diene rubber (a2) forms a continuous phase, and the multi-component copolymer (a1) forms a dispersed phase.
The rubber composition of the present invention has a high balance between wear resistance, crack growth resistance and workability.

In the rubber composition of the present invention, the multi-component copolymer (a1) has a content of the conjugated diene unit of 1 to 50 mol%, a content of the non-conjugated olefin unit of 40 to 97 mol%, and the aromatic The group vinyl unit content is preferably 2 to 35 mol%. In this case, the wear resistance and crack growth resistance of the rubber composition are further improved.

The rubber composition of the present invention contains styrene-butadiene rubber as the conjugated diene rubber (a2), and the content of the styrene-butadiene rubber in the rubber component (a) exceeds 50% by mass. It is preferable. In this case, the wear resistance and crack growth resistance of the rubber composition are further improved.

Here, it is preferable that the styrene-butadiene rubber has a glass transition temperature (Tg) measured by a differential scanning calorimeter (DSC) of −60 ° C. to 0 ° C. In this case, the wear resistance, crack growth resistance and workability of the rubber composition are further improved.

The styrene-butadiene rubber preferably has a styrene content of 5 to 50% by mass. In this case, the wear resistance, crack growth resistance and workability of the rubber composition are further improved.

The styrene-butadiene rubber preferably has a vinyl bond content in the styrene-butadiene rubber of 15 to 60% by mass. In this case, the wear resistance, crack growth resistance and workability of the rubber composition are further improved.

In the rubber composition of the present invention, the multi-component copolymer (a1) preferably has a melting point of 30 to 130 ° C. measured by a differential scanning calorimeter (DSC). In this case, the wear resistance, crack growth resistance and workability of the rubber composition are further improved.

In the rubber composition of the present invention, the multi-component copolymer (a1) preferably has a glass transition temperature of 0 ° C. or less as measured by a differential scanning calorimeter (DSC). In this case, the workability of the rubber composition is further improved.

In the rubber composition of the present invention, the multi-component copolymer (a1) preferably has a crystallinity of 0.5 to 50%. In this case, the wear resistance, crack growth resistance and workability of the rubber composition are further improved.

In the rubber composition of the present invention, the multi-component copolymer (a1) preferably has a main chain consisting only of an acyclic structure. In this case, the crack growth resistance of the rubber composition is further improved.

In the rubber composition of the present invention, the multi-component copolymer (a1) is preferably such that the non-conjugated olefin unit is an acyclic non-conjugated olefin unit. In this case, the weather resistance of the rubber composition is improved.

Here, it is more preferable that the non-cyclic non-conjugated olefin unit is composed of only ethylene units. In this case, the weather resistance of the rubber composition is further improved.

In the rubber composition of the present invention, it is preferable that in the multi-component copolymer (a1), the aromatic vinyl unit includes a styrene unit. In this case, the weather resistance of the rubber composition is further improved.

In the rubber composition of the present invention, in the multi-component copolymer (a1), the conjugated diene unit preferably contains a 1,3-butadiene unit and / or an isoprene unit. In this case, the wear resistance and crack growth resistance of the rubber composition are further improved.

The tire of the present invention is characterized by using the above rubber composition. Such a tire of the present invention is excellent in wear resistance and crack growth resistance.

The conveyor belt of the present invention is characterized by using the above rubber composition. Such a conveyor belt of the present invention is excellent in wear resistance and crack growth resistance.

The rubber crawler of the present invention is characterized by using the above rubber composition. Such a rubber crawler of the present invention is excellent in wear resistance and crack growth resistance.

Further, the vibration isolator of the present invention is characterized by using the above rubber composition. Such a vibration isolator of the present invention is excellent in wear resistance and crack growth resistance.

The seismic isolation device of the present invention is characterized by using the above rubber composition. Such a seismic isolation device of the present invention is excellent in wear resistance and crack growth resistance.

The hose of the present invention is characterized by using the above rubber composition. Such a hose of the present invention is excellent in wear resistance and crack growth resistance.

ADVANTAGE OF THE INVENTION According to this invention, the rubber composition which highly balanced abrasion resistance, crack growth resistance, and workability | operativity can be provided.
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 excellent in wear resistance and crack growth resistance.

Hereinafter, the rubber composition, tire, conveyor belt, rubber crawler, vibration isolator, seismic isolation device, and hose of the present invention will be described in detail based on the embodiments.

<Rubber composition>
The rubber composition of the present invention contains, as a rubber component (a), a conjugated diene unit, a non-conjugated olefin unit, and an aromatic vinyl unit, and a differential scanning calorimeter (DSC) at 0 to 120 ° C. A multi-component copolymer (a1) having an endothermic peak energy of 10 to 150 J / g and a conjugated diene rubber (a2) other than the multi-component copolymer (a1), wherein the rubber component (a ), The content of the multi-component copolymer (a1) is 5% by mass or more and less than 50% by mass, the conjugated diene rubber (a2) forms a continuous phase, and the multi-component copolymer (a1) ) Form a dispersed phase.

Since the rubber composition of the present invention includes a multi-component copolymer (a1) containing a conjugated diene unit, a non-conjugated olefin unit, and an aromatic vinyl unit, the rubber composition is excellent in wear resistance and crack growth resistance.
In the rubber composition of the present invention, the content of the multi-component copolymer (a1) in the rubber component (a) is 5% by mass or more and less than 50% by mass, and the conjugated diene rubber (a2) is a continuous phase. And the domain size of the polymer phase composed of the multi-component copolymer (a1) is reduced because the multi-component copolymer (a1) forms a dispersed phase, and therefore the multi-component copolymer (a1) due to strain is reduced. The crystal collapse is promoted, and the wear resistance and crack growth resistance are further improved.
Furthermore, in the rubber composition of the present invention, the conjugated diene rubber (a2) other than the multi-component copolymer (a1), which usually does not have a crystal component, forms a continuous phase. Since the unvulcanized viscosity largely depends on the viscosity of the continuous phase, the unvulcanized viscosity of the rubber composition as a whole can be effectively reduced.
Therefore, the rubber composition of the present invention can highly balance wear resistance, crack growth resistance, and workability (viscosity reduction).

The rubber composition of the present invention contains, as a rubber component (a), a conjugated diene unit, a non-conjugated olefin unit, and an aromatic vinyl unit, and a differential scanning calorimeter (DSC) at 0 to 120 ° C. A multi-component copolymer (a1) having an endothermic peak energy of 10 to 150 J / g.
The multi-component copolymer (a1) has an endothermic peak energy measured by a differential scanning calorimeter (DSC) at 0 to 120 ° C. of 10 to 150 J / g, preferably 25 to 130 J / g. When the endothermic peak energy of the multi-component copolymer (a1) is less than 10 J / g, the crystallinity of the multi-component copolymer (a1) is insufficient and the crystals of the multi-component copolymer (a1) when strained. Collapse is insufficient, and the effect of improving wear resistance and crack growth resistance is reduced. On the other hand, when the endothermic peak energy of the multi-component copolymer (a1) exceeds 150 J / g, the crystallinity of the multi-component copolymer (a1) is too high, and the viscosity of the dispersed phase formed from the multi-component copolymer (a1). As a result, the unvulcanized viscosity of the rubber composition as a whole cannot be sufficiently reduced.

In the rubber composition of the present invention, the content of the multi-component copolymer (a1) in the rubber component (a) is 5% by mass or more and less than 50% by mass, and 20 to 40% by mass. preferable. When the content of the multi-component copolymer (a1) in the rubber component (a) is less than 5% by mass, the effect of improving the wear resistance and crack growth resistance by the multi-component copolymer (a1) cannot be sufficiently obtained. . On the other hand, when the content of the multi-component copolymer (a1) in the rubber component (a) is 50% by mass or more, the domain size of the polymer phase composed of the multi-component copolymer (a1) increases, and the multi-component copolymer due to strain increases. The crystal collapse of the polymer (a1) does not proceed sufficiently, the effect of improving wear resistance and crack growth resistance is reduced, and the influence on the viscosity of the multi-component copolymer (a1) is increased, resulting in a rubber composition. The unvulcanized viscosity of the whole product cannot be sufficiently reduced.

In the rubber composition of the present invention, the conjugated diene rubber (a2) forms a continuous phase (so-called sea-island sea phase), and the multi-component copolymer (a1) is a dispersed phase (so-called sea-island island). Phase). Here, the polymer phase formed from the conjugated diene rubber (a2) and the polymer phase formed from the multi-component copolymer (a1) are incompatible, and the conjugated diene rubber (a2). ) Form a continuous phase, and the multi-component copolymer (a1) forms a dispersed phase can be confirmed by a scanning electron microscope (SEM).
In the rubber composition of the present invention, since the conjugated diene rubber (a2) having no crystal component forms a continuous phase, the rubber composition as a whole has a low unvulcanized viscosity and excellent workability.
In the rubber composition of the present invention, the multi-component copolymer (a1) forms a dispersed phase, and the domain size of the polymer phase composed of the multi-component copolymer (a1) is small. Crystal collapse of the coalescence (a1) is promoted, and the wear resistance and crack growth resistance are further improved.

Whether or not the polymer phase formed from the conjugated diene rubber (a2) and the polymer phase formed from the multi-component copolymer (a1) are incompatible with each other depends on the rubber composition. (1) Visual observation, (2) Dynamic viscoelasticity curve, and (3) Scanning electron microscope (SEM).
For (1), the transparency of the rubber composition is confirmed by visual inspection. If it is transparent, it is compatible. If it is opaque, it is semi-compatible. If it is opaque, it is non-transparent. It can be judged as compatible.
For (2), in the curve of tan δ obtained by dynamic viscoelasticity measurement, if the glass transition temperature (Tg) peak is one and it is sharp, the compatibility and the Tg peak are one, but broad. Can be determined as semi-compatible, and when two or more Tg peaks are present, it can be determined as incompatible.
As for (3), in the SEM image, when only one phase is observed, it can be judged as compatible, and when more than one phase is observed, it can be judged as semi-compatible or incompatible.
In principle, the determination of whether or not incompatibility is made is based only on (1) and (2). If a clear determination cannot be made only by (1) and (2), 3) Final decision is made.

The multi-component copolymer (a1) contains at least a conjugated diene unit, a non-conjugated olefin unit, and an aromatic vinyl unit, and consists only of a conjugated diene unit, a non-conjugated olefin unit, and an aromatic vinyl unit. It may also contain other monomer units.

The conjugated diene unit is a structural unit derived from a conjugated diene compound as a monomer. The conjugated diene compound preferably has 4 to 8 carbon atoms. Specific examples of the conjugated diene compound include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and the like. The conjugated diene compound may be a single kind or a combination of two or more kinds. And, from the viewpoint of effectively improving the wear resistance and crack growth resistance of rubber compositions and tires using the resulting multi-component copolymer, the conjugated diene compound as a monomer of the multi-component copolymer, It preferably contains 1,3-butadiene and / or isoprene, more preferably consists only of 1,3-butadiene and / or isoprene, and more preferably consists only of 1,3-butadiene. In other words, the conjugated diene unit in the multi-component copolymer preferably contains 1,3-butadiene units and / or isoprene units, and more preferably consists only of 1,3-butadiene units and / or isoprene units. Preferably, it consists only of 1,3-butadiene units.

In the multi-component copolymer (a1), the content of the conjugated diene unit is preferably 1 mol% or more, more preferably 3 mol% or more, and preferably 50 mol% or less, % Or less, more preferably 30 mol% or less, still more preferably 20 mol% or less, and even more preferably 15 mol% or less. When the content of the conjugated diene unit is 1 mol% or more of the entire multi-component copolymer, a rubber composition and a rubber product excellent in elongation can be obtained, and when it is 50 mol% or less, the weather resistance is excellent.

The non-conjugated olefin unit is a structural unit derived from a non-conjugated olefin compound as a monomer. The non-conjugated olefin compound preferably has 2 to 10 carbon atoms. Specific examples of such non-conjugated olefin compounds include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene and other α-olefins, vinyl pivalate, 1-phenylthioethene. And heteroatom-substituted alkene compounds such as N-vinylpyrrolidone. The non-conjugated olefin compound may be a single kind or a combination of two or more kinds. The non-conjugated olefin compound as a monomer of the multi-component copolymer further reduces the crystallinity of the resulting multi-component copolymer, and improves the weather resistance of rubber compositions and tires using such a multi-component copolymer. From the viewpoint of further improvement, it is preferably an acyclic non-conjugated olefin compound, and the acyclic non-conjugated olefin compound is more preferably an α-olefin, and an α-olefin containing ethylene. Is more preferable, and it is particularly preferable that it consists only of ethylene. In other words, the non-conjugated olefin unit in the multi-component copolymer is preferably an acyclic non-conjugated olefin unit, and the acyclic non-conjugated olefin unit is preferably an α-olefin unit. More preferably, it is more preferably an α-olefin unit containing an ethylene unit, and further preferably only an ethylene unit.

In the multi-component copolymer (a1), the content of the non-conjugated olefin unit is preferably 40 mol% or more, more preferably 45 mol% or more, and even more preferably 55 mol% or more, It is particularly preferably 65 mol% or more, more preferably 97 mol% or less, still more preferably 95 mol% or less, and still more preferably 90 mol% or less. When the content of the non-conjugated olefin unit is 40 mol% or more of the entire multi-polymer, the content of the conjugated diene unit or the aromatic vinyl unit is decreased as a result, the weather resistance is improved, and the resistance at high temperature is increased. Breakability (particularly, breaking strength (Tb)) is improved. Further, when the content of the non-conjugated olefin unit is 97 mol% or less, the content of the conjugated diene unit or the aromatic vinyl unit increases as a result, and fracture resistance at high temperature (particularly, elongation at break (Eb)) Will improve. Further, the content of the non-conjugated olefin unit is preferably in the range of 45 to 95 mol%, more preferably in the range of 55 to 90 mol% with respect to the entire multi-component copolymer.

The aromatic vinyl unit is a structural unit derived from an aromatic vinyl compound as a monomer. The aromatic vinyl compound preferably has 8 to 10 carbon atoms. Examples of such aromatic vinyl compounds include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, and the like. . The aromatic vinyl compound may be a single type or a combination of two or more types. And the aromatic vinyl compound as a monomer of the multi-component copolymer further reduces the crystallinity of the resulting multi-component copolymer, the weather resistance of rubber compositions and tires using such a multi-component copolymer, From the viewpoint of further improving the toughness, it is preferable that styrene is contained, and it is more preferable that the material only consists of styrene. In other words, the aromatic vinyl unit in the multi-component copolymer preferably includes a styrene unit, and more preferably includes only a styrene unit.
The aromatic ring in the aromatic vinyl unit is not included in the main chain of the multi-component copolymer unless it is bonded to an adjacent unit.

The multi-component copolymer (a1) preferably has a content of the aromatic vinyl unit of 2 mol% or more, more preferably 3 mol% or more, and preferably 35 mol% or less. More preferably, it is 30 mol% or less, More preferably, it is 25 mol% or less, Most preferably, it is 20 mol% or less. When the content of the aromatic vinyl unit is 2 mol% or more, the fracture resistance at high temperatures is improved. Moreover, the effect by a conjugated diene unit and a nonconjugated olefin unit becomes remarkable as content of an aromatic vinyl unit is 35 mol% or less. The content of the aromatic vinyl unit is preferably in the range of 2 to 35 mol%, more preferably in the range of 3 to 30 mol%, still more preferably in the range of 3 to 25 mol% with respect to the entire multi-component copolymer.

The number of types of monomers of the multi-component copolymer (a1) is not particularly limited as long as the multi-component copolymer contains a conjugated diene unit, a non-conjugated olefin unit, and an aromatic vinyl unit. The multi-component copolymer (a1) may have other structural units other than the conjugated diene unit, the non-conjugated olefin unit, and the aromatic vinyl unit, but the content of the other structural unit is desired. From the viewpoint of obtaining the above effect, it is preferably 30 mol% or less, more preferably 20 mol% or less, still more preferably 10 mol% or less, and not contained, that is, the content of the entire multi-component copolymer. Is particularly preferably 0 mol%.

From the viewpoint of making the wear resistance, crack growth resistance, weather resistance, and crystallinity preferable, the multi-component copolymer (a1) includes a kind of conjugated diene compound, a kind of non-conjugated olefin compound, And a polymer obtained by polymerization using at least one kind of aromatic vinyl compound. In other words, the multi-component copolymer (a1) is preferably a multi-component copolymer containing one kind of conjugated diene unit, one kind of non-conjugated olefin unit, and one kind of aromatic vinyl unit. More preferably, it is a terpolymer comprising only a conjugated diene unit, a non-conjugated olefin unit, and a single aromatic vinyl unit, and is composed only of a 1,3-butadiene unit, an ethylene unit, and a styrene unit. More preferably, it is a terpolymer. Here, the “one type of conjugated diene unit” includes conjugated diene units having different bonding modes.

The multi-component copolymer (a1) preferably has a polystyrene-equivalent weight average molecular weight (Mw) of 10,000 to 10,000,000, more preferably 100,000 to 9,000,000. 150,000 to 8,000,000 is more preferable. When the Mw of the multi-component copolymer is 10,000 or more, the wear resistance of the rubber composition can be further improved, and when the Mw is 10,000,000 or less, high workability is achieved. Can be held.

The multi-component copolymer (a1) preferably has a polystyrene-equivalent number average molecular weight (Mn) of 10,000 to 10,000,000, more preferably 50,000 to 9,000,000. More preferably, it is 100,000 to 8,000,000. When the Mn of the multi-component copolymer is 10,000 or more, the wear resistance of the rubber composition can be further improved, and when the Mn is 10,000,000 or less, high workability is achieved. Can be held.

The multi-component copolymer (a1) preferably has a molecular weight distribution [Mw / Mn (weight average molecular weight / number average molecular weight)] of 1.00 to 4.00, preferably 1.50 to 3.50. Is more preferable, and it is still more preferable that it is 1.80 to 3.00. The wider the molecular weight distribution of the multi-component copolymer, the better the workability of the rubber composition. In addition, when the molecular weight distribution of the multi-component copolymer is 4.00 or less, sufficient homogeneity can be brought about in the physical properties of the multi-component copolymer.

The above-mentioned weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) are determined by gel permeation chromatography (GPC) using polystyrene as a standard substance.

In the rubber composition of the present invention, the multi-component copolymer (a1) preferably has a melting point measured by a differential scanning calorimeter (DSC) of 30 to 130 ° C., more preferably 50 to 120 ° C. . If the melting point of the multi-component copolymer (a1) is 30 ° C. or higher, the crystallinity of the multi-component copolymer (a1) is increased, and the wear resistance and crack growth resistance of the rubber composition are further improved, If it is 130 degrees C or less, the workability | operativity of a rubber composition will improve further.
Here, the melting point is a value measured by the method described in Examples.

In the rubber composition of the present invention, the multi-component copolymer (a1) preferably has a glass transition temperature (Tg) measured by a differential scanning calorimeter (DSC) of 0 ° C. or lower. When the glass transition temperature of the multi-component copolymer (a1) is 0 ° C. or lower, the workability of the rubber composition is further improved.
Here, the glass transition temperature is a value measured by the method described in Examples.

In the rubber composition of the present invention, the multi-component copolymer (a1) preferably has a crystallinity of 0.5 to 50%, more preferably 3 to 45%. If the degree of crystallinity of the multi-component copolymer (a1) is 0.5% or more, sufficient crystallinity attributable to the non-conjugated olefin unit is ensured, and the rubber composition has wear resistance and crack growth resistance. Further improvement. In addition, when the crystallinity of the multi-component copolymer (a1) is 50% or less, workability during kneading of the rubber composition is improved, and a rubber composition containing the multi-component copolymer (a1) is blended. Since the tackiness of the rubber is improved, the workability when molding rubber products such as tires by attaching rubber members made from the rubber composition to each other is also improved.
Here, the crystallinity is a value measured by the method described in Examples.

The multi-component copolymer (a1) preferably has a main chain consisting only of an acyclic structure. Thereby, the crack growth resistance of the rubber composition can be further improved. Incidentally, 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 a 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 It shows that it consists only of an acyclic structure.

The multi-component copolymer (a1) can be produced through a polymerization process using a conjugated diene compound, a non-conjugated olefin compound, and an aromatic vinyl compound as monomers, and, if necessary, a coupling process, washing You may pass through a process and other processes.
Here, in the production of the multi-component copolymer (a1), it is preferable to add only a non-conjugated olefin compound and an aromatic vinyl compound without adding a conjugated diene compound and polymerize them in the presence of a catalyst. . In particular, when using the polymerization catalyst composition described later, since the conjugated diene compound is more reactive than the non-conjugated olefin compound and the aromatic vinyl compound, the non-conjugated olefin compound and / or in the presence of the conjugated diene compound. Alternatively, it is difficult to polymerize the aromatic vinyl compound. Moreover, it is easy to polymerize the conjugated diene compound first, and then additionally polymerize the non-conjugated olefin compound and the aromatic vinyl compound later because of the characteristics of the catalyst.

As the polymerization method, any method such as a solution polymerization method, a suspension polymerization method, a liquid phase bulk polymerization method, an emulsion polymerization method, a gas phase polymerization method, and a solid phase polymerization method can be used. In addition, when a solvent is used for the polymerization reaction, such a solvent is not particularly limited as long as it is inert in the polymerization reaction, and examples thereof include toluene, cyclohexane, and normal hexane.

The polymerization process may be performed in one stage, or may be performed in two or more stages. The one-step polymerization process means all kinds of monomers to be polymerized, that is, conjugated diene compounds, non-conjugated olefin compounds, aromatic vinyl compounds, and other monomers, preferably conjugated diene compounds, non-conjugated. In this step, the olefin compound and the aromatic vinyl compound are polymerized by reacting simultaneously. The multi-stage polymerization process means that a polymer is formed by first reacting part or all of one or two kinds of monomers (first polymerization stage), and then the remaining kinds of monomers. Or a step of polymerizing by performing one or more stages (second polymerization stage to final polymerization stage) in which the remainder of the one or two kinds of monomers is added and polymerized. In particular, in the production of multi-component copolymers, it is preferable to carry out the polymerization process in multiple stages.

In the polymerization step, the polymerization reaction is preferably performed in an atmosphere of an inert gas, preferably nitrogen gas or argon gas. The polymerization temperature of the polymerization reaction is not particularly limited, but is preferably in the range of −100 ° C. to 200 ° C., for example, and can be about room temperature. The pressure for 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. Also, the reaction time of the above polymerization reaction is not particularly limited and is preferably in the range of, for example, 1 second to 10 days, but can be appropriately selected depending on conditions such as the type of catalyst and polymerization temperature. In addition, the polymerization process may be performed in one stage, or may be performed in two or more stages.
In the polymerization step of the conjugated diene compound, the polymerization may be stopped using a polymerization terminator such as methanol, ethanol, isopropanol.

The polymerization process is preferably performed in multiple stages. More preferably, a first step of obtaining a polymerization mixture by mixing a first monomer raw material containing at least an aromatic vinyl compound and a polymerization catalyst, and a conjugated diene compound, a non-conjugated olefin compound, and It is preferable to carry out the second step of introducing the second monomer raw material containing at least one selected from the group consisting of aromatic vinyl compounds. 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. Moreover, the 1st monomer raw material may contain the whole quantity of the aromatic vinyl compound to be used, and may contain only one part. 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 performed in an atmosphere of an inert gas, preferably nitrogen gas or argon gas, in the reactor. The temperature (reaction temperature) in the first step is not particularly limited. 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 spent in the first step (reaction time) can be appropriately selected depending on conditions such as the type of polymerization catalyst and reaction temperature. For example, when the reaction temperature is 25 to 80 ° C., 5 minutes A range of ˜500 minutes is preferred.

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

The second monomer raw material used in the second step is a conjugated diene compound only, or a conjugated diene compound and a non-conjugated olefin compound, or a conjugated diene compound and an aromatic vinyl compound, or a conjugated diene compound or a non-conjugated olefin. It is preferable that they are a compound and an aromatic vinyl compound.
When the second monomer raw material includes 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 preliminarily used as a solvent or the like. After mixing together, it may be introduced into the polymerization mixture, or each monomer raw material may be introduced from a single state. Each monomer raw material may be added simultaneously or sequentially. In the second step, the method for introducing the second monomer raw material into the polymerization mixture is not particularly limited, but it is continuously added to the polymerization mixture by controlling the flow rate of each monomer raw material. It is preferable to perform (so-called metering). Here, in the case of using 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 atmospheric pressure), the polymerization reaction system is used at a predetermined pressure. Can be introduced.

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

Here, the polymerization step of the non-conjugated olefin compound, aromatic vinyl compound, and conjugated diene compound includes the following first polymerization catalyst composition, second polymerization catalyst composition, third polymerization catalyst composition, or It is preferable to include a step of polymerizing various monomers in the presence of the fourth polymerization catalyst composition.

-First polymerization catalyst composition-
As the first polymerization catalyst composition (hereinafter also referred to as “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, the rare earth element compound or the reaction product having no bond between the rare earth element and carbon,
Component (B1): an ionic compound (B1-1) composed of a non-coordinating anion and a cation, an aluminoxane (B1-2), a Lewis acid, a complex of a metal halide and a Lewis base, and an active halogen And a polymerization catalyst composition containing at least one selected from the group consisting of at least one halogen compound (B1-3) among the organic compounds.
When the first polymerization catalyst composition contains at least one of the ionic compound (B1-1) and the halogen compound (B1-3), the polymerization catalyst composition further comprises:
(C1) Component: 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. 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 a periodic rule. When it is a metal selected from group 1 of the table, a is 1 and b and c are 0, and when Y is a metal selected from groups 2 and 12 of the periodic table , A and b are 1 and c is 0, and 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) have no carbon atom to be supplied to the component (A1), the carbon source for the component (A1) is the above ( C1) component is required. Even when the polymerization catalyst composition contains the aluminoxane (B1-2), the polymerization catalyst composition can contain the component (C1). The first polymerization catalyst composition may contain other components contained in a normal rare earth compound polymerization catalyst composition, such as a cocatalyst.
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.
Furthermore, 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. Here, the reaction of the rare earth element compound and the rare earth element compound with the Lewis base is performed. The object does not have a bond between rare earth element and carbon. When the rare earth element compound and the reactant do not have a rare earth element-carbon bond, the compound is stable and easy to handle. Here, the rare earth element compound is a rare earth element (M), that is, a lanthanoid element composed of elements having atomic numbers 57 to 71 in the periodic table, or a compound containing scandium or yttrium.
Specific examples of the lanthanoid element include lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium. In addition, the said (A1) component may be used individually by 1 type, and may be used in combination of 2 or more type.

The rare earth element compound is preferably a rare earth metal divalent or trivalent salt or complex compound, and one or more coordinations selected from a hydrogen atom, a halogen atom and an organic compound residue. More preferably, the rare earth element compound contains a child. Furthermore, the reaction product of the rare earth element compound or the rare earth element compound and a Lewis base is represented by the following general formula (II) or (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 independently represents a hydrogen atom, a halogen atom, an alkoxy group, a thiolate group, an amino group, a silyl group, an aldehyde residue, A ketone residue, a carboxylic acid residue, a thiocarboxylic acid residue or a phosphorus compound residue, L ¹¹ represents a Lewis base, and w represents 0 to 3.

Examples of the group (ligand) bonded to the rare earth element of the rare earth element compound include a hydrogen atom, a halogen atom, an alkoxy group (a group in which an alcohol hydroxyl group is removed, and forms a metal alkoxide), a thiolate group ( A group obtained by removing hydrogen from a thiol group of a thiol compound and forming a metal thiolate), an amino group (a group obtained by removing one hydrogen atom bonded to a nitrogen atom of ammonia, a primary amine, or a secondary amine) And forms a metal amide), silyl group, aldehyde residue, ketone residue, carboxylic acid residue, thiocarboxylic acid residue, and phosphorus compound residue.
Specific examples of the group (ligand) include a hydrogen atom; an aliphatic alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group; Phenoxy group, 2,6-di-tert-butylphenoxy group, 2,6-diisopropylphenoxy group, 2,6-dineopentylphenoxy group, 2-tert-butyl-6-isopropylphenoxy group, 2-tert-butyl -6-neopentylphenoxy group, 2-isopropyl-6-neopentylphenoxy group; thiomethoxy group, thioethoxy group, thiopropoxy group, thio n-butoxy group, thioisobutoxy group, thiosec-butoxy group, thiotert-butoxy Aliphatic thiolate groups such as thiophenoxy groups, 2,6-di-tert-butyl Ofenoxy group, 2,6-diisopropylthiophenoxy group, 2,6-dineopentylthiophenoxy group, 2-tert-butyl-6-isopropylthiophenoxy group, 2-tert-butyl-6-thioneopentylphenoxy group, Arylthiolate groups such as 2-isopropyl-6-thioneopentylphenoxy group and 2,4,6-triisopropylthiophenoxy group; aliphatic amino groups such as dimethylamino group, diethylamino group and diisopropylamino group; phenylamino group; 2,6-di-tert-butylphenylamino group, 2,6-diisopropylphenylamino group, 2,6-dineopentylphenylamino group, 2-tert-butyl-6-isopropylphenylamino group, 2-tert- Butyl-6-neopentylphenylamino group, -Arylamino groups such as isopropyl-6-neopentylphenylamino group, 2,4,6-tri-tert-butylphenylamino group; bistrialkylsilylamino groups such as bistrimethylsilylamino group; trimethylsilyl group, tris (trimethylsilyl) Silyl groups such as silyl group, bis (trimethylsilyl) methylsilyl group, trimethylsilyl (dimethyl) silyl group, triisopropylsilyl (bistrimethylsilyl) silyl group; halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom, etc. .
As the group (ligand), a residue of an aldehyde such as salicylaldehyde, 2-hydroxy-1-naphthaldehyde, 2-hydroxy-3-naphthaldehyde; 2′-hydroxyacetophenone, 2′-hydroxybutyrophenone Residues of hydroxyphenones such as 2′-hydroxypropiophenone; residues of diketones such as acetylacetone, benzoylacetone, propionylacetone, isobutylacetone, valerylacetone, ethylacetylacetone; isovaleric acid, caprylic acid, octanoic acid, Lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, linoleic acid, cyclopentanecarboxylic acid, naphthenic acid, ethylhexanoic acid, pivalic acid, versatic acid [trade name, manufactured by Shell Chemical Co., C10 Monocarbo Synthetic acids composed of a mixture of isomers of acids], residues of carboxylic acids such as phenylacetic acid, benzoic acid, 2-naphthoic acid, maleic acid, succinic acid; hexanethioic acid, 2,2-dimethylbutanethioic acid, Residues of thiocarboxylic acids such as decanethioic acid, thiobenzoic acid; dibutyl phosphate, dipentyl phosphate, dihexyl phosphate, diheptyl phosphate, dioctyl phosphate, bis (2-ethylhexyl phosphate), bis (1-methyl phosphate) Heptyl), dilauryl phosphate, dioleyl phosphate, diphenyl phosphate, bis (p-nonylphenyl) phosphate, bis (polyethylene glycol-p-nonylphenyl) phosphate, (butyl) phosphate (2-ethylhexyl), phosphorus Acid (1-methylheptyl) (2-ethylhexyl), phosphoric acid (2-ethylhexyl) (p-nonylphenyl) Phosphoric acid ester residues such as: 2-ethylhexylphosphonic acid monobutyl, 2-ethylhexylphosphonic acid mono-2-ethylhexyl, phenylphosphonic acid mono-2-ethylhexyl, 2-ethylhexylphosphonic acid mono-p-nonylphenyl, phosphonic acid Residues of phosphonates such as mono-2-ethylhexyl, mono-1-methylheptyl phosphonate, mono-p-nonylphenyl phosphonate; dibutylphosphinic acid, bis (2-ethylhexyl) phosphinic acid, bis (1-methyl) Heptyl) phosphinic acid, dilaurylphosphinic acid, dioleylphosphinic acid, diphenylphosphinic acid, bis (p-nonylphenyl) phosphinic acid, butyl (2-ethylhexyl) phosphinic acid, (2-ethylhexyl) (1-methylheptyl) phosphine acid (2-ethylhexyl) (p-nonylphenyl) phosphinic acid, butylphosphinic acid, 2-ethylhexylphosphinic acid, 1-methylheptylphosphinic acid, oleylphosphinic acid, laurylphosphinic acid, phenylphosphinic acid, p-nonylphenylphosphinic acid And phosphinic acid residues such as
In addition, these groups (ligand) may be used individually by 1 type, and may be used in combination of 2 or more type.

In the component (A1) used in the first polymerization catalyst composition, examples of the Lewis base that reacts with the rare earth element compound include tetrahydrofuran, diethyl ether, dimethylaniline, trimethylphosphine, lithium chloride, neutral olefins, Diolefins and the like. Here, when the rare earth element compound reacts with a plurality of Lewis bases (in the general formulas (II) and (III), when w is 2 or 3), the Lewis base L ¹¹ may be the same. 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 lanthanoid elements, scandium and yttrium, and NQ ¹ , NQ ² and NQ ³ are amino groups, which may be the same or different, provided that It preferably contains a compound represented by (having an MN bond).
That is, the compound represented by the general formula (IV) is a metal amide having three MN bonds. Having three MN bonds has the advantage that the structure is stable because each bond is chemically equivalent and therefore easy to handle.

In the 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-tert-butylphenylamino group; bistrialkylsilylamino groups such as bistrimethylsilylamino group Either may be used, but a bistrimethylsilylamino group is preferred.

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 mol of the component (A1).

The ionic compound (B1-1) comprises a non-coordinating anion and a cation, and reacts with a reaction product of the rare earth element compound or the Lewis base as the component (A1) to form a cationic transition metal compound. Examples include ionic compounds that can be generated.
Here, as the non-coordinating anion, for example, tetraphenyl borate, tetrakis (monofluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis ( Pentafluorophenyl) borate, tetrakis (tetrafluoromethylphenyl) borate, tetra (tolyl) borate, tetra (xylyl) borate, (triphenyl, pentafluorophenyl) borate, [tris (pentafluorophenyl), phenyl] borate, tri Decahydride-7,8-dicarbaound 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, and a ferrocenium cation having a transition metal. Specific examples of the carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation and tri (substituted phenyl) carbonium cation, and more specifically, as tri (substituted phenyl) carbonyl cation, Examples include tri (methylphenyl) carbonium cation, tri (dimethylphenyl) carbonium cation, and the like. Specific examples of ammonium cations include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, and tributylammonium cation (eg, tri (n-butyl) ammonium cation); 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 Is mentioned. Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation.
Accordingly, the ionic compound (B1-1) is preferably a compound selected and combined from the above-mentioned non-coordinating anions and cations, specifically, N, N-dimethylanilinium tetrakis (pentafluorophenyl). Borate, triphenylcarbonium tetrakis (pentafluorophenyl) borate and the like are preferable. Moreover, these ionic compounds (B1-1) can be used alone or in a mixture of two or more. The content of the ionic compound (B1-1) in the first polymerization catalyst composition is preferably 0.1 to 10 times mol and about 1 time mol to the component (A1). Is more preferable.

The aluminoxane (B1-2) is a compound obtained by bringing an organoaluminum compound into contact with a condensing agent. For example, a chain having a repeating unit represented by the general formula: (—Al (R ′) O—) Aluminoxane or cyclic aluminoxane (wherein R ′ is a hydrocarbon group having 1 to 10 carbon atoms, some of the hydrocarbon groups may be substituted with a halogen atom and / or an alkoxy group, and the polymerization degree of the repeating unit) Is preferably 5 or more, more preferably 10 or more). Here, specific examples of R ′ include a methyl group, an ethyl group, a propyl group, and an isobutyl group, and among these, a methyl group is preferable. Examples of the organoaluminum compound used as the raw material for the aluminoxane include trialkylaluminums such as trimethylaluminum, triethylaluminum, tributylaluminum, triisobutylaluminum, and mixtures thereof, and trimethylaluminum is particularly preferable. For example, an aluminoxane using a mixture of trimethylaluminum and tributylaluminum as a raw material can be preferably used. The content of the aluminoxane (B1-2) in the first polymerization catalyst composition is such that the element ratio Al / M of the aluminum element Al of the aluminoxane to the rare earth element M constituting the component (A1) is about 10 to 1000. It is preferable that

The halogen compound (B1-3) is composed of at least one of a Lewis acid, a complex compound of a metal halide and a Lewis base, and an organic compound containing an active halogen. For example, the rare earth element compound as the component (A1) or By reacting with the reaction product with the Lewis base, a cationic transition metal compound, a halogenated transition metal compound, or a compound having a transition metal center with insufficient charge can be generated. 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, boron-containing halogen compounds such as B (C ₆ F ₅ ) ₃ and aluminum-containing halogen compounds such as Al (C ₆ F ₅ ) ₃ can be used. A halogen compound containing an element belonging to Group 4, Group 5, Group 6, or Group 8 can also be used. Preferably, aluminum halide or organometallic halide is used. Moreover, as a halogen element, chlorine or bromine is preferable.
Specific examples of the Lewis acid include methyl aluminum dibromide, methyl aluminum dichloride, ethyl aluminum dibromide, ethyl aluminum dichloride, butyl aluminum dibromide, butyl aluminum dichloride, dimethyl aluminum bromide, dimethyl aluminum chloride, diethyl aluminum bromide, diethyl Aluminum chloride, dibutylaluminum bromide, dibutylaluminum chloride, methylaluminum sesquibromide, methylaluminum sesquichloride, ethylaluminum sesquibromide, ethylaluminum sesquichloride, dibutyltin dichloride, aluminum tribromide, antimony trichloride, antimony pentachloride, phosphorus trichloride , Pentachloride , Tin tetrachloride, titanium tetrachloride, tungsten hexachloride, etc., among which diethylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, diethylaluminum bromide, ethylaluminum sesquibromide, ethylaluminum dibromide preferable.

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

Moreover, as a Lewis base which comprises the complex compound of the said metal halide and a Lewis base, a phosphorus compound, a carbonyl compound, a nitrogen compound, an ether compound, alcohol, etc. are preferable. Specifically, tributyl phosphate, tri-2-ethylhexyl phosphate, triphenyl phosphate, tricresyl phosphate, triethylphosphine, tributylphosphine, triphenylphosphine, diethylphosphinoethane, diphenylphosphinoethane, acetylacetone, benzoylacetone , Propionitrile acetone, valeryl acetone, ethyl acetylacetone, methyl acetoacetate, ethyl acetoacetate, phenyl acetoacetate, dimethyl malonate, diethyl malonate, diphenyl malonate, acetic acid, octanoic acid, 2-ethyl-hexanoic acid, olein Acid, stearic acid, benzoic acid, naphthenic acid, versatic acid, triethylamine, N, N-dimethylacetamide, tetrahydrofuran, diphenyl ether, 2-ethyl-hexyl alcohol Examples include oleyl alcohol, stearyl alcohol, phenol, benzyl alcohol, 1-decanol, and lauryl alcohol. Among these, tri-2-ethylhexyl phosphate, tricresyl phosphate, acetylacetone, 2-ethylhexanoic acid, versatic acid, 2 -Ethylhexyl alcohol, 1-decanol, lauryl alcohol are preferred.
The Lewis base is reacted at a ratio of 0.01 to 30 mol, preferably 0.5 to 10 mol, per mol of the metal halide. When the reaction product with the Lewis base is used, the metal remaining in the polymer can be reduced.

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

The component (C1) used in the first polymerization catalyst composition is 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. 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 a periodic rule. When it is a metal selected from group 1 of the table, a is 1 and b and c are 0, and when Y is a metal selected from groups 2 and 12 of the periodic table , A and b are 1 and c is 0, and 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)
(Wherein, R ¹ and R ² is a hydrocarbon group or a hydrogen atom, monovalent 1-10 carbon atoms, 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).
Examples of the organoaluminum compound of the general formula (V) include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, and 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, dihydrogen hydride Isohexyl aluminum, dioctyl aluminum hydride, diisooctyl aluminum hydride; ethyl aluminum dihydride, n-propyl al Bromide dihydride, include isobutyl aluminum dihydride and the like, among these, triethylaluminum, triisobutylaluminum, hydrogenated diethylaluminum, hydrogenated diisobutylaluminum are preferred. The organometallic compound as the component (C1) described above can be used singly 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 for the component (A1).

Addition of the additive (D1) that can be an anionic ligand is preferable because it provides an effect that a multi-component copolymer having a higher cis-1,4 bond content can be synthesized in a high yield.
The additive (D1) is not particularly limited as long as it can exchange with the amino group of the component (A1), but preferably has any of OH, NH, and SH groups.

Specific examples of compounds having an OH group include aliphatic alcohols and aromatic alcohols. Specifically, 2-ethyl-1-hexanol, dibutylhydroxytoluene, alkylated phenol, 4,4′-thiobis- (6-tert-butyl-3-methylphenol), 4,4′-butylidenebis- (6 -T-butyl-3-methylphenol), 2,2'-methylenebis- (4-methyl-6-t-butylphenol), 2,2'-methylenebis- (4-ethyl-6-t-butylphenol), 2 , 6-di-t-4-ethylphenol, 1,1,3-tris- (2-methyl-4-hydroxy-5-t-butylphenyl) butane, n-octadecyl-3- (4-hydroxy-3 , 5-di-t-butylphenyl) propionate, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, dill Li thiodipropionate, distearyl thiodipropionate, may be mentioned di-myristyl thio propionate, but is not limited thereto. For example, as a hindered phenol type, triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [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 ′ Hexamethylene bis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 3,5-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, 1,3,5- Trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, octyl Diphenylamine, 2,4-bis [(octylthio) methyl] -o-cresol, and the like. Further, examples of the hydrazine series include N, N′-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine.

Examples of those having an NH group include primary amines and secondary amines such as alkylamines and arylamines. Specific examples 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, and compounds represented by the following general formulas (VI) and (VII).

Wherein R ¹ , R ² and R ³ are each independently —O—C _j H _{2j + 1} , — (O—C _k H _2k —) _a —O—C _m H _{2m + 1} or — C _n H _{2n + 1} , j, m and n are each independently 0 to 12, k and a are each independently 1 to 12, and R ⁴ is 1 to 12 carbon atoms. 12 is a linear, branched, or cyclic, saturated or unsaturated alkylene group, cycloalkylene group, cycloalkylalkylene group, cycloalkenylalkylene group, alkenylene group, cycloalkenylene group, cycloalkylalkenylene group, cyclohexane An alkenylalkenylene group, an arylene group or an aralkylene group.)
Specific examples of those represented by the general formula (VI) include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, (mercaptomethyl) dimethylethoxysilane, mercaptomethyltri And methoxysilane.

Wherein W is —NR ⁸ —, —O— or —CR ⁹ R ¹⁰ — (wherein R ⁸ and R ⁹ are —C _p H _{2p + 1} , R ¹⁰ is —C _q H _{2q + 1} , p and q are each independently 0 to 20, and R ⁵ and R ⁶ are each independently —M—C _r H _2r — (where M is —O— or —CH ₂ —, and r is 1 to 20, and R ⁷ is —O—C _j H _{2j + 1} , — (O—C _k H _2k —). _a —O—C _m H _{2m + 1} or —C _n H _{2n + 1} , j, m and n are each independently 0 to 12, and k and a are each independently 1 to is 12, R ⁴ is a 1 to 12 carbon atoms, a straight-chain, branched, or cyclic, saturated or unsaturated, alkylene group, cycloalkylene group, cycloalkylalkylene group, a cycloalkenyl alkylene group, an alkenylene , Cycloalkenylene group, a cycloalkyl alkenylene group, cycloalkenyl alkenylene group, an arylene group or an aralkylene group.)
Specific examples of the compound represented by the general formula (VII) include 3-mercaptopropyl (ethoxy) -1,3-dioxa-6-methylaza-2-silacyclooctane, 3-mercaptopropyl (ethoxy) -1,3. -Dioxa-6-butylaza-2-silacyclooctane, 3-mercaptopropyl (ethoxy) -1,3-dioxa-6-dodecylaza-2-silacyclooctane, and the like.

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

The additive (D1) is preferably added in an amount of 0.01 to 10 mol, particularly 0.1 to 1.2 mol with respect to 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. Further, the addition amount is preferably the same amount (1.0 mol) as the rare earth element compound, but an excessive amount may be added. Moreover, it is preferable that the addition amount be 1.2 mol or less because there is little loss of reagent.

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

When the coordination 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 ditolylphosphino 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 preferably exemplified.

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

When the coordination atom contained in E ¹ and E ² is O, the neutral electron donating group E ¹ or E ² is an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, or a butoxy group; Examples thereof include aryloxy groups such as phenoxy group and 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 alkylthio group such as a methylthio group, an ethylthio group, a propylthio group, or a butylthio group; Examples thereof include arylthio groups such as phenylthio group and tolylthio group.

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

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

-Second polymerization catalyst composition-
As the second polymerization catalyst composition (hereinafter also referred to as “second polymerization catalyst composition”), the following general formula (IX):

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

(In the formula, M represents a lanthanoid element, scandium or yttrium, Cp ^R each independently represents an unsubstituted or substituted indenyl group, and X ′ represents a hydrogen atom, a halogen atom, an 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, and w represents an integer of 0 to 3), Formula (XI):

(In the formula, M represents a lanthanoid element, scandium or yttrium, Cp ^{R ′} represents unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl, and X represents a hydrogen atom, a halogen atom, an alkoxy group or a thiolate group. , An amino group, a silyl group or a 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] ⁻ represents non- And a polymerization catalyst composition containing at least one complex selected from the group consisting of a half metallocene cation complex represented by the following formula:

The second polymerization catalyst composition may further contain other components contained in the polymerization catalyst composition containing a normal metallocene complex, such as a promoter. Here, the metallocene complex is a complex compound in which one or more cyclopentadienyl or a derivative thereof is bonded to a central metal, and in particular, one cyclopentadienyl or a derivative thereof bonded to the central metal. A certain metallocene complex may be called a half metallocene complex.
In the polymerization reaction system, the concentration of the complex contained in the 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 having an indenyl ring as a basic skeleton can be represented by C ₉ H _7-x R _x or C ₉ H _11-x R _x . Here, X is an integer of 0 to 7 or 0 to 11. In addition, each R is preferably independently a hydrocarbyl group or a metalloid group. The number of carbon atoms in the hydrocarbyl group is preferably 1-20, more preferably 1-10, and even more preferably 1-8. Specific examples of the hydrocarbyl group include a methyl group, an ethyl group, a phenyl group, and a benzyl group. On the other hand, examples of metalloid group metalloids include germyl Ge, stannyl Sn, and silyl Si, and the metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group that the metalloid group has is the above hydrocarbyl group. It is the same. Specific examples of the metalloid group include a trimethylsilyl group. Specific examples of the substituted indenyl include 2-phenylindenyl, 2-methylindenyl and the like. In addition, two Cp ^R in general formula (IX) and (X) may mutually be same or different.

In the half metallocene cation complex represented by the general formula (XI), Cp ^{R ′} in the formula is unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl, and among these, unsubstituted or substituted indenyl It is preferable that

In the general formula (XI), Cp ^{R ′} having the cyclopentadienyl ring as a basic skeleton is represented by C ₅ H _5-x R _x . Here, X is an integer of 0 to 5. In addition, each R is preferably independently a hydrocarbyl group or a metalloid group. The number of carbon atoms in the hydrocarbyl group is preferably 1-20, more preferably 1-10, and even more preferably 1-8. Specific examples of the hydrocarbyl group include a methyl group, an ethyl group, a phenyl group, and a benzyl group. On the other hand, examples of metalloid group metalloids include germyl Ge, stannyl Sn, and silyl Si, and the metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group that the metalloid group has is the above hydrocarbyl group. It is the same. Specific examples of the metalloid group include a trimethylsilyl group. Specific examples of Cp ^{R ′} having a cyclopentadienyl ring as a basic skeleton include the following.

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

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

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

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

The metallocene complex represented by the general formula (IX) includes a silylamide ligand [—N (SiR ₃ ) ₂ ]. The R groups (R ^a to R ^f in the general formula (IX)) contained in the silylamide ligand are each independently an alkyl group having 1 to 3 carbon atoms or a hydrogen atom. Further, it is preferable that at least one of R ^a to R ^f is a hydrogen atom. By making at least one of R ^a to R ^f a hydrogen atom, the synthesis of the catalyst is facilitated, and the bulk around silicon is reduced, so that non-conjugated olefin compounds and aromatic vinyl compounds are introduced. It becomes easy. From the same viewpoint, it is more preferable that at least one of R ^a to R ^c is a hydrogen atom and at least one of R ^d to R ^f is a hydrogen atom. Furthermore, a methyl group is preferable as the alkyl group.

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

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 or an iodine atom, but is preferably a chlorine atom or a bromine atom.

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

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

In the general formula (XI), examples of the amino group represented by X include aliphatic amino groups such as dimethylamino group, diethylamino group and diisopropylamino group; phenylamino group, 2,6-di-tert-butylphenylamino group, 2 , 6-diisopropylphenylamino group, 2,6-dineopentylphenylamino group, 2-tert-butyl-6-isopropylphenylamino group, 2-tert-butyl-6-neopentylphenylamino group, 2-isopropyl- Examples thereof include arylamino groups such as 6-neopentylphenylamino group and 2,4,6-tri-tert-butylphenylamino group; bistrialkylsilylamino groups such as bistrimethylsilylamino group. Among these, bistrimethylsilylamino Groups are preferred.

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

In the general formula (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, Linear or branched aliphatic hydrocarbon groups such as isobutyl, sec-butyl, tert-butyl, neopentyl, hexyl and octyl; aromatic hydrocarbons such as phenyl, tolyl and naphthyl Groups; aralkyl groups such as benzyl groups, etc .; hydrocarbon groups containing silicon atoms such as trimethylsilylmethyl groups, bistrimethylsilylmethyl groups, etc., among these, methyl groups, ethyl groups, isobutyl groups, trimethylsilylmethyl Groups and the like are preferred.

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

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

The metallocene complex represented by the above general formulas (IX) and (X) and the half metallocene cation complex represented by the above general formula (XI) may further have 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 includes a plurality of neutral Lewis bases L, the neutral Lewis bases L may be the same or different.

Further, the metallocene complex represented by the general formulas (IX) and (X) and the half metallocene cation complex represented by the general formula (XI) may exist as a monomer, and may be a dimer. Or it may exist as a multimer more than that.

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

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

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

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

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

Here, in the compound represented by the general formula (XII), M represents a lanthanoid element, scandium or yttrium, and Cp ^{R ′} independently represents unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl. , X represents a hydrogen atom, a halogen atom, an 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, w represents An integer from 0 to 3 is shown. In the ionic compound represented by the general formula [A] ⁺ [B] ⁻ , [A] ⁺ represents a cation, and [B] ⁻ represents a non-coordinating anion.

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

The ionic compound represented by the general formula [A] ⁺ [B] ⁻ used for the above reaction is a compound selected and combined from the above non-coordinating anions and cations, and is an N, N-dimethylaniline. Preference is given to nium tetrakis (pentafluorophenyl) borate, triphenylcarbonium tetrakis (pentafluorophenyl) borate and the like. 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 based on the metallocene complex. When the half metallocene cation complex represented by the general formula (XI) is used for 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, or 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 You may form the half metallocene cation complex represented by this. Further, by using a combination of a metallocene complex represented by the general formula (IX) or (X) and an ionic compound represented by the general formula [A] ⁺ [B] ⁻ , A half metallocene cation complex represented by (XI) can also be formed.

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

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

On the other hand, as the organoaluminum compound, the general formula AlRR′R ″ (wherein R and R ′ are each independently a monovalent hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, or a hydrogen atom). , R ″ is a monovalent hydrocarbon group having 1 to 10 carbon atoms). 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, and dialkylaluminum hydride. Among these, trialkylaluminum is preferable. Examples of the trialkylaluminum include triethylaluminum and triisobutylaluminum. The content of the organoaluminum compound in the polymerization catalyst composition is preferably 1 to 50 times mol, more preferably about 10 times mol relative to the metallocene complex.

Furthermore, in the polymerization catalyst composition, each of the metallocene complex represented by the general formulas (IX) and (X) and the half metallocene cation complex represented by the general formula (XI) is used as an appropriate promoter. In combination, the cis-1,4 bond content and the molecular weight of the resulting polymer can be increased.

-Third polymerization catalyst composition-
As the third polymerization catalyst composition (hereinafter, also referred to as “third polymerization catalyst composition”), as the rare earth element-containing compound, the following general formula (XIII):
R _a MX _b QY _b (XIII)
(In the formula, each R independently represents unsubstituted or substituted indenyl, the R is coordinated to M, M represents a lanthanoid element, scandium or yttrium, and each X independently represents carbon. 1 represents a monovalent hydrocarbon group of 1 to 20, wherein X is μ-coordinated to M and Q, Q represents a group 13 element of the periodic table, and Y represents each independently a carbon number A polymerization catalyst composition comprising a metallocene composite catalyst represented by 1-20 monovalent hydrocarbon groups or hydrogen atoms, wherein Y is coordinated to Q, and a and b are 2. Is mentioned.

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

(In the formula, M ¹ represents a lanthanoid element, scandium or yttrium, Cp ^R independently represents an unsubstituted or substituted indenyl group, and R ^A and R ^B each independently represents one having 1 to 20 carbon atoms. R ^A and R ^B are μ-coordinated to M ¹ and Al, and R ^C and R ^D each independently represent a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom. Metallocene-based composite catalysts represented by
By using the metallocene polymerization catalyst, a multi-component copolymer can be produced. In addition, by using the metallocene composite catalyst, for example, a catalyst previously combined with an aluminum catalyst, it is possible to reduce or eliminate the amount of alkylaluminum used during the synthesis of the multi-component copolymer. When a conventional catalyst system is used, it is necessary to use a large amount of alkylaluminum at the time of synthesizing the multicomponent copolymer. For example, in the conventional catalyst system, it is necessary to use an alkylaluminum of 10 molar equivalents or more with respect to the metal catalyst. Catalysis is exerted.

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

In the general formula (XIII), each R is independently an unsubstituted indenyl or a substituted indenyl, and the R is coordinated to the metal M. Specific examples of substituted indenyl include, for example, 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 a group 13 element in the periodic table, and specific examples include boron, aluminum, gallium, indium, thallium and the like.

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

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

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

In the general formula (XIV), Cp ^R is unsubstituted indenyl or substituted indenyl. Cp ^R having an indenyl ring as a basic skeleton can be represented by C ₉ H _7X R _X or C ₉ H _11X R _X. Here, X is an integer of 0 to 7 or 0 to 11. In addition, each R is preferably independently a hydrocarbyl group or a metalloid group. The number of carbon atoms in the hydrocarbyl group is preferably 1-20, more preferably 1-10, and even more preferably 1-8. Specific examples of the hydrocarbyl group include a methyl group, an ethyl group, a phenyl group, and a benzyl group. On the other hand, examples of metalloid group metalloids include germyl Ge, stannyl Sn, and silyl Si, and the metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group that the metalloid group has is the above hydrocarbyl group. It is the same. Specific examples of the metalloid group include a trimethylsilyl group.
Specific examples of the substituted indenyl include 2-phenylindenyl, 2-methylindenyl and the like. Note that the two Cp ^R 's in formula (XIV) may be the same or different from each other.

In the general formula (XIV), R ^A and R ^B each independently represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, and R ^A and R ^B are μ-coordinated to M ¹ and Al. doing. Here, the monovalent hydrocarbon group having 1 to 20 carbon atoms includes methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group. Tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, stearyl group and the like. Note that the μ coordination is a coordination mode having a crosslinked structure.

In the general formula (XIV), R ^C and R ^D are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom. Here, the monovalent hydrocarbon group having 1 to 20 carbon atoms includes methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tridecyl group. Tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, stearyl group and the like.

The metallocene composite catalyst is, for example, in a solvent, represented by the following general formula (XV):

( ^Wherein M ² represents a lanthanoid element, scandium or yttrium, Cp ^R independently represents unsubstituted or substituted indenyl, and R ^E to R ^J each independently represents 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 0-3), an organoaluminum compound represented by AlR ^K R ^L R ^M It is obtained by reacting with. In addition, since reaction temperature should just be about room temperature, it can manufacture on mild conditions. The reaction time is arbitrary, but is about several hours to several tens of hours. The reaction solvent is not particularly limited, but is preferably a solvent that dissolves the raw material and the product. For example, toluene or hexane may be used. The structure of the metallocene composite catalyst is preferably determined by ¹ H-NMR or X-ray structural analysis.

In the metallocene complex represented by the general formula (XV), Cp ^R is unsubstituted indenyl or substituted indenyl, and has the same meaning as Cp ^R in the general formula (XIV). In the above 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 formula (XIV).

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

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

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

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

Specific examples of the organoaluminum compound include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, tripentylaluminum, tri Hexyl aluminum, tricyclohexyl aluminum, trioctyl aluminum; diethyl aluminum hydride, di-n-propyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl aluminum hydride, dihexyl aluminum hydride, diisohexyl aluminum hydride , Dioctylaluminum hydride, diisooctylaluminum hydride; ethylaluminum dihydride, n-propylaluminum Muzi hydride, isobutylaluminum dihydride and the like. Among these, triethylaluminum, triisobutylaluminum, hydrogenated diethylaluminum, hydrogenated diisobutylaluminum are preferred. Moreover, these organoaluminum compounds can be used individually by 1 type, or 2 or more types can be mixed and used for them. The amount of the organoaluminum compound used for the production of the metallocene composite catalyst is preferably 1 to 50 times mol, more preferably about 10 times mol relative to the metallocene complex.

The third polymerization catalyst composition may include the metallocene composite catalyst and a boron anion, and further, other components contained in the polymerization catalyst composition including a normal metallocene catalyst, such as a promoter. It is preferable to contain. The metallocene composite catalyst and boron anion are also referred to as a two-component catalyst. According to the third polymerization catalyst composition, since the boron anion is further contained in the same manner as the metallocene composite catalyst, the content of each monomer component in the 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 a tetravalent boron anion. For example, tetraphenylborate, tetrakis (monofluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis (pentafluorophenyl) borate, tetrakis (tetrafluoromethyl) Phenyl) borate, tetra (tolyl) borate, tetra (xylyl) borate, (triphenyl, pentafluorophenyl) borate, [tris (pentafluorophenyl), phenyl] borate, tridecahydride-7,8-dicarboundecaborate 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, and a ferrocenium cation having a transition metal. Examples of the carbonium cation include trisubstituted carbonium cations such as a triphenylcarbonium cation and a tri (substituted phenyl) carbonium cation. The tri (substituted phenyl) carbonyl cation is specifically exemplified by tri (methylphenyl). ) Carbonium cation and the like. Examples of amine cations include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, and tributylammonium cation; N, N-dimethylanilinium cation, N, N-diethylanilinium cation, N, N— N, N-dialkylanilinium cations such as 2,4,6-pentamethylanilinium cation; dialkylammonium cations such as diisopropylammonium cation and dicyclohexylammonium cation. Examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation. Among these cations, N, N-dialkylanilinium cation or carbonium cation is preferable, and N, N-dialkylanilinium cation is particularly preferable. Therefore, as the ionic compound, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbonium tetrakis (pentafluorophenyl) borate and the like are preferable. 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 based on the metallocene composite catalyst.

When a boron anion is present in the reaction system in which the metallocene complex represented by the general formula (XV) is reacted with the organoaluminum compound, the metallocene composite catalyst of the general formula (XIV) can be synthesized. Can not. Therefore, for the preparation of the third polymerization catalyst composition, it is necessary to synthesize the metallocene composite catalyst in advance, isolate and purify the metallocene composite catalyst, and then combine with the boron anion.

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

-Fourth polymerization catalyst composition-
The fourth polymerization catalyst composition (hereinafter also referred to as “fourth polymerization catalyst composition”)
A rare earth element compound (component (A2)),
・ Cyclopentadiene skeleton-containing compound selected from substituted or unsubstituted cyclopentadiene, substituted or unsubstituted indene (compound having an indenyl group), and substituted or unsubstituted fluorene (hereinafter simply referred to as “cyclopentadiene skeleton-containing compound”) ) (Component (B2)),
It is necessary to include.
In addition, the fourth polymerization catalyst composition,
・ Organic metal compound (component (C2)),
・ Aluminoxane compound ((D2 component)),
・ Halogen compounds (component (E2)),
May be included.

The fourth polymerization catalyst composition preferably has high solubility in aliphatic hydrocarbons, and is preferably a homogeneous solution in aliphatic hydrocarbons. Here, examples of the aliphatic hydrocarbon include hexane, cyclohexane, pentane, and the like.
And it is preferable that a 4th polymerization catalyst composition does not contain an aromatic hydrocarbon. Here, examples of the aromatic hydrocarbon include benzene, toluene, xylene, and the like.
In addition, "it does not contain an aromatic hydrocarbon" means that the ratio of the aromatic hydrocarbon contained in a polymerization catalyst composition is less than 0.1 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 compounds 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 include lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, 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, the rare earth element-containing compound and the reaction product of the rare earth element-containing compound and the Lewis base preferably do not have a bond between the rare earth element and carbon. When the rare earth element-containing compound and the reactant do not have a rare earth element-carbon bond, the compound is stable and easy to handle.
In addition, the said (A2) component may be used individually by 1 type, and may be used in combination of 2 or more type.

As the component (A2), the following general formula (XVI):
M- (AQ ¹ ) (AQ ² ) (AQ ³ ) (XVI)
[Wherein M is a scandium, yttrium or lanthanoid element; AQ ¹ , AQ ² and AQ ³ are functional groups which may be the same or different; A is nitrogen, oxygen or sulfur; Yes; provided that it has at least one MA bond]. Here, the lanthanoid elements are specifically lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium. The compound is a component that can improve the catalytic activity in the reaction system, shorten the reaction time, and increase the reaction temperature.

As M in the general formula (XVI), gadolinium is particularly preferable from the viewpoint of enhancing catalyst activity and reaction controllability.

When A in the general formula (XVI) is nitrogen, examples of the functional group represented by AQ ¹ , AQ ² and AQ ³ (that is, NQ ¹ , NQ ² and NQ ³ ) include an amino group. And in this case, it has three MN bonds.
Examples of the amino group include aliphatic amino groups such as dimethylamino group, diethylamino group, and diisopropylamino group; phenylamino group, 2,6-di-tert-butylphenylamino group, 2,6-diisopropylphenylamino group, 2,6-dineopentylphenylamino group, 2-tert-butyl-6-isopropylphenylamino group, 2-tert-butyl-6-neopentylphenylamino group, 2-isopropyl-6-neopentylphenylamino group, Examples include arylamino groups such as 2,4,6-tri-tert-butylphenylamino group; bistrialkylsilylamino groups such as bistrimethylsilylamino group, and are particularly soluble in aliphatic hydrocarbons and aromatic hydrocarbons. From the viewpoint, a bistrimethylsilylamino group is preferable. The said amino group may be used individually by 1 type, and may be used in combination of 2 or more type.
According to the above configuration, the component (A2) can be a compound having three MN bonds, and each bond becomes chemically equivalent, and the structure of the compound becomes stable, so that handling is easy.
Moreover, if it is set as the said structure, the catalyst activity in a reaction system can further be 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 rare earth element-containing compound represented by the general formula (XVI) (that is, M- (OQ ¹ ) (OQ ² ) (OQ ³ )) is particularly limited. For example, the following general formula (XVII):
(RO) ₃ M (XVII)
Rare earth alcoholate represented by the following general formula (XVIII):
(R-CO ₂ ) ₃ M ... (XVIII)
And 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.
As the component (A2), since it is preferable not to have a bond between a rare earth element and carbon, the above-described compound (XVII) or compound (XVIII) can be suitably used.

When A in the general formula (XVI) is sulfur, the rare earth element-containing compound represented by the general formula (XVI) (that is, M- (SQ ¹ ) (SQ ² ) (SQ ³ )) is particularly limited. 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)
And the like. Here, in the general formulas (XIX) and (XX), R may be the same or different and is an alkyl group having 1 to 10 carbon atoms.
In addition, as the component (A2), since it is preferable not to have a bond between a rare earth element and carbon, the above-described compound (XIX) or compound (XX) can be suitably used.

The component (B2) is a compound selected from substituted or unsubstituted cyclopentadiene, substituted or unsubstituted indene, and substituted or unsubstituted fluorene.
In addition, the said (B2) component may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of the substituted or unsubstituted cyclopentadiene include cyclopentadiene, pentamethylcyclopentadiene, tetramethylcyclopentadiene, isopropylcyclopentadiene, trimethylsilyl-tetramethylcyclopentadiene, and the like.

Examples of the substituted or unsubstituted indene include indene, 2-phenyl-1H-indene, 3-benzyl-1H-indene, 3-methyl-2-phenyl-1H-indene, and 3-benzyl-2-phenyl-1H. -Indene, 1-benzyl-1H-indene, 1-methyl-3-dimethylbenzylsilyl-indene, 1,3- (t-BuMe ₂ Si) ₂ -indene and the like, and particularly the viewpoint of reducing the molecular weight distribution Therefore, 3-benzyl-1H-indene and 1-benzyl-1H-indene are preferable.

Examples of the substituted or unsubstituted fluorene include fluorene, trimethylsilylfluorene, isopropylfluorene, and the like.

As the organometallic compound (component (C2)), the following general formula (XXI):
YR ⁴ _a R ⁵ _b R ⁶ _c (XXI)
[Wherein Y is a metal element selected from the group consisting of elements of Group 1, Group 2, Group 12 and Group 13 of the Periodic Table; R ⁴ and R ⁵ are carbon atoms of 1; To 10 monovalent hydrocarbon groups or hydrogen atoms, and R ⁶ is a monovalent hydrocarbon group having 1 to 10 carbon atoms, provided that R ⁴ , R ⁵ and R ⁶ are the same as each other. And when Y is a Group 1 metal element, a is 1 and b and c are 0, and Y is a Group 2 or Group 12 metal element. A and b are 1 and c is 0, and when Y is a Group 13 metal element, a, b and c are 1). Is mentioned.
When the polymerization catalyst composition further contains a component (C2), the polymerization activity can be increased.
Here, from the viewpoint of enhancing the catalytic activity, it is preferable that at least one of R ⁴ , R ⁵ and R ⁶ is different in general formula (XXI).

Specifically, the component (C2) is represented by the following general formula (XXII):
AlR ⁴ _a R ⁵ _b R ⁶ _c (XXII)
[Wherein, R ⁴ and R ⁵ are monovalent hydrocarbon groups or hydrogen atoms having 1 to 10 carbon atoms; R ⁶ is a monovalent hydrocarbon group having 1 to 10 carbon atoms; R ⁴ , R ⁵ and R ⁶ may be the same or different from each other].

Examples of the organoaluminum compound include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, tripentylaluminum, and trihexyl. Aluminum, tricyclohexyl aluminum, trioctyl aluminum; diethyl aluminum hydride, di-n-propyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl aluminum hydride, dihexyl aluminum hydride, diisohexyl aluminum hydride, Dioctylaluminum hydride, diisooctylaluminum hydride; ethylaluminum dihydride, n-propylaluminium Dihydride, include isobutyl aluminum dihydride and the like, particularly, triethylaluminum, triisobutylaluminum, hydrogenated diethylaluminum, preferably diisobutylaluminum hydride, more particularly, diisobutylaluminum hydride are preferred.
The said organoaluminum compound may be used individually by 1 type, and may be used in combination of 2 or more type.

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

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

Examples of the component (D2) include the following formula (XXIII):
-(Al (R ⁷ ) O) _n- (XXIII)
(Wherein, R ⁷ is a hydrocarbon group having 1 to 10 carbon atoms, wherein a portion of the hydrocarbon group may be substituted by halogen and / or alkoxy group; R ⁷ is between the repeating units And may be the same or different; n is 5 or more).
The molecular structure of the aluminoxane may be linear or cyclic.

N in the formula (XXIII) is preferably 10 or more.
Moreover, regarding R ⁷ in the above formula (XXIII), examples of the hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isobutyl group, and the like, and a methyl group is particularly preferable. The hydrocarbon group may be one kind or a combination of two or more kinds. Regarding R ⁷ in formula (XXIII), the hydrocarbon group is preferably a combination of a methyl group and an isobutyl group.

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

The component (D2) is particularly represented by the following formula (XXIV):
-(Al (CH ₃ ) _x (iC ₄ H ₉ ) _y O) _m- (XXIV)
(In the formula, x + y is 1; m is 5 or more). Examples of TMAO include a product name “TMAO341” manufactured by Tosoh Fine Chemical Co., Ltd.

In addition, the component (D2) is particularly represented by the following formula (XXV):
-(Al (CH ₃ ) _0.7 (iC ₄ H ₉ ) _0.3 O) _k- (XXV)
(Wherein k is 5 or more), and may be a modified aluminoxane (hereinafter also referred to as “MMAO”). An example of MMAO is a product name “MMAO-3A” manufactured by Tosoh Fine Chemical Co., Ltd.

Furthermore, the component (D2) is particularly represented by the following formula (XXVI):
-[(CH ₃ ) AlO] _i- (XXVI)
(Wherein i is 5 or more), a modified aluminoxane (hereinafter also referred to as “PMAO”). An example of PMAO is “PMAO-211” manufactured by Tosoh Fine Chemical Co., Ltd.

The component (D2) is preferably MMAO or TMAO among the above-mentioned MMAO, TMAO, and PMAO from the viewpoint of improving the effect of improving the catalyst activity, and in particular, from the viewpoint of further enhancing the effect of improving the catalyst activity. More preferably, it is TMAO.

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

These compounds react with the component (A2), that is, a rare earth element-containing compound having an MA bond, or a reaction product of the rare earth element-containing compound and a Lewis base to form a cationic transition metal compound, a halogenated transition, A metal compound and / or a transition metal compound in which electrons are insufficient at the transition metal center are generated.
By further including the component (E2), the amount of cis-1,4 bonds of the conjugated diene unit can be particularly increased.

Examples of the (E2-1) component include elements of Group 3, Group 4, Group 5, Group 6, Group 8, Group 13, Group 14 or Group 15 of the Periodic Table. Examples of the halogen-containing compounds include aluminum halides and organometallic halides.
Examples of halogen-containing compounds that are Lewis acids include titanium tetrachloride, tungsten hexachloride, tri (pentafluorophenyl) borate, methylaluminum dibromide, methylaluminum dichloride, ethylaluminum dibromide, ethylaluminum dichloride, butylaluminum dibromide. , Butylaluminum dichloride, dimethylaluminum bromide, dimethylaluminum chloride, diethylaluminum bromide, diethylaluminum chloride, dibutylaluminum bromide, dibutylaluminum chloride, methylaluminum sesquibromide, methylaluminum sesquichloride, ethylaluminum sesquichloride, ethylaluminum sesquichloride, aluminum G Examples include bromide, tri (pentafluorophenyl) aluminum, dibutyltin dichloride, tin tetrachloride, phosphorus trichloride, phosphorus pentachloride, antimony trichloride, antimony pentachloride, etc., especially ethyl aluminum dichloride, ethyl aluminum dibromide, diethyl Aluminum chloride, diethylaluminum bromide, ethylaluminum sesquichloride, and ethylaluminum sesquibromide are preferred.
As halogen, chlorine or bromine is preferable.
The above-mentioned halogen-containing compound that is a Lewis acid (component (D-1)) 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. , 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, bromide Manganese, manganese iodide, rhenium chloride, rhenium bromide, rhenium iodide, copper chloride, copper iodide, silver chloride, silver bromide, silver iodide, gold chloride, gold iodide, gold bromide, etc. In particular, magnesium chloride, calcium chloride, barium chloride, zinc chloride, manganese chloride, and copper chloride are preferable, and more particularly, magnesium chloride. Um, zinc chloride, manganese chloride, copper chloride are preferable.
The Lewis base used for the component (E2-2) is preferably a phosphorus compound, a carbonyl compound, a nitrogen compound, an ether compound, or an alcohol.
For example, tributyl phosphate, tri-2-ethylhexyl phosphate, triphenyl phosphate, tricresyl phosphate, triethylphosphine, tributylphosphine, triphenylphosphine, diethylphosphinoethane, diphenylphosphinoethane, acetylacetone, benzoylacetone, propio Nitrile acetone, valeryl acetone, ethyl acetylacetone, methyl acetoacetate, ethyl acetoacetate, phenyl acetoacetate, dimethyl malonate, diethyl malonate, diphenyl malonate, acetic acid, octanoic acid, 2-ethylhexanoic acid, oleic acid, stearic acid Benzoic acid, naphthenic acid, versatic acid, triethylamine, N, N-dimethylacetamide, tetrahydrofuran, diphenyl ether, 2-ethylhexyl alcohol, olei Examples include alcohol, stearyl alcohol, phenol, benzyl alcohol, 1-decanol, lauryl alcohol and the like, and 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 0.01 to 30 moles, preferably 0.5 to 10 moles per mole of the metal halide. When the reaction product with the Lewis base is used, the metal remaining in the polymer can be reduced.
The above-mentioned complex compound of metal halide and Lewis base (component (E2-2)) may be used alone or in combination of two or more.

Examples of the component (E3-3) include benzyl chloride.

Hereinafter, it describes about the mixture ratio between each component of a 4th polymerization catalyst composition.
The molar ratio of the amount of the component (B2) (cyclopentadiene skeleton-containing compound) to the component (A2) is preferably more than 0 and more preferably 0.5 or more from the viewpoint of obtaining sufficient catalyst activity. Preferably, it is 1 or more, particularly preferably 3 or less, more preferably 2.5 or less, and 2.2 or less from the viewpoint of suppressing a decrease in catalyst activity. Particularly preferred.

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

From the viewpoint of improving the catalytic activity in the reaction system, the molar ratio of aminium in component (D2) (aluminoxane) to the rare earth element in component (A2) is preferably 10 or more, and more preferably 100 or more. More preferably, from the viewpoint of suppressing a decrease in catalyst activity in the reaction system, it is preferably 1000 or less, more preferably 800 or less.

From the viewpoint of improving the catalytic activity, the molar ratio of the component (E2) component (halogen compound) to the component (A2) is preferably 0 or more, more preferably 0.5 or more. It is particularly preferably 0 or more, and is preferably 20 or less, and more preferably 10 or less, from the viewpoint of maintaining the solubility of the component (E2) and suppressing a decrease in catalytic activity.
Therefore, according to the above range, the effect of increasing the cis-1,4 bond amount or 1,4 bond amount of the conjugated diene unit can be enhanced.

The fourth polymerization catalyst composition includes 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). And an ionic compound composed of a ferrocenium cation having a transition metal). Here, the ionic compound has high solubility in aromatic hydrocarbons and low solubility in hydrocarbons. Therefore, if it is set as the polymerization catalyst composition which does not contain an ionic compound, a conjugated diene polymer can be manufactured, reducing environmental impact and manufacturing cost further.
In addition, "it does not contain an ionic compound" means that the ratio of the ionic compound contained in a polymerization catalyst composition is less than 0.01 mass%.

The coupling step is a step of performing a reaction (coupling reaction) for modifying at least a part (for example, a terminal) of the polymer chain of the multi-component copolymer obtained in the polymerization step.
In the coupling step, the coupling reaction is preferably performed when the polymerization reaction reaches 100%.
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) dioctyl tin (IV); Examples include isocyanate compounds such as 4,4′-diphenylmethane diisocyanate; alkoxysilane compounds such as glycidylpropyltrimethoxysilane, and the like. These may be used individually by 1 type and may use 2 or more types together.
Among these, bis (-1-octadecyl maleate) dioctyltin (IV) is preferable from the viewpoint of reaction efficiency and low gel formation.
In addition, the number average molecular weight (Mn) can be increased by performing a coupling reaction.

The washing step is a step of washing the multi-component copolymer obtained in the polymerization step. The medium used for washing is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include methanol, ethanol, isopropanol and the like. When a catalyst derived from a Lewis acid is used as a polymerization catalyst. Can be used in particular by adding an acid (for example, hydrochloric acid, sulfuric acid, nitric acid) to these solvents. The amount of the acid to be added is preferably 15 mol% or less with respect to the solvent. Above this, the acid remains in the copolymer, which may adversely affect the reaction during kneading and vulcanization.
By this washing step, the amount of catalyst residue in the copolymer can be suitably reduced.

The rubber composition of the present invention contains a conjugated diene rubber (a2) other than the above-described multi-component copolymer (a1) as the rubber component (a).
The conjugated diene rubber (a2) other than the multi-component copolymer (a1) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, in addition to natural rubber (NR), isoprene rubber (IR ), Butadiene rubber (BR), chloroprene rubber (CR), styrene-butadiene rubber (SBR), styrene-isoprene rubber (SIR), acrylonitrile-butadiene rubber (NBR), and the like. Among these, styrene-butadiene rubber (SBR) is preferable from the viewpoint of wear resistance and crack growth resistance of the rubber composition. These conjugated diene rubbers (a2) may be used alone or in combination of two or more.

In the rubber composition of the present invention, the content of the conjugated diene rubber (a2) in the rubber component (a) is 95% by mass or less, preferably 80% by mass or less, and preferably It exceeds 50 mass%, More preferably, it is 60 mass% or more. If the content of the conjugated diene rubber (a2) in the rubber component (a) exceeds 50% by mass, the workability of the rubber composition is improved. If the content is 60% by mass or more, the workability of the rubber composition is improved. Further, when the amount is 80% by mass or less, the effect of the multi-component copolymer (a1) is sufficiently exerted, and the wear resistance and crack growth resistance of the rubber composition are further improved.

The rubber composition of the present invention contains styrene-butadiene rubber as the conjugated diene rubber (a2), and the content of the styrene-butadiene rubber in the rubber component (a) exceeds 50% by mass. Is preferred. When a styrene-butadiene rubber generally having a high glass transition temperature is included as the conjugated diene rubber (a2), the affinity between the continuous phase consisting of the conjugated diene rubber (a2) and the dispersed phase consisting of the multi-component copolymer (a1) Since the properties of the dispersed phase consisting of the multi-component copolymer (a1) become small and the domain size of the multi-component copolymer (a1) decreases, the crystal collapse of the multi-component copolymer (a1) is further promoted. The wear resistance and crack growth resistance of the composition are further improved. In addition, if the content of the styrene-butadiene rubber in the rubber component (a) exceeds 50% by mass, the effect of the styrene-butadiene rubber becomes remarkable, and the wear resistance and crack growth resistance of the rubber composition are improved. Further improvement. From the viewpoint of wear resistance and crack growth resistance of the rubber composition, the content of the styrene-butadiene rubber in the rubber component (a) is preferably in the range of 60 to 95% by mass.

The styrene-butadiene rubber preferably has a glass transition temperature (Tg) measured by a differential scanning calorimeter (DSC) of −60 ° C. to 0 ° C., more preferably −30 ° C. to 0 ° C. If the glass transition temperature (Tg) of the styrene-butadiene rubber is −60 ° C. or higher, the affinity between the continuous phase composed of the conjugated diene rubber (a2) and the dispersed phase composed of the multi-component copolymer (a1) is further increased. This improves the wear resistance and crack growth resistance of the rubber composition. If the glass transition temperature (Tg) of the styrene-butadiene rubber is 0 ° C. or lower, the viscosity of the continuous phase composed of the conjugated diene rubber (a2) is lowered, and the workability of the rubber composition is further improved.
Here, the glass transition temperature is a value measured by the method described in Examples.

The styrene-butadiene rubber preferably has a styrene content of 5 to 50% by mass, more preferably 8 to 45% by mass. If the styrene content of the styrene-butadiene rubber is 5% by mass or more, the affinity between the continuous phase composed of the conjugated diene rubber (a2) and the dispersed phase composed of the multi-component copolymer (a1) is further improved. Further, the wear resistance and crack growth resistance of the rubber composition are further improved. Further, when the styrene content of the styrene-butadiene rubber is 50% by mass or less, the affinity is improved, the viscosity of the continuous phase composed of the conjugated diene rubber (a2) is lowered, and the workability of the rubber composition is improved. Further improvement.
Here, the styrene content is the amount of styrene units bonded in the styrene-butadiene rubber, and is determined from the integral ratio of the ¹ H-NMR spectrum.

In the styrene-butadiene rubber, the vinyl bond content in the styrene-butadiene rubber is preferably 15 to 60% by mass, and more preferably 30 to 60% by mass. When the vinyl bond content of the styrene-butadiene rubber is 15% by mass or more, the affinity between the continuous phase composed of the conjugated diene rubber (a2) and the dispersed phase composed of the multi-component copolymer (a1) is further improved. Further, the wear resistance and crack growth resistance of the rubber composition are further improved. Further, when the vinyl bond content of the styrene-butadiene rubber is 60% by mass or less, the affinity is improved and the viscosity of the continuous phase composed of the conjugated diene rubber (a2) is lowered, and the workability of the rubber composition is improved. Further improvement.
Here, the vinyl bond content is the amount of butadiene units having vinyl bonds (1,2-bonds) in the styrene-butadiene rubber, and is determined from the integral ratio of the ¹ H-NMR spectrum.

The rubber composition of the present invention preferably contains a filler. When the rubber composition contains a filler, the wear resistance and crack growth resistance of the rubber composition can be further improved.
The filler tends to be distributed more in the continuous phase formed from the conjugated diene rubber (a2) than in the dispersed phase formed from the multi-component copolymer (a1). The wear resistance and crack growth resistance of the rubber composition as a whole are further improved by improving the properties and crack growth resistance.
The filler is not particularly limited, and carbon black, silica, aluminum hydroxide, clay, alumina, talc, mica, kaolin, glass balloon, glass beads, calcium carbonate, magnesium carbonate, magnesium hydroxide, magnesium oxide, oxidation Titanium, potassium titanate, barium sulfate and the like can be mentioned. Among these, carbon black and silica are preferable. These may be used alone or in combination of two or more.
The blending amount of the filler is not particularly limited and may be appropriately selected depending on the intended purpose. It is preferably 10 to 100 parts by weight, preferably 20 to 80 parts by weight with respect to 100 parts by weight of the rubber component (a). Is more preferable, and 30 to 60 parts by mass is particularly preferable. When the blending amount of the filler is 10 parts by mass or more, the effect of improving the reinforcement by blending the filler is sufficiently obtained, and when it is 100 masses or less, good workability is maintained. can do.

The rubber composition of the present invention preferably contains a crosslinking agent. There is no restriction | limiting in particular as this crosslinking agent, According to the objective, it can select suitably, For example, a sulfur type crosslinking agent, an organic peroxide type crosslinking agent, an inorganic crosslinking agent, a polyamine crosslinking agent, a resin crosslinking agent, sulfur Compound-based crosslinking agents, oxime-nitrosamine-based crosslinking agents and the like can be mentioned. In addition, as a rubber composition for tires, a sulfur-based crosslinking agent (vulcanizing agent) is more preferable among these.
The content of the crosslinking agent is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the rubber component (a).

When using the vulcanizing agent, a vulcanization accelerator can be used in combination. Examples of the vulcanization accelerator include guanidine, aldehyde-amine, aldehyde-ammonia, thiazole, sulfenamide, thiourea, thiuram, dithiocarbamate, and xanthate compounds.

Further, the rubber composition of the present invention, if necessary, softener, vulcanization aid, colorant, flame retardant, lubricant, foaming agent, plasticizer, processing aid, antioxidant, anti-aging agent, Known materials such as tackifiers, scorch inhibitors, ultraviolet inhibitors, antistatic agents, anti-coloring agents, and other compounding agents can be used depending on the intended use.

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

<Tire>
The tire of the present invention is characterized by using the above rubber composition. Since the tire of the present invention uses the rubber composition described above, it is excellent in wear resistance and crack growth resistance.
The application site of the rubber composition of the present invention in a tire is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include tread, base tread, sidewall, side reinforcing rubber, and bead filler. .
As a method for manufacturing the tire, a conventional method can be used. For example, on a tire molding drum, members normally used for manufacturing tires such as a carcass layer, a belt layer, a tread layer and the like made of an unvulcanized rubber composition and / or a cord are sequentially laminated, and the drum is removed and a green tire is removed. To do. Then, a desired tire (for example, a pneumatic tire) can be manufactured by heating and vulcanizing the green tire according to a conventional method.

<Conveyor belt>
The conveyor belt of the present invention is characterized by using the above rubber composition. Since the conveyor belt of this invention uses the rubber composition mentioned above, it is excellent in abrasion resistance and crack growth resistance.
In one embodiment, the rubber composition is a surface layer rubber on the inner peripheral side that comes into contact with a driving pulley, a driven pulley, a shape-retaining rotor, etc., at least below a reinforcing member made of a steel cord or the like among conveyor belts. It can be used for (lower surface cover rubber), and can also be used for outer layer surface rubber (upper surface cover rubber) on the upper side of the reinforcing material and in contact with the transport article.
As a specific production example of the conveyor belt of the present invention, a reinforcing material is sandwiched between sheets made of the rubber composition, and the rubber composition is bonded to the reinforcing material by heat-pressing and vulcanizing and bonding. Adhesion and coating may be mentioned.

<Rubber crawler>
The rubber crawler of the present invention is characterized by using the above rubber composition. Since the rubber crawler of the present invention uses the rubber composition described above, it is excellent in wear resistance and crack growth resistance.
In one embodiment, the rubber crawler includes a steel cord, an intermediate rubber layer that covers the steel cord, a core metal disposed on the intermediate rubber layer, and a body that surrounds the intermediate rubber layer and the metal core. And a plurality of lugs on the grounding surface side of the main rubber layer. Here, the rubber composition may be used in any part of the rubber crawler of the present invention. However, since it is excellent in wear resistance and crack growth resistance, the rubber composition is preferably used in the main rubber layer, particularly in the lug.

<Vibration isolator>
The vibration isolator of the present invention is characterized by using the above rubber composition. Since the vibration isolator of the present invention uses the above-described rubber composition, it is excellent in wear resistance and crack growth resistance.
The type of the vibration isolator of the present invention is not particularly limited. For example, engine mount, torsional damper, rubber bush, strut mount, bound bumper, helper rubber, member mount, stabilizer bush, air spring, center support, rubber propeller It can be used for shafts, anti-vibration levers, companion dampers, damping rubbers, idler arm bushings, steering column bushings, coupling rubbers, body mounts, muffler supports, dynamic dampers, and piping rubbers.

<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-described rubber composition, it is excellent in wear resistance and crack growth resistance.
In one embodiment, the seismic isolation device includes a laminate in which soft layers and hard layers are alternately laminated, and a plug that is press-fitted into a hollow portion formed at the center of the laminate. In one embodiment, the rubber composition described above can be used for at least one of the soft layer and the plug.

<Hose>
The hose of the present invention is characterized by using the above rubber composition. Since the hose of the present invention uses the above-described rubber composition, it is excellent in wear resistance and crack growth resistance.
In one embodiment, the hose is provided between an inner surface rubber layer (inner tube rubber) positioned on the radially inner side, an outer surface rubber layer positioned on the radially outer side, and the inner surface rubber layer and the outer surface rubber layer as necessary. And a reinforcing layer located on the surface. In one embodiment, the rubber composition described above can be used for at least one of the inner rubber layer and the outer rubber layer. Moreover, the rubber composition mentioned above can also be used for the hose which consists of a single rubber layer.

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

<Method for analyzing copolymer>
The number average molecular weight (Mn), weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn), content of butadiene unit, ethylene unit and styrene unit, melting point, endothermic peak energy of the copolymer synthesized by the following methods: The glass transition temperature and crystallinity were measured to confirm the main chain structure.

(1) Number average molecular weight (Mn), weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)
Gel permeation chromatography [GPC: Tosoh HLC-8121GPC / HT, column: Tosoh GMH _HR -H (S) HT × 2, detector: differential refractometer (RI)], based on monodisperse polystyrene The polystyrene-reduced number average molecular weight (Mn), weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the copolymer were determined. The measurement temperature is 40 ° C.

(2) Content of butadiene unit, ethylene unit and styrene unit The content (mol%) of butadiene unit, ethylene unit and styrene unit in the copolymer was determined by ¹ H-NMR spectrum (100 ° C, d-tetrachloroethane standard). : 6 ppm) from the integration ratio of each peak.

(3) Melting point ( _Tm )
The melting point of the copolymer was measured according to JIS K 7121-1987 using a differential scanning calorimeter (DSC, “DSCQ2000” manufactured by TA Instruments Japan Co., Ltd.).

(4) Endothermic peak energy Using a differential scanning calorimeter (DSC, manufactured by T.A. Instruments Japan, “DSCQ2000”), the rate of temperature increase is 10 ° C./min according to JIS K 7121-1987. The temperature was increased from −150 ° C. to 150 ° C., and the endothermic peak energy at 0 to 120 ° C. at that time (1st run) was measured.

(5) Glass transition temperature (Tg)
Using a differential scanning calorimeter (DSC, manufactured by T.A. Instruments Japan, "DSCQ2000"), the glass transition temperature (Tg) of the copolymer was determined in accordance with JIS K 7121-1987.

(6) Crystallinity The crystal melting energy of 100% crystalline polyethylene and the melting peak energy of the obtained copolymer were measured, and the crystallinity was calculated from the energy ratio of polyethylene and copolymer. The melting peak energy was measured with a differential scanning calorimeter (DSC, manufactured by TA Instruments Japan, “DSCQ2000”).

(7) Confirmation of main chain structure The synthesized copolymer was measured for ¹³ C-NMR spectrum.

<Synthesis Method of Ternary Copolymer>
To a sufficiently dried 1000 mL pressure-resistant stainless steel reactor, 160 g of styrene and 600 mL of toluene were added.
In a glove box under a nitrogen atmosphere, a mono (bis (1,3-tert-butyldimethylsilyl) indenyl) bis (bis (dimethylsilyl) amido) gadolinium complex {1,3-[(t-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 dissolved in 40 mL of toluene to obtain a catalyst solution.
The catalyst solution was added to the pressure resistant stainless steel reactor and heated to 70 ° C.
Next, ethylene was charged into the pressure resistant stainless steel reactor at a pressure of 1.5 MPa, and further 80 mL of a toluene solution containing 20 g of 1,3-butadiene was charged into the pressure resistant stainless steel reactor over 8 hours. Copolymerization was carried out for 5 hours.
Next, 1 ml of 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) (NS-5) 5 mass% isopropanol solution was added to the pressure resistant stainless steel reactor to stop the reaction.
Next, the copolymer was separated using a large amount of methanol and vacuum-dried at 50 ° C. to obtain a terpolymer.
About the obtained terpolymer, number average molecular weight (Mn), weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), butadiene unit, ethylene unit, styrene unit content, melting point (T _m ), Endothermic peak energy, glass transition temperature (Tg), and crystallinity were measured by the above methods. The results are shown in Table 1.
Further, when the main chain structure of the obtained ternary copolymer was confirmed by the above method, no peak was observed at 10 to 24 ppm in the ¹³ C-NMR spectrum chart. The polymer was confirmed to have a main chain consisting only of an acyclic structure.

(Comparative Examples C1-C5, Examples C5-C6, and Comparative Examples S1-S5)
<Preparation and evaluation of rubber composition>
According to the formulation shown in Table 2 and Table 3, a rubber composition was produced using a normal Banbury mixer. The obtained rubber composition was observed with a scanning electron microscope (SEM), and the rubber component of the continuous phase and the rubber component of the dispersed phase were confirmed. Furthermore, with respect to the obtained rubber composition, the wear resistance, crack growth resistance, and workability were evaluated by the following methods. The results are shown in Tables 2 and 3.

(8) Abrasion resistance Using a Lambourn type abrasion tester, the amount of wear was measured at a slip rate of 60% at room temperature, and the reciprocal of the measurement result was used. In Table 3, the index is expressed as an index with Comparative Example S5 as 100. It shows that abrasion resistance is so favorable that a numerical value is large.

(9) Crack growth resistance (hysteresis loss ratio at 250% elongation)
A 0.5 mm crack was made in the center of a JIS No. 3 test piece, repeated fatigue was performed at a constant strain of 0 to 100% at room temperature, and the number of times until the sample was cut was measured. In Table 2, it was displayed as an index when Comparative Example C5 was 100, and in Table 3, it was displayed as an index when Comparative Example S5 was 100. The larger the value, the better the crack growth resistance.

(10) Workability (unvulcanized viscosity)
According to JIS K6300-1994, the unvulcanized viscosity [Mooney viscosity ML _{1 + 4} (130 ° C.)] of the rubber composition was measured at 130 ° C., and in Table 2, the unvulcanized viscosity of Comparative Example C5 The workability was evaluated according to the following criteria from the index when the reciprocal number of 100 was set to 100, and from the index when the reciprocal number of the unvulcanized viscosity of Comparative Example S5 was set to 100 in Table 3.
◎: When the index value is 90 or more ○: When the index value is 70 or more and less than 90 △: When the index value is 50 or more and less than 70 ×: When the index value is less than 50

(Comparative Examples C6-C9, Examples C1-C4, Comparative Examples S6-S9, and Examples S1-S4)
According to the formulation shown in Table 2 and Table 3, a rubber composition is produced using a normal Banbury mixer. The obtained rubber composition is observed with a scanning electron microscope (SEM) to confirm the rubber component of the continuous phase and the rubber component of the dispersed phase. Further, the obtained rubber composition is evaluated for wear resistance, crack growth resistance and workability by the above methods. The results are shown in Tables 2 and 3.

* 1 Ternary copolymer: Ternary copolymer synthesized by the above method * 2 SBR1: Styrene-butadiene rubber, manufactured by JSR Corporation. Product name “# 0202”, glass transition temperature = −25 ° C., styrene content = 45 mass%, vinyl bond content = 19 mass%
* 3 SBR2: Styrene-butadiene rubber, manufactured by JSR Corporation. Product name “# 1500”, glass transition temperature = −60 ° C., styrene content = 24 mass%, vinyl bond content = 19 mass%
* 4 BR: Butadiene rubber, manufactured by Ube Industries, trade name “BR150L”
* 5 NR: Natural rubber, RSS # 3
* 6 Carbon Black: HAF carbon black, manufactured by Asahi Carbon Co., Ltd., trade name “# 70”
* 7 Anti-aging agent 6PPD: N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, manufactured by Ouchi Shinsei Chemical Industry Co., Ltd., trade name "NOCRACK 6C (registered trademark)"
* 8 Wax: Made by Seiko Chemical Co., Ltd., trade name “Suntite (registered trademark)”
* 9 Softener: Process oil * 10 Vulcanization accelerator MBTS: Di-2-benzothiazolyl disulfide, manufactured by Sanshin Chemical Industry Co., Ltd., trade name “Sunceller DM”
* 11 Vulcanization accelerator TBBS: N-tert-butyl-2-benzothiazolylsulfenamide, 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”
* 13 Silica: Tosoh Silica Co., Ltd., trade name “Nipseal AQ (registered trademark)”
* 14 Silane coupling agent: Bis (3-triethoxysilylpropyl) disulfide (average sulfur chain length: 2.35), manufactured by Evonik, trade name “Si75 (registered trademark)”

From Tables 2 and 3, it can be seen that the rubber compositions of the examples according to the present invention have a high balance between wear resistance, crack growth resistance and workability.

The rubber composition of the present invention can be used for various rubber products such as tires, conveyor belts, rubber crawlers, vibration isolators, seismic isolation devices and hoses.

Claims

The rubber component (a) contains a conjugated diene unit, a non-conjugated olefin unit, and an aromatic vinyl unit, and has an endothermic peak energy measured by a differential scanning calorimeter (DSC) at 0 to 120 ° C. of 10 A multi-component copolymer (a1) of ˜150 J / g, and a conjugated diene rubber (a2) other than the multi-component copolymer (a1),
The content of the multi-component copolymer (a1) in the rubber component (a) is 5% by mass or more and less than 50% by mass,
The rubber composition, wherein the conjugated diene rubber (a2) forms a continuous phase and the multi-component copolymer (a1) forms a dispersed phase.
The multi-component copolymer (a1) has a content of the conjugated diene unit of 1 to 50 mol%, a content of the non-conjugated olefin unit of 40 to 97 mol%, and a content of the aromatic vinyl unit of 2 The rubber composition according to claim 1, wherein the rubber composition is ˜35 mol%.
The conjugated diene rubber (a2) contains styrene-butadiene rubber, and the content of the styrene-butadiene rubber in the rubber component (a) exceeds 50% by mass. Rubber composition.
The rubber composition according to claim 3, wherein the styrene-butadiene rubber has a glass transition temperature (Tg) measured by a differential scanning calorimeter (DSC) of -60 ° C to 0 ° C.
The rubber composition according to claim 3 or 4, wherein the styrene-butadiene rubber has a styrene content of 5 to 50 mass%.
The rubber composition according to any one of claims 3 to 5, wherein the styrene-butadiene rubber has a vinyl bond content in the styrene-butadiene rubber of 15 to 60% by mass.
The rubber composition according to any one of claims 1 to 6, wherein the multi-component copolymer (a1) has a melting point of 30 to 130 ° C as measured by a differential scanning calorimeter (DSC).
The rubber composition according to any one of claims 1 to 7, wherein the multi-component copolymer (a1) has a glass transition temperature of 0 ° C or less as measured by a differential scanning calorimeter (DSC).
The rubber composition according to any one of claims 1 to 8, wherein the multi-component copolymer (a1) has a crystallinity of 0.5 to 50%.
The rubber composition according to any one of claims 1 to 9, wherein the multi-component copolymer (a1) has a main chain composed only of an acyclic structure.
The rubber composition according to any one of claims 1 to 10, wherein in the multi-component copolymer (a1), the non-conjugated olefin unit is an acyclic non-conjugated olefin unit.
The rubber composition according to claim 11, wherein the non-cyclic non-conjugated olefin unit consists of only ethylene units.
The rubber composition according to any one of claims 1 to 12, wherein in the multi-component copolymer (a1), the aromatic vinyl unit includes a styrene unit.
The rubber composition according to any one of claims 1 to 13, wherein in the multi-component copolymer (a1), the conjugated diene unit includes a 1,3-butadiene unit and / or an isoprene unit.
A tire using the rubber composition according to any one of claims 1 to 14.
A conveyor belt comprising the rubber composition according to any one of claims 1 to 14.
A rubber crawler using the rubber composition according to any one of claims 1 to 14.
A vibration isolator using the rubber composition according to any one of claims 1 to 14.
A seismic isolation device using the rubber composition according to any one of claims 1 to 14.
A hose using the rubber composition according to any one of claims 1 to 14.