JPWO2019163835A1 - Rubber composition, tires, conveyor belts, rubber crawlers, anti-vibration devices, seismic isolation devices and hoses - Google Patents

Abstract

An object of the present invention is to provide a rubber composition having a highly balanced wear resistance, crack growth resistance, and workability, and the solution thereof is a copolymerization as a rubber component (a). A copolymer containing a diene unit, a non-conjugated olefin unit, and an aromatic vinyl unit, and having a heat absorption peak energy of 10 to 150 J / g measured by a differential scanning calorimeter (DSC) at 0 to 120 ° C. The content of the multiple copolymer (a1) in the rubber component (a) contains the polymer (a1) and a conjugated diene rubber (a2) other than the multiple copolymer (a1). , 5% by mass or more and less than 50% by mass, the conjugated diene rubber (a2) forms a continuous phase, and the multiple copolymer (a1) forms a dispersed phase. It is a composition.

Description

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

In recent years, in order to improve the durability of rubber products such as tires, conveyor belts, rubber crawler, vibration isolators, seismic isolation devices, hoses, etc., rubber compositions having excellent wear resistance and crack growth resistance have been required. There is.
In response to this requirement, the present inventors have used a multi-element copolymer containing a conjugated diene unit, a non-conjugated olefin unit, and an aromatic vinyl unit as the rubber component of the rubber composition. It has been found that the abrasion 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 studies by the present inventors, the rubber composition containing the multiple copolymer has a high viscosity in an unvulcanized state, and further improvement is required from the viewpoint of workability (viscosity reduction). It turned out that there was.

Therefore, it is an object of the present invention 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 having excellent wear resistance and crack growth resistance.

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

The rubber composition of the present invention contains a conjugated diene unit, a non-conjugated olefin unit, and an aromatic vinyl unit as the rubber component (a), and is a differential scanning calorimeter (DSC) at 0 to 120 ° C. A multiple copolymer (a1) having a heat absorption peak energy of 10 to 150 J / g measured in 1 and a conjugated diene rubber (a2) other than the multiple copolymer (a1) are included.
The content of the multiple 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 multiple copolymer (a1) forms a dispersed phase.
The rubber composition of the present invention has a high balance of wear resistance, crack growth resistance, and workability.

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

Here, the styrene-butadiene rubber preferably has a glass transition temperature (Tg) of −60 ° C. to 0 ° C. as 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.

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.

Further, the styrene-butadiene rubber preferably has a vinyl bond content of 15 to 60% by mass in the styrene-butadiene rubber. 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 multiple copolymer (a1) preferably has a melting point of 30 to 130 ° C. as 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 multiple copolymer (a1) preferably has a glass transition temperature of 0 ° C. or lower 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 multiple 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, it is preferable that the main chain of the multiple copolymer (a1) has only 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, it is preferable that the non-conjugated olefin unit is an acyclic non-conjugated olefin unit in the multiple copolymer (a1). In this case, the weather resistance of the rubber composition is improved.

Here, it is more preferable that the acyclic non-conjugated olefin unit comprises only an ethylene unit. 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 the aromatic vinyl unit contains a styrene unit in the multiple copolymer (a1). 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 the conjugated diene unit contains 1,3-butadiene unit and / or isoprene unit in the multiple copolymer (a1). In this case, the wear resistance and crack growth resistance of the rubber composition are further improved.

Further, the tire of the present invention is characterized in that the above rubber composition is used. The tire of the present invention is excellent in wear resistance and crack growth resistance.

Further, the conveyor belt of the present invention is characterized in that the above rubber composition is used. The conveyor belt of the present invention is excellent in wear resistance and crack growth resistance.

Further, the rubber crawler of the present invention is characterized in that the above rubber composition is used. The rubber crawler of the present invention is excellent in wear resistance and crack growth resistance.

Further, the anti-vibration device of the present invention is characterized in that the above-mentioned rubber composition is used. The vibration isolator of the present invention is excellent in wear resistance and crack growth resistance.

Further, the seismic isolation device of the present invention is characterized in that the above rubber composition is used. The seismic isolation device of the present invention is excellent in wear resistance and crack growth resistance.

Further, the hose of the present invention is characterized in that the above rubber composition is used. The hose of the present invention is excellent in wear resistance and crack growth resistance.

According to the present invention, it is possible to provide a rubber composition having a high balance between wear resistance, crack growth resistance, and workability.
Further, according to the present invention, it is possible to provide a tire, a conveyor belt, a rubber crawler, a vibration isolator, a seismic isolation device and a hose having excellent 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 thereof.

<Rubber composition>
The rubber composition of the present invention contains a conjugated diene unit, a non-conjugated olefin unit, and an aromatic vinyl unit as the rubber component (a), and is a differential scanning calorimeter (DSC) at 0 to 120 ° C. The rubber component (a1) contains a multiple copolymer (a1) having a heat absorption peak energy of 10 to 150 J / g and a conjugated diene rubber (a2) other than the multiple copolymer (a1). ), The content of the multiple 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 multiple copolymer (a1) is formed. ) Form a dispersed phase.

Since the rubber composition of the present invention contains a multidimensional copolymer (a1) containing a conjugated diene unit, a non-conjugated olefin unit, and an aromatic vinyl unit, it is excellent in abrasion resistance and crack growth resistance.
Further, in the rubber composition of the present invention, the content of the multiple 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. Since the multiplex copolymer (a1) forms a dispersed phase, the domain size of the polymer phase composed of the multiplex copolymer (a1) becomes smaller, so that the multiplex copolymer (a1) due to strain Crystal collapse is promoted, and wear resistance and crack growth resistance are further improved.
Further, in the rubber composition of the present invention, the conjugated diene rubber (a2) other than the multiple copolymer (a1), which usually does not have a crystal component, forms a continuous phase, and the rubber composition as a whole 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 a conjugated diene unit, a non-conjugated olefin unit, and an aromatic vinyl unit as the rubber component (a), and is a differential scanning calorimeter (DSC) at 0 to 120 ° C. Contains the multi-component copolymer (a1) having a heat absorption peak energy of 10 to 150 J / g measured in 1.
The endothermic peak energy of the multiple copolymer (a1) measured by a differential scanning calorimeter (DSC) at 0 to 120 ° C. is 10 to 150 J / g, preferably 25 to 130 J / g. If the endothermic peak energy of the multi-element copolymer (a1) is less than 10 J / g, the crystallinity of the multi-dimensional copolymer (a1) is insufficient, and the crystals of the multi-dimensional copolymer (a1) when strained. Insufficient disintegration reduces the effect of improving wear resistance and crack growth resistance. On the other hand, when the heat absorption peak energy of the multi-element copolymer (a1) exceeds 150 J / g, the crystallinity of the multi-element copolymer (a1) is too high and the viscosity of the dispersed phase formed from the multi-element copolymer (a1) is high. The effect on the rubber composition becomes large, and 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 multiple copolymer (a1) in the rubber component (a) is 5% by mass or more and less than 50% by mass, and is 20 to 40% by mass. preferable. If the content of the multi-element copolymer (a1) in the rubber component (a) is less than 5% by mass, the effect of improving the wear resistance and crack growth resistance of the multi-dimensional copolymer (a1) cannot be sufficiently obtained. .. On the other hand, when the content of the multi-element copolymer (a1) in the rubber component (a) is 50% by mass or more, the domain size of the polymer phase composed of the multi-element copolymer (a1) becomes large, and the multi-element copolymer due to strain increases. The crystal collapse of the polymer (a1) does not proceed sufficiently, the effect of improving the abrasion resistance and the crack growth resistance becomes small, and the influence on the viscosity of the multiple copolymer (a1) becomes large, so that the rubber composition The unpolymerized viscosity of the entire 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-structured sea phase), and the multiple copolymer (a1) is a dispersed phase (so-called sea-island-structured island). Phase) is formed. Here, the polymer phase formed from the conjugated diene rubber (a2) and the polymer phase formed from the multiple copolymer (a1) are incompatible with each other, and the conjugated diene rubber (a2) is also incompatible. ) Form a continuous phase, and the multiple copolymer (a1) forms a dispersed phase, which 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 unvulcanized viscosity of the rubber composition as a whole is low and the workability is excellent.
Further, in the rubber composition of the present invention, the multidimensional copolymer (a1) forms a dispersed phase, and the domain size of the polymer phase composed of the multidimensional copolymer (a1) is small. Crystal collapse of the coalescence (a1) is promoted, and 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 multiple copolymer (a1) are incompatible with each other depends on the rubber composition. , (1) Visual inspection, (2) Dynamic viscoelastic curve, (3) Scanning electron microscope (SEM) can be used for comprehensive judgment.
Regarding (1), the transparency of the rubber composition is visually confirmed, and if it is transparent, it is compatible, if there are opaque parts, it is semi-compatible, and if it is almost completely opaque, it is not. It can be judged that it is compatible.
Regarding (2), in the curve of tan δ obtained by dynamic viscoelasticity measurement, when the glass transition temperature (Tg) peak is one and sharp, the compatibility and the Tg peak are one, but broad. If it is, it can be determined that it is semi-compatible, and if there are two or more Tg peaks, it can be determined that it is incompatible.
Regarding (3), in the SEM image, it can be determined that when only one phase is observed, it is compatible, and when two or more phases are observed, it is semi-phase compatible or incompatible.
In principle, the judgment as to whether or not the product has incompatibility is made only by (1) and (2), and when a clear judgment cannot be made only by (1) and (2), ( Make the final decision according to 3).

The multiple copolymer (a1) contains at least a conjugated diene unit, a non-conjugated olefin unit, and an aromatic vinyl unit, and comprises only a conjugated diene unit, a non-conjugated olefin unit, and an aromatic vinyl unit. It may contain other monomeric 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 such conjugated diene compounds include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and the like. The conjugated diene compound may be used alone or in combination of two or more. The conjugated diene compound as a monomer of the multiple copolymer is obtained from the viewpoint of effectively improving the abrasion resistance and crack growth resistance of the obtained rubber composition, tire, etc. using the multiple copolymer. It preferably contains 1,3-butadiene and / or isoprene, more preferably only 1,3-butadiene and / or isoprene, and even more preferably only 1,3-butadiene. In other words, the conjugated diene unit in the multi-dimensional copolymer preferably contains 1,3-butadiene units and / or isoprene units, and may consist only of 1,3-butadiene units and / or isoprene units. It is preferably composed of only 1,3-butadiene units, more preferably.

The content of the conjugated diene unit in the multiple copolymer (a1) is preferably 1 mol% or more, more preferably 3 mol% or more, and preferably 50 mol% or less, preferably 40 mol. % Or less, more preferably 30 mol% or less, even 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 total amount of the multiple copolymer, a rubber composition and a rubber product having excellent elongation can be obtained, which is preferable, and when it is 50 mol% or less, the weather resistance is excellent.

The non-conjugated olefin unit is a structural unit derived from the 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 α-olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene and 1-octene, vinyl pivalate and 1-phenylthioethane. , N-Vinylpyrrolidone and other heteroatomic substituted alkene compounds and the like. The non-conjugated olefin compound may be one kind alone or a combination of two or more kinds. Then, the non-conjugated olefin compound as the monomer of the multiple copolymer further reduces the crystallinity of the obtained multiple copolymer and improves the weather resistance of the rubber composition and tires using the multiple 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, which is an α-olefin containing ethylene. Is more preferable, and it is particularly preferable that it is composed only of ethylene. In other words, the non-conjugated olefin unit in the multi-element copolymer is preferably an acyclic non-conjugated olefin unit, and the acyclic non-conjugated olefin unit is an α-olefin unit. More preferably, it is an α-olefin unit containing an ethylene unit, and further preferably it is composed of only an ethylene unit.

The content of the non-conjugated olefin unit in the multiple copolymer (a1) is preferably 40 mol% or more, more preferably 45 mol% or more, still more preferably 55 mol% or more. It is particularly preferably 65 mol% or more, preferably 97 mol% or less, further preferably 95 mol% or less, and even more preferably 90 mol% or less. When the content of the non-conjugated olefin unit is 40 mol% or more of the whole multi-component polymer, as a result, the content of the conjugated diene unit or the aromatic vinyl unit is reduced, the weather resistance is improved, and the resistance at high temperature is improved. Destructibility (particularly, breaking strength (Tb)) is improved. 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 the fracture resistance at high temperature (particularly, elongation at break (Eb)). Is improved. 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% of the entire multi-polymer 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 used alone or in combination of two or more. Then, the aromatic vinyl compound as the monomer of the multiple copolymer further reduces the crystallinity of the obtained multiple copolymer, and the weather resistance of the rubber composition and tires using the multiple copolymer and the like. From the viewpoint of further improving toughness, it is preferable to contain styrene, and it is more preferable to contain only styrene. In other words, the aromatic vinyl unit in the multiple copolymer preferably contains a styrene unit, and more preferably consists of only a styrene unit.
The aromatic ring in the aromatic vinyl unit is not included in the main chain of the multiple copolymer unless it is bonded to an adjacent unit.

The content of the aromatic vinyl unit in the multiple copolymer (a1) is preferably 2 mol% or more, more preferably 3 mol% or more, and more preferably 35 mol% or less. It is more preferably 30 mol% or less, further preferably 25 mol% or less, and particularly preferably 20 mol% or less. When the content of the aromatic vinyl unit is 2 mol% or more, the fracture resistance at high temperature is improved. Further, when the content of the aromatic vinyl unit is 35 mol% or less, the effect of the conjugated diene unit and the non-conjugated olefin unit becomes remarkable. 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%, and even more preferably in the range of 3 to 25 mol%.

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

The multipolymer (a1) has, as a monomer, a kind of conjugated diene compound, a kind of non-conjugated olefin compound, from the viewpoint of preferable wear resistance, crack growth resistance, weather resistance and crystallinity. And it is preferable that it is a polymer obtained by polymerizing using at least one kind of aromatic vinyl compound. In other words, the multiple copolymer (a1) is preferably a multiple copolymer containing a kind of conjugated diene unit, a kind of non-conjugated olefin unit, and a kind of aromatic vinyl unit. More preferably, it is a ternary copolymer consisting only of a conjugated diene unit, a non-conjugated olefin unit, and an aromatic vinyl unit of 1,3-butadiene unit, an ethylene unit, and a styrene unit. It is more preferably a ternary copolymer. Here, the "kind of conjugated diene unit" includes a conjugated diene unit having a different binding mode.

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

The polystyrene-equivalent weight average molecular weight (Mw) of the multiple copolymer (a1) is preferably 10,000 to 1,000,000, more preferably 100,000 to 9,000,000. , 150,000 to 8,000,000, more preferably. When the Mw of the multiple 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 retained.

The polystyrene-equivalent number average molecular weight (Mn) of the multiple copolymer (a1) is preferably 10,000 to 1,000,000, and more preferably 50,000 to 9,000,000. It is more preferably 100,000 to 8,000,000. When the Mn of the multiple 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 retained.

The multidimensional 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 1.80 to 3.00 is even more preferable. The wider the molecular weight distribution of the multiple copolymer, the better the workability of the rubber composition. Further, when the molecular weight distribution of the multi-dimensional copolymer is 4.00 or less, sufficient homogeneity can be brought about in the physical properties of the multi-dimensional copolymer.

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

In the rubber composition of the present invention, the multiple copolymer (a1) preferably has a melting point of 30 to 130 ° C., more preferably 50 to 120 ° C., as measured by a differential scanning calorimeter (DSC). .. When the melting point of the multi-element copolymer (a1) is 30 ° C. or higher, the crystallinity of the multi-dimensional copolymer (a1) is high, the wear resistance and crack growth resistance of the rubber composition are further improved, and the multi-element copolymer (a1) is further improved. When the temperature is 130 ° C. or lower, the workability of the rubber composition is further improved.
Here, the melting point is a value measured by the method described in Examples.

In the rubber composition of the present invention, the multiple copolymer (a1) preferably has a glass transition temperature (Tg) of 0 ° C. or lower as measured by a differential scanning calorimeter (DSC). When the glass transition temperature of the multiple 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 multiple copolymer (a1) preferably has a crystallinity of 0.5 to 50%, more preferably 3 to 45%. When the crystallinity of the multiple copolymer (a1) is 0.5% or more, sufficient crystallinity due to the non-conjugated olefin unit is secured, and the rubber composition has abrasion resistance and crack growth resistance. Further improvement. Further, when the crystallinity of the multidimensional copolymer (a1) is 50% or less, the workability at the time of kneading the rubber composition is improved, and the rubber composition containing the multidimensional copolymer (a1) is blended. Since the tackiness of the rubber member is improved, the workability when the rubber members made from the rubber composition are attached to each other and the rubber product such as a tire is formed is also improved.
Here, the crystallinity is a value measured by the method described in Examples.

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

The multiple copolymer (a1) can be produced through a polymerization step using a conjugated diene compound, a non-conjugated olefin compound, and an aromatic vinyl compound as monomers, and further, a coupling step and washing, if necessary. It may go through a step and other steps.
Here, in the production of the multiple copolymer (a1), it is preferable to add only the non-conjugated olefin compound and the aromatic vinyl compound without adding the conjugated diene compound in the presence of a catalyst, and polymerize them. .. In particular, when the polymerization catalyst composition described later is used, the conjugated diene compound is more reactive than the non-conjugated olefin compound and the aromatic vinyl compound. Therefore, in the presence of the conjugated diene compound, the non-conjugated olefin compound and / Alternatively, it tends to be difficult to polymerize the aromatic vinyl compound. Further, it is also liable to be difficult due to the characteristics of the catalyst to first polymerize the conjugated diene compound and then additionally polymerize the non-conjugated olefin compound and the aromatic vinyl compound.

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

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

In the polymerization step, the polymerization reaction is preferably carried out in an atmosphere of an inert gas, preferably nitrogen gas or argon gas. The polymerization temperature of the above polymerization reaction is not particularly limited, but is preferably in the range of -100 ° C. to 200 ° C., and may be about room temperature. The pressure of the polymerization reaction is preferably in the range of 0.1 to 10.0 MPa in order to sufficiently incorporate the conjugated diene compound into the polymerization reaction system. The reaction time of the polymerization reaction is also not particularly limited, and is preferably in the range of 1 second to 10 days, but can be appropriately selected depending on conditions such as the type of catalyst and the polymerization temperature. Further, the polymerization step may be carried out in one step or in multiple steps of two or more steps.
Further, in the polymerization step of the conjugated diene compound, the polymerization may be stopped by using a polymerization terminator such as methanol, ethanol or isopropanol.

The polymerization step is preferably carried out in multiple steps. More preferably, the first step of mixing the first monomer raw material containing at least an aromatic vinyl compound with the polymerization catalyst to obtain a polymerization mixture, and the conjugated diene compound, the non-conjugated olefin compound and the polymerization mixture with respect to the polymerization mixture. 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 an aromatic vinyl compound. In addition, the first monomer raw material may contain the entire amount of the aromatic vinyl compound used, or may contain only a part of the aromatic vinyl compound. Further, the non-conjugated olefin compound is contained in at least one of the first monomer raw material and the second monomer raw material.

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

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

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

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

Here, the polymerization steps of the above-mentioned non-conjugated olefin compound, aromatic vinyl compound, and conjugated diene compound are the first polymerization catalyst composition, the second polymerization catalyst composition, the third polymerization catalyst composition or the following. 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, which does not have a bond between the rare earth element and carbon, and the rare earth element compound or reaction product.
Component (B1): An ionic compound (B1-1) composed of a non-coordinating anion and a cation, an aluminoxane (B1-2), and a complex compound of a Lewis acid, a metal halide and a Lewis base, and an active halogen. Examples thereof include a polymerization catalyst composition containing at least one selected from the group consisting of at least one halogen compound (B1-3) among the containing organic compounds.
When the first polymerization catalyst composition contains at least one of an ionic compound (B1-1) and a halogen compound (B1-3), the polymerization catalyst composition further comprises.
Component (C1): The following general formula (I):
YR ¹ _a R ² _b R ³ _c・ ・ ・ (I)
(In the formula, Y is a metal selected from Group 1, Group 2, Group 12 and Group 13 of the Periodic Table, and R ¹ and R ² are monovalent hydrocarbons having 1 to 10 carbon atoms. It is a group or a hydrogen atom, R ³ is a monovalent hydrocarbon group having 1 to 10 carbon atoms, R ¹ , R ² and R ³ may be the same or different from each other, and Y is the periodic table. When the metal is selected from the first group of the table, a is 1 and b and c are 0, and when Y is the metal selected from the second and twelfth groups of the periodic table. , A and b are 1 and c is 0, and a, b and c are 1 when Y is a metal selected from Group 13 of the Periodic Table). including.

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

The component (A1) used in the first polymerization catalyst composition is a rare earth element compound or a reaction product of the rare earth element compound and a Lewis base, and here, a reaction of the rare earth element compound and the rare earth element compound with a Lewis base. The compound does not have a bond between a rare earth element and carbon. When the rare earth element compound and the reactant do not have a rare earth element-carbon bond, the compound is stable and easy to handle. Here, the rare earth element compound is a rare earth element (M), that is, a 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. The component (A1) may be used alone or in combination of two or more.

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

Examples of the group (ligand) bonded to the rare earth element of the above rare earth element compound include a hydrogen atom, a halogen atom, an alkoxy group (a group excluding hydrogen from the hydroxyl group of the alcohol and forming a metal alkoxide), and a thiolate group ( A group obtained by removing hydrogen from the 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 an ammonia, a primary amine, or a secondary amine). , Which forms a metal amide), silyl groups, aldehyde residues, ketone residues, carboxylic acid residues, thiocarboxylic acid residues, phosphorus compound residues.
Specifically, the group (ligand) is 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, or 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, thion-butoxy group, thioisobutoxy group, thiosec-butoxy group, thiotert-butoxy Aggregate thiolate groups such as groups; thiophenoxy group, 2,6-di-tert-butylthiophenoxy group, 2,6-diisopropylthiophenoxy group, 2,6-dineopentylthiophenoxy group, 2-tert-butyl Arylthiolate groups such as -6-isopropylthiophenoxy group, 2-tert-butyl-6-thioneopentylphenoxy group, 2-isopropyl-6-thioneopentylphenoxy group, 2,4,6-triisopropylthiophenoxy group. An aliphatic amino group such as a dimethylamino group, a diethylamino group, or a diisopropylamino group; a phenylamino group, a 2,6-di-tert-butylphenylamino group, a 2,6-diisopropylphenylamino group, a 2,6-dineo group. Pentylphenylamino group, 2-tert-butyl-6-isopropylphenylamino group, 2-tert-butyl-6-neopentylphenylamino group, 2-isopropyl-6-neopentylphenylamino group, 2,4,6- Arylamino groups such as tri-tert-butylphenylamino group; bistrialkylsilylamino groups such as bistrimethylsilylamino group; trimethylsilyl group, tris (trimethylsilyl) silyl group, bis (trimethylsilyl) methylsilyl group, trimethylsilyl (dimethyl) silyl group, Cyril groups such as triisopropylsilyl (bistrimethylsilyl) silyl group; halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom can be mentioned.
As the group (ligon), further residues of aldehydes 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; Lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, phosphoric acid, cyclopentanecarboxylic acid, naphthenic acid, ethylhexanoic acid, pivalic acid, versatic acid [trade name manufactured by Shell Chemical Co., Ltd., C10 Synthetic acids composed of a mixture of isomers of monocarboxylic acids], residues of carboxylic acids such as phenylacetic acid, benzoic acid, 2-naphthoic acid, maleic acid, succinic acid; hexanethioic acid, 2,2-dimethylbutanthio Residues of thiocarboxylic acids such as acids, decantioic acid, thiobenzoic acid; dibutyl phosphate, dipentyl phosphate, dihexyl phosphate, diheptyl phosphate, dioctyl phosphate, bis phosphate (2-ethylhexyl), bis phosphate (1) -Methylheptyl), dilauryl phosphate, diorail phosphate, diphenyl phosphate, bis (p-nonylphenyl) phosphate, bis phosphate (polyethylene glycol-p-nonylphenyl), (butyl) phosphate (2-ethylhexyl) , Residues of phosphoesters such as phosphate (1-methylheptyl) (2-ethylhexyl), phosphate (2-ethylhexyl) (p-nonylphenyl); monobutyl 2-ethylhexylphosphonate, mono-ethylhexylphosphonate -2-Ethylhexyl, mono-2-ethylhexyl phenylphosphonate, mono-p-nonylphenyl 2-ethylhexyl phosphonate, mono-2-ethylhexyl phosphonate, mono-1-methylheptyl phosphonate, mono-p-nonyl phosphonate Residues of phosphonic acid esters such as phenyl; dibutylphosphinic acid, bis (2-ethylhexyl) phosphinic acid, bis (1-methylheptyl) phosphinic acid, dilaurylphosphinic acid, dioleylphosphinic acid, diphenylphosphinic acid, bis (p) -Nonylphenyl) phosphonate, butyl (2-ethylhexyl) phosphonate, (2-ethylhexyl) (1-methylheptyl) phosphy Acid, (2-ethylhexyl) (p-nonylphenyl) phosphinic acid, butylphosphinic acid, 2-ethylhexylphosphinic acid, 1-methylheptylphosphinic acid, oleylphosphinic acid, laurylphosphinic acid, phenylphosphinic acid, p-nonylphenyl Residues of phosphinic acid such as phosphinic acid can also be mentioned.
These groups (ligands) may be used alone or in combination of two or more.

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, and the like. Examples thereof include sex diolefins. Here, when the rare earth element compound reacts with a plurality of Lewis bases (in the general formulas (II) and (III), w is 2 or 3), the Lewis base L ¹¹ may be the same. It may be different.

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

In the above general formula (IV), ^{as the amino group represented by NQ (NQ 1} , NQ ² , and NQ ³ ), 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 Any of them may be used, but a bistrimethylsilylamino group is preferable.

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

The ionic compound (B1-1) is composed of a non-coordinating anion and a cation, and reacts with a rare earth element compound which is a component of the above (A1) or a reaction product thereof with a Lewis base to form a cationic transition metal compound. Examples thereof include ionic compounds that can be produced.
Here, examples of the non-coordinating anion include tetraphenyl borate, tetrakis (monofluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, and tetrakis (tetrafluorophenyl). Pentafluorophenyl) borate, tetrakis (tetrafluoromethylphenyl) borate, tetra (trill) borate, tetra (xysilyl) borate, (triphenyl, pentafluorophenyl) borate, [tris (pentafluorophenyl), phenyl] borate, tri Decahydride-7,8-dicarbound decaborate and the like.
On the other hand, examples of the cation include a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptatrienyl cation, a ferrosenium cation having a transition metal, and the like. Specific examples of the carbonium cation include tri-substituted carbonium cations such as triphenyl carbonium cation and tri (substituted phenyl) carbonium cation, and more specifically, as the tri (substituted phenyl) carbonyl cation, Examples thereof include a tri (methylphenyl) carbocation cation and a tri (dimethylphenyl) carbocation cation. Specific examples of ammonium cations include trialkylammonary cations such as trimethylammonium cations, triethylammonary cations, tripropylammonium cations, and tributylammonary cations (eg, tri (n-butyl) ammonium cations); N, N-dimethylanilinium. N, N-dialkylanilinium cations such as cations, N, N-diethylanilinium cations, N, N-2,4,6-pentamethylanilinium cations; dialkylammonium cations such as diisopropylammonium cations and dicyclohexylammonium cations, etc. Can be mentioned. Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation.
Therefore, as the ionic compound (B1-1), a compound selected and combined from the above-mentioned non-coordinating anions and cations is preferable, and specifically, N, N-dimethylanilinium tetrakis (pentafluorophenyl). Borate, triphenylcarbonium tetrakis (pentafluorophenyl) borate and the like are preferable. Further, these ionic compounds (B1-1) can be used alone or in combination of two or more. The content of the ionic compound (B1-1) in the first polymerization catalyst composition is preferably 0.1 to 10 times mol, more preferably about 1 times mol, with respect to the component (A1). Is more preferable.

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

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

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

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

Further, as the Lewis base constituting the complex compound of the metal halide and the Lewis base, a phosphorus compound, a carbonyl compound, a nitrogen compound, an ether compound, an alcohol and the like are preferable. Specifically, tributyl phosphate, tri-2-ethylhexyl phosphate, triphenyl phosphate, tricredil phosphate, triethylphosphine, tributylphosphine, triphenylphosphine, diethylphosphinoetan, diphenylphosphinoetan, acetylacetone, benzoylacetone. , Propionitrile acetone, Valeryl acetone, Ethyl acetyl acetone, 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-dimethylacetoamide, tetrahydrofuran, diphenyl ether, 2-ethyl-hexyl alcohol, oleyl alcohol, stearyl alcohol, phenol, benzyl alcohol, 1-decanol, lauryl Examples thereof include alcohols, and among these, tri-2-ethylhexyl phosphate, tricresyl phosphate, acetylacetone, 2-ethylhexanoic acid, versatic acid, 2-ethylhexyl alcohol, 1-decanol, and lauryl alcohol are preferable.
The Lewis base is reacted at a ratio of 0.01 to 30 mol, preferably 0.5 to 10 mol, per 1 mol of the metal halide. The reaction with the Lewis base can be used to reduce the amount of metal remaining in the polymer.

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

The component (C1) used in the first polymerization catalyst composition has the following general formula (I):
YR ¹ _a R ² _b R ³ _c・ ・ ・ (I)
(In the formula, Y is a metal selected from Group 1, Group 2, Group 12 and Group 13 of the Periodic Table, and R ¹ and R ² are monovalent hydrocarbons having 1 to 10 carbon atoms. It is a group or a hydrogen atom, R ³ is a monovalent hydrocarbon group having 1 to 10 carbon atoms, R ¹ , R ² and R ³ may be the same or different from each other, and Y is the periodic table. When the metal is selected from the first group of the table, a is 1 and b and c are 0, and when Y is the metal selected from the second and twelfth groups of the periodic table. , A and b are 1 and c is 0, and a, b and c are 1 when Y is a metal selected from Group 13 of the Periodic Table). The following general formula (V):
AlR ¹ R ² R ³ ... (V)
(In the formula, R ¹ and R ² are monovalent hydrocarbon groups or hydrogen atoms ^{having 1 to 10 carbon atoms, R 3} is a monovalent hydrocarbon group having 1 to 10 carbon ^{atoms, and R 1} and R are ² and R ³ may be the same or different from each other), and are preferably organoaluminum compounds.
Examples of the organic aluminum compound of the general formula (V) include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, and trypentyl. Aluminum, trihexylaluminum, tricyclohexylaluminum, trioctylaluminum; diethylaluminum hydride, di-n-propylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride, dihexylaluminum hydride, dihydride Isohexylaluminum, dioctylaluminate hydride, diisooctylaluminate hydride; ethylaluminum dihydride, n-propylaluminum dihydride, isobutylaluminum dihydride, etc., among these, triethylaluminum, triisobutylaluminum, hydrogenated Diethylaluminum and hydride diisobutylaluminum are preferred. The organometallic compound as the component (C1) described above may be used alone or in combination of two or more.
The content of the organometallic compound in the first polymerization catalyst composition is preferably 1 to 50 times mol, more preferably about 10 times mol, with respect to the component (A1).

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

Specific examples of the compound have an OH group include aliphatic alcohols and aromatic alcohols. Specifically, 2-ethyl-1-hexanol, dibutylhydroxytoluene, alkylated phenol, 4,4'-thiobis- (6-t-butyl-3-methylphenol), 4,4'-butylidenebis- (6). -T-Butyl-3-methylphenol), 2,2'-methylenebis- (4-methyl-6-t-butylphenol), 2,2'-methylenebis- (4-ethyl-6-t-butylphenol), 2 , 6-di-t-4-ethylphenol, 1,1,3-tris- (2-methyl-4-hydroxy-5-t-butylphenyl) butane, n-octadecyl-3- (4-hydroxy-3) , 5-di-t-butylphenyl) propionate, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, dilaurylthiodipropionate, distearylthiodipropio Nate, dimyristylthiopropionate and the like can be mentioned, but the present invention is not limited thereto. For example, as hindered phenol-based ones, triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3) , 5-Di-t-Butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3 , 5-Triazine, Pentaerythryl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5-di-) t-Butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, N, N'-hexamethylenebis (3,5-di-t) -Butyl-4-hydroxy-hydrocinnamamide), 3,5-t-butyl-4-hydroxybenzylphosophonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3) , 5-Di-t-Butyl-4-hydroxybenzyl) benzene, Tris- (3,5-di-t-Butyl-4-hydroxybenzyl) -isocyanurate, octylated diphenylamine, 2,4-bis [(octylthio) ) Methyl] -o-cresol and the like. Moreover, as a hydrazine system, N, N'-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine can be mentioned.

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

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

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

(Wherein, W is, -NR ⁸ -, - O-or -CR ⁹ R ¹⁰ - (wherein, R ⁸ and R ⁹ is _{-C p H 2p + 1, R} 10 is -C _q It is H _{2q + 1} , p and q are each independently represented by 0 to 20), and R ⁵ and R ⁶ are independently _{−MC r} H 2r − (where, here). M is −O− or −CH ₂₋ , and r is 1 to 20), and R ⁷ is _{−OC j} H _{2j + 1} , − ( _{OC k} H _2k −). _{Represented by a} −O—C _m H _{2 m + 1} or −C _n H _{2n + 1} , j, m and n are 0 to 12 independently, and k and a are 1 to 1 independently. 12 and R ⁴ has 1 to 12 carbon atoms and is linear, branched, or cyclic, saturated or unsaturated, alkylene group, cycloalkylene group, cycloalkylalkylene group, cycloalkenylalkylene group, alkenylene. Group, cycloalkenylene group, cycloalkylalkenylene group, cycloalkenyl alkenylene group, arylene group or aralkylene group.)
Specific examples of those represented by the general formula (VII) are 3-mercaptopropyl (ethoxy) -1,3-dioxa-6-methylaza-2-silacyclooctane and 3-mercaptopropyl (ethoxy) -1,3. Examples thereof include −dioxa-6-butylaza-2-silacyclooctane, 3-mercaptopropyl (ethoxy) -1,3-dioxa-6-dodecylaza-2-silacyclooctane.

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

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. The amount added is preferably the same as that of the rare earth element compound (1.0 mol), but an excessive amount may be added. Further, when the addition amount is 1.2 mol or less, the loss of the reagent is small, which is preferable.

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

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

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

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

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

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

The cross-linking groups T ¹ and T ² may be any group capable of cross-linking X with E ¹ and E ^2, and an arylene group which may have a substituent on the aryl ring is exemplified. Further, T ¹ and T ² may be the same group or different groups.
The arylene group may be a phenylene group, a naphthylene group, a pyridylene group, a thienylene group (preferably a phenylene group, a naphthylene group) or the like. Further, any group may be substituted on the aryl ring of the arylene group. Examples of the substituent include an alkyl group such as a methyl group and an ethyl group; an aryl group such as a phenyl group and a tolyl group; a halogen group such as fluoro, chloro and bromo; and a silyl group such as a trimethylsilyl group.
As the arylene group, a 1,2-phenylene group is more preferably exemplified.

-Second polymerization catalyst composition-
The second polymerization catalyst composition (hereinafter, also referred to as “second polymerization catalyst composition”) includes the following general formula (IX):
(In the formula, M represents a lanthanoid element, scandium or yttrium, Cp ^R independently represents an unsubstituted or substituted indenyl, and R ^{a to} R ^f independently represent an alkyl having 1 to 3 carbon atoms. It represents a group or a hydrogen atom, L represents a neutral Lewis base, w represents an integer of 0 to 3), and a metallocene complex represented by the following general formula (X):
(In the formula, M represents a lanthanoid element, scandium or yttrium, Cp ^R independently represents an unsubstituted or substituted indenyl, and X'is a hydrogen atom, a halogen atom, an alkoxy group, a thiolate group or an amino group. , A silyl group or a monovalent hydrocarbon group having 1 to 20 carbon atoms, L represents a neutral Lewis base, w represents an integer of 0 to 3), and the following general Equation (XI):
(Wherein, M is a lanthanoid element, scandium or yttrium, Cp R ^'is an unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl, X is a hydrogen atom, a halogen atom, an alkoxy group, a thiolate group , an amino group, a monovalent hydrocarbon group of the silyl group or a C 1 to 20, L is a neutral Lewis base, w is, an integer of 0 to 3, [B] ^- is a non Examples thereof include a polymerization catalyst composition containing at least one complex selected from the group consisting of half metallocene cation complexes represented by (showing a coordinating anion).

The second polymerization catalyst composition may further contain other components contained in the polymerization catalyst composition containing a normal metallocene complex, for example, a co-catalyst and the like. Here, the metallocene complex is a complex compound in which one or more cyclopentadienyl or a derivative thereof is bonded to a central metal, and in particular, one cyclopentadienyl or a derivative thereof is bonded to the central metal. A certain metallocene complex may be referred to as a half metallocene complex.
In the polymerization reaction system, the concentration of the complex contained in the second polymerization catalyst composition is preferably in the range of 0.1 to 0.0001 mol / L.

In the metallocene complexes represented by the general formulas (IX) and (X), Cp ^R in the formula is unsubstituted indenyl or substituted indenyl. ^{Cp R} with an indenyl ring as the basic skeleton can be represented by C ₉ H _7-x R _x or C ₉ H _11-x R _x . Here, X is an integer of 0 to 7 or 0 to 11. Further, it is preferable that R is independently a hydrocarbyl group or a metalloid group. The number of carbon atoms of the hydrocarbyl group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 8. Specific preferred examples of the hydrocarbyl group include a methyl group, an ethyl group, a phenyl group, and a benzyl group. On the other hand, examples of the metalloid of the metalloid group include gelmil Ge, stanyl Sn, and silyl Si, and the metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group of the metalloid group is the above-mentioned hydrocarbyl group. The same is true. Specific examples of the metalloid group include a trimethylsilyl group and the like. Specific examples of the substituted indenyl include 2-phenylindenyl, 2-methylindenyl and the like. ^{The two Cp Rs} in the general formulas (IX) and (X) may be the same or different from each other.

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

In the general formula (XI), Cp R ^'having a basic skeleton of the above cyclopentadienyl ring, represented by _{C 5 H 5-x R x} . Here, X is an integer of 0 to 5. Further, it is preferable that R is independently a hydrocarbyl group or a metalloid group. The number of carbon atoms of the hydrocarbyl group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 8. Specific preferred examples of the hydrocarbyl group include a methyl group, an ethyl group, a phenyl group, and a benzyl group. On the other hand, examples of the metalloid of the metalloid group include gelmil Ge, stanyl Sn, and silyl Si, and the metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group of the metalloid group is the above-mentioned hydrocarbyl group. The same is true. Specific examples of the metalloid group include a trimethylsilyl group and the like. A cyclopentadienyl ring as Cp R ^'having a basic skeleton, specifically, are exemplified as follows.
(In the formula, R represents a hydrogen atom, a methyl group or an ethyl group.)

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

In the general formula (XI), Cp ^{R 'having} a basic skeleton of the above fluorenyl ring may be represented by C ₁₃ H _9-x R x or _{C 13 H 17-x R x} . Here, X is an integer of 0 to 9 or 0 to 17. Further, it is preferable that R is independently a hydrocarbyl group or a metalloid group. The number of carbon atoms of the hydrocarbyl group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 8. Specific preferred examples of the hydrocarbyl group include a methyl group, an ethyl group, a phenyl group, and a benzyl group. On the other hand, examples of the metalloid of the metalloid group include gelmil Ge, stanyl Sn, and silyl Si, and the metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group of the metalloid group is the above-mentioned hydrocarbyl group. The same is true. Specific examples of the metalloid group include a trimethylsilyl group and the like.

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

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

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

In the general formula (XI), X is a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkoxy group, a thiolate group, an amino group, a silyl group and a monovalent hydrocarbon group having 1 to 20 carbon atoms. .. Here, the halogen atom represented by X may be any of a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, but a chlorine atom or a bromine atom is preferable.

In the general formula (XI), the alkoxy group represented by X includes an aliphatic alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group and a tert-butoxy group; a phenoxy group. , 2,6-di-tert-butylphenoxy group, 2,6-diisopropylphenoxy group, 2,6-dineopentylphenoxy group, 2-tert-butyl-6-isopropylphenoxy group, 2-tert-butyl-6 Examples thereof include aryloxy groups such as −neopentylphenoxy group and 2-isopropyl-6-neopentylphenoxy group, and among these, 2,6-di-tert-butylphenoxy group is preferable.

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

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

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

Further, in the general formula (XI), as the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by X, specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and the like. Linear or branched aliphatic hydrocarbon groups such as isobutyl group, sec-butyl group, tert-butyl group, neopentyl group, hexyl group and octyl group; aromatic hydrocarbons such as phenyl group, trill group and naphthyl group. Group: In addition to an aralkyl group such as a benzyl group; a hydrocarbon group containing a silicon atom such as a trimethylsilylmethyl group and a bistrimethylsilylmethyl group can be mentioned. Among these, a methyl group, an ethyl group, an isobutyl group and a trimethylsilylmethyl group can be mentioned. Groups and the like are preferred.

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

In the general formula (XI), examples of the non-coordinating anion represented by ^{[B] − include a tetravalent boron anion.} Specific examples of the tetravalent boron anion include tetraphenyl borate, tetrakis (monofluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, and tetrakis (tetrakis). Pentafluorophenyl) borate, tetrakis (tetrafluoromethylphenyl) borate, tetra (trill) borate, tetra (kisilyl) borate, (triphenyl, pentafluorophenyl) borate, [tris (pentafluorophenyl), phenyl] borate, tri Examples thereof include decahydride-7,8-dicarbundecaborate, and among these, tetrakis (pentafluorophenyl) borate is preferable.

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

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

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

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

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

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

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

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

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

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

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

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

Further, in the above-mentioned polymerization catalyst composition, 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) are used as appropriate cocatalysts, respectively. By combining them, the cis-1,4 bond content and the molecular weight of the obtained polymer can be increased.

-Third polymerization catalyst composition-
The third polymerization catalyst composition (hereinafter, also referred to as “third polymerization catalyst composition”) is a rare earth element-containing compound having the following general formula (XIII):
R _a MX _b QY _b ... (XIII)
(In the formula, R each independently represents an unsubstituted or substituted indenyl, the R is coordinated to M, M represents a lanthanoid element, scandium or yttrium, and X is an independent carbon. It represents a monovalent hydrocarbon group of numbers 1 to 20, in which X is μ-coordinated to M and Q, Q is a Group 13 element of the Periodic Table, and Y is an independent carbon number. A polymerization catalyst composition containing a metallocene-based composite catalyst represented by 1 to 20 monovalent hydrocarbon groups or hydrogen atoms, where Y is coordinated to Q, and a and b are 2). Can be mentioned.

In a preferred example of the metallocene-based composite catalyst, the following general formula (XIV):
(Wherein, M ¹ is a lanthanoid element, scandium or yttrium, Cp ^R is independently a non-substituted or substituted indenyl, R ^A and R ^B having from 1 to 20 carbon atoms each independently represents a hydrocarbon group, said R ^a and R ^B are coordinated μ to M ¹ and Al, R ^C and R ^D are each independently a hydrocarbon group or a hydrogen atom having 1 to 20 carbon atoms (Indicated), a metallocene-based composite catalyst represented by) can be mentioned.
By using the above-mentioned metallocene-based polymerization catalyst, a multidimensional copolymer can be produced. Further, by using the above-mentioned metallocene-based composite catalyst, for example, a catalyst that is previously combined with an aluminum catalyst, it is possible to reduce or eliminate the amount of alkylaluminum used in the synthesis of multiple copolymers. If a conventional catalyst system is used, it is necessary to use a large amount of alkylaluminum at the time of synthesizing the multiple copolymer. For example, in the conventional catalyst system, it is necessary to use alkylaluminum of 10 molar equivalents or more with respect to the metal catalyst, but in the case of the metallocene-based composite catalyst, it is excellent to add alkylaluminum of about 5 molar equivalents. Catalytic action is exhibited.

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

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

In the above general formula (XIII), Q represents an element of Group 13 of the periodic table, and specific examples thereof include boron, aluminum, gallium, indium, and thallium.

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

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

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

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

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

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

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

In the metallocene complex represented by the general formula (XV), Cp ^R is an unsubstituted indenyl or a substituted indenyl, and is synonymous with ^{Cp R in the general formula (XIV).} Further, in the above formula (XV), the metal M ² is a lanthanoid element, scandium or yttrium, and is synonymous with ^{the metal M 1 in the above formula (XIV).}

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

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

Further, the metallocene complex represented by the above general formula (XV) may exist as a monomer, or may exist as a dimer or a multimer of more than that.

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

Specific examples of the organic aluminum compound include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, tripentylaluminum, and tri. Hexyl aluminum, tricyclohexyl aluminum, trioctyl aluminum; diethyl aluminum hydride, di-n-propyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl aluminum hydride, dihexyl aluminum hydride, diisohexyl aluminum hydride , Dioctyl aluminum hydride, Diisooctyl aluminum hydride; ethylaluminum dihydride, n-propylaluminum dihydride, isobutylaluminum dihydride, etc., among these, triethylaluminum, triisobutylaluminum, diethylaluminum hydride, etc. Diisobutylaluminum hydride is preferred. Further, these organoaluminum compounds may be used alone or in combination of two or more. The amount of the organoaluminum compound used for producing the metallocene-based composite catalyst is preferably 1 to 50 times mol, more preferably about 10 times mol, with respect to the metallocene complex.

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

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

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

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

Examples of the third polymerization catalyst co-catalyst which can be used in the compositions, for example, other organic aluminum compound represented by AlR ^K R ^L R ^M described above, aluminoxane can be preferably used. As the aluminoxane, an alkylaminoxane is preferable, and examples thereof include methylaluminoxane (MAO) and modified methylaluminoxane. Further, as the modified methylaluminoxane, MMAO-3A (manufactured by Tosoh Finechem Co., Ltd.) or the like is preferable. 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”) is
・ Rare earth element compounds ((A2) component) and
-Cyclopentadiene skeleton-containing compound selected from substituted or unsubstituted cyclopentadiene, substituted or unsubstituted inden (compound having an indenyl group), and substituted or unsubstituted fluorene (hereinafter, simply "cyclopentadiene skeleton-containing compound" ((B2) component) and
Must be included.
In addition, the fourth polymerization catalyst composition may be used in addition to the above.
-Organometallic compound ((C2) component),
・ Aluminoxane compound ((D2 component)),
-Halogen compound ((E2) component),
May include.

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

The component (A2) can be a rare earth element-containing compound having a metal-nitrogen bond (MN bond) or a reaction product of the rare earth element-containing compound and a Lewis base.
Examples of the rare earth element-containing compound include a compound containing a lanthanoid element composed of scandium, yttrium, or an element having an atomic number of 57 to 71. Specific examples of the lanthanoid element are lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, elbium, thulium, ytterbium, and lutetium.
Examples of the Lewis base include tetrahydrofuran, diethyl ether, dimethylaniline, trimethylphosphine, lithium chloride, neutral olefins, neutral diolefins and the like.
Here, it is preferable that the rare earth element-containing compound and the reaction product of the rare earth element-containing compound and the Lewis base 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.
The component (A2) may be used alone or in combination of two or more.

The component (A2) includes the following general formula (XVI):
M- (AQ ¹ ) (AQ ² ) (AQ ³ ) ... (XVI)
[In the formula, M is a scandium, yttrium or lanthanoid element; AQ ¹ , AQ ² and AQ ³ are functional groups that may be the same or different; A is nitrogen, oxygen or sulfur. Yes; however, compounds represented by [with at least one MA bond] are preferred. Here, the lanthanoid element is specifically lanthanium, cerium, placeodim, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, forminium, erbium, thulium, ytterbium, and lutetium. The compound is a component capable of improving the catalytic activity in the reaction system, shortening the reaction time, and raising the reaction temperature.

As M in the general formula (XVI), gadolinium is particularly preferable from the viewpoint of enhancing catalytic 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 the like. And in this case, it has three MN bonds.
Examples of the amino group include an aliphatic amino group such as a dimethylamino group, a diethylamino group and a diisopropylamino group; a phenylamino group, a 2,6-di-tert-butylphenylamino group and a 2,6-diisopropylphenylamino group. 2,6-Dineopentylphenylamino group, 2-tert-butyl-6-isopropylphenylamino group, 2-tert-butyl-6-neopentylphenylamino group, 2-isopropyl-6-neopentylphenylamino group, Arylamino groups such as 2,4,6-tri-tert-butylphenylamino group; bistrialkylsilylamino groups such as bistrimethylsilylamino group can be mentioned, and in particular, solubility in aliphatic hydrocarbons and aromatic hydrocarbons can be mentioned. From the viewpoint, a bistrimethylsilylamino group is preferable. The amino group may be used alone or in combination of two or more.
According to the above configuration, the component (A2) can be a compound having three MN bonds, the bonds are chemically equivalent, and the structure of the compound is stable, so that handling is easy.
Further, with the above configuration, the catalytic activity in the reaction system can be further improved. Therefore, the reaction time can be further shortened and the reaction temperature can be further increased.

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

The component (B2) is a compound selected from substituted or unsubstituted cyclopentadiene, substituted or unsubstituted indene, and substituted or unsubstituted fluorene.
The above component (B2) may be used alone or in combination of two or more.

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

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

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

The organometallic compound (component (C2)) includes the following general formula (XXI):
YR ⁴ _a R ⁵ _b R ⁶ _c・ ・ ・ (XXI)
[In the equation, Y is a metal element selected from the group consisting of the elements of Group 1, Group 2, Group 12 and Group 13 of the periodic table; R ⁴ and R ⁵ are carbon atoms 1. It is a monovalent hydrocarbon group or a hydrogen atom of ^{10 to 10, where R 6} is a monovalent hydrocarbon group having 1 to 10 carbon atoms, except that R ⁴ , R ⁵ and R ⁶ are the same as each other. It may or may not be different; if Y is a Group 1 metal element, a is 1 and b and c are 0, and Y is a Group 2 or 12 metal element. When a and b are 1 and c is 0, and when Y is a Group 13 metal element, a, b and c are 1). Can be mentioned.
When the polymerization catalyst composition further contains the component (C2), the polymerization activity can be enhanced.
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 the general formula (XXI).}

Specifically, the component (C2) is described by the following general formula (XXII):
AlR ⁴ _a R ⁵ _b R ⁶ _c・ ・ ・ (XXII)
[In the formula, 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].

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

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

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

Examples of the component (D2) include the following formula (XXIII):
− (Al (R ⁷ ) O) _n − ・ ・ ・ (XXIII)
(In the formula, R ⁷ is a hydrocarbon group having 1 to 10 carbon atoms, where some of the hydrocarbon groups may be substituted with halogen and / or alkoxy groups; R ⁷ is between repeating units. Can be the same or different; n is 5 or more).
The molecular structure of the aluminoxane may be linear or cyclic.

N in the above formula (XXIII) is preferably 10 or more.
^{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 the formula (XXIII), as the hydrocarbon group, a combination of a methyl group and an isobutyl group is preferable.

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

The component (D2) is particularly composed of the following formula (XXIV):
− (Al (CH ₃ ) _x (i−C ₄ H ₉ ) _y O) _m − ··· (XXIV)
It may be a modified aluminoxane (hereinafter, also referred to as “TMAO”) represented by (in the formula, x + y is 1; m is 5 or more). Examples of TMAO include the product name "TMAO341" manufactured by Tosoh Fine Chemicals Co., Ltd.

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

Further, the component (D2) is particularly composed of the following formula (XXVI):
− [(CH ₃ ) AlO] _i − ・ ・ ・ (XXVI)
It may be a modified aluminoxane (hereinafter, also referred to as “PMAO”) represented by (i is 5 or more in the formula). As the PMAO, for example, the product name "PMAO-211" manufactured by Tosoh Fine Chemicals Co., Ltd. can be mentioned.

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

The halogen compound ((E2) component) is a halogen-containing compound (hereinafter, also referred to as “(E2-1) component”) which is a Lewis acid, or a complex compound of a metal halide and a Lewis base (hereinafter, “(E2-E2-) component”). It is at least one compound selected from the group consisting of "2) component") and an organic compound containing an active halogen (hereinafter, also referred to as "(E2-3) component").

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 or a halogenated transition. A metal compound and / or a transition metal compound in a state where the transition metal center is deficient in electrons is generated.
By further including the component (E2), the amount of cis-1,4 bond in the conjugated diene unit can be particularly increased.

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

Examples of the metal halide used for the component (E2-2) include beryllium chloride, beryllium bromide, beryllium iodide, magnesium chloride, magnesium bromide, magnesium iodide, calcium chloride, calcium bromide, and 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, renium chloride, renium bromide, renium 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 magnesium chloride, zinc chloride, manganese chloride, and copper chloride are particularly preferable.
As the Lewis base used in the component (E2-2), a phosphorus compound, a carbonyl compound, a nitrogen compound, an ether compound, and an alcohol are preferable.
For example, tributyl phosphate, tri-2-ethylhexyl phosphate, triphenyl phosphate, tricredil phosphate, triethylphosphine, tributylphosphine, triphenylphosphine, diethylphosphinoetan, diphenylphosphinoetan, acetylacetone, benzoylacetone, propio. Nitrileacetone, Valerylacetone, Ethylacetylacetone, Methyl acetoacetate, Ethyl acetoacetate, phenylacetoacetate, 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-dimethylacetoamide, tetrahydrofuran, diphenyl ether, 2-ethylhexyl alcohol, oleyl alcohol, stearyl alcohol, phenol, benzyl alcohol, 1-decanol, lauryl alcohol and the like. In particular, tri-2-ethylhexyl phosphate, tricresyl phosphate, acetylacetone, 2-ethylhexanoic acid, versatic acid, 2-ethylhexyl alcohol, 1-decanol, and lauryl alcohol are preferable.
The number of moles of the Lewis base is 0.01 to 30 mol, preferably 0.5 to 10 mol, per 1 mol of the metal halide. The reaction with the Lewis base can be used to reduce the amount of metal remaining in the polymer.
The complex compound ((E2-2) component) of the metal halide and the Lewis base may be used alone or in combination of two or more.

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

Hereinafter, the blending ratio between each component of the fourth polymerization catalyst composition will be described.
The molar ratio of the blending 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 catalytic activity. It is preferably 1 or more, more preferably 3 or less, further preferably 2.5 or less, and 2.2 or less from the viewpoint of suppressing a decrease in catalytic activity. Especially preferable.

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

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

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

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

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 multiple copolymer obtained in the polymerization step.
In the coupling step, it is preferable to carry out the coupling reaction 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) dioctyltin (IV); Isocyanate compounds such as 4,4'-diphenylmethane diisocyanate; alkoxysilane compounds such as glycidylpropyltrimethoxysilane, and the like can be mentioned. These may be used alone or in combination of two or more.
Among these, bis (-1-octadecyl maleate) dioctyltin (IV) is preferable in terms of reaction efficiency and low gel formation.
By carrying out the coupling reaction, the number average molecular weight (Mn) can be increased.

The washing step is a step of washing the multidimensional copolymer obtained in the polymerization step. The medium used for cleaning is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include methanol, ethanol and isopropanol. When a catalyst derived from Lewis acid is used as the polymerization catalyst. Can be used by adding an acid (for example, hydrochloric acid, sulfuric acid, nitric acid) to these solvents. The amount of acid to be added is preferably 15 mol% or less with respect to the solvent. If it is more than this, the acid may remain 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-based rubber (a2) other than the above-mentioned multiple copolymer (a1) as the rubber component (a).
The conjugated diene rubber (a2) other than the multiple 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 other synthetic diene rubbers. 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% by mass, more preferably 60% by 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, and if it is 60% by mass or more, the workability of the rubber composition is improved. If it is 80% by mass or less, the action of the multi-element copolymer (a1) is sufficiently exhibited, and the abrasion resistance and crack growth resistance of the rubber composition are further improved.

The rubber composition of the present invention contains a 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 preferable. When the conjugated diene rubber (a2) contains styrene-butadiene rubber having a generally high glass transition temperature, the affinity between the continuous phase made of the conjugated diene rubber (a2) and the dispersed phase made of the multipolymer (a1). When the property becomes good and the domain size of the dispersed phase composed of the multi-dimensional copolymer (a1) becomes small, and the domain size becomes small, the crystal collapse of the multi-dimensional copolymer (a1) is further promoted. The abrasion resistance and crack growth resistance of the composition are further improved. Further, when 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 abrasion resistance and crack growth resistance of the rubber composition become remarkable. Further improve. 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) of −60 ° C. to 0 ° C., more preferably −30 ° C. to 0 ° C., as measured by a differential scanning calorimeter (DSC). When the glass transition temperature (Tg) of the styrene-butadiene rubber is -60 ° C. or higher, the affinity between the continuous phase made of the conjugated diene rubber (a2) and the dispersed phase made of the multipolymer (a1) is further improved. By improving, the abrasion resistance and crack growth resistance of the rubber composition are further improved. Further, when the glass transition temperature (Tg) of the styrene-butadiene rubber is 0 ° C. or lower, the viscosity of the continuous phase made of the conjugated diene rubber (a2) becomes low, 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. When the styrene content of the styrene-butadiene rubber is 5% by mass or more, the affinity between the continuous phase made of the conjugated diene rubber (a2) and the dispersed phase made of the multiple copolymer (a1) is further improved. , 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 made of the conjugated diene rubber (a2) is lowered, and the workability of the rubber composition is improved. Further improve.
Here, the styrene content is the amount of styrene unit bonded in the styrene-butadiene rubber, and is determined from the integration ratio of ^{1 1 H-NMR spectrum.}

Further, the styrene-butadiene rubber preferably has a vinyl bond content of 15 to 60% by mass, more preferably 30 to 60% by mass, in the styrene-butadiene rubber. When the vinyl bond content of the styrene-butadiene rubber is 15% by mass or more, the affinity between the continuous phase made of the conjugated diene rubber (a2) and the dispersed phase made of the multiple copolymer (a1) is further improved. , 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, the viscosity of the continuous phase made of the conjugated diene rubber (a2) is lowered, and the workability of the rubber composition is improved. Further improve.
Here, the vinyl bond content is the amount of vinyl-bonded (1,2-bonded) butadiene units in the styrene-butadiene rubber, and is determined from the integration 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 multiple copolymer (a1), and the wear resistance of the continuous phase is increased. By improving the properties and crack growth resistance, the wear resistance and crack growth resistance of the rubber composition as a whole are further improved.
The filler is not particularly limited, and is carbon black, silica, aluminum hydroxide, clay, alumina, talc, mica, kaolin, glass balloon, glass beads, calcium carbonate, magnesium carbonate, magnesium hydroxide, magnesium oxide, and oxidation. Examples thereof include titanium, potassium titanate, and barium sulfate, and 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, but is preferably 10 to 100 parts by mass with respect to 100 parts by mass of the rubber component (a), and is preferably 20 to 80 parts by mass. 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 reinforcing property by blending the filler can be sufficiently obtained, and when it is 100 mass or less, good workability is maintained. can do.

The rubber composition of the present invention preferably contains a cross-linking agent. The cross-linking agent is not particularly limited and may be appropriately selected depending on the intended purpose. For example, sulfur-based cross-linking agent, organic peroxide-based cross-linking agent, inorganic cross-linking agent, polyamine cross-linking agent, resin cross-linking agent, sulfur. Examples thereof include compound-based cross-linking agents and oxime-nitrosoamine-based cross-linking agents. Of these, a sulfur-based cross-linking agent (vulcanizing agent) is more preferable as the rubber composition for tires.
The content of the cross-linking 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 the vulcanization agent is used, a vulcanization accelerator may be further used in combination. Examples of the vulcanization accelerator include guadinin-based, aldehyde-amine-based, aldehyde-ammonia-based, thiazole-based, sulfenamide-based, thiourea-based, thiuram-based, dithiocarbamate-based, and zantate-based compounds.

Further, the rubber composition of the present invention contains, if necessary, a softener, a vulcanization aid, a colorant, a flame retardant, a lubricant, a foaming agent, a plasticizer, a processing aid, an antioxidant, an antistatic agent, and the like. Known agents such as tackifiers, anti-scorch agents, anti-ultraviolet agents, antistatic agents, anti-coloring agents, and other compounding agents can be used according to the purpose of 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, etc., which will be described later.

<Tire>
The tire of the present invention is characterized by using the above-mentioned rubber composition. Since the tire of the present invention uses the 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 treads, base treads, sidewalls, side reinforcing rubbers and bead fillers. ..
As a method for manufacturing the tire, a conventional method can be used. For example, members used for normal tire manufacturing such as a carcass layer, a belt layer, and a tread layer made of an unvulcanized rubber composition and / or a cord are sequentially laminated on a tire molding drum, and the drum is removed to form a green tire. To do. Then, by heating and vulcanizing this green tire according to a conventional method, a desired tire (for example, a pneumatic tire) can be manufactured.

<Conveyor belt>
The conveyor belt of the present invention is characterized in that the above rubber composition is used. Since the conveyor belt 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 composition is applied to the inner peripheral rubber of the conveyor belt, which is at least below the reinforcing material made of a steel cord or the like and which comes into contact with the drive pulley, the driven pulley, the shape-retaining rotor, or the like. It can be used for (bottom cover rubber), and can also be used for the surface rubber (top cover rubber) on the outer peripheral side that comes into contact with the transported article on the upper side of the reinforcing material.
As a specific production example of the conveyor belt of the present invention, a reinforcing material is sandwiched between sheets made of the above rubber composition, and the rubber composition is heat-bonded and vulcanized and bonded to form a rubber composition on the reinforcing material. Adhesion and coating can be mentioned.

<Rubber crawler>
The rubber crawler of the present invention is characterized in that the above rubber composition is used. Since the rubber crawler of the present invention uses the above-mentioned rubber composition, it is excellent in wear resistance and crack growth resistance.
In one embodiment, the rubber crawler comprises a steel cord, an intermediate rubber layer covering the steel cord, a core metal arranged on the intermediate rubber layer, and a main body surrounding the intermediate rubber layer and the core metal. It is provided with a rubber layer, and further has a plurality of lugs on the ground surface side of the main body rubber layer. Here, the rubber composition may be used for any part of the rubber crawler of the present invention, but it is preferably used for the main body rubber layer, particularly for the lug, because it is excellent in wear resistance and crack growth resistance.

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

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

<Hose>
The hose of the present invention is characterized by using the above rubber composition. Since the hose of the present invention uses the rubber composition described above, it is excellent in wear resistance and crack growth resistance.
In one embodiment, the hose is located between the inner rubber layer (inner tube rubber) located on the inner side in the radial direction, the outer rubber layer located on the outer side in the radial direction, and the inner rubber layer and the outer rubber layer as required. It is provided with a reinforcing layer located at. Then, in one embodiment, the above-mentioned rubber composition can be used for at least one of the inner surface rubber layer and the outer surface rubber layer. The rubber composition described above can also be used for a hose composed of a single rubber layer.

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

<Analysis method of copolymer>
Number average molecular weight (Mn), weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn), butadiene unit, ethylene unit and styrene unit content, melting point, heat absorption peak energy of the copolymer synthesized by the following method. , The glass transition temperature and the crystallinity were measured, and the main chain structure was confirmed.

(1) Number average molecular weight (Mn), weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)
Gel permeation chromatography [GPC: HLC-8121 GPC / HT manufactured by Tosoh, column: GMH _HR- H (S) HT x 2 manufactured by Tosoh, detector: differential refractometer (RI)] based on monodisperse polystyrene , The polystyrene-equivalent 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 is determined by ¹ H-NMR spectrum (100 ° C, d-tetrachloroethane standard). : 6 ppm) was calculated from the integration ratio of each peak.

(3) Melting point (T _m )
The melting point of the copolymer was measured using a differential scanning calorimeter (DSC, manufactured by TA Instruments Japan, "DSCQ2000") in accordance with JIS K 7121-1987.

(4) Endothermic peak energy Using a differential scanning calorimeter (DSC, manufactured by TA Instruments Japan, "DSCQ2000"), the rate of temperature rise at 10 ° C / min in accordance with JIS K 7121-1987. The temperature was raised 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 TA Instruments Japan, "DSCQ2000"), the glass transition temperature (Tg) of the copolymer was set according to JIS K 7121-1987.

(6) Crystallinity The crystallinity was calculated from the crystal melting energy of polyethylene, which is a 100% crystal component, and the melting peak energy of the obtained copolymer, and the energy ratio of polyethylene and the 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 ¹³ C-NMR spectrum was measured for the synthesized copolymer.

<Synthesis method of ternary copolymer>
160 g of styrene and 600 mL of toluene were added to a sufficiently dried 1000 mL pressure resistant stainless steel reactor.
In a glove box under a nitrogen atmosphere, a mono (bis (1,3-tert-butyldimethylsilyl) indenyl) bis (bis (dimethylsilyl) amide) gadolinium complex {1,3-[(t-Bu)) is placed in a glass container. ) 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 prepare a catalytic 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 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, for a total of 8 at 70 ° C. Copolymerization was carried out for 5 hours.
Then, 1 ml of an isopropanol solution of 2,2'-methylene-bis (4-ethyl-6-t-butylphenol) (NS-5) in an amount of 5% by mass was added to the pressure-resistant stainless steel reactor to terminate the reaction.
Then, the copolymer was separated using a large amount of methanol and vacuum dried at 50 ° C. to obtain a ternary copolymer.
Regarding the obtained ternary copolymer, the 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 ), The heat absorption 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, so that the synthesized ternary copolymer was synthesized. It was confirmed that the main chain of the polymer consisted only of an acyclic structure.

(Comparative Example C1-C5, Example C5-C6, and Comparative Example S1-S5)
<Preparation and evaluation of rubber composition>
A rubber composition was produced using a normal Bunbury mixer according to the formulation shown in Tables 2 and 3. The obtained rubber composition was 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 was evaluated for wear resistance, crack growth resistance, and workability by the following methods. The results are shown in Tables 2 and 3.

(8) Abrasion resistance Using a runbone type abrasion tester, the amount of abrasion was measured at a slip ratio of 60% at room temperature, and the reciprocal of the measurement result was used. , In Table 3, it is represented by an index with Comparative Example S5 as 100. The larger the value, the better the wear resistance.

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

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

(Comparative Example C6-C9, Example C1-C4, Comparative Example S6-S9, and Example S1-S4)
A rubber composition is produced using a normal Bunbury mixer according to the formulation shown in Tables 2 and 3. 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 method. The results are shown in Tables 2 and 3.

* 1 Three-way copolymer: Three-way 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% by mass, vinyl bond content = 19% by mass
* 3 SBR2: Styrene-butadiene rubber, manufactured by JSR Corporation. Product name "# 1500", glass transition temperature = -60 ° C, styrene content = 24% by mass, vinyl bond content = 19% by mass
* 4 BR: Butadiene rubber, manufactured by Ube Industries, Ltd., product name "BR150L"
* 5 NR: Natural rubber, RSS # 3
* 6 Carbon black: HAF carbon black, manufactured by Asahi Carbon Co., Ltd., product name "# 70"
* 7 Anti-aging agent 6PPD: N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd., trade name "Nocrack 6C (registered trademark)"
* 8 Wax: Made by Seiko Kagaku Co., Ltd., trade name "Santite (registered trademark)"
* 9 Softener: Process oil * 10 Vulcanization accelerator MBTS: Di-2-benzothiazolyl disulfide, manufactured by Sanshin Kagaku Kogyo Co., Ltd., trade name "Suncellor DM"
* 11 Vulcanization accelerator TBBS: N-tert-butyl-2-benzothiazolyl sulfeneamide, manufactured by Sanshin Kagaku Kogyo Co., Ltd., trade name "Sunseller NS"
* 12 Vulcanization accelerator DPG: 1,3-diphenylguanidine, manufactured by Sanshin Chemical Industry Co., Ltd., trade name "Sun Cellar D"
* 13 Silica: Made by Toso Silica, trade name "Nipseal AQ (registered trademark)"
* 14 Silane coupling agent: Bis (3-trietoxysilylpropyl) 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 of 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 (20)

The rubber component (a) contains a conjugated diene unit, a non-conjugated olefin unit, and an aromatic vinyl unit, and has a heat absorption peak energy of 10 measured by a differential scanning calorimeter (DSC) at 0 to 120 ° C. Includes a multi-element copolymer (a1) at ~ 150 J / g and a conjugated diene-based rubber (a2) other than the multi-dimensional copolymer (a1).
The content of the multiple copolymer (a1) in the rubber component (a) is 5% by mass or more and less than 50% by mass.
A rubber composition, wherein the conjugated diene-based rubber (a2) forms a continuous phase, and the multiple 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, which is ~ 35 mol%. The invention according to claim 1 or 2, wherein the conjugated diene rubber (a2) contains a 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) of −60 ° C. to 0 ° C. measured by a differential scanning calorimeter (DSC). The rubber composition according to claim 3 or 4, wherein the styrene-butadiene rubber has a styrene content of 5 to 50% by mass. The rubber composition according to any one of claims 3 to 5, wherein the styrene-butadiene rubber has a vinyl bond content of 15 to 60% by mass in the styrene-butadiene rubber. The rubber composition according to any one of claims 1 to 6, wherein the multiple 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 multiple copolymer (a1) has a glass transition temperature of 0 ° C. or lower as measured by a differential scanning calorimeter (DSC). The rubber composition according to any one of claims 1 to 8, wherein the multiple copolymer (a1) has a crystallinity of 0.5 to 50%. The rubber composition according to any one of claims 1 to 9, wherein the multiple copolymer (a1) has only a non-cyclic structure in the main chain. The rubber composition according to any one of claims 1 to 10, wherein the multiple copolymer (a1) is a non-conjugated olefin unit in which the non-conjugated olefin unit is acyclic. The rubber composition according to claim 11, wherein the acyclic non-conjugated olefin unit comprises only an ethylene unit. The rubber composition according to any one of claims 1 to 12, wherein the multiple copolymer (a1) contains a styrene unit as the aromatic vinyl unit. The rubber composition according to any one of claims 1 to 13, wherein the multiple copolymer (a1) contains 1,3-butadiene units and / or isoprene units in the conjugated diene unit. A tire according to any one of claims 1 to 14, wherein the rubber composition is used. A conveyor belt according to any one of claims 1 to 14, wherein the rubber composition is used. A rubber crawler using the rubber composition according to any one of claims 1 to 14. An anti-vibration device according to any one of claims 1 to 14, wherein the rubber composition is used. A seismic isolation device according to any one of claims 1 to 14, wherein the rubber composition is used. A hose using the rubber composition according to any one of claims 1 to 14.