阅读说明：本技术 多元共聚物、橡胶组合物、树脂组合物、轮胎以及树脂制品 (Multipolymer, rubber composition, resin composition, tire and resin product ) 是由 庄田靖宏 种村骏 于 2020-04-21 设计创作，主要内容包括：本发明所要解决的问题为提供一种共聚物,其在低应变区域中具有降低的发热性。所述问题的解决方案为一种多元共聚物,其包括非共轭烯烃单元、共轭二烯单元、和芳香族乙烯基单元,所述多元共聚物的特征在于,通过差示扫描量热计(DSC)测量的在100-120℃的源自所述非共轭烯烃单元的结晶度(C-(100-120))相对于在0-100℃的源自所述非共轭烯烃单元的结晶度(C-(0-100))的比率[(C-(100-120)/C-(0-100))×100]为23％以下。(The problem to be solved by the present invention is to provide a copolymer having reduced heat generation in a low strain region. The solution to the problem is a multipolymer comprising non-conjugated olefin units, conjugated diene units, and aromatic vinyl units, the multipolymer being characterized by a crystallinity (C) derived from the non-conjugated olefin units at 100-120 ℃ as measured by a Differential Scanning Calorimeter (DSC) 100‑120 ) Relative to the degree of crystallinity (C) at 0-100 ℃ derived from the non-conjugated olefin unit 0‑100 ) Ratio of (C) 100‑120 /C 0‑100 )×100]Is 23% or less.)

1. A multipolymer comprising non-conjugated olefin units, conjugated diene units, and aromatic vinyl units, characterized in that:

a crystallinity (C) derived from the non-conjugated olefin unit at 100-120 ℃ as measured by a Differential Scanning Calorimeter (DSC)_100-120) Relative to the degree of crystallinity (C) at 0-100 ℃ derived from the non-conjugated olefin unit_0-100) Ratio of (C)_100-120/C_0-100)×100]Is 23% or less.

2. The multipolymer of claim 1, wherein the crystallinity (C) derived from non-conjugated olefin units at 0-100 ℃. (C)_0-100) Is more than 10 percent.

3. The multipolymer of claim 1 or 2, wherein the content of the non-conjugated olefin units is in the range of 40 to 97 mol%, the content of the conjugated diene units is in the range of 1 to 50 mol% and the content of the aromatic vinyl units is in the range of 2 to 35 mol%.

4. The multipolymer of any of claims 1 to 3, wherein its melting point as measured by Differential Scanning Calorimetry (DSC) is in the range of 50 to 90 ℃.

5. The multipolymer of any of claims 1 to 4, wherein its glass transition temperature as measured by Differential Scanning Calorimetry (DSC) is 0 ℃ or less.

6. The multipolymer of any of claims 1 to 5, wherein the backbone of the multipolymer consists solely of acyclic structures.

7. A rubber composition characterized by comprising the multipolymer according to any one of claims 1 to 6.

8. A resin composition characterized by comprising the multipolymer according to any one of claims 1 to 6.

9. A tire characterized by using the rubber composition according to claim 7.

10. A resin article characterized by using the resin composition according to claim 8.

Technical Field

The present invention relates to a multipolymer, a rubber composition, a resin composition, a tire and a resin product.

Background

In general, rubber products (such as tires, conveyor belts, vibration-proof rubber, vibration-isolating rubber, etc.) and resin products are required to have excellent durability (fracture resistance, wear resistance, and crack growth resistance, etc.) and weather resistance. Various polymers, and rubber compositions and resin compositions comprising the polymers, respectively, have been developed to meet such demands for rubber articles and resin articles as described above.

For example, PTL 1 discloses a copolymer of a conjugated diene compound and a non-conjugated olefin, in which the cis-1, 4-bond content of a conjugated diene unit thereof (a moiety derived from the conjugated diene compound) is more than 70.5 mol%, and the non-conjugated olefin is contained in an amount of 10 mol% or more. PTL 1 also discloses that the copolymer is used for producing a rubber composition excellent in crack growth resistance and weather resistance.

Reference list

Patent document

PTL 1：WO2012/014455

Disclosure of Invention

Problems to be solved by the invention

However, although it is a fact that the chain length of the non-conjugated olefin unit of the copolymer is an important factor affecting the heat generating property of the copolymer in the low strain region, PTL 1 does not discuss the chain length of the non-conjugated olefin unit of the copolymer.

In view of this, it is an object of the present invention to provide a polymer which exhibits reduced heat build-up in a low strain region.

Further, another object of the present invention is to provide a rubber composition, a resin composition, a tire, and a resin article each containing the polymer and exhibiting reduced heat generation in a low strain region.

Means for solving the problems

The polymer of the present invention designed to solve the above problems is a multipolymer, and its main characteristics are as follows.

The multipolymer of the present invention is a multipolymer comprising nonconjugated olefin units, conjugated diene units, and aromatic vinyl units, characterized in that:

a crystallinity (C) derived from the non-conjugated olefin unit at 100-120 ℃ as measured by a Differential Scanning Calorimeter (DSC)_100-120) Relative to the degree of crystallinity (C) at 0-100 ℃ derived from the non-conjugated olefin unit_0-100) Ratio of (C)_100-120/C_0-100)×100]Is 23% or less.

The above-mentioned multipolymer of the present invention exhibits reduced heat build-up in the low strain region.

In a preferred embodiment of the multipolymer of the present invention, the crystallinity (C) derived from non-conjugated olefin units at 0 to 100 ℃ is as described_0-100) Is more than 10 percent. In this case, the fracture resistance of the multipolymer is improved.

In another preferred example of the multipolymer of the present invention, the content of the non-conjugated olefin units is in the range of 40 to 97 mol%, the content of the conjugated diene units is in the range of 1 to 50 mol%, and the content of the aromatic vinyl units is in the range of 2 to 35 mol%. In this case, the fracture resistance and weather resistance of the multipolymer are improved.

In the multipolymer of the present invention, the melting point thereof as measured by a Differential Scanning Calorimeter (DSC) is preferably in the range of 50 to 90 ℃. In this case, the fracture resistance and the processability of the multipolymer are improved.

In the multipolymer of the present invention, the glass transition temperature thereof as measured by a Differential Scanning Calorimeter (DSC) is preferably 0 ℃ or lower. In this case, the processability of the multipolymer is improved.

In the multipolymer of the present invention, the main chain is preferably composed of only acyclic structures. In this case, the fracture resistance of the multipolymer is improved.

The rubber composition of the present invention is characterized by containing the above-mentioned multipolymer. The rubber composition of the present invention exhibits reduced heat build-up in a low strain region.

The resin composition of the present invention is characterized by containing the above-mentioned multipolymer. The resin composition of the present invention exhibits reduced heat build-up in a low strain region.

In the present invention, the "rubber composition" means a composition having rubber-like elasticity at room temperature, and is distinguished from a "resin composition" means a composition which is relatively hard and does not have rubber-like elasticity at room temperature.

The tire of the present invention is characterized by using the rubber composition. The tire of the present invention exhibits reduced heat build-up in a low strain region and has low rolling resistance.

The resin product of the present invention is characterized by using the resin composition. The resin product of the present invention exhibits reduced heat build-up.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, a multipolymer exhibiting reduced heat generation in a low strain region can be provided.

Further, according to the present invention, a rubber composition, a resin composition, a tire, and a resin article each exhibiting reduced heat generation property in a low strain region can be provided.

Drawings

In the drawings, wherein:

FIG. 1 is a DSC of the multipolymer of example 1.

Detailed Description

Hereinafter, the multipolymer, the rubber composition, the resin composition, the tire and the resin article of the present invention will be specifically and illustratively described based on embodiments thereof.

< multipolymer >

The multipolymer of the invention is a multicomponentA copolymer comprising non-conjugated olefin units, conjugated diene units, and aromatic vinyl units, characterized in that: crystallinity (C) derived from non-conjugated olefin units at 100-120 ℃ as measured by Differential Scanning Calorimeter (DSC)_100-120) Relative to the degree of crystallinity (C) at 0-100 ℃ derived from non-conjugated olefin units_0-100) Ratio of (C)_100-120/C_0-100)×100]Is 23% or less.

In DSC measurement of a multipolymer having non-conjugated olefin units, conjugated diene units, and aromatic vinyl units therein, an endothermic peak in the range of 100-120 ℃ is derived from non-conjugated olefin units having a long chain length, and an endothermic peak in the range of 0 to 100 ℃ is derived from non-conjugated olefin units having a short chain length. The nonconjugated olefin unit having a short chain length functions as a pseudo crosslinking point (pseudo crosslinking point) in the molecular chain of the multipolymer, thereby producing a function of reducing hysteresis loss. In contrast, a long chain length of the non-conjugated olefin unit means that sufficient crystalline components (hard portions) are present in the multipolymer, whereby the non-conjugated olefin unit having a long chain length functions like a filler in the same manner as the crystalline polyethylene, and contributes to the generation of hysteresis loss even at low strain. In this respect, in the multipolymer of the present invention, the crystallinity (C) derived from the non-conjugated olefin unit at 100-120 ℃ as measured by DSC_100-120) Relative to the degree of crystallinity (C) at 0-100 ℃ derived from non-conjugated olefin units_0-100) Ratio of (C)_100-120/C_0-100)×100]Is 23% or less. That is, the proportion of the non-conjugated olefin unit having a long chain length is low, whereas the proportion of the non-conjugated olefin unit having a short chain length is high, whereby a relatively small hysteresis loss is generated by low strain, and therefore in the multipolymer of the present invention, the heat generation property in the low strain region is reduced.

Further, in the multipolymer comprising the non-conjugated olefin units of the present invention, the crystalline component derived from the non-conjugated olefin units collapses by applying a high strain thereto, so that the multipolymer can dissipate energy. That is, the multipolymer of the present invention has high energy dissipation capability in a high strain region, so that breakage caused by high strain is well suppressed by excellent energy dissipation, and thus exhibits satisfactory fracture resistance.

The crystalline component of the multipolymer constitutes the hard part of the multipolymer. Therefore, the addition of a multipolymer containing a large amount of non-conjugated olefin units having a long chain length to the rubber composition and the resin composition deteriorates the processability in the kneading step. However, when the multipolymer is blended with a rubber composition or a resin composition, the multipolymer of the present invention having a small content of non-conjugated olefin units having a long chain length can reliably exhibit satisfactory processability in a kneading process.

In the multipolymer of the present invention, the crystallinity (C)_100-120) Relative to degree of crystallinity (C)_0-100) Ratio of (C)_100-120/C_0-100) X 100 is 23% or less. However, from the viewpoint of further reducing the heat generation property in the low strain region, the ratio [ (C)_100-120/C_0-100)×100]Preferably 22% or less, and more preferably 21% or less. Ratio [ (C)_100-120/C_0-100)×100]The lower limit of (B) is not particularly limited, but usually 5.0% or 4.0% or 3.0% or 2.0% or 1.0% or 0.1%. Ratio [ (C)_100-120/C_0-100)×100]The lower limit of (b) may be 0%.

In the present invention, the degree of crystallinity (C)_100-120) And degree of crystallinity (C)_0-100) Each represents a value measured according to the method described in the examples.

In the multipolymer of the present invention, the crystallinity (C) derived from the non-conjugated olefin unit at 100-120 ℃ as measured by a Differential Scanning Calorimeter (DSC)_100-120) Preferably 4.0% or less, more preferably 2.5% or less, and still more preferably 1.0% or less. Degree of crystallinity (C)_100-120) The lower limit of (b) is not particularly limited and may be 0%. Crystallinity (C) from non-conjugated olefin units at 100-120 ℃ as measured by DSC_100-120) Lower means that the chain length of the non-conjugated olefin unit is shorter, and therefore the heat generation property is more reduced in the low strain region, and when a multipolymer is copolymerized withThe better the processability in the kneading step when the rubber composition or the resin composition is blended.

In the multipolymer of the present invention, the crystallinity (C) derived from non-conjugated olefin units at 0 to 100 ℃ as measured by a Differential Scanning Calorimeter (DSC)_0-100) Preferably 10% or more, more preferably 15% or more, and still more preferably 16% or more. Degree of crystallinity (C)_0-100) The upper limit of (b) is not particularly limited, but is usually 50% or less. As described above, in the multipolymer of the present invention, the crystalline component derived from the non-conjugated olefin unit collapses by applying a high strain thereto, so that the multipolymer can dissipate energy. In this respect, the degree of crystallinity (C)_0-100) Setting to 10% or more reliably increases the ability to dissipate energy in the high strain region, thereby improving the fracture resistance of the multipolymer.

The multipolymer of the present invention comprising at least a non-conjugated olefin unit, a conjugated diene unit and an aromatic vinyl unit may consist of only a non-conjugated olefin unit, a conjugated diene unit and an aromatic vinyl unit, or further comprise other monomer units.

The non-conjugated olefin unit is a structural unit derived from a non-conjugated olefin compound as a monomer. "non-conjugated olefin compound" means in the present invention an aliphatic unsaturated hydrocarbon compound having at least one carbon-carbon double bond. In the case where the non-conjugated olefinic compound has two or more carbon-carbon double bonds, the carbon-carbon double bonds are not conjugated. The kind of the non-conjugated olefin compound is not particularly limited, but the non-conjugated olefin compound preferably has 2 to 10 carbon atoms. Specific examples of the above-mentioned non-conjugated olefin compounds include: α -olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene and 1-octene, etc.; heteroatom-substituted olefinic compounds, such as vinyl pivalate, 1-phenylthioethylene, N-vinylpyrrolidone; and the like. A single species or a combination of two or more species in these examples may be used as the non-conjugated olefin compound. The non-conjugated olefin compound as a monomer of the multipolymer is preferably a non-cyclic non-conjugated olefin compound from the viewpoint of improving the weather resistance of a rubber composition, a resin composition or the like using the resultant multipolymer. The acyclic unconjugated olefin compound is preferably an α -olefin, and particularly preferably ethylene. Such as an α -olefin, particularly an acyclic nonconjugated olefin compound such as ethylene, has a double bond at the α -position of the olefin, whereby the compound can be efficiently polymerized with a conjugated diene compound described below, and further the weather resistance of a rubber composition or a resin composition using the obtained multipolymer can be improved.

In the multipolymer of the present invention, the non-conjugated olefin units are preferably non-cyclic non-conjugated olefin units. When the non-conjugated olefin unit is an acyclic non-conjugated olefin unit, the weather resistance of a rubber composition or a resin composition or the like using the resulting multipolymer is improved.

In the multipolymer of the present invention, it is particularly preferred that the non-conjugated olefin units consist only of ethylene units. In the case where the non-conjugated olefin unit is composed of only an ethylene unit, a non-conjugated olefin compound from which the non-conjugated olefin unit is derived, that is, ethylene, is easily obtained, and thus the production cost of the multipolymer can be reduced.

In the multipolymer of the present invention, the content of the non-conjugated olefin units is preferably 40 mol% or more, more preferably 45 mol% or more, still more preferably 55 mol% or more, particularly preferably 60 mol% or more, and preferably 97 mol% or less, more preferably 95 mol% or less, still more preferably 90 mol% or less. When the content of the non-conjugated olefin unit is not less than 40 mol% of the whole of the multipolymer, the multipolymer shows high energy dissipation capability in a high strain region thereof. Further, in this case, the content of the conjugated diene unit and/or the aromatic vinyl unit is thus reduced, thereby improving the weather resistance and/or the fracture resistance (particularly, the breaking strength (Tb)) of the multipolymer at high temperatures. When the content of the non-conjugated olefin unit is 97 mol% or less, the content of the conjugated diene unit and/or the aromatic vinyl unit is thereby increased, thereby improving the fracture resistance (particularly, elongation at break (Eb)) of the multipolymer at high temperature. The content of the non-conjugated olefin unit is preferably in the range of 40 to 97 mol%, more preferably in the range of 45 to 95 mol%, and still more preferably in the range of 55 to 90 mol% of the entire multipolymer.

The conjugated diene unit is a structural unit derived from a conjugated diene compound as a monomer. "conjugated diene compound" means in the present invention a diene compound in which a double bond is conjugated. Although the kind of the conjugated diene compound is not particularly limited, the conjugated diene compound preferably has 4 to 8 carbon atoms. Specific examples of the conjugated diene compound include 1, 3-butadiene, isoprene, 1, 3-pentadiene, and 2, 3-dimethyl-1, 3-butadiene, and the like. From the viewpoint of availability, 1, 3-butadiene and isoprene are preferable among these examples, and 1, 3-butadiene is particularly preferable. A single kind or a combination of two or more kinds of these examples may be used as the conjugated diene compound.

In the multipolymer of the present invention, the conjugated diene units preferably comprise 1, 3-butadiene units and/or isoprene units. When the conjugated diene unit includes a 1, 3-butadiene unit and/or an isoprene unit, a conjugated diene compound from which the conjugated diene unit is derived (i.e., 1, 3-butadiene, isoprene) is easily obtained, and thus the production cost of the multipolymer can be reduced.

Further, in the multipolymer of the present invention, it is particularly preferable that the conjugated diene unit is composed of only 1, 3-butadiene units. When the conjugated diene unit is composed of only 1, 3-butadiene units, the conjugated diene compound from which the conjugated diene unit is derived (i.e., 1, 3-butadiene) is particularly easily obtained, and thus the production cost of the copolymer can be further reduced.

In the multipolymer of the present invention, the content of the conjugated diene unit is preferably not less than 1 mol%, more preferably not less than 3 mol%, and preferably not more than 50 mol%, more preferably not more than 40 mol%, still more preferably not more than 30 mol%, still more preferably not more than 25 mol%, particularly preferably not more than 15 mol%. The content of the conjugated diene unit is preferably not less than 1 mol% of the whole of the multipolymer, because this remarkably promotes the vulcanization of the multipolymer and makes it possible to obtain a rubber composition and a tire excellent in elongation. The content of the conjugated diene unit is not more than 50 mol% of the entire multipolymer, and excellent weather resistance is realized. The content of the conjugated diene is preferably in the range of 1 to 50 mol%, more preferably in the range of 3 to 40 mol% of the entire multipolymer.

The aromatic vinyl unit is a structural unit derived from an aromatic vinyl compound as a monomer. "aromatic vinyl compound" means in the present invention an aromatic compound which has been substituted with at least a vinyl group. When the multipolymer contains aromatic vinyl units, the chain length of the non-conjugated olefin units can be shortened more easily than in other cases. Although the kind of the aromatic vinyl compound is not particularly limited, the aromatic vinyl compound preferably has 8 to 10 carbon atoms. Examples of the aromatic vinyl compound include styrene, α -methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene and the like. Among these examples, styrene is preferred from the viewpoint of easy availability. A single species or a combination of two or more species in the examples may be used as the aromatic vinyl compound.

The multipolymer of the present invention preferably comprises styrene units as aromatic vinyl units. When the multipolymer includes styrene units, an aromatic vinyl compound (i.e., styrene) from which aromatic vinyl units are derived is easily obtained, and thus the production cost of the multipolymer can be reduced.

In the multipolymer of the present invention, the content of the aromatic vinyl unit is preferably not less than 2 mol%, more preferably not less than 3 mol%, and preferably not more than 35 mol%, more preferably not more than 30 mol%, still more preferably not more than 25 mol%. The content of the aromatic vinyl unit of not less than 2 mol% improves the fracture resistance at high temperatures. When the content of the aromatic vinyl unit is 35 mol% or less, the effect caused by the non-conjugated olefin unit and the conjugated diene unit is 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 still more preferably in the range of 3 to 25 mol% of the entire multipolymer.

It is preferable that in the multipolymer of the present invention, the content of the non-conjugated olefin unit is in the range of 40 to 97 mol%, the content of the conjugated diene unit is in the range of 1 to 50 mol%, and the content of the aromatic vinyl unit is in the range of 2 to 35 mol%. In this case, the fracture resistance and weather resistance of a rubber composition or a resin composition or the like having the multipolymer blended therein are improved.

In the multipolymer of the present invention, the content of butene units is preferably 0 mol%. Therefore, since the hydrogenated styrene-ethylene/butylene-styrene (SEBS) copolymer contains a butylene unit, when "the content of the butylene unit is 0 mol%" therein, the multi-component copolymer does not include the SEBS.

The number of kinds of monomers of the multipolymer is not particularly limited as long as the multipolymer includes conjugated diene units, non-conjugated olefin units and aromatic vinyl units therein. In other words, the multipolymer may include optional structural units in addition to the conjugated diene units, the non-conjugated olefin units and the aromatic vinyl units. However, from the viewpoint of obtaining the desired effect, the content of the optional structural unit is preferably 30 mol% or less, more preferably 20 mol% or less, still more preferably 10 mol% or less, and particularly preferably 0 mol%. That is, it is particularly preferred that the multipolymer does not contain any optional structural units other than the essentially required units described above.

The weight average molecular weight (Mw) of the multipolymer of the invention in terms of polystyrene is preferably in the range of 10,000 to 10,000,000, more preferably in the range of 100,000 to 9,000,000, and still more preferably in the range of 150,000 to 8,000,000. The weight average molecular weight (Mw) of the multipolymer of 10,000 or more ensures satisfactory mechanical strength of the multipolymer, and the Mw of the multipolymer of 10,000,000 or less ensures good processability of the multipolymer.

Further, the number average molecular weight (Mn) of the multipolymer of the present invention in terms of polystyrene is preferably in the range of 10,000 to 10,000,000, more preferably in the range of 50,000 to 9,000,000, and still more preferably in the range of 100,000 to 8,000,000. The number average molecular weight (Mn) of the multipolymer of 10,000 or more ensures satisfactory mechanical strength of the multipolymer, and the Mn of the multipolymer of 10,000,000 or less ensures good processability of the multipolymer.

Still further, the molecular weight distribution [ Mw/Mn (weight average molecular weight/number average molecular weight) ] of the multipolymer of the present invention is preferably in the range of 1.00 to 4.00, more preferably in the range of 1.50 to 3.50, and still more preferably in the range of 1.80 to 3.00. By setting the molecular weight distribution of the multipolymer to be less than or equal to 4.00, the physical properties of the multipolymer can be satisfactorily homogenized.

The above weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw/Mn) with respect to polystyrene as a standard substance were determined by Gel Permeation Chromatography (GPC).

In the multipolymer of the present invention, its melting point as measured by a Differential Scanning Calorimeter (DSC) is preferably in the range of 50 to 90 ℃ and more preferably in the range of 60 to 80 ℃. When the melting point of the multipolymer is equal to or higher than 50 ℃, the crystallinity of the multipolymer is increased, and thus the fracture resistance thereof is further improved. When the melting point of the multipolymer is equal to or lower than 90 ℃, the processability is improved.

The melting point represents a value measured by using a differential scanning calorimeter according to JIS K7121-1987 in the present invention.

In the multipolymer of the present invention, the endothermic energy at its endothermic peak in the range of 0 ℃ to 120 ℃ as measured by a Differential Scanning Calorimeter (DSC) is preferably in the range of 10J/g to 150J/g, and more preferably in the range of 30J/g to 120J/g. When the endothermic energy at the endothermic peak of the multipolymer is 10J/g or more, the crystallinity of the multipolymer is sufficiently high and the fracture resistance of the multipolymer is further improved. When the endothermic energy at the endothermic peak of the multipolymer is not more than 150J/g, the processability of the multipolymer is improved.

In the present invention, "endothermic energy at endothermic peak" means a value of endothermic energy at endothermic peak measured in the range of 0 ℃ to 120 ℃ by using a differential scanning calorimeter when a sample is heated from-150 ℃ to 150 ℃ at a temperature rising rate of 10 ℃/minute in the first run according to JIS K7121-1987.

In the multipolymer of the present invention, the glass transition temperature (Tg) as measured by a Differential Scanning Calorimeter (DSC) is preferably equal to or lower than 0 ℃ and more preferably in the range of-100 ℃ to-10 ℃. When the glass transition temperature of the multipolymer is equal to or lower than 0 ℃, the processability is improved.

In the present invention, the "glass transition temperature" represents a value measured by using a differential scanning calorimeter in accordance with JIS K7121-.

It is preferable that the main chain of the multipolymer of the present invention is composed of only acyclic structures, because this improves the fracture resistance of the multipolymer. NMR was used as a main measure to determine whether the main chain of the multipolymer consisted of only acyclic structures. Specifically, when a peak derived from a cyclic structure present in the main chain (for example, any peak appearing in the range of 10ppm to 24ppm in the case of a three-membered ring structure, a four-membered ring structure and a five-membered ring structure) is not observed, the result indicates that the main chain of the multipolymer is composed of only a non-cyclic structure.

The multipolymer can be produced by a polymerization step using a non-conjugated olefin compound, a conjugated diene compound, and an aromatic vinyl compound as monomers, and optionally a coupling step, a washing step, and other steps.

In the present invention, it is preferable to first add only the non-conjugated olefin compound and the aromatic vinyl compound without adding the conjugated diene compound thereto when producing the multipolymer, and polymerize the two compounds thus added in the presence of a polymerization catalyst, because the conjugated diene compound is generally more reactive than the non-conjugated olefin compound and the aromatic vinyl compound when using the catalyst composition described below in particular, whereby it is presumed that it is difficult to satisfactorily polymerize the non-conjugated olefin compound and/or the aromatic vinyl compound in the presence of the conjugated diene compound. In this respect, it is also generally difficult to separately polymerize the conjugated diene compound in advance and then separately polymerize the non-conjugated olefin compound and the aromatic vinyl compound, due to the characteristics of the catalyst.

Any polymerization method such as solution polymerization, suspension polymerization, liquid phase bulk polymerization, emulsion polymerization, gas phase polymerization, or solid phase polymerization may be used for the polymerization process. In the case of using a solvent in the relevant polymerization reaction, any solvent is acceptable as long as the solvent is inert in the polymerization reaction. Examples of the solvent include toluene, cyclohexane, n-hexane and the like.

The polymerization process may be performed by one step, or may be performed by a plurality of (i.e., two or more) steps. The polymerization process carried out by one step means a process in which polymerization is effected by simultaneously reacting all monomers to be polymerized (i.e., the non-conjugated olefin compound, the conjugated diene compound, the aromatic vinyl compound and other monomers, preferably the non-conjugated olefin compound, the conjugated diene compound and the aromatic vinyl compound). The polymerization procedure, which is carried out by multiple steps, comprises: a step of forming a polymer by first partially/totally polymerizing one/two or more kinds of monomers (first polymerization step); and then adding the remaining part of the monomers of the first polymerization step and the remaining types/kinds of monomers that have not been used in the first polymerization step to the polymer formed in the first polymerization step, thereby completing at least one process of polymerization (second polymerization step to final polymerization step). In particular, in the production of the multipolymer, it is preferable that the polymerization step is carried out in multiple steps.

In the polymerization step, the polymerization reaction is preferably carried out in an inert gas atmosphere, and preferably in a nitrogen or argon atmosphere.

The temperature in the polymerization reaction is not particularly limited, but is preferably in the range of, for example, -100 ℃ to 200 ℃ and may be in the vicinity of room temperature. The above-mentioned crystallinity (C) at 100-120 ℃ derived from the non-conjugated olefin unit can be adjusted by controllably setting the polymerization temperature, and by selecting the type and/or composition of the polymer catalyst described below_100-120) And a crystallinity (C) derived from a non-conjugated olefin unit at 0 to 100 DEG C_0-100)。

The pressure during the polymerization reaction is preferably in the range of 0.1MPa to 10.0MPa from the viewpoint of capturing a sufficient amount of the conjugated diene compound into the polymerization reaction system. Although not particularly limited, the reaction time taken for the polymerization reaction is preferably in the range of, for example, 1 second to 10 days. The reaction time can be appropriately set depending on conditions such as the kind of the catalyst and the polymerization reaction temperature.

In the step of polymerizing the conjugated diene compound, the polymerization reaction can be terminated by using a polymerization terminator such as methanol, ethanol, or isopropanol.

The above polymerization process is preferably carried out by multiple steps, and more preferably by: a first step of mixing a first monomer raw material including at least an aromatic vinyl compound with a polymerization catalyst to obtain a polymerization mixture; and a second step of introducing a second monomer raw material including at least one selected from the group consisting of a conjugated diene compound, a non-conjugated olefin compound and an aromatic vinyl compound into the polymerization mixture. Still more preferably, the first monomer raw material does not include a conjugated diene compound, but the second monomer raw material includes a conjugated diene compound.

The first monomer raw material used in the first step may include a non-conjugated olefin compound, and an aromatic vinyl compound. Further, the first monomer raw material may contain the whole amount or a part of the aromatic vinyl compound used. It should be noted that the non-conjugated olefin compound is to be included in at least one of the first monomer feed and the second monomer feed.

The first step is preferably performed in a reaction vessel under an inert gas atmosphere, and desirably under an atmosphere of nitrogen or argon. The temperature (reaction temperature) in the first step is not particularly limited, but is preferably in the range of, for example, -100 ℃ to 200 ℃ and may be in the vicinity of room temperature. The pressure during the first step is not particularly limited, but is preferably in the range of 0.1 to 10.0MPa from the viewpoint of trapping a sufficient amount of the aromatic vinyl compound in the polymerization reaction system. The reaction time may be appropriately set according to conditions such as the kind of the catalyst and the polymerization reaction temperature, but when the reaction temperature is set in the range of 25 ℃ to 80 ℃, for example, the time taken for the first step (reaction time) is preferably in the range of 5 minutes to 500 minutes.

Any polymerization method such as solution polymerization, suspension polymerization, liquid phase bulk polymerization, emulsion polymerization, gas phase polymerization, or solid phase polymerization may be used for the polymerization method to obtain the polymerization mixture in the first step. In the case of using a solvent in the relevant polymerization reaction, any solvent is acceptable as long as the solvent is inert in the polymerization reaction. Examples of the solvent include toluene, cyclohexane, n-hexane and the like.

The second monomer raw material used in the second step preferably includes i) only a conjugated diene compound, or ii) a conjugated diene compound and a non-conjugated olefin compound, or iii) a conjugated diene compound and an aromatic vinyl compound, or iv) a conjugated diene compound, a non-conjugated olefin compound, and an aromatic vinyl compound.

In the case where the second monomer raw material includes at least one selected from the group consisting of a non-conjugated olefin compound and an aromatic vinyl compound in addition to the conjugated diene compound, these monomer raw materials may be introduced into the polymerization mixture after the monomer raw materials and the solvent are mixed with each other, or alternatively, the monomer raw materials may be introduced into the polymerization mixture separately (without being mixed with each other). The monomer raw materials may be added all together, or may be added one by one with a time lag therebetween. In the second step, the method of introducing the second monomer raw material into the polymerization mixture is not particularly limited, but the second monomer raw material is preferably continuously added to the polymerization mixture with the flow rate of each monomer raw material being controlled or metered. In this aspect, in the case where a monomer raw material that is gaseous under the conditions of the polymerization reaction system (for example, ethylene or the like that is a non-conjugated olefin compound that is gaseous under the conditions of room temperature and standard atmospheric pressure) is used, the monomer raw material may be introduced into the polymerization reaction system at a predetermined pressure.

In the second step, the polymerization step is preferably performed in a reaction vessel in an inert gas atmosphere, desirably in a nitrogen or argon atmosphere. The temperature (reaction temperature) in the second step is not particularly limited, but is preferably in the range of, for example, -100 ℃ to 200 ℃ and may be in the vicinity of room temperature. Too high a reaction temperature may adversely affect the selectivity of the cis-1, 4 bond of the conjugated diene unit in the reaction. The pressure in the second step is not particularly limited from the viewpoint of trapping a sufficient amount of monomer such as a conjugated diene compound in the polymerization reaction system, but is preferably in the range of 0.1MPa to 10.0 MPa. The time (reaction time) taken for the second step is preferably in the range of 0.1 hour to 10 days, for example. The reaction time can be appropriately set depending on conditions such as the kind of the polymerization catalyst and the polymerization temperature.

In the second step, the polymerization reaction may be terminated by using a polymerization terminator such as methanol, ethanol, isopropanol, or the like.

In the present invention, the step of polymerizing the conjugated diene compound, the non-conjugated olefin compound, and the aromatic vinyl compound preferably includes a step of polymerizing each monomer in the presence of at least one of the following components (a) to (F) as a catalyst component. In the polymerization process, at least one of the following components (a) to (F) is preferably used as a catalyst component, and more preferably at least two of the following components (a) to (F) are used in combination as a catalyst composition.

A component (A): rare earth element compound or reaction product produced by reaction between the rare earth element compound and Lewis base

A component (B): organometallic compounds

A component (C): aluminoxanes

A component (D): ionic compound

A component (E): halogen compound

A component (F): a compound having a cyclopentadiene skeleton selected from the group consisting of substituted/unsubstituted cyclopentadiene (a compound having a cyclopentadienyl group), substituted/unsubstituted indene (a compound having an indenyl group), and substituted/unsubstituted fluorene (a compound having a fluorenyl group), which compound as the component (F) is hereinafter sometimes simply referred to as "a compound having a cyclopentadiene skeleton".

Components (A) to (F) will be described in detail below.

The "rare earth element compound or a reaction product resulting from a reaction between the rare earth element compound and a lewis base" as the component (a) specifically includes: i) a rare earth element compound or a reaction product resulting from a reaction between the rare earth element compound and a lewis base, the compound/reaction product having a bond between the rare earth element and carbon (the compound/reaction product is hereinafter sometimes referred to as "component (a-1)"); and ii) a rare earth element compound or a reaction product resulting from a reaction between the rare earth element compound and a Lewis base, the compound/reaction product having no bond between the rare earth element and carbon (the compound/reaction product is hereinafter sometimes referred to as "component (A-2)").

Examples of the component (A-1) include:

a metallocene complex represented by the following general formula (I):

(in the formula (I), M represents a lanthanoid, scandium or yttrium; Cp^REach independently represents an unsubstituted/substituted indenyl group; r^a～R^fEach independently represents C_1-3An alkyl group or a hydrogen atom; l represents a neutral lewis base; and w represents an integer in the range of 0 to 3);

a metallocene complex represented by the following general formula (II):

(in the formula (II), M represents a lanthanoid, scandium or yttrium; Cp^REach independently represents an unsubstituted/substituted indenyl group; x' represents a hydrogen atom, a halogen atom, an alkoxy group, a mercapto group, an amino group, a silyl group, or C_1-20A monovalent hydrocarbon group; l represents a neutral lewis base; and w represents an integer in the range of 0 to 3); and

a half-metallocene cationic complex represented by the following general formula (III):

(in the formula (III), M represents a lanthanoid, scandium or yttrium; Cp^R’Represents unsubstituted/substituted cyclopentadienyl, unsubstituted/substituted indenyl or unsubstituted/substituted fluorenyl; x represents a hydrogen atom, a halogen atom, an alkoxy group, a mercapto group, an amino group, a silyl group, or C_1-20A monovalent hydrocarbon group; l represents a neutral lewis base; w represents an integer in the range of 0 to 3); and [ B]^-Represents a non-coordinating anion).

In each of the metallocene complexes represented by the general formulae (I) and (II), Cp^RIs unsubstituted/substituted indenyl. Cp having indenyl ring as basic skeleton^RCan be represented as C₉H_7-X R_XOr C₉H_11-X R_XWherein X represents an integer in the range of 0 to 7 or 0 to 11; r preferably each independently represents a hydrocarbyl group or a metalloid group; and the number of carbon atoms of the hydrocarbon group is preferably in the range of 1 to 20, more preferably in the range of 1 to 10, and still more preferably in the range of 1 to 8. Specifically, preferred examples of the hydrocarbon group include methyl, ethyl, phenyl, benzyl and the like. Examples of the metalloid group include germylge, stannyl Sn, and silyl Si. The metalloid group preferably includes a hydrocarbon group defined in the same manner as the above-mentioned hydrocarbon group. Specific examples of the metalloid group include trimethylsilyl and the like. Specific examples of the substituted indenyl group include 2-phenylindenyl and 2-methylindenyl, etc. Two Cp in the general formula (I)^RMay be of the same kind or of different kinds. Two Cp in the general formula (II)^RMay be of the same kind or of different kinds.

In the half-metallocene cation complex represented by the general formula (III), Cp^R’Is unsubstituted/substituted cyclopentadienyl, unsubstituted/substituted indenyl or unsubstituted/substituted fluorenyl. Among these examples, unsubstituted/substituted indenyl is preferred as Cp^R’。

In the general formula (III), Cp having a cyclopentadienyl ring as a basic skeleton^R’Is represented as C₅H_5-X R_XWherein X is an integer in the range of 0-5; r preferably each independently represents a hydrocarbyl group or a pseudoA metal group; and the number of carbon atoms of the hydrocarbon group is preferably in the range of 1 to 20, more preferably in the range of 1 to 10, and still more preferably in the range of 1 to 8. Specifically, preferred examples of the hydrocarbon group include methyl, ethyl, phenyl, benzyl and the like. Examples of the metalloid group include germylge, stannyl Sn, and silyl Si. The metalloid group preferably includes a hydrocarbon group defined in the same manner as the above-mentioned hydrocarbon group. Specific examples of the metalloid group include trimethylsilyl and the like. Cp having cyclopentadienyl ring as basic skeleton^R’Specific examples of (a) include compounds represented by the following structural formula:

(in these formulae, R represents a hydrogen atom, a methyl group or an ethyl group.)

In the general formula (III), Cp having an indenyl ring as a basic skeleton^R’And preferred examples thereof with Cp in the general formula (I)^RAnd Cp in the general formula (II)^RDefined in the same manner.

In the general formula (III), Cp having a fluorenyl ring as a basic skeleton^R’Is represented as C₁₃H_9-XR_XOr C₁₃H_17-XR_XWherein X is an integer in the range of 0 to 9 or 0 to 17; r preferably each independently represents a hydrocarbyl group or a metalloid group; and the number of carbon atoms of the hydrocarbon group is preferably in the range of 1 to 20, more preferably in the range of 1 to 10, and still more preferably in the range of 1 to 8. Specifically, preferred examples of the hydrocarbon group include methyl, ethyl, phenyl, benzyl and the like. Examples of the metalloid group include germylge, stannyl Sn, and silyl Si. The metalloid group preferably includes a hydrocarbon group defined in the same manner as the above-mentioned hydrocarbon group. Specific examples of the metalloid group include trimethylsilyl and the like.

The central metal M in each of the formulae (I), (II) and (III) is a lanthanide, scandium or yttrium. The lanthanide series of elements includes the 15 elements of the periodic table having atomic numbers 57-71, any one of which is acceptable. Preferred examples of the central metal M include samarium Sm, neodymium Nd, praseodymium Pr, gadolinium Gd, cerium Ce, holmium Ho, scandium Sc, and yttrium Y.

The metallocene complex represented by the general formula (I) includes a silylamino ligand [ -N (SiR)₃)₂]. The R group included in the silylamine ligand (i.e., R in the general formula (I))^a～R^f) Each independently represents C_1-3Alkyl groups or hydrogen atoms. Preferably, R is^a～R^fAt least one of them is a hydrogen atom. When R is^a～R^fWhen at least one of them is a hydrogen atom, since steric hindrance around the silicon atom is relatively small, the catalyst can be easily synthesized, and the non-conjugated olefin compound and the aromatic vinyl compound can be easily introduced. For similar reasons, it is more preferred that R^a～R^cAt least one of which is a hydrogen atom and R^d～R^fAt least one of them is a hydrogen atom. Methyl is preferred as alkyl.

The metallocene complex represented by the general formula (II) includes a silyl ligand [ -SiX'₃]. Silyl ligand [ -SiX'₃]The X' group included and preferred examples thereof are defined in the same manner as the X group in the following formula (III).

In the general formula (III), X is selected from the group consisting of a hydrogen atom, a halogen atom, an alkoxy group, a mercapto group, an amino group, a silyl group, and C_1-20Monovalent hydrocarbon radicals. Acceptable examples of the halogen atom represented by X in the general formula (III) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Preferably a chlorine atom or a bromine atom.

In the general formula (III), examples of the alkoxy group represented by X include: aliphatic alkoxy groups such as methoxy, ethoxy, propoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy and the like; and aryloxy groups such as phenoxy group, 2, 6-di-t-butylphenoxy group, 2, 6-diisopropylphenoxy group, 2, 6-dineopentylphenoxy group, 2-t-butyl-6-isopropylphenoxy group, 2-t-butyl-6-neopentylphenoxy group, 2-isopropyl-6-neopentylphenoxy group and the like. Of these examples, 2, 6-di-tert-butylphenoxy is preferred as alkoxy group.

In the general formula (III), examples of the hydrocarbylthio group represented by X include: aliphatic hydrocarbylthio groups such as thiomethoxy, thioethoxy, thiopropoxy, thio-n-butoxy, thio-isobutoxy, thio-sec-butoxy, and thio-tert-butoxy, and the like; and arylhydrocarbylthio groups such as thiophenoxy, 2, 6-di-tert-butylthiophenoxy, 2, 6-diisopropylthiophenoxy, 2, 6-dineopentylthiophenoxy, 2-tert-butyl-6-isopropylthiophenoxy, 2-tert-butyl-6-thioneopentylphenoxy, 2-isopropyl-6-thioneopentylphenoxy, and 2,4, 6-triisopropylthiophenoxy and the like. Of these examples, 2,4, 6-triisopropylthiophenoxy is preferred as the hydrocarbylthio group.

In the general formula (III), examples of the amine group represented by X include: aliphatic amine groups such as dimethylamino group, diethylamino group, diisopropylamine group and the like; arylamine groups such as phenylamino group, 2, 6-di-t-butylphenyl group, 2, 6-diisopropylphenylamino group, 2, 6-dineopentylphenylamino group, 2-t-butyl-6-isopropylphenylamino group, 2-t-butyl-6-neopentylphenylphenylamino group, 2-isopropyl-6-neopentylphenylphenylamino group, 2,4, 6-tri-t-butylphenyl phenylamino group and the like; bis (trialkylsilyl) amine groups such as bis (trimethylsilyl) amine groups; and the like. Among these examples, a bis (trimethylsilyl) amine group is preferable as the amine group.

In the general formula (III), 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, a (triisopropylsilyl) bis (trimethylsilyl) silyl group and the like. Among these examples, a tris (trimethylsilyl) silyl group is preferable as the silyl group.

In the general formula (III), C represented by X_1-20Specific examples of the monovalent hydrocarbon group include: straight/branched aliphatic hydrocarbon groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, hexyl, octyl; aromatic hydrocarbon groups such as phenyl, tolyl, and naphthyl; aralkyl groups such as benzyl; hydrocarbon radicals containing silicon atoms, e.g. trimethylSilylmethyl, bis (trimethylsilyl) methyl; and the like. Among these examples, methyl, ethyl, isobutyl, and trimethylsilylmethyl and the like are preferred as C_1-20A monovalent hydrocarbon group.

In the general formula (III), bistrimethylsilylamino or C_1-20Monovalent hydrocarbon groups are preferred as X.

In the general formula (III), a group represented by [ B ]]^-Examples of non-coordinating anions that are represented include tetravalent boron anions. Specific examples of the tetravalent boron anion include tetraphenyl borate, tetrakis (monofluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis (pentafluorophenyl) borate, tetrakis (tetrafluoromethylphenyl) borate, tetrakis (tolyl) borate, tetraxylyl borate, triphenyl (pentafluorophenyl) borate, [ tris (pentafluorophenyl) phenyl ] borate]Borate, and tridecyl-7, 8-dicarbonylundecanoborate, and the like. Of these examples, tetrakis (pentafluorophenyl) borate is preferred as the tetravalent boron anion.

The metallocene complex represented by the general formulae (I) and (II) and the half-metallocene cationic complex represented by the general formula (III), respectively, each further comprises 0 to 3, preferably 0 to 1, neutral Lewis bases L. Examples of the neutral Lewis base L include tetrahydrofuran, diethyl ether, dimethylaniline, trimethylphosphine, lithium chloride, neutral olefins, and neutral diolefins and the like. When the complex includes a plurality of neutral lewis bases L, the neutral lewis bases L may be the same kind or different kinds.

The metallocene complex represented by the general formulae (I) and (II) and the half-metallocene cationic complex represented by the general formula (III), respectively, may each exist as any one of a monomer, a dimer or other kind of multimer.

The metallocene complex represented by the general formula (I) can be obtained by, for example, reacting a lanthanoid trihalide, scandium trihalide, or yttrium trihalide with an indenyl salt (such as an indenyl potassium salt or a lithium salt) and a bis (trialkylsilyl) amine salt (such as a potassium salt or a lithium salt of bis (trialkylsilyl) amine) in a solvent. The reaction temperature may be set around room temperature, which allows for manufacturing under mild conditions. The reaction time may be set as desired, and is usually in the range of several hours to several days. The kind of the reaction solvent is not limited, but a solvent capable of dissolving the raw materials and the reaction product is preferable. For example, toluene may be used. Examples of the reaction for obtaining the metallocene complex represented by the general formula (I) are shown below.

(in the above reaction example, X "represents a halide.)

The metallocene complex represented by the general formula (II) can be obtained by, for example, reacting a lanthanoid trihalide, scandium trihalide or yttrium trihalide with an indenyl salt (e.g., indenyl potassium salt or lithium salt) and a silyl salt (e.g., silyl potassium salt or lithium salt) in a solvent. The reaction temperature may be set around room temperature, which allows for manufacturing under mild conditions. The reaction time may be set as desired, and is usually in the range of several hours to several days. The kind of the reaction solvent is not limited, but a solvent capable of dissolving the raw materials and the reaction product is preferable. For example, toluene may be used. Examples of the reaction for obtaining the metallocene complex represented by the general formula (II) are shown below.

(in the above reaction example, X "represents a halide.)

The half-metallocene cation complex represented by the general formula (III) can be obtained by, for example, the reaction shown below.

In the compound represented by the general formula (IV), M represents a lanthanoid, scandium, or yttrium; cp^R’Each independently represents an unsubstituted/substituted cyclopentadienyl group, an unsubstituted/substituted indenyl group or an unsubstituted/substituted fluorenyl group(ii) a And X represents a hydrogen atom, a halogen atom, an alkoxy group, a mercapto group, an amino group, a silyl group, or C_1-20A monovalent hydrocarbon group. L represents a neutral Lewis base, and w represents an integer in the range of 0 to 3. In the general formula [ A]⁺[B]^-Among the ionic compounds represented by (A)]⁺Represents a cation, [ B ]]^-Represents a non-coordinating anion.

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

The compound represented by the general formula [ A ] used in the above reaction]⁺[B]^-The ionic compound represented is, for example, a compound obtained by combining a non-coordinating anion and a cation respectively selected from the above examples, and is preferably N, N-dimethylaniline tetrakis (pentafluorophenyl) borate, triphenylcarbeniumtetrakis (pentafluorophenyl) borate, or the like. When compared in mol, from the formula [ A ]]⁺[B]^-The amount of the ionic compound added to the metallocene complex is preferably 0.1 to 10 times, more preferably about 1 time the amount of the metallocene complex. Wherein a half-metallocene cation complex represented by the general formula (III) is used for the polymerizationIn the case of the polymerization reaction, the half-metallocene cation complex represented by the general formula (III) may be directly supplied into the polymerization reaction system, or alternatively, the half-metallocene cation complex represented by the general formula (III) may be obtained by providing the compound represented by the general formula (IV) and the compound represented by the general formula [ A ] used in the above-mentioned reaction and the compound represented by the general formula [ A ] separately in the polymerization reaction system]⁺[B]^-The ionic compound represented is formed in the polymerization reaction system. Further alternatively, the half-metallocene cationic complex represented by the general formula (III) can be prepared by using the metallocene complex represented by the general formula (I) or the general formula (II) and the general formula [ A ] in combination in the polymerization reaction system]⁺[B]^-The ionic compound represented by (a) is formed in the polymerization reaction system.

The structures of the metallocene complex represented by the general formula (I), the metallocene complex represented by the general formula (II), and the half-metallocene cationic complex represented by the general formula (III) are each preferably determined by X-ray structural analysis.

Other examples of the component (A-1) include metallocene-based composite catalysts represented by the following formula (V):

R_aMX_bQY_b …(V)

(in the formula (V), R independently represents an unsubstituted/substituted indenyl group; M is coordinated to R; M represents a lanthanoid, scandium or yttrium; and X independently represents C_1-20A monovalent hydrocarbon group; m and Q coordinate to X mu; q represents an element of group 13 of the periodic table; y independently of one another represents C_1-20A monovalent hydrocarbon group or a hydrogen atom; q coordinates to Y; and a-b-2).

Preferred examples of the metallocene-based composite catalyst represented by the formula (V) include metallocene-based composite catalysts represented by the following formula (VI):

(in the formula (VI), M¹Represents a lanthanide, scandium or yttrium; cp^REach independently represents an unsubstituted/substituted indenyl group; r^AAnd R^BEach independentlyIs represented by C_1-20A hydrocarbyl group; m¹And Al and R^AAnd R^BMu coordination; and R is^CAnd R^DEach independently represents C_1-20A hydrocarbon group or a hydrogen atom. )

The objective multipolymer can be efficiently produced by using the metallocene-based composite catalyst. Further, by using the above-mentioned metallocene-based composite catalyst, for example, a composite which has been prepared in advance in combination with an aluminum catalyst, the amount of aluminum alkyl used in the synthesis of a multipolymer can be reduced or even eliminated. It should be noted in this regard that if a conventional catalyst system not using the above metallocene-based composite catalyst is employed, a large amount of aluminum alkyl is required during the synthesis of the multipolymer. For example, in a conventional catalyst system in which the above-mentioned metallocene-based composite catalyst is not used, the aluminum alkyl must be used in an amount of at least 10 times the stoichiometric equivalent of the relevant metal catalyst. In contrast, in the case of using the above metallocene-based composite catalyst, an excellent catalytic effect was demonstrated by adding an amount of aluminum alkyl of about 5 times the stoichiometric equivalent of the relevant metal catalyst.

In the metallocene-based composite catalyst, the metal M in the general formula (V) is a lanthanoid, scandium, or yttrium. The lanthanide series of elements includes the 15 elements with atomic numbers 57-71, any of which is acceptable. Preferred examples of the metal M include samarium Sm, neodymium Nd, praseodymium Pr, gadolinium Gd, cerium Ce, holmium Ho, scandium Sc, and yttrium Y.

In formula (V), each R independently represents an unsubstituted/substituted indenyl group, and M is coordinated to R. Specific examples of substituted indenyl groups include 1,2, 3-trimethylindenyl, heptamethylindenyl, and 1,2,4,5,6, 7-hexamethylindenyl, and the like.

In formula (V), Q represents an element of group 13 in the periodic table, and specific examples thereof include boron, aluminum, gallium, indium, thallium, and the like.

In formula (V), X each independently represents C_1-20A monovalent hydrocarbon group, and M and Q coordinate to X μ. C_1-20Examples of monovalent hydrocarbon groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, tridecylTetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl, and the like. The expression "M and Q are coordinated to X. mu. means that M and Q are coordinated to X in a cross-linked manner.

In formula (V), Y independently represents C_1-20A monovalent hydrocarbon group or a hydrogen atom, and Q is coordinated to Y. In this respect, C_1-20Examples of monovalent hydrocarbon groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl, and the like.

In the formula (VI), the metal M¹Is a lanthanide, scandium or yttrium. The lanthanide series of elements includes the 15 elements with atomic numbers 57-71, any of which is acceptable. Metal M¹Preferred examples of (b) include samarium Sm, neodymium Nd, praseodymium Pr, gadolinium Gd, cerium Ce, holmium Ho, scandium Sc, and yttrium Y.

In the formula (VI), Cp^RIs unsubstituted/substituted indenyl. Cp having indenyl ring as basic skeleton^RCan be represented as C₉H_7-X R_XOr C₉H_11-X R_XWherein X is an integer in the range of 0 to 7 or 0 to 11; r preferably each independently represents a hydrocarbyl group or a metalloid group; and the number of carbon atoms of the hydrocarbon group is preferably in the range of 1 to 20, more preferably in the range of 1 to 10, and still more preferably in the range of 1 to 8. Specifically, preferred examples of the hydrocarbon group include methyl, ethyl, phenyl, benzyl and the like. Examples of the metalloid group include germylge, stannyl Sn, and silyl Si. The metalloid group preferably includes a hydrocarbon group defined in the same manner as the above-mentioned hydrocarbon group. Specific examples of the metalloid group include trimethylsilyl and the like.

Specific examples of the substituted indenyl group include 2-phenylindenyl and 2-methylindenyl, etc. Two Cp's in the formula (VI)^RMay be of the same kind or of different kinds.

In the formula (VI), R^AAnd R^BEach independently represents C_1-20A monovalent hydrocarbon group, and M¹And Al and R^AAnd R^BMu coordinate. At this pointAspect, C_1-20Examples of monovalent hydrocarbon groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl, and the like. Expression "M¹And Al and R^AAnd R^BMu coordinate "means M¹And Al and R^AAnd R^BCoordinated in a cross-linking manner.

In the formula (VI), R^CAnd R^DEach independently represents C_1-20A monovalent hydrocarbon group or a hydrogen atom. In this respect, C_1-20Examples of monovalent hydrocarbon groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl, and the like.

The metallocene-based composite catalyst can be prepared by, for example, reacting a metallocene complex represented by the following formula (VII) with AlR^KR^LR^MThe organoaluminum compound represented by the formula (I) is obtained by reacting in a solvent.

(in the formula (VII), M²Represents a lanthanide, scandium or yttrium; cp^REach independently represents an unsubstituted/substituted indenyl group; r^E～R^JEach independently represents C_1-3An alkyl group or a hydrogen atom; l represents a neutral lewis base; and w represents an integer in the range of 0 to 3).

The reaction temperature may be set around room temperature, which allows for manufacturing under mild conditions. The reaction time may be set as desired, and is usually in the range of several hours to several days. The kind of the reaction solvent is not particularly limited, but a solvent capable of dissolving the raw materials and the reaction product is preferable. For example, toluene or hexane may be used. The structure of the metallocene-based composite catalyst is preferably obtained by¹H-NMR or X-ray structural analysis.

In a metallocene represented by the general formula (VII)In the complex, Cp^REach independently represents an unsubstituted/substituted indenyl group and is substituted with Cp in the general formula (VI)^RDefined in the same manner; metal M²Is a lanthanide, scandium or yttrium, and is reacted with a metal M in formula (VI)¹Defined in the same manner.

The metallocene complex represented by the formula (VII) includes a silylamino ligand [ -N (SiR)₃)₂]. The R group included in the silylamine ligand (i.e., R in the general formula (VII))^E～R^J) Each independently represents C_1-3Alkyl groups or hydrogen atoms. Preferably, R is^E～R^JAt least one of them is a hydrogen atom. When R is^E～R^JWhen at least one of them is a hydrogen atom, the catalyst can be easily synthesized. Methyl is preferred as alkyl.

The metallocene complex represented by the formula (VII) further includes 0 to 3, preferably 0 to 1, neutral Lewis bases L. Examples of the neutral Lewis base L include tetrahydrofuran, diethyl ether, dimethylaniline, trimethylphosphine, lithium chloride, neutral olefins, and neutral diolefins and the like. When the complex includes a plurality of neutral lewis bases L, the neutral lewis bases L may be the same kind or different kinds.

The metallocene complex represented by the general formula (VII) may exist as any one of a monomer, a dimer or other kinds of multimers.

The organoaluminum compound used for the production of the metallocene-based composite catalyst is represented by AlR^KR^LR^MIs represented by the formula (I) in which R^KAnd R^LEach independently represents C_1-20A monovalent hydrocarbon group or a hydrogen atom; r^MIs represented by C_1-20A monovalent hydrocarbon group; and R is^MCan be with R^KOr R^LThe same species or different species. C_1-20Examples of monovalent hydrocarbon groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl, and the like.

Specific examples of the organoaluminum compound include: trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-tert-butylaluminum, tripentylaluminum, trihexylaluminum, tricyclohexylaluminum, trioctylaluminum; diethylaluminum hydride, di-n-propylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride, dihexylaluminum hydride, diisohexylaluminum hydride, dioctylaluminum hydride, diisooctylaluminum hydride; ethyl aluminum dihydride, n-propyl aluminum dihydride, isobutyl aluminum dihydride, and the like. Among these examples, triethylaluminum, triisobutylaluminum, diethylaluminum hydride and diisobutylaluminum hydride are preferable as the organoaluminum compound. A single kind or a combination of two or more kinds of these examples may be used as the organoaluminum compound. The amount of the organoaluminum compound used for the production of the metallocene-based composite catalyst is preferably 1 to 50 times, more preferably about 10 times, the amount of the metallocene complex when compared in mol.

Component (A-2)

The component (A-2) is a rare earth element compound or a reaction product resulting from a reaction between the rare earth element compound and a Lewis base, wherein each of the rare earth element compound and the reaction product thereof has no bond between the relevant rare earth element and a carbon atom. A rare earth element compound having no bond between the relevant rare earth metal and a carbon atom or a reaction product resulting from the reaction between the rare earth element compound and a lewis base is stable as a compound and easy to handle. In the present invention, the term "rare earth element compound" refers to a compound containing a rare earth element (M) (i.e., one of lanthanides consisting of elements having atomic numbers 57 to 71 in the periodic table; or scandium or yttrium).

Specific examples of lanthanides include lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium. A single species or a combination of two or more species in the examples may be used as the component (A-2).

The rare earth element compound preferably contains a salt or a complex of a divalent/trivalent rare earth metal, and more preferably a rare earth element compound having at least one ligand selected from a hydrogen atom, a halogen atom, and an organic compound residue. Further, the rare earth element compound or the reaction product resulting from the reaction of the rare earth element compound and the lewis base is preferably represented by the following general formula (VIII) or general formula (IX):

M¹¹X¹¹ ₂·L¹¹w …(VIII)

M¹¹X¹¹ ₃·L¹¹w …(IX)

(in these formulae, M¹¹Denotes the lanthanide, scandium or yttrium, X¹¹Each independently represents a hydrogen atom, a halogen atom, an alkoxy group, a hydrocarbylthio group, an amine group, a silyl group, an aldehyde residue, a ketone residue, a carboxylic acid residue, a thiocarboxylic acid residue, or a phosphorus compound residue, L¹¹Represents a Lewis base, and w represents an integer in the range of 0 to 3. )

Examples of the group (ligand) bonded to the rare earth element of the rare earth element compound include a hydrogen atom, a halogen atom, an alkoxy group (a group which is obtained by removing hydrogen from a hydroxyl group of an alcohol and which is capable of forming a metal alkoxide), a hydrocarbylthio group (a group which is obtained by removing hydrogen from a thiol group of a thiol compound and is capable of forming a metal thiolate), an amine group (a group which is obtained by removing one hydrogen atom bonded to a nitrogen atom of ammonia, a primary amine or a secondary amine and is capable of forming a metal amide), a silyl group, an aldehyde residue, a ketone residue, a carboxylic acid residue, a thiocarboxylic acid residue, and a phosphorus compound residue.

Specific examples of the group (ligand) to be bonded to the rare earth element of the rare earth element compound include: a hydrogen atom; aliphatic alkoxy groups such as methoxy, ethoxy, propoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy and the like; 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; aliphatic hydrocarbylthio groups such as thiomethoxy, thioethoxy, thiopropoxy, thio-n-butoxy, thio-isobutoxy, thio-sec-butoxy, and thio-tert-butoxy, and the like; arylhydrocarbylthio groups such as thiophenoxy, 2, 6-di-tert-butylthiophenoxy, 2, 6-diisopropylthiophenoxy, 2, 6-dineopentylthiophenoxy, 2-tert-butyl-6-isopropylthiophenoxy, 2-tert-butyl-6-thioneopentylphenoxy, 2-isopropyl-6-thioneopentylphenoxy, and 2,4, 6-triisopropylthiophenoxy, etc.; aliphatic amine groups such as dimethylamino group, diethylamino group, and diisopropylamine group, etc.; arylamine groups such as phenylamino group, 2, 6-di-tert-butylphenyl group, 2, 6-diisopropylphenylamino group, 2, 6-dineopentylphenylamino group, 2-tert-butyl-6-isopropylphenylamino group, 2-tert-butyl-6-neopentylphenylphenylamino group, 2-isopropyl-6-neopentylphenylphenylamino group, 2,4, 6-tri-tert-butylphenyl phenylamino group and the like; a ditrialkylsilylamine group such as a bistrimethylsilylamine group; silyl groups such as trimethylsilyl, tris (trimethylsilyl) silyl, bis (trimethylsilyl) methylsilyl, trimethylsilyl (dimethyl) silyl, triisopropylsilyl (bistrimethylsilyl) silyl, and the like; halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom; and the like.

Specific examples of the ligand further include: aldehyde residues such as salicylaldehyde, 2-hydroxy-1-naphthaldehyde, and 2-hydroxy-3-naphthaldehyde; residues of hydroxybenzophenones such as 2 ' -hydroxyacetophenone, 2 ' -hydroxybenzophenone, and 2 ' -hydroxypropiophenone; a ketone residue (particularly, a diketone residue) such as acetylacetone, benzoylacetone, propionitrile acetone, isobutyl acetone, valeryl acetone, and ethyl acetylacetone; such as isovaleric acid, capric acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, linoleic acid, cyclopentanecarboxylic acid, naphthenic acid, ethylhexanoic acid, pivalic acid, versatic acid (a product manufactured by Shell Chemicals, which is a product made by C)₁₀Synthetic acids formed from mixtures of isomers of monocarboxylic acids), residues of carboxylic acids such as phenylacetic acid, benzoic acid, 2-naphthoic acid, maleic acid, and succinic acid; residues of thiocarboxylic acids such as hexanethioic acid, 2-dimethylbutanethioic acid, decanethioic acid, and thiobenzoic acid; such as dibutyl phosphate, dipentyl phosphate, dihexyl phosphate, diheptyl phosphate, dioctyl phosphate, bis (2-ethylhexyl) phosphate, bis (1-methylheptyl) phosphate, dilauryl phosphate, dioleyl phosphate, diphenyl phosphate, bis (p-nonylphenyl) phosphate) Phosphoric acid ester residues such as bis (polyethylene glycol-p-nonylphenyl) phosphate, (butyl) (2-ethylhexyl) phosphate, (1-methylheptyl) (2-ethylhexyl) phosphate, and (2-ethylhexyl) (p-nonylphenyl) phosphate; residues of phosphonic acid esters such as monobutyl (2-ethylhexyl) phosphonate, mono-2-ethylhexyl phenylphosphonate, mono-p-nonylphenyl (2-ethylhexyl) phosphonate, mono-2-ethylhexyl phosphonate, mono-1-methylheptyl phosphonate, and mono-p-nonylphenyl phosphonate; such as the residue of phosphinic acids such as dibutylphosphinic acid, bis (2-ethylhexyl) phosphinic acid, bis (1-methylheptyl) phosphinic acid, dilaurylphosphinic acid, dioleylphosphinic acid, diphenylphosphinic acid, bis (p-nonylphenyl) phosphinic acid, butyl (2-ethylhexyl) phosphinic acid, (2-ethylhexyl) (1-methylheptyl) phosphinic acid, (2-ethylhexyl) (p-nonylphenyl) phosphinic acid, butylphosphinic acid, 2-ethylhexyl phosphinic acid, 1-methylheptylphosphinic acid, oleylphosphinic acid, laurylphosphinic acid, phenylphosphinic acid, and p-nonylphenylphosphinic acid. A single species or a combination of two or more species from the above examples may be used as the ligand.

Examples of the lewis base to be reacted with the rare earth element compound include tetrahydrofuran, diethyl ether, dimethylaniline, trimethylphosphine, lithium chloride, neutral olefins, neutral diolefins and the like. In this regard, in the case where the rare earth element compound is reacted with a plurality of lewis bases (i.e., in the case where w ═ 2 or 3 in formula (VIII) and formula (IX)), these lewis bases L¹¹May be of the same kind or of different kinds.

The rare earth element compound is preferably a compound represented by the following general formula (X).

M-(AQ¹)(AQ²)(AQ³) …(X)

(in the general formula (X), M is selected from scandium, yttrium, and lanthanoid elements; AQ¹、AQ²And AQ³Each represents a functional group which may be the same kind or different kind; "A" represents an element selected from nitrogen, oxygen and sulfur; and the compound substantially comprises at least one M-a bond).

Specific examples of lanthanides include lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium. The above compound is a component capable of improving catalytic activity in a reaction system, shortening reaction time, and increasing reaction temperature.

From the viewpoint of improving the catalytic activity and reaction controllability, gadolinium is preferable as "M" in the general formula (X).

When "A" in the formula (X) represents nitrogen, is represented by AQ¹、AQ²And AQ³(i.e., NQ)¹、NQ²And NQ³) Examples of the functional group include amine group and the like. In this case, the rare earth element compound has three M-N bonds.

Examples of amine groups include: aliphatic amine groups such as dimethylamino group, diethylamino group, diisopropylamine group; arylamine groups such as phenylamino group, 2, 6-di-tert-butylphenyl group, 2, 6-diisopropylphenylamino group, 2, 6-dineopentylphenylamino group, 2-tert-butyl-6-isopropylphenylamino group, 2-tert-butyl-6-neopentylphenylphenylamino group, 2-isopropyl-6-neopentylphenylphenylamino group, 2,4, 6-tri-tert-butylphenyl phenylamino group and the like; and ditrialkylsilylamines such as bistrimethylsilylamine. Among these examples, a bistrimethylsilylamine group is preferable as the amine group from the viewpoint of solubility to aliphatic hydrocarbons and aromatic hydrocarbons. A single species or a combination of two or more of these examples may be used as the amine group.

According to the above structural feature, the component (A-2) may be a compound having three M-N bonds chemically equivalent to each other, whereby the component (A-2) has a stable structure and is easy to handle.

Further, according to the above structural features, the catalytic activity in the reaction system can be further improved. Thereby further shortening the reaction time and further increasing the reaction temperature.

When "A" in the formula (X) is oxygen, the compound represented by the formula (X) (i.e., M- (OQ)¹)(OQ²)(OQ³) The kind of the rare earth element-containing compound is not particularly limited. In this case, examples of the rare earth element-containing compound include:

rare earth mercaptides represented by the following general formula (XI); and

(RO)₃M …(XI)

a rare earth carboxylate represented by the following general formula (XII).

(R-CO₂)₃M …(XII)

In the general formula (XI) and the general formula (XII), "R" represents C respectively_1-10Alkyl groups, which may be the same species or different species.

When "A" in the formula (X) is sulfur, the compound represented by the formula (X) (i.e., M- (SQ)¹)(SQ²)(SQ³) The kind of the rare earth element-containing compound is not particularly limited. In this case, examples of the rare earth element-containing compound include:

rare earth alkylmercaptides represented by the following general formula (XIII); and

(RS)₃M …(XIII)

a compound represented by the following general formula (XIV).

(R-CS₂)₃M …(XIV)

In the general formula (XIII) and the general formula (XIV), "R" represents C_1-10Alkyl groups, which may be the same species or different species.

The above organometallic compound (component (B)) is represented by the following general formula (XV):

YR¹ _aR² _bR³ _c …(XV)

(in the general formula (XV), Y represents a metal selected from group 1,2, 12 and 13 elements in the periodic Table, and R represents¹And R²Each represents C_1-10Hydrocarbon radicals or hydrogen atoms, R³Is represented by C_1-10Hydrocarbyl radical, R¹、R²And R³May be the same kind or different kind, when Y is a metal selected from group 1 elements of the periodic table, a ═ 1 and b ═ c ═ 0, when Y is a metal selected from group 2 and group 12 elements of the periodic table, a ═ b ═ 1 and c ═ 0, and when Y is a metal selected from group 13 elements of the periodic table, a ═ b ═ c ═ 1).

In the general formula (XV), from R¹、R²And R³Is represented by C_1-10Details of hydrocarbon radicalsExamples include: straight/branched aliphatic hydrocarbon groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, hexyl, octyl and the like; aromatic hydrocarbon groups such as phenyl, tolyl, and naphthyl; aralkyl groups such as benzyl; and the like. Among these examples, methyl, ethyl, isobutyl, and the like are preferable.

Component (B) is preferably an organoaluminum compound represented by general formula (XVI):

AlR¹R²R³… (XVI)

(in the general formula (XVI), R¹And R²Each represents C_1-10A hydrocarbon group or a hydrogen atom, and R³Is represented by C_1-10A hydrocarbon group, wherein R¹、R²And R³May be of the same kind or of different kinds. )

The organoaluminum compound corresponds to a compound represented by the general formula (XV) wherein Y is Al and a ═ b ═ c ═ 1.

Examples of the organoaluminum compound represented by the general formula (XVI) include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, tripentylaluminum, trihexylaluminum, tricyclohexylaluminum, trioctylaluminum; diethylaluminum hydride, di-n-propylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride, dihexylaluminum hydride, diisohexylaluminum hydride, dioctylaluminum hydride, diisooctylaluminum hydride; ethyl aluminum dihydride, n-propyl aluminum dihydride, isobutyl aluminum dihydride, and the like. Among these examples, triethylaluminum, triisobutylaluminum, diethylaluminum hydride, and diisobutylaluminum hydride are preferable as the organoaluminum compound.

A single species or a combination of two or more species in the above examples may be used as the component (B). When the component (B) is used together with the component (A), the content of the component (B) is preferably 1 to 50 times, more preferably about 10 times, the content of the component (A) when compared in mol.

The above-mentioned aluminoxane (component (C)) is a compound obtained by contacting an organoaluminum compound with a condensing agent. The catalytic activity in the polymerization reaction system can be further increased by using the component (C) in i) so that the objective copolymer can be easily obtained, ii) the reaction time is further shortened and the reaction temperature is increased.

Examples of the above-mentioned organoaluminum compounds include trialkylaluminums such as trimethylaluminum, triethylaluminum, triisobutylaluminum and mixtures thereof. Of these examples, trimethylaluminum and a mixture of trimethylaluminum and tributylaluminum are preferred as the organoaluminum compound.

Examples of the condensing agent include water and the like.

Examples of the component (C) include aluminoxanes represented by the following general formula (XVII):

-(Al(R⁷)O)_n-…(XVII)

(in the general formula (XVII), R⁷Is represented by C_1-10A hydrocarbyl group; a part of the hydrocarbon group may be substituted with a halogen atom and/or an alkoxy group; each R⁷The same species or different species may be present in the repeating unit; and n is preferably ≧ 5).

The molecular structure of the aluminoxane may be linear or cyclic.

Preferably, "n" in the general formula (XVII) is ≧ 10.

Further, as R in the general formula (XVII)⁷Examples of the hydrocarbon group of (1) include methyl, ethyl, propyl, isobutyl and the like. Among these examples, methyl is particularly preferred. A single species or a combination of two or more of these examples may be used as the hydrocarbon group. In this respect, it is preferred to use methyl and isobutyl groups in combination as the hydrocarbon group or R in the general formula (XVII)⁷。

Preferably, the aluminoxane has high solubility to aliphatic hydrocarbons and low solubility to aromatic hydrocarbons. Preferred examples of the aluminoxane include commercially available aluminoxanes sold as hexane solutions.

Examples of the aliphatic hydrocarbon include hexane, cyclohexane and the like.

Acceptable examples of the component (C) include, in particular, modified aluminoxanes represented by the following general formula (XVIII) (the particular modified aluminoxanes are hereinafter sometimes referred to as "TMAO").

-(Al(CH₃)_x(i-C₄H₉)_yO)_m-…(XVIII)

(in the general formula (XVIII), x + y is 1; "m" is 5. gtoreq.)

Examples of TMAO include those manufactured by Tosoh Finechem Corporation under the trade name "TMAO-341".

Specifically, the component (C) may be a modified aluminoxane represented by the following general formula (XIX) (this specific modified aluminoxane is hereinafter sometimes referred to as "MMAO").

-(Al(CH₃)_0.7(i-C₄H₉)_0.3O)_k-…(XIX)

(in the general formula (XIX), "k" is 5 or more.)

Examples of MMAO include those manufactured by Tosoh Finechem Corporation under the trade name "MMAO-3A".

Alternatively, the component (C) may be, in particular, a modified aluminoxane represented by the general formula (XX) (which is hereinafter sometimes referred to as "PMAO").

-[(CH₃)AlO]_i-…(XX)

(in the general formula (XX), i is 5. gtoreq.)

Examples of PMAO include those manufactured by Tosoh Finechem Corporation under the trade name "PMAO-211".

Among the above MMAO, TMAO and PMAO, the component (C) is preferably MMAO or TMAO from the viewpoint of enhancing the catalytic activity-improving effect, and particularly TMAO is more preferably from the viewpoint of further enhancing the catalytic activity-improving effect.

A single species or a combination of two or more species in the above examples may be used as component (C).

When component (C) is used together with component (A), component (C) is used so that the aluminum content in component (C) is preferably 10mol or more, more preferably 100mol or more, and preferably 1000mol or less, more preferably 800mol or less, relative to 1mol of the rare earth element in component (A), from the viewpoint of improving the catalytic activity.

The ionic compound (component (D)) is composed of a non-coordinating anion and a cation. When the component (D) is used together with the component (a), examples of the component (D) include ionic compounds and the like capable of reacting with the component (a) and generating cationic transition metal compounds.

Examples of the non-coordinating anion include tetravalent boron anions such as tetraphenyl borate, tetrakis (mono-fluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis (pentafluorophenyl) borate, tetrakis (tetrafluoromethylphenyl) borate, tetrakis (tolyl) borate, tetraxylyl borate, triphenyl (pentafluorophenyl) borate, [ tris (pentafluorophenyl) phenyl ] borate, tridecyl-7, 8-dicarbonylundecanoborate, and the like. Of these examples, tetrakis (pentafluorophenyl) borate is preferred as the tetravalent boron anion.

Examples of the cation include a carbonium cation, an oxonium cation, an amine cation, a phosphonium cation, a cycloheptatriene cation, and a ferrocenium cation having a transition metal, and the like. Specific examples of the carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation (which is also referred to as "trityl cation"), and tris (substituted phenyl) carbonium cation, and the like. Specific examples of the tri (substituted phenyl) carbonium cation include a tri (methylphenyl) carbonium cation, a tri (dimethylphenyl) carbonium cation, and the like. Examples of amine cations include ammonium cations and the like. Specific examples of ammonium cations include: trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation (e.g., tri (n-butyl) ammonium cation); n, N-dialkylanilinium cations such as N, N-dimethylanilinium cation, N-diethylanilinium cation, N-2,4, 6-pentamethylanilinium cation; dialkylammonium cations such as diisopropylammonium cation, dicyclohexylammonium cation; and the like. Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tris (methylphenyl) phosphonium cation, tris (dimethylphenyl) phosphonium cation, and the like. Among these examples of the cation, an N, N-dialkylanilinium cation or a carbonium cation is preferable, and an N, N-dialkylanilinium cation is particularly preferable.

Therefore, a compound as a combination of non-coordinating anions and cations respectively selected from the above examples is preferably used as the ionic compound (component (D)). Specifically, N-dimethylaniline tetrakis (pentafluorophenyl) borate, triphenylcarbeniumtetrakis (pentafluorophenyl) borate, and the like are preferable as the component (D).

A single species or a combination of two or more species in the above examples may be used as component (D). When the component (D) is used together with the above-mentioned component (a), the component (D) is used so that the content thereof is preferably 0.1 to 10 times, more preferably about 1 time, the content of the component (a) when compared in mol.

Examples of the above-mentioned halogen compound (component (E)) include: when component (E) is used together with, for example, the above-mentioned component (A), component (E) can react with compound (A) to produce a cationic transition metal compound, a halogenated transition metal compound, or a compound having an insufficient charge at the transition metal center.

Examples of the component (E-1) include halogen compounds containing an element of group 3, 4,5,6, 8, 13, 14 or 15 of the periodic Table. Preferred examples of the component (E-1) include aluminum halides or organometallic halides. Chlorine or bromine is preferred as halogen element.

Specific examples of the halogen-containing compound as the lewis acid include methyl aluminum dibromide, methyl aluminum dichloride, ethyl aluminum dibromide, ethyl aluminum dichloride, butyl aluminum dibromide, butyl aluminum dichloride, dimethyl aluminum bromide, dimethyl aluminum chloride, diethyl aluminum bromide, diethyl aluminum chloride, dibutyl aluminum bromide, dibutyl aluminum chloride, methyl aluminum sesquibromide, methyl aluminum sesquichloride, ethyl aluminum sesquibromide, ethyl aluminum sesquichloride, dibutyl tin dichloride, aluminum tribromide, tris (pentafluorophenyl) aluminum, tris (pentafluorophenyl) borate, antimony trichloride, antimony pentachloride, phosphorus trichloride, phosphorus pentachloride, tin tetrachloride, titanium tetrachloride, tungsten hexachloride, and the like. Among these examples, diethylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, diethylaluminum bromide, ethylaluminum sesquibromide, and ethylaluminum dibromide are particularly preferable as the halogen-containing compound of the lewis acid.

A single species or a combination of two or more species among these examples may be used as the component (E-1).

Examples of the metal halide constituting the above-mentioned component (E-2) include beryllium chloride, beryllium bromide, beryllium iodide, magnesium chloride, magnesium bromide, magnesium iodide, calcium chloride, calcium bromide, calcium iodide, barium chloride, barium bromide, barium iodide, zinc chloride, zinc bromide, zinc iodide, cadmium chloride, cadmium bromide, cadmium iodide, mercury chloride, mercury bromide, mercury iodide, manganese chloride, manganese bromide, manganese iodide, rhenium chloride, rhenium bromide, rhenium iodide, copper chloride, copper iodide, silver chloride, silver bromide, silver iodide, gold chloride, gold iodide, gold bromide and the like. Among these examples, magnesium chloride, calcium chloride, barium chloride, manganese chloride, zinc chloride and copper chloride are preferable as the metal halide. Magnesium chloride, manganese chloride, zinc chloride and copper chloride are particularly preferred.

Further, preferable examples of the Lewis base constituting the component (E-2) include phosphorus compounds, carbonyl compounds, nitrogen compounds, ether compounds, alcohols and the like. Specifically, acceptable examples of the lewis base include tributyl phosphate, tri-2-ethylhexyl phosphate, triphenyl phosphate, tricresyl phosphate, triethylphosphine, tributylphosphine, triphenylphosphine, diethylphosphinoethane, diphenylphosphinoethane, acetylacetone, benzoylacetone, propionylacetone, valerylacetone, ethylacetoacetone, methyl acetoacetate, ethyl acetoacetate, phenyl acetoacetate, dimethyl malonate, diethyl malonate, diphenyl malonate, acetic acid, octanoic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, benzoic acid, naphthenic acid, versatic acid, triethylamine, N-dimethylacetamide, tetrahydrofuran, diphenyl ether, 2-ethylhexyl alcohol, oleyl alcohol, stearyl alcohol, phenol, benzyl alcohol, 1-decanol, lauryl alcohol and the like. Among these examples, tri-2-ethylhexyl phosphate, tricresyl phosphate, acetylacetone, 2-ethylhexanoic acid, versatic acid, 2-ethylhexyl alcohol, 1-decanol, and lauryl alcohol are preferable as Lewis bases.

0.01 to 30mol (preferably 0.5 to 10mol) of the Lewis base is reacted with 1mol of the metal halide. By using the reaction product thus obtained from the reaction of the metal halide with the Lewis base, the metal remaining in the copolymer can be reduced.

A single species or a combination of two or more species in the above examples may be used as the component (E-2).

Examples of the above-mentioned component (E-3) include benzyl chloride and the like.

A single species or a combination of two or more species in the above examples may be used as the halogen component (E).

When the component (E) is used together with the above-mentioned component (A), the component (E) is used so that the content thereof is preferably 0 to 5 times, more preferably 1 to 5 times the content of the component (A) when compared in mol.

The compound having a cyclopentadienyl skeleton (component (F)) has a group selected from the group consisting of cyclopentadienyl group, indenyl group and fluorenyl group. Specifically, the compound (F) having a cyclopentadiene skeleton is at least one compound selected from the group consisting of substituted/unsubstituted cyclopentadiene, substituted/unsubstituted indene, and substituted/unsubstituted fluorene. A single species or a combination of two or more species in the above examples may be used as component (F).

Examples of the substituted/unsubstituted cyclopentadiene include cyclopentadiene, pentamethylcyclopentadiene, tetramethylcyclopentadiene, isopropylcyclopentadiene, trimethylsilyl-tetramethylcyclopentadiene, and (1-benzyldimethylsilyl) cyclopenta [ I ] phenanthrene and the like.

Examples of substituted/unsubstituted indenes include indene, 2-phenyl-1H-indene, 3-benzyl-1H-indene, 3-methyl-2-phenyl-1H-indene, 3-benzyl-2-phenyl-1H-indene, 1-benzyl-1H-indene, 1-methyl-3-dimethylbenzylsilyl-indene, 1, 3-bis (tert-butyldimethylsilyl) indene, (1-benzyldimethylsilyl-3-cyclopentyl) indene, and (1-benzyl-3-tert-butyldimethylsilyl) indene, and the like. From the viewpoint of making the molecular weight distribution narrow, 3-benzyl-1H-indene and 1-benzyl-1H-indene are particularly preferable.

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

In particular, the compound having a cyclopentadiene skeleton (component (F)) is preferably a substituted cyclopentadiene, a substituted indene, or a substituted fluorene, and more preferably a substituted indene. In these preferred cases, the polymerization catalyst is sufficiently large in volume from the viewpoint of favorably increasing its steric hindrance effect, thereby successfully shortening the reaction time and raising the reaction temperature. Further, in these preferred cases, the polymerization catalyst has a large number of electrons in the conjugated system, thereby successfully further improving the catalytic activity in the reaction system.

Examples of substituents for substituted cyclopentadienes, substituted indenes, and substituted fluorenes include hydrocarbyl or metalloid groups. The number of carbon atoms of the hydrocarbon group is preferably in the range of 1 to 20, more preferably in the range of 1 to 10, and still more preferably in the range of 1 to 8. Specifically, preferred examples of the hydrocarbon group include methyl, ethyl, phenyl, benzyl and the like. On the other hand, examples of the metalloid group include germylge, stannyl Sn, and silyl Si. The metalloid group preferably includes a hydrocarbon group defined in the same manner as the above-mentioned hydrocarbon group. Specific examples of the metalloid group include trimethylsilyl and the like.

A single species or a combination of two or more species in the above examples may be used as component (F). From the viewpoint of improving the catalytic activity, when the component (F) is used together with the above-mentioned component (A), the component (F) is used so that the content thereof is preferably > 0 times, more preferably ≥ 0.5 times, still more preferably ≥ 1 times, and preferably ≤ 3 times, more preferably ≤ 2.5 times, still more preferably ≤ 2.2 times the content of the component (A) when compared in mol.

The above components (a) to (F) may be combined with each other in various ways to form a catalyst composition, and the thus-obtained catalyst composition is preferably employed in the above polymerization process. Preferred examples of the catalyst composition include the first catalyst composition and the second catalyst composition described below.

The first catalyst composition comprises the above-mentioned component (A-1), component (B), and component (D). Preferably, the first catalyst composition further comprises at least one of component (C) and component (E) as an optional component. In this aspect, in the case where the component (A-1) is a metallocene-based composite catalyst represented by the general formula (V), it is also optional to include the component (B).

The second catalyst composition comprises the above-mentioned component (A-2), component (B), and component (D). Preferably, the second catalyst composition further comprises at least one of component (C), component (E) and component (F) as optional components. When the second catalyst composition comprises component (F), the catalytic activity is increased.

The coupling step is a step of performing a reaction (coupling reaction) of modifying at least a part (for example, a terminal) of the polymer chain of the multipolymer obtained in the polymerization step.

In the coupling step, the coupling reaction is preferably carried out when the conversion rate in the polymerization reaction reaches 100%.

The kind of the coupling agent used in the coupling reaction is not particularly limited and may be appropriately selected according to the purpose. Examples of coupling agents include: (i) tin-containing compounds such as bis (1-octadecyl maleate) dioctyltin (IV); (ii) isocyanate compounds such as 4, 4' -diphenylmethane diisocyanate; (iii) alkoxysilane compounds such as glycidylpropyltrimethoxysilane; and the like. A single species or a combination of two or more of these examples may be used as the coupling agent. Among these examples, bis (1-octadecyl maleate) dioctyltin (IV) is preferable as the coupling agent from the viewpoint of high reaction efficiency and relatively little gel formation.

By performing the coupling reaction, the number average molecular weight (Mn) of the resulting multipolymer can be increased.

The washing step is a step of washing the multipolymer obtained in the polymerization step. The kind of the solvent used in the washing step is not particularly limited and may be appropriately selected according to the purpose. Examples of the solvent include methanol, ethanol, isopropanol and the like. In particular, when a catalyst derived from a lewis acid is used as the polymerization catalyst, an acid (e.g., hydrochloric acid, sulfuric acid, nitric acid) may be added to these solvents as described above to be used in the washing process. The amount of the acid added is preferably 15 mol% or less with respect to the solvent. The addition of the acid in an amount exceeding 15 mol% relative to the solvent may cause the acid to remain in the multipolymer, possibly adversely affecting the kneading process and the vulcanization reaction.

The amount of catalyst residues in the multipolymer can be reduced to an appropriate level by the washing process.

< rubber composition >

The rubber composition of the present invention is characterized by comprising the above-mentioned multipolymer. The rubber composition of the present invention exhibiting reduced heat build-up in a low strain region can reduce the rolling resistance of a tire when it is applied to the tire.

The rubber composition of the present invention comprises the above-mentioned multipolymer as a rubber component, and optionally may further comprise other rubber components, fillers, crosslinking agents and other components.

The content of the multipolymer in the rubber component of the rubber composition of the present invention is preferably in the range of 10 to 100% by mass, more preferably in the range of 20 to 100% by mass, and still more preferably in the range of 30 to 100% by mass. When the content of the multipolymer in the rubber component of the rubber composition is 10% by mass or more, the intended effect of the multipolymer will be sufficiently exhibited, whereby the rubber composition exhibits satisfactory reduced heat generation property at low strain thereof and the rolling resistance of the tire can be reduced when the rubber composition is applied to the tire.

The kind of the rubber component other than the multipolymer of the present invention is not particularly limited and may be appropriately selected depending on the purpose. Examples of the other rubber component include Natural Rubber (NR), polyisoprene rubber (IR), polybutadiene rubber (BR), acrylonitrile-butadiene rubber (NBR), chloroprene rubber, ethylene-propylene rubber (EPM), ethylene-propylene-nonconjugated diene rubber (EPDM), polysulfide rubber, silicone rubber, fluorine rubber, urethane rubber, and the like. A single species or a combination of two or more of these examples may be used as the other rubber component.

The rubber composition can be improved in its reinforcing property by including a filler therein. The kind of the filler is not particularly limited, and examples thereof include carbon black, silica, aluminum hydroxide, clay, alumina, talc, mica, kaolin, glass spheres, glass beads, calcium carbonate, magnesium hydroxide, magnesium oxide, titanium dioxide, potassium titanate, barium sulfate, and the like. Among these examples, carbon black is preferably used. A single species or a combination of two or more of these examples may be used as the filler.

The content of the filler is not particularly limited and may be appropriately selected according to the purpose, but is preferably 10 to 100 parts by mass, more preferably 20 to 80 parts by mass, and most preferably 30 to 60 parts by mass, relative to 100 parts by mass of the rubber component. The content of the filler of 10 parts by mass or more relative to 100 parts by mass of the rubber component ensures the effect of improving the reinforcement of the rubber composition by the filler. The content of the filler is 100 parts by mass or less with respect to 100 parts by mass of the rubber component, ensuring good processability of the rubber composition.

The kind of the crosslinking agent is not particularly limited and may be appropriately selected depending on the purpose. Examples of the crosslinking agent include a sulfur-based crosslinking agent, an organic peroxide-based crosslinking agent, an inorganic crosslinking agent, a polyamine crosslinking agent, a resin crosslinking agent, a sulfur compound-based crosslinking agent, an oxime-nitrosamine-based crosslinking agent, and the like. Among these examples, a sulfur-based crosslinking agent (sulfur-based vulcanizing agent) is preferably applied to the rubber composition for a tire.

The content of the crosslinking agent is not particularly limited and may be appropriately selected according to the purpose, but is preferably in the range of 0.1 to 20 parts by mass with respect to 100 parts by mass of the rubber component.

The vulcanization accelerator may be used in combination with a vulcanizing agent. Examples of the vulcanization accelerator include guanidine-based, aldehyde-amine-based, aldehyde-ammonia-based, thiazole-based, sulfenamide-based, thiourea-based, thiuram-based, dithiocarbamate-based, and xanthate-based compounds and the like.

Further, other known additives such as a softening agent, a vulcanization-accelerating assistant, a coloring agent, a flame retardant, a lubricant, a foaming agent, a plasticizer, a processing aid, an antioxidant, an anti-aging agent, an anti-scorching agent, an ultraviolet ray protecting agent, an antistatic agent, and a coloring preventing agent may be optionally used in the rubber composition of the present invention depending on the use.

The rubber composition of the present invention is suitable for vibration-proof rubber, vibration-isolating rubber, belts such as conveyor belts, rubber crawler belts, various hoses, and the like, in addition to the following tires.

< resin composition >

The resin composition of the present invention is characterized by containing the above-mentioned multipolymer. The resin composition of the present invention exhibits reduced heat build-up in its low strain region.

The resin composition of the present invention comprises the above-mentioned multipolymer as a resin component, and optionally may further comprise other resin components and various additives.

In the present invention, in the case where the resin composition contains a multipolymer, the multipolymer is regarded as the resin component, and the content of the multipolymer in the entire resin component is preferably 10 mass% or more.

Examples of the above-mentioned "other resin component" include: thermoplastic resins such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyamide, polycarbonate, polyoxymethylene, polyphenylene oxide and the like; and thermosetting resins such as phenol resin, epoxy resin, urea resin, melamine resin, and the like.

Further, examples of the above-mentioned "additives" include antistatic agents, lubricants, nucleating agents, tackifiers, antifogging agents, mold release agents, plasticizers, fillers, antioxidants, pigments, dyes, perfumes, flame retardants, and the like.

< tire >

The tire of the present invention is characterized by using the above rubber composition. The tire of the present invention thus exhibits reduced heat build-up in its low strain region, as well as low rolling resistance.

The tire site to which the rubber composition of the present invention is applied is not particularly limited, and the tire site may be appropriately selected according to the purpose. Examples of tire locations include treads, subtreads, sidewalls, sidewall reinforcing rubber, and bead fillers, among others.

The tire of the present invention can be manufactured by a conventional method. For example, a desired tire such as a pneumatic tire may be manufactured by: laminating members generally used for tire manufacture such as a carcass layer made of an unvulcanized rubber composition and/or cords, a belt layer, and a tread layer in this order on a tire forming drum; removing the drum to obtain a green tyre; and the green tire is heated and vulcanized according to a conventional method.

< resin article >

The resin product of the present invention is characterized by using the above resin composition. The resin article of the present invention exhibits reduced heat build-up in its low strain region.

The use of the resin article of the present invention is not particularly limited, and the resin article is applicable to various articles each having a resin portion in at least a part thereof.

Examples

The present invention will be described in further detail below by way of examples. The present invention is not limited in any way by these examples.

(example 1)

The copolymer was synthesized by: 55g of styrene and 870g of toluene were put into a sufficiently dried 2000mL pressure-resistant stainless steel reactor;

on the other hand, in a glove box under a nitrogen atmosphere, 0.05mmol of ((1-benzyldimethylsilyl-3-methyl) indenyl) bis (dimethylsilyl) amino) gadolinium complex { (1-BnME)₂Si-3-Me)C₉H₅Gd[N(SiHMe₂)₂]₂0.05mmol of dimethylanilinium tetrakis (pentafluorophenyl) borate [ Me₂NHPhB(C₆F₅)₄]0.3mmol of trimethylaluminum, and 0.14mmol of diisobutylaluminum hydride were put into a glass vessel, and the above substances were dissolved in 30g of toluene to obtain a catalyst solution;

adding the thus obtained catalyst solution to a pressure-resistant stainless steel reactor, and heating the mixture in the reactor to 75 ℃;

then, by adjusting the pressure of ethylene: ethylene was added to a pressure-resistant stainless steel reactor at 1.6MPa, and 80g of a toluene solution containing 25g of 1, 3-butadiene was charged into the reactor over 4 hours to conduct copolymerization;

the copolymerization reaction was terminated by adding a 5 mass% isopropanol solution (1mL) of 2, 2-methylene-bis (4-ethyl-6-tert-butylphenol) (NS-5) to a pressure-resistant stainless steel reactor; and is

The copolymer was isolated by using a large amount of methanol, and the resulting copolymer was vacuum-dried at 50 ℃ to obtain the copolymer of example 1.

(example 2)

The copolymer was synthesized by: 44g of styrene and 870g of toluene were put into a sufficiently dried 2000mL pressure-resistant stainless steel reactor;

on the other hand, in a glove box under a nitrogen atmosphere, 0.05mmol of ((1-benzyldimethylsilyl-3-methyl) indenyl) bis (dimethylsilyl) amino) gadolinium complex { (1-BnME)₂Si-3-Me)C₉H₅Gd[N(SiHMe₂)₂]₂0.05mmol of dimethylanilinium tetrakis (pentafluorophenyl) borate [ Me₂NHPhB(C₆F₅)₄]0.3mmol of trimethylaluminum, and 0.14mmol of diisobutylaluminum hydride were put into a glass vessel, and the above substances were dissolved in 30g of toluene to obtain a catalyst solution;

adding the thus obtained catalyst solution to a pressure-resistant stainless steel reactor, and heating the mixture in the reactor to 75 ℃;

then, by adjusting the pressure of ethylene: ethylene was added to a pressure-resistant stainless steel reactor at 1.2MPa, and 80g of a toluene solution containing 25g of 1, 3-butadiene was charged into the reactor over 4 hours to conduct copolymerization;

the copolymerization reaction was terminated by adding a 5 mass% isopropanol solution (1mL) of 2, 2-methylene-bis (4-ethyl-6-tert-butylphenol) (NS-5) to a pressure-resistant stainless steel reactor; and is

The copolymer was isolated by using a large amount of methanol, and the resulting copolymer was vacuum-dried at 50 ℃ to obtain the copolymer of example 2.

(example 3)

The copolymer was synthesized by: 33g of styrene and 870g of toluene were charged into a sufficiently dried 2000mL pressure-resistant stainless steel reactor;

on the other hand, in a glove box under a nitrogen atmosphere, 0.05mmol of ((1-benzyldimethylsilane)3-methyl-indenyl) bis (dimethylsilyl) amino) gadolinium (E) yl complex { (1-BnMe)₂Si-3-Me)C₉H₅Gd[N(SiHMe₂)₂]₂0.05mmol of dimethylanilinium tetrakis (pentafluorophenyl) borate [ Me₂NHPhB(C₆F₅)₄]0.3mmol of trimethylaluminum, and 0.14mmol of diisobutylaluminum hydride were put into a glass vessel, and the above substances were dissolved in 30g of toluene to obtain a catalyst solution;

adding the thus obtained catalyst solution to a pressure-resistant stainless steel reactor, and heating the mixture in the reactor to 75 ℃;

then, by adjusting the pressure of ethylene: ethylene was added to a pressure-resistant stainless steel reactor at 1.2MPa, and 80g of a toluene solution containing 25g of 1, 3-butadiene was charged into the reactor over 4 hours to conduct copolymerization;

the copolymerization reaction was terminated by adding a 5 mass% isopropanol solution (1mL) of 2, 2-methylene-bis (4-ethyl-6-tert-butylphenol) (NS-5) to a pressure-resistant stainless steel reactor; and is

The copolymer was isolated by using a large amount of methanol, and the resulting copolymer was vacuum-dried at 50 ℃ to obtain the copolymer of example 3.

Comparative example 1

The copolymer was synthesized by: 55g of styrene and 870g of toluene were put into a sufficiently dried 2000mL pressure-resistant stainless steel reactor;

on the other hand, in a glove box under a nitrogen atmosphere, 0.05mmol of ((1-benzyldimethylsilyl-3-methyl) indenyl) bis (dimethylsilyl) amino) gadolinium complex { (1-BnME)₂Si-3-Me)C₉H₅Gd[N(SiHMe₂)₂]₂0.05mmol of dimethylanilinium tetrakis (pentafluorophenyl) borate [ Me₂NHPhB(C₆F₅)₄]0.3mmol of trimethylaluminum, and 0.35mmol of diisobutylaluminum hydride were put into a glass vessel, and the above substances were dissolved in 30g of toluene to obtain a catalyst solution;

adding the thus obtained catalyst solution to a pressure-resistant stainless steel reactor, and heating the mixture in the reactor to 75 ℃;

then, at the pressure of ethylene: ethylene was added to a pressure-resistant stainless steel reactor at 1.0MPa, and copolymerization was carried out at 75 ℃ for a total of 4 hours by throwing 8g of a toluene solution containing 2g of 1, 3-butadiene (i.e., 1, 3-butadiene) every 24 minutes so that 80g of a toluene solution containing 20g of 1, 3-butadiene was thrown in total;

the copolymerization reaction was terminated by adding a 5 mass% isopropanol solution (1mL) of 2, 2-methylene-bis (4-ethyl-6-tert-butylphenol) (NS-5) to a pressure-resistant stainless steel reactor; and is

The copolymer was isolated by using a large amount of methanol, and the resulting copolymer was vacuum-dried at 50 ℃ to obtain the copolymer of comparative example 1.

< analysis of multipolymer)

The number average molecular weight (Mn), weight average molecular weight (Mw), molecular weight distribution (Mw/Mn), content (mol%) of each of ethylene units, butadiene units, and styrene units, crystallinity, melting point (Tm), and glass transition temperature (Tg) of each of the thus-obtained multipolymers were measured by the following methods, respectively, in order to determine the main chain structure of the multipolymer.

(1) Number average molecular weight (Mn), weight average molecular weight (Mw), and molecular weight distribution (Mw/Mn)

By using gel permeation chromatography [ GPC: HLC-8121GPC/HT manufactured by Tosoh Corporation, gel column: GMH manufactured by Tosoh Corporation_HR-h(s) HT × 2, detector: differential Refractometer (RI)]The number average molecular weight (Mn), weight average molecular weight (Mw), and molecular weight distribution (Mw/Mn) of each multipolymer in terms of polystyrene were determined for monodisperse styrene as a standard substance. The measurement temperature was 40 ℃.

(2) Content of ethylene Unit, butadiene Unit and styrene Unit >

By¹The content (mol%) of ethylene units, butadiene units and styrene units in each of the multicomponent copolymers was determined by integrating the ratio of the peaks in an H-NMR spectrum (100 ℃ C., d-tetrachloroethane standard: 6 ppm).

(3) Degree of crystallinity

Each of the multipolymer samples was heated from-150 ℃ to 150 ℃ at a temperature rising rate of 10 ℃/min to measure an endothermic peak energy (endothermic energy at an endothermic peak) of the multipolymer sample in a range of 0 ℃ to 100 ℃ during heating (Δ H)₁) And endothermic peak energy (. DELTA.H) in the range of 100 ℃ to 120 ℃₂)。

Further, with Δ H₁And Δ H₂In a similar manner to the measurement of (a) has a crystal composition ratio of: 100% of the crystalline melting energy (. DELTA.H) of polyethylene₀)。

Endothermic peak energy (. DELTA.H) in the range of 0 ℃ to 100 ℃ from a multipolymer sample₁) Energy of crystal melting (. DELTA.H) relative to polyethylene₀) Ratio of (Δ H)₁/ΔH₀) To calculate the degree of crystallinity (C) derived from ethylene units (non-conjugated olefin units) in the range of 0 ℃ to 100 DEG C_0-100(%)). Further, the endothermic peak energy (. DELTA.H) at 100 ℃ to 120 ℃ from the multipolymer sample₂) Energy of crystal melting (. DELTA.H) relative to polyethylene₀) Ratio of (Δ H)₂/ΔH₀) To calculate the degree of crystallinity (C) derived from ethylene units (non-conjugated olefin units) in the range of 100 ℃ to 120 ℃_100-120(%)). Then, based on the thus determined crystallinity (C)_0-100(%) and crystallinity (C)_100-120(%)) to calculate the ratio [ (C)_100-120/C_0-100)×100]。

The endothermic peak energy of the multicomponent copolymer sample and the crystal melting energy of polyethylene were measured by a Differential Scanning Calorimeter (DSC) "DSCQ 2000" manufactured by TA Instruments Japan, respectively. The measurement results are shown in Table 1. Further, FIG. 1 shows the DSC chart of the multipolymer of example 1 for reference.

(4) Melting Point (Tm)

The melting point (T.sub.CQ.sub.2000) of each multicomponent copolymer sample was measured by using a Differential Scanning Calorimeter (DSC) "DSCQ 2000" manufactured by TA Instruments Japan in accordance with JIS K7121-_m)。

(5) Glass transition temperature (Tg)

According to JIS K7121-_g)。

(6) Confirmation of the backbone Structure

Measuring the respective multipolymers thus synthesized¹³C-NMR spectrum. It was confirmed that the main chain of each multicomponent copolymer was constituted only of a non-cyclic structure because of the presence of the non-cyclic structure therein¹³In the C-NMR spectrum, no peak was observed in the range of 10ppm to 24 ppm.

[ Table 1]

As can be understood from Table 1, each of the copolymers of examples 1 to 3 exhibited a significantly low crystallinity (C) derived from ethylene units at 100-120 ℃ as measured by a Differential Scanning Calorimeter (DSC)_100-120) Relative to the degree of crystallinity (C) derived from ethylene units at 0-100 DEG C_0-100) Ratio of (C)_100-120/C_0-100)×100]。

< preparation of rubber composition and evaluation thereof >

Samples of the rubber compositions were made according to the blending formulation shown in Table 2 by using a conventional Banbury mixer. The loss tangent (tan. delta.) of each of the rubber composition samples thus prepared was measured by the following method. The results are shown in Table 2.

(7) Loss tangent (tan delta)

By using a viscoelasticity tester "ARES" manufactured by Rheometric Scientific, inc. under strain: 0.3% and frequency: tan δ (loss tangent) at 50 ℃ of vulcanized rubber samples respectively obtained by vulcanizing rubber composition samples at 145 ℃ for 33 minutes was measured under a condition of 10 Hz. The tan δ value thus measured is converted into "tan δ (index)" by the formula shown below.

tan δ (index) { (tan δ of the rubber composition of comparative example 4)/(tan δ of the rubber composition of example/comparative example) } × 100

The larger the index means that tan δ is smaller, that is, heat generation property in a low strain region (0.3% tan δ) is more reduced, and thus the performance of the rubber composition is better.

[ Table 2]

1 SBR: styrene-butadiene copolymer rubber, trade name "# 0202" manufactured by JSR Corporation "

2, silicon dioxide: trade name "Nipsil AQ" manufactured by Toso silicon Corporation "

3 silane coupling agent: bis (3-triethoxysilylpropyl) disulfide (average sulfur chain length: 2.35), trade name manufactured by Evonic Industries, AG

4, oil: petroleum-based hydrocarbon processing oil, trade name "DAIANA processing oil NS-28" manufactured by Idemitsu Kosan Co., Ltd "

5, wax: microcrystalline wax, trade name "SUNTIGHT" manufactured by Seiko Chemical Co., Ltd.

6 anti-aging agent 6C: n- (1, 3-dimethylbutyl) -N' -phenyl-p-phenylenediamine, trade name "Nocrac 6C" manufactured by Ouchi-Shinko Chemical Industrial Co., Ltd "

7 vulcanization accelerator DPG: 1, 3-diphenylguanidine, manufactured by SANSHIN CHEMICAL INDUSTRY CO., LTD, under the trade name "Sanceler D"

8 vulcanization accelerator MBTS: bis-2-benzothiazolyl disulfide, manufactured by SANSHIN CHEMICAL INDUSTRY CO., LTD., under the trade name "Sanceler DM"

9 vulcanization accelerator NS: n-tert-butyl-2-benzothiazylsulfonamide, manufactured by SANSHIN CHEMICAL INDUSTRY CO., LTD., under the trade name "Sanceler NS"

10 zinc oxide, manufactured by HAKUSUI TECH co, ltd

As can be understood from Table 2, the rubber compositions of examples 4 to 6, which respectively comprise the multipolymers of examples 1 to 3, consistently exhibited significantly reduced heat generation in the low strain region thereof.

Industrial applicability

The multipolymer of the present invention is useful as a rubber component of a rubber composition and/or a resin component of a resin composition. The rubber composition of the present invention is suitable for various rubber articles including tires. The resin composition of the present invention is suitable for various resin articles.