WO2019116659A1

WO2019116659A1 - Vibration-damping rubber composition and vibration-damping rubber

Info

Publication number: WO2019116659A1
Application number: PCT/JP2018/034520
Authority: WO
Inventors: 堀川　泰郎; 奈保子伊藤
Original assignee: 株式会社ブリヂストン
Priority date: 2017-12-13
Filing date: 2018-09-18
Publication date: 2019-06-20
Also published as: JPWO2019116659A1; JP7348070B2

Abstract

Provided is a vibration-damping rubber composition having a high durability and being capable of sufficiently damping vibration. The vibration-damping rubber composition, which comprises a rubber component containing a multicomponent copolymer having a conjugated diene unit, a non-conjugated olefin unit and an aromatic vinyl unit and a filler as an optional component, is characterized in that the content of the filler is 0-90 parts by mass per 100 parts by mass of the rubber component.

Description

Vibration-proof rubber composition and vibration-proof rubber

The present invention relates to a vibration-proof rubber composition and a vibration-proof rubber.

In the field of automobiles, general industrial machines and the like, anti-vibration rubber is used to prevent vibration and noise of engines and vehicle bodies. Although the vibration-proof rubber is conventionally manufactured using various rubber compositions, what mix | blended fillers, such as carbon black, is common.

For example, in Patent Document 1, in order to achieve both the dynamic characteristics of the vibration-proof rubber and the fatigue resistance, a large particle size (small specific surface area) and a large particle size / high structure carbon black with developed structure are used. Is disclosed.

Further, in Patent Document 2, silica as a filler, sulfur as a crosslinking agent (vulcanizing agent), and an alkylphenol disulfide or bismaleimide compound are blended in a rubber component formed by blending a natural rubber and a butyl rubber. There is disclosed a rubber composition for high heat resistance, high durability, low dynamic magnification, high damping vibration proof rubber.

Further, Patent Document 3 discloses a vibration-proof rubber composition having a low dynamic magnification and high durability, which contains a rubber component, hydrophobized silica, and a silane coupling agent.

JP, 2006-143860, A JP, 2006-199792, A JP, 2006-037002, A

Here, the vibration-proof rubber is naturally required to have a performance (vibration damping property) to sufficiently damp the vibration as a performance to be provided, and to have the performance, it is required that the static spring constant is small. . However, the vibration-proof rubber composition described in the above-mentioned document has a problem that the static spring constant becomes high and the dynamic magnification is adversely affected as a result of the addition of the filler to enhance the durability. Therefore, the conventional rubber composition has room for improvement in that the static spring constant is reduced to improve the vibration damping property while maintaining high durability.

Then, this invention solves the problem of the said prior art, and an object of this invention is to provide the anti-vibration rubber composition which is highly durable and can fully attenuate a vibration. Moreover, this invention aims at providing the vibration-proof rubber which is excellent in durability and a vibration damping property using this vibration-proof rubber composition.

The vibration-proof rubber composition of the present invention comprises a rubber component containing a multicomponent copolymer having conjugated diene units, non-conjugated olefin units and aromatic vinyl units, and a filler as an optional component, The filler content is 0 to 90 parts by mass with respect to 100 parts by mass of the rubber component.

The vibration-proof rubber of the present invention is characterized by containing the above-mentioned vibration-proof rubber composition.

According to the present invention, it is possible to provide a vibration-proof rubber composition having high durability and capable of sufficiently damping vibration. Further, according to the present invention, it is possible to provide a vibration-proof rubber which is excellent in durability and vibration damping property using such a vibration-proof rubber composition.

(Anti-vibration rubber composition)
The vibration-proof rubber composition (Hereafter, it may be called "the rubber composition of this embodiment.") Which concerns on one Embodiment of this invention is demonstrated in detail. The rubber composition of the present embodiment is characterized by containing a rubber component including a multicomponent copolymer having a conjugated diene unit, a nonconjugated olefin unit, and an aromatic vinyl unit. In addition, the rubber composition of the present embodiment can further contain a filler, a softener, a liquid rubber, and other components, as necessary.

<Rubber component>
As described above, the rubber composition of the present embodiment contains a multicomponent copolymer as a rubber component, and can further contain other rubber components.

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

<< Multi-copolymer >>
As described above, the multicomponent copolymer used in the present embodiment has a conjugated diene unit, a nonconjugated olefin unit, and an aromatic vinyl unit.
The conjugated diene unit in the multicomponent copolymer can easily form a crosslinked structure with other molecular chains. Therefore, the multi-component copolymer is, for example, cracked or creeped as compared with a copolymer formed by using a non-conjugated diene compound such as known ethylene-propylene-non-conjugated diene copolymer (EPDM). The occurrence of stagnation is suppressed. In addition, the molecular chain portion composed of the non-conjugated olefin unit and the aromatic vinyl unit in the above multi-component copolymer has a high strength structure due to molecular chain orientation, crystal elongation and the like by repetition of dynamic elongation and compression. Can. Therefore, the rubber composition of the present embodiment can exhibit high durability by containing the above-described multicomponent copolymer, and can have high durability even without containing a large amount of filler. It is considered that the static spring constant is low and the vibration damping property is good.

In the present specification, “conjugated diene unit” refers to a unit corresponding to a unit derived from a conjugated diene compound in a copolymer, and “nonconjugated olefin unit” refers to a nonconjugated olefin compound in a copolymer The term “aromatic vinyl unit” refers to a unit corresponding to a unit derived from an aromatic vinyl compound in a copolymer.
Further, in the present specification, “conjugated diene compound” refers to a conjugated diene compound, and “non-conjugated olefin compound” is an aliphatic unsaturated hydrocarbon and has one or more carbon-carbon double bonds. The term “aromatic vinyl compound” refers to an aromatic compound substituted with at least a vinyl group, and is not included in the conjugated diene compound.
And in this specification, "a multi-element copolymer" refers to the copolymer formed by polymerizing three or more types of monomers.

The conjugated diene unit in the multicomponent copolymer is usually a unit derived from a conjugated diene compound as a monomer, and the conjugated diene compound preferably has 4 to 8 carbon atoms. Specific examples of such conjugated diene compounds include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and the like. The conjugated diene compounds may be used alone or in combination of two or more. And, from the viewpoint of effectively improving the durability, the conjugated diene compound used as a monomer preferably contains at least one of 1,3-butadiene and isoprene, and only 1,3-butadiene and / or isoprene. More preferably, In other words, the conjugated diene units in the multicomponent copolymer preferably contain at least one of 1,3-butadiene units and isoprene units, and consist of only 1,3-butadiene units and / or isoprene units. Is more preferred.

The non-conjugated olefin unit in the multicomponent copolymer is usually a unit derived from a non-conjugated olefin compound as a monomer, and the non-conjugated olefin compound preferably has 2 to 10 carbon atoms . As such non-conjugated olefin compounds, specifically, α-olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene or 1-octene, vinyl pivalate, 1-phenylthio Examples thereof include ethene and heteroatom-substituted alkene compounds such as N-vinyl pyrrolidone. The non-conjugated olefin compounds may be used alone or in combination of two or more. The non-conjugated olefin compound used as a monomer preferably has no cyclic structure from the viewpoint of further improving the durability, and from the viewpoint of further improving the durability and the breaking strength, an α-olefin (ethylene It is more preferable to include the above, and it is more preferable to consist of ethylene only. In other words, the non-conjugated olefin unit in the multicomponent copolymer preferably has no cyclic structure from the viewpoint of further improving the durability, and from the viewpoint of further improving the durability and the breaking strength, α It is more preferred to contain an olefin unit (including an ethylene unit), and even more preferable to consist of only an ethylene unit.

The aromatic vinyl unit in the multicomponent copolymer is usually a unit derived from an aromatic vinyl compound as a monomer, and the aromatic vinyl compound preferably has 8 to 10 carbon atoms. . As such aromatic vinyl compounds, specifically, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene Etc. The above aromatic vinyl compounds may be used alone or in combination of two or more. The aromatic vinyl compound used as a monomer preferably contains styrene, and more preferably consists of styrene, from the viewpoint of ease of control of the melting point, the glass transition temperature, and the energy of the endothermic peak. In other words, the aromatic vinyl units in the multicomponent copolymer preferably contain styrene units, and more preferably consist only of styrene units.

The multicomponent copolymer may also contain any unit other than the conjugated diene unit, the nonconjugated olefin unit and the aromatic vinyl unit described above. However, from the viewpoint of obtaining the desired effects of the present invention, in the multicomponent copolymer of the present invention, the ratio of any unit other than the conjugated diene unit, the nonconjugated olefin unit and the aromatic vinyl unit is 10 mol% or less Is preferable, and 0 mol% is more preferable.

The number of types of monomers of the multicomponent copolymer is not particularly limited as long as the multicomponent copolymer has a conjugated diene unit, a nonconjugated olefin unit, and an aromatic vinyl unit. However, from the viewpoint of making the durability more preferable, the multi-component copolymer should contain at least one conjugated diene compound, one non-conjugated olefin compound, and one aromatic vinyl compound as monomers. It is preferable that it is a copolymer formed by using and copolymerizing. In other words, the multicomponent copolymer of the present invention is preferably a multicomponent copolymer having one conjugated diene unit, one nonconjugated olefin unit, and one aromatic vinyl unit. The multicomponent copolymer is more preferably a ternary copolymer consisting of only one conjugated diene unit, one nonconjugated olefin unit, and one aromatic vinyl unit, and 1,3 More preferably, it is a ternary copolymer consisting only of butadiene units, ethylene units and styrene units. Here, “one conjugated diene unit” includes conjugated diene units having different bonding modes.

The multicomponent copolymer preferably has a conjugated diene unit ratio of 1 mol% or more and 50 mol% or less. When the ratio of conjugated diene units is 1 mol% or more, the multicomponent copolymer can be uniformly behaved as an elastomer, and the effect of further improving the durability can be obtained, and at 50 mol% or less As a result, the effect of including non-conjugated olefin units and aromatic vinyl units can be sufficiently obtained. From the same viewpoint, the proportion of conjugated diene units in the multicomponent copolymer is more preferably 40 mol% or less.

The multicomponent copolymer preferably has a proportion of non-conjugated olefin units of 40 mol% or more and 97 mol% or less. When the proportion of non-conjugated olefin units is 40 mol% or more, the durability can be further improved, and by being 97 mol% or less, the effect of containing conjugated diene units and aromatic vinyl units is sufficiently obtained. Can be obtained. From the same viewpoint, the proportion of the non-conjugated olefin unit in the multicomponent copolymer is more preferably 45 mol% or more, and more preferably 93 mol% or less.

The multicomponent copolymer preferably has a proportion of aromatic vinyl units of 2 mol% or more and 35 mol% or less. When the proportion of the aromatic vinyl unit is 2 mol% or more, the breaking strength and the elongation can be further improved, and when it is 35 mol% or less, the effect of including the conjugated diene unit and the non-conjugated olefin unit You can get enough. From the same viewpoint, the proportion of the aromatic vinyl unit in the multicomponent copolymer is more preferably 5 mol% or more, and more preferably 25 mol% or less.

There is no restriction | limiting in particular as a chain structure of the said multi-component copolymer, According to the objective, it can select suitably, For example, a conjugated diene unit was made into A, a nonconjugated olefin unit was made into B, and an aromatic vinyl unit was made into C. in the _{_{_{case, a x -B y -C z (}}} x, y, z is 1 or more is an integer) block copolymer employing a configuration such as, a, B, random copolymers of a configuration in which C is a random arrangement Alternating copolymer having a configuration such as a polymer, a tapered copolymer in which the random copolymer and the block copolymer are mixed, (ABC) _w (w is an integer of 1 or more), etc. It can be combined.
Further, the multicomponent copolymer may have a structure (linear structure) in which a conjugated diene unit, a nonconjugated olefin unit, and an aromatic vinyl unit are linearly linked, or a conjugated diene unit or a nonconjugated olefin unit, And at least one of the aromatic vinyl units may be branched to form a chained structure (branched structure). In addition, when the said multi-component copolymer is branched structure, branched chain can also be made into binary or multi-component (namely, branched chain is a conjugated diene unit, a non conjugated olefin unit, and an aromatic vinyl unit). Can include at least two of them).

The multicomponent copolymer preferably has a melting point of 30 to 130 ° C. as measured by differential scanning calorimetry (DSC). When the melting point is 30 ° C. or more, cold flow can be suppressed, and when the melting point is 130 ° C. or less, processability and moldability can be improved. From the same viewpoint, the melting point of the multicomponent copolymer is more preferably 40 ° C. or higher, and more preferably 120 ° C. or lower.
The melting point of the multicomponent copolymer can be specifically measured using a differential scanning calorimeter (DSC) in accordance with JIS K 7121-1987.

The multicomponent copolymer preferably has an endothermic peak energy of 10 to 130 J / g as measured by differential scanning calorimetry (DSC) at 0 to 120 ° C. When the energy of the endothermic peak is 10 J / g or more, the durability can be further improved regardless of the amount of the filler used, and by being 130 J / g or less, the fracture elongation can be improved. . From the same viewpoint, the energy of the endothermic peak of the multicomponent copolymer is more preferably 15 J / g or more, and more preferably 90 J / g or less.
Specifically, according to JIS K 7121-1987, the energy of the endothermic peak of the multicomponent copolymer is raised from -150 ° C. to 150 ° C. at a temperature rise rate of 10 ° C./min. It can be measured by determining an endothermic peak (enthalpy relaxation) at 0 to 120 ° C. in the first run.

The multicomponent copolymer preferably has a glass transition temperature of 0 ° C. or less as measured by differential scanning calorimetry (DSC). When the glass transition temperature is 0 ° C. or lower, low temperature properties (such as a small change in characteristics at low temperatures) can be improved. From the same viewpoint, the glass transition temperature of the multicomponent copolymer is more preferably −10 ° C. or less.
The glass transition temperature of the multicomponent copolymer can be specifically measured using a differential scanning calorimeter (DSC) in accordance with JIS K 7121-1987.

The multicomponent copolymer preferably has a main chain consisting of only a non-cyclic structure. Thereby, durability can be further improved.
In addition, NMR is used as a main measurement means to confirm whether or not the main chain of the multicomponent copolymer has a cyclic structure. Specifically, when no peak derived from a cyclic structure present in the main chain (for example, a peak appearing at 10 to 24 ppm for a 3-membered ring to a 5-membered ring) is observed, the main chain of the multicomponent copolymer is , Indicates that it consists only of non-cyclic structure.

In the rubber composition of the present embodiment, the proportion of the multicomponent copolymer in the rubber component is preferably 20% by mass or more. When the proportion of the multicomponent copolymer is 20% by mass or more, the durability of the vibration-proof rubber composition can be further improved. From the same viewpoint, the proportion of the multicomponent copolymer in the rubber component of the rubber composition of the present embodiment is more preferably 30% by mass or more. On the other hand, the proportion of the multicomponent copolymer in the rubber component is preferably 100% by mass or less, more preferably 95% by mass or less, and still more preferably 90% by mass or less.

<< Method for Producing Multicomponent Copolymer >>
The multicomponent copolymer may be produced, for example, by carrying out the step (polymerization step) of copolymerizing at least a conjugated diene compound, a nonconjugated olefin compound and an aromatic vinyl compound as monomers. it can. In addition, in the production of the multicomponent copolymer, other steps such as a coupling step and a washing step can be carried out, if necessary, in addition to the above-mentioned polymerization step. Here, in the production of the multi-component copolymer, it is preferable to add only the non-conjugated olefin compound and the aromatic vinyl compound without adding the conjugated diene compound in the presence of the polymerization catalyst, and polymerize these. In particular, when the polymerization catalyst composition described below is used, the conjugated diene compound is more reactive than the nonconjugated olefin compound and the aromatic vinyl compound, so that the nonconjugated olefin compound and / or Or, it tends to be difficult to polymerize the aromatic vinyl compound. In addition, it is likely to be difficult in view of the characteristics of the catalyst to polymerize the conjugated diene compound first and to additionally polymerize the non-conjugated olefin compound and the aromatic vinyl compound later.

In the polymerization step, any polymerization method such as solution polymerization method, suspension polymerization method, liquid phase bulk polymerization method, emulsion polymerization method, gas phase polymerization method, solid phase polymerization method and the like can be used. When a solvent is used for the polymerization reaction, the solvent may be any solvent which is inactive in the polymerization reaction, and examples thereof include toluene, cyclohexane and normal hexane.

In the polymerization step, the polymerization reaction is preferably carried out under an atmosphere of an inert gas, preferably nitrogen gas or argon gas. The polymerization temperature of the above-mentioned polymerization reaction is not particularly limited, but, for example, the range of −100 ° C. to 200 ° C. is preferable, and may be around room temperature. When the polymerization temperature is increased, the selectivity of cis-1,4 bond in the conjugated diene unit may be lowered. Further, the pressure of the above-mentioned polymerization reaction is preferably in the range of 0.1 to 10.0 MPa in order to sufficiently introduce the conjugated diene compound into the polymerization reaction system. The reaction time of the polymerization reaction can be appropriately selected according to the conditions such as the type of polymerization catalyst and the polymerization temperature, but for example, the range of 1 second to 10 days is preferable.
In the polymerization step, the polymerization reaction may be terminated using a polymerization terminator such as methanol, ethanol or isopropanol.

The polymerization step may be performed in one step, or may be performed in multiple steps of two or more steps. One-step polymerization processes are all kinds of monomers to be polymerized, ie conjugated diene compounds, non-conjugated olefin compounds, aromatic vinyl compounds and other monomers, preferably conjugated diene compounds, non-conjugated In this step, an olefin compound and an aromatic vinyl compound are reacted at the same time to be polymerized. In the multistage polymerization process, part or all of one or two kinds of monomers are first reacted to form a polymer (first polymerization stage), and then the remaining kinds of monomers And a step of performing polymerization by performing one or more stages (second polymerization stage to final polymerization stage) in which the remainder of the one or two types of monomers is added and polymerized. In particular, in the production of multicomponent copolymers, it is preferable to carry out the polymerization step in multiple steps.

In the polymerization step, a step (first step) of mixing a first monomer raw material containing at least an aromatic vinyl compound and a polymerization catalyst to obtain a polymerization mixture, and a conjugated diene compound or non-conjugated with respect to the polymerization mixture It is preferable to carry out the step (second step) of introducing a second monomer raw material containing at least one selected from the group consisting of an olefin compound and an aromatic vinyl compound. Furthermore, it is more preferable that the said 1st monomer raw material does not contain a conjugated diene compound, and the said 2nd monomer raw material contains a conjugated diene compound.

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

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

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

The second monomer raw material used in the second step is only the conjugated diene compound, the conjugated diene compound and the nonconjugated olefin compound only, the conjugated diene compound and the aromatic vinyl compound only, or the conjugated diene compound, Non-conjugated olefin compounds and aromatic vinyl compounds are preferred. When the second monomer material contains at least one selected from the group consisting of non-conjugated olefin compounds and aromatic vinyl compounds in addition to conjugated diene compounds, these monomer materials may be used as solvents in advance. And may be introduced into the polymerization mixture, or each monomer raw material may be introduced from a single state. Moreover, each monomer raw material may be added simultaneously or may be added one by one. Although there is no restriction | limiting in particular as a method to introduce | transduce a 2nd monomer raw material with respect to a polymerization mixture in a 2nd process, The flow rate of each monomer raw material is controlled and it adds continuously with respect to a polymerization mixture It is preferable to do so (so-called "mid-ring"). Here, in the case of using a monomer raw material (for example, ethylene as a non-conjugated olefin compound under conditions of room temperature and normal pressure) which is a gas under the conditions of the polymerization reaction system, the polymerization reaction system is performed at a predetermined pressure Can be introduced.

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

The coupling step is a step of performing a reaction (coupling reaction) of modifying at least a part (for example, an end) of the polymer chain of the multicomponent copolymer obtained in the polymerization step using a coupling agent or the like. . The coupling step is preferably performed when the polymerization reaction reaches 100%. By performing the coupling step, the number average molecular weight (Mn) of the multicomponent copolymer can be increased.

There is no restriction | limiting in particular as a coupling agent used for a coupling reaction, According to the objective, it can select suitably, For example, tin containing compounds, such as bis (1-octadecyl maleate) diokuteru tin (lV); Isocyanate compounds such as 4'-diphenylmethane diisocyanate; and alkoxysilane compounds such as glycidyl propyl trimethoxysilane. These may be used alone or in combination of two or more. Among these, bis (1-octadecyl maleate) diquatel tin (IV) is preferable from the viewpoint of improvement of reaction efficiency and reduction of gel formation.

The washing step is a step of washing the multicomponent copolymer obtained in the polymerization step or the coupling step. By performing the washing step, the amount of catalyst residue in the multicomponent copolymer can be suitably reduced. The medium used for the washing is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include solvents such as methanol, ethanol and isopropanol. Moreover, when using the catalyst derived from Lewis acid as a polymerization catalyst, an acid (for example, hydrochloric acid, a sulfuric acid, nitric acid etc.) can be added and used with respect to the solvent mentioned above especially. The amount of the acid to be added is 15 mol% or less based on the solvent from the viewpoint of avoiding that the acid remains in the multicomponent copolymer and adversely affects the reaction during kneading and vulcanization. preferable.

Here, the polymerization step may be performed in the presence of a first polymerization catalyst composition, a second polymerization catalyst composition, a third polymerization catalyst composition, or a fourth polymerization catalyst composition shown below. preferable. Hereinafter, the first polymerization catalyst composition, the second polymerization catalyst composition, the third polymerization catalyst composition, and the fourth polymerization catalyst composition will be described.

-First polymerization catalyst composition-
The first polymerization catalyst composition (hereinafter also referred to as "first polymerization catalyst composition") will be described.
As a first polymerization catalyst composition,
Component (A1): a rare earth element compound or a reaction product of the rare earth element compound and a Lewis base, wherein the rare earth element compound or the reaction product does not have a bond between the rare earth element and carbon.
Component (B1): an ionic compound (B1-1) consisting of a non-coordinating anion and a cation, an aluminoxane (B1-2), a Lewis acid, a complex compound of a metal halide and a Lewis base, and an active halogen And a polymerization catalyst composition containing at least one selected from the group consisting of at least one halogen compound (B1-3) among organic compounds.
When the first polymerization catalyst composition contains at least one selected from the group consisting of the ionic compound (B1-1) and the halogen compound (B1-3), the polymerization catalyst composition further comprises
Component (C1): The following formula (I):
YR ¹ _a R ² _b R ³ _c ... (I)
(Wherein Y is a metal selected from Groups 1, 2, 12, and 13 of the periodic table, and R ¹ and R ² are monovalent hydrocarbon having 1 to 10 carbon atoms) R ³ is a monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ¹ , R ² and R ³ may be identical to or different from one another, and Y is a periodic group. When it is a metal selected from Table Group 1, a is 1 and b and c are 0, and Y is a metal selected from Group 2 and Group 12 of the periodic table , A and b are 1 and c is 0, and when Y is a metal selected from Group 13 of the periodic table, a, b and c are 1. including.

The above-mentioned ionic compound (B1-1) and the above-mentioned halogen compound (B1-3) do not have carbon atoms to be supplied to the component (A1), and therefore the above-mentioned ((1) C1) The component is required. Even when the polymerization catalyst composition contains the aluminoxane (B1-2), the polymerization catalyst composition can contain the component (C1). In addition, the first polymerization catalyst composition may contain other components contained in a general rare earth element compound polymerization catalyst composition, such as a cocatalyst.
In the polymerization reaction system, the concentration of the component (A1) contained in the first polymerization catalyst composition is preferably in the range of 0.1 to 0.0001 mol / l.
Furthermore, the polymerization catalyst composition preferably contains an additive (D1) that can be an anionic ligand.

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

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

As a group (ligand) to be bonded to the rare earth element of the above rare earth element compound, a hydrogen atom, a halogen atom, an alkoxy group (a group excluding hydrogen of hydroxyl group of alcohol to form metal alkoxide), a thiolate group ( It is a group except hydrogen of thiol group of thiol compound and forms metal thiolate. Amino group (ammonia, primary amine, or one hydrogen atom bonded to nitrogen atom of secondary amine is removed) Groups which form metal amides), silyl groups, aldehyde residues, ketone residues, carboxylic acid residues, thiocarboxylic acid residues or phosphorus compound residues. Specifically, hydrogen atom; aliphatic alkoxy group such as methoxy group, ethoxy group, propoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group; phenoxy group, 2,6-di- tert-Butylphenoxy group, 2,6-diisopropylphenoxy group, 2,6-dineopentylphenoxy group, 2-tert-butyl-6-isopropylphenoxy group, 2-tert-butyl-6-neopentylphenoxy group, 2 Aromatic alkoxy groups such as -isopropyl-6-neopentylphenoxy group; thiomethoxy group, thioethoxy group, thiopropoxy group, thio n-butoxy group, thioisobutoxy group, thio sec-butoxy group, thio tert-butoxy group, etc. Aliphatic thiolate group; thiophenoxy group, 2,6-di-tert-butyl Ophenoxy group, 2,6-diisopropylthiophenoxy group, 2,6-dineopentylthiophenoxy group, 2-tert-butyl-6-isopropylthiophenoxy group, 2-tert-butyl-6-neopentylthiophenoxy group, Arylthiolate groups such as 2-isopropyl-6-neopentylthiophenoxy group, 2,4,6-triisopropylthiophenoxy group; aliphatic amino groups such as dimethylamino group, diethylamino group, diisopropylamino group; phenylamino group, 2,6-di-tert-butylphenylamino group, 2,6-diisopropylphenylamino group, 2,6-dineopentylphenylamino group, 2-tert-butyl-6-isopropylphenylamino group, 2-tert- Butyl-6-neopentylphenylamino group, -Arylamino groups such as isopropyl-6-neopentylphenylamino group and 2,4,6-tri-tert-butylphenylamino group; bistrialkylsilylamino groups such as bistrimethylsilylamino group; trimethylsilyl group, tris (trimethylsilyl) group Silyl groups such as silyl group, bis (trimethylsilyl) methylsilyl group, trimethylsilyl (dimethyl) silyl group, triisopropylsilyl (bistrimethylsilyl) silyl group; halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom etc. . Furthermore, residues of aldehydes such as salicylaldehyde, 2-hydroxy-1-naphthaldehyde, 2-hydroxy-3-naphthaldehyde; 2′-hydroxyacetophenone, 2′-hydroxybutyrophenone, 2′-hydroxypropiophenone, etc. Residues of hydroxyphenone; residues of diketones such as acetylacetone, benzoylacetone, propionylacetone, isobutylacetone, valerylacetone and ethylacetylacetone; isovaleric acid, caprylic acid, octanoic acid, lauric acid, myristic acid, palmitic acid, Stearic acid, isostearic acid, oleic acid, linoleic acid, cyclopentanecarboxylic acid, naphthenic acid, ethylhexanoic acid, pivalic acid, versatic acid (trade name of Shell Chemical Co., Ltd., a mixture of C10 monocarboxylic acid isomers Of synthetic acids, phenylacetic acid, benzoic acid, 2-naphthoic acid, maleic acid, succinic acid and other carboxylic acid residues; hexanethioic acid, 2,2-dimethylbutanethioic acid, decanethioic acid, thiobenzoic acid Residues of thiocarboxylic acids 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, bis (polyethylene glycol-p-nonylphenyl) phosphate, (butyl) (2-ethylhexyl) phosphate, 1-methylheptyl phosphate Phosphoric acid esters such as (2-ethylhexyl), phosphoric acid (2-ethylhexyl) (p-nonylphenyl), etc. Residues of monoethyl-2-ethylhexylphosphonate, mono-2-ethylhexyl 2-ethylhexylphosphonate, mono-2-ethylhexyl phenylphosphonate, mono-p-nonylphenyl 2-ethylhexylphosphonate, mono-2-ethylhexyl phosphonate Residues of phosphonic acid esters such as mono-1-methylheptyl phosphonic acid and mono-p-nonylphenyl phosphonic acid; dibutylphosphinic acid, bis (2-ethylhexyl) phosphinic acid, bis (1-methylheptyl) phosphinic acid, Dilaurylphosphinic acid, dioleoylphosphinic acid, diphenylphosphinic acid, bis (p-nonylphenyl) phosphinic acid, butyl (2-ethylhexyl) phosphinic acid, (2-ethylhexyl) (1-methylheptyl) phosphinic acid, (2- Ethyl hex Sil) (p-nonylphenyl) phosphinic acid, butyl phosphinic acid, 2-ethylhexyl phosphinic acid, 1-methylheptyl phosphinic acid, oleyl phosphinic acid, lauryl phosphinic acid, phenyl phosphinic acid, phosphinic acid such as p-nonyl phenyl phosphinic acid The residue of can also be mentioned. In addition, these ligands may be used individually by 1 type, and may be used combining 2 or more types.

In the component (A1) used for the first polymerization catalyst composition, examples of the Lewis base which reacts with the rare earth element compound include tetrahydrofuran, diethyl ether, dimethyl aniline, trimethyl phosphine, lithium chloride, neutral olefins, and the like. Diolefins and the like. Here, when the above-mentioned rare earth element compounds react with a plurality of Lewis bases (in the formulas (II) and (III), when w is 2 or 3, the Lewis bases L ¹¹ are different even though they are identical. It may be

Preferably, the rare earth element compound contains a compound represented by the following formula (IV).
^{^{^{M- (NQ 1) (NQ 2}}} ) (NQ 3) ··· (IV)
(Wherein, M is at least one selected from lanthanoid elements, scandium and yttrium, and NQ ¹ , NQ ² and NQ ³ are amino groups and may be the same or different, provided that M − With N bond)
That is, the compound represented by the above formula (IV) is characterized by having three M—N bonds. Having three M—N bonds has the advantage that the structure is stable because each bond is chemically equivalent, and hence it is easy to handle.

In the above formula (IV), as the amino group represented by NQ (NQ ¹ , NQ ² and NQ ³ ), aliphatic amino groups such as dimethylamino, diethylamino and diisopropylamino; phenylamino, 2, 6 -Di-tert-butylphenylamino group, 2,6-diisopropylphenylamino group, 2,6-dineopentylphenylamino group, 2-tert-butyl-6-isopropylphenylamino group, 2-tert-butyl-6 -Arylamino groups such as neopentylphenylamino group, 2-isopropyl-6-neopentylphenylamino group and 2,4,6-tri-tert-butylphenylamino group; bistrialkylsilylamino groups such as bistrimethylsilylamino group Although any may be used, the bistrimethylsilylamino group is preferred. There.

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

The ionic compound (B1-1) comprises a non-coordinating anion and a cation, and reacts with the rare earth element compound which is the component (A1) or a reactant thereof with a Lewis base to form a cationic transition metal compound. The ionic compound etc. which can be produced can be mentioned. Here, as the non-coordinating anion, for example, tetraphenyl borate, tetrakis (monofluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis ( Pentafluorophenyl) borate, tetrakis (tetrafluoromethylphenyl) borate, tetra (tolyl) borate, tetra (xylyl) borate, (triphenyl, pentafluorophenyl) borate, [tris (pentafluorophenyl), phenyl] borate, tri And decahydride-7,8-dicarbaundecaborate and the like. On the other hand, examples of the cation include carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptatrienyl cation, ferrocenium cation having a transition metal, and the like. Specific examples of the carbonium cation include trisubstituted carbonium cations such as triphenyl carbonium cation, tri (substituted phenyl) carbonium cation and the like, and as the tri (substituted phenyl) carbonyl cation, more specifically, Examples include tri (methylphenyl) carbonium cation, tri (dimethylphenyl) carbonium cation and the like. Specific examples of the ammonium cation include trialkyl ammonium cations such as trimethyl ammonium cation, triethyl ammonium cation, tripropyl ammonium cation, tributyl ammonium cation (for example, tri (n-butyl) ammonium cation); N, N-dimethylanilinium N, N-dialkylanilinium cations such as cations, N, N-diethylanilinium cations, N, N, 2,4,6-pentamethylanilinium cations; dialkylammonium cations such as diisopropyl ammonium cation, dicyclohexyl ammonium cation, etc. Can be mentioned. Specific examples of the phosphonium cation include triaryl phosphonium cations such as triphenyl phosphonium cation, tri (methyl phenyl) phosphonium cation, tri (dimethyl phenyl) phosphonium cation and the like. Accordingly, as the ionic compound, compounds selected and combined respectively from the above-mentioned non-coordinating anions and cations are preferable, and specifically, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbo Preferred are tetrakis (pentafluorophenyl) borate and the like. In addition, these ionic compounds can be used alone or in combination of two or more. The content of the ionic compound (B1-1) in the first polymerization catalyst composition is preferably 0.1 to 10 times mol and preferably about 1 time mol to the component (A1). Is more preferred.

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

The halogen compound (B1-3) is made of at least one of a Lewis acid, a complex compound of a metal halide and a Lewis base, and an organic compound containing an active halogen, and for example, a rare earth element compound or the above component (A1) The cationic transition metal compound, the halogenated transition metal compound and the transition metal center can form a charge deficient compound by reacting with the reactant with the Lewis base. The total content of the halogen compounds (B1-3) in the first polymerization catalyst composition is preferably 1 to 5 times the mol of the component (A1).

As the Lewis acid, boron-containing halogen compounds such as B (C ₆ F ₅ ) ₃ and aluminum-containing halogen compounds such as Al (C ₆ F ₅ ) ₃ can be used, and Group 3 and Group 3 in the periodic table It is also possible to use a halogen compound containing an element belonging to Group 4, Group 5, Group 6 or Group 8. Preferably, an aluminum halide or an organometallic halide is mentioned. Moreover, as a halogen element, chlorine or a bromine is preferable. Specific examples of the above Lewis acid include methylaluminum dibromide, methylaluminum dichloride, ethylaluminum dibromide, ethylaluminum dichloride, butylaluminum dibromide, butylaluminum dichloride, dimethylaluminum bromide, dimethylaluminum chloride, diethylaluminum bromide, diethyl Aluminum chloride, dibutylaluminum bromide, dibutylaluminum chloride, methylaluminum sesquibromide, methylaluminum sesquichloride, ethylaluminum sesquibromide, ethylaluminum sesquichloride, dibutyltin dichloride, aluminum tribromide, antimony trichloride, antimony pentachloride, phosphorus trichloride , Pentachloride Among them, diethylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, diethylaluminum bromide, ethylaluminum sesquibromide and ethylaluminum dibromide are particularly preferred. preferable.

Examples of metal halides which constitute a complex compound of the above metal halide and a Lewis base include beryllium chloride, beryllium bromide, beryllium iodide, magnesium chloride, magnesium bromide, magnesium iodide, calcium chloride, calcium bromide, iodine Calcium chloride, barium chloride, barium bromide, barium iodide, zinc chloride, zinc bromide, zinc iodide, zinc iodide, cadmium chloride, cadmium bromide, cadmium iodide, mercury iodide, mercury chloride, mercury bromide, mercury iodide, manganese chloride, Manganese bromide, manganese iodide, rhenium chloride, rhenium bromide, rhenium iodide, copper chloride, copper bromide, copper iodide, silver chloride, silver bromide, silver iodide, gold chloride, gold iodide, bromide Gold and the like can be mentioned, and among these, magnesium chloride, calcium chloride, barium chloride, manganese chloride, zinc chloride, chloride Preferably, magnesium chloride, manganese chloride, zinc chloride, copper chloride being particularly preferred.

Moreover, as a Lewis base which comprises the complex compound of the said metal halide and Lewis base, a phosphorus compound, a carbonyl compound, a nitrogen compound, an ether compound, alcohol etc. are preferable. Specifically, tributyl phosphate, tri-2-ethylhexyl phosphate, triphenyl phosphate, tricresyl phosphate, triethyl phosphine, tributyl phosphine, triphenyl phosphine, diethyl phosphino ethane, diphenyl phosphino ethane, acetyl acetone, benzoyl acetone Propionylacetone, valerylacetone, ethylacetylacetone, methyl acetoacetate, ethyl acetoacetate, phenylacetoacetate, dimethyl malonate, diethyl malonate, diphenyl malonate, acetic acid, octanoic acid, 2-ethylhexanoic acid, oleic acid, stearin Acid, benzoic acid, naphthenic acid, versatic acid, triethylamine, N, N-dimethylacetamide, tetrahydrofuran, diphenyl ether, 2-ethylhexyl alcohol, olei Alcohol, stearyl alcohol, phenol, benzyl alcohol, 1-decanol, lauryl alcohol etc. are mentioned, Among these, tri-2-ethylhexyl phosphate, tricresyl phosphate, acetylacetone, 2-ethylhexanoic acid, versatic acid, 2- Ethyl hexyl alcohol, 1-decanol and lauryl alcohol are preferred.

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

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

The component (C1) used in the first polymerization catalyst composition has the following formula (I):
YR ¹ _a R ² _b R ³ _c ... (I)
(Wherein, Y is a metal selected from Groups 1, 2, 12, and 13 of the periodic table, and R 1 and R 2 each represent a monovalent hydrocarbon group having 1 to 10 carbon atoms or R ³ is a hydrogen atom, R ³ is a monovalent hydrocarbon group having 1 to 10 carbon atoms, R ¹ , R ² and R ³ may be identical to or different from one another, and Y is a group of periodic table 1 A is 1 and b and c are 0 when it is a metal selected from group a, and when a is a metal selected from groups 2 and 12 of the periodic table, a and and b is 1 and c is 0, and when Y is a metal selected from Group 13 of the periodic table, a, b and c are 1. Following formula (V):
AlR ¹ R ² R ³ ... (V)
Wherein R ¹ and R ^{2 each} represent a monovalent hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom, R 3 represents a monovalent hydrocarbon group having 1 to 10 carbon atoms, R ¹ and R ² And R ³ may be the same as or different from one another.

As the organoaluminum compound represented by the formula (V), trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, tri-t-butylaluminum Pentylaluminum, trihexylaluminum, tricyclohexylaluminum, trioctylaluminum; diethylaluminum hydride, di-n-propylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride, dihexylaluminum hydride, hydrogenation Diisohexylaluminum, hydrogenated dioctylaluminum, hydrogenated diisooctylaluminum; ethylaluminum dihydrate, n-propyl alcohol Mini um dihydride, include isobutyl aluminum dihydride and the like, among these, triethylaluminum, triisobutylaluminum, hydrogenated diethylaluminum, hydrogenated diisobutylaluminum are preferred. The organoaluminum compound as the component (C1) described above can be used singly or in combination of two or more. The content of the organoaluminum compound in the first polymerization catalyst composition is preferably 1 to 50 times mol, and more preferably about 10 times mol to the component (A1).

The addition of the additive (D1) capable of becoming an anionic ligand is preferable because it has the effect of being able to synthesize a multicomponent copolymer having a higher cis-1,4 bond content in a high yield. .

The additive (D1) is not particularly limited as long as it can be exchanged with the amino group of the component (A1), but it is preferable to have any of an OH group, an NH group and an SH group.

Specific examples of the compound having an OH group include aliphatic alcohols and aromatic alcohols. Specifically, 2-ethyl-1-hexanol, dibutylhydroxytoluene, alkylated phenol, 4,4'-thiobis (6-t-butyl-3-methylphenol), 4,4'-butylidenebis (6-t- Butyl-3-methylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 2,6-di- t-Butyl-4-ethylphenol, 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, n-octadecyl-3- (4-hydroxy-3,5-di) -T-Butylphenyl) propionate, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, dilaurate Thiodipropionate, distearyl thiodipropionate, it may be mentioned di-myristyl thiodipropionate, etc., but is not limited thereto. For example, as a hindered phenol type, triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5 -Triazine, pentaerythryl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylene bis [3- (3,5-di-t-) Butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, N, N'-ha Samethylene bis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide), 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, 1,3,5-trimethyl-2 4,6-Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, octylated diphenylamine, 2 And 4-bis [(octylthio) methyl] -o-cresol and the like. Moreover, N, N'-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine can be mentioned as a hydrazine system.

As what has a NH group, primary amines or secondary amines, such as an alkylamine and an arylamine, can be mentioned. Specifically, dimethylamine, diethylamine, pyrrole, ethanolamine, diethanolamine, dicyclohexylamine, N, N'-dibenzylethylenediamine, bis (2-diphenylphosphinophenyl) amine and the like can be mentioned.

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

(Wherein, R ¹ , R ² and R ³ are each independently —O—C _j H _{2j + 1} , — (O—C _k H _{2 k} −) _a —O—C _m H _{2 m + 1} or —C _n H _{2 n + 1} J, m and n each independently represent an integer of 0 to 12, k and a each independently represent an integer of 1 to 12, and R ⁴ represents a carbon number of 1 to 12, and Chain, branched or cyclic, saturated or unsaturated, alkylene group, cycloalkylene group, cycloalkyl alkylene group, cycloalkenyl alkylene group, alkenylene group, cycloalkenylene group, cycloalkyl alkenylene group, cycloalkenyl alkenylene group, arylene group Or an aralkylene group)
Specific examples of the compound represented by the formula (VI) include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, (mercaptomethyl) dimethylethoxysilane, mercaptomethyltrimethoxysilane, etc. Can be mentioned.

(Wherein, W is ^-NR 8 -, - O- or ^-CR 9 ^{R 10} - (wherein, ^{R 8} and ^{R 9} are _{_{^{-C p H 2p + 1, R}}} 10 is _-C q _{H 2q + 1,} p and q are each independently an integer of 0 to 20.) R ⁵ and R ⁶ are each independently -M-C _r H _2r- (wherein, M is -O- or- CH ₂ - and is, r is represented by an integer of 1 ~ 20), ^{R 7} is _{_{_{_{-O-C j H 2j + 1}}}} , -. (O-C k H 2k -) a -O-C m H 2m + 1 Or -C _n H _{2n + 1} , j, m and n each independently represent an integer of 0 to 12, k and a each independently represent an integer of 1 to 12, and R ⁴ represents 1 carbon atom To 12 and is a linear, branched or cyclic, saturated or unsaturated alkylene group, cycloalkylene group, cyclic Alkyl alkylene group, a cycloalkenyl alkylene group, an alkenylene group, a cycloalkenylene group, a cycloalkyl alkenylene group, cycloalkenyl alkenylene group, an arylene group or an aralkylene group.)

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

Moreover, as an additive (D1), the anionic tridentate ligand precursor suitably represented by following formula (VIII) can be used.
E ¹ -T ¹ -X-T ² -E ² ... (VIII)
(X represents an anionic electron donating group containing a coordinating atom selected from periodic table group 15 atoms, and E ¹ and E ² are each independently a periodic table group 15 and 16 atoms And a neutral electron donating group containing a coordinating atom selected from: T ¹ and T ² each represent a bridging group bridging X and E ¹ and E ² )

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

In the above formula (VIII), the neutral electron donating groups E1 and E2 are groups containing a coordinating atom selected from Groups 15 and 16 of the periodic table. E1 and E2 may be the same group or different groups. Examples of the coordination atom include nitrogen N, phosphorus P, oxygen O, sulfur S and the like, preferably P.

When the coordinating atom contained in E ¹ and E ² is P, as the neutral electron donating group E ¹ or E ² , a diaryl phosphino group such as a diphenyl phosphino group or a ditolyl phosphino group A dialkyl phosphino group such as a dimethyl phosphino group and a diethyl phosphino group; and an alkylaryl phosphino group such as a methyl phenyl phosphino group, and a diaryl phosphino group is preferable.

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

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

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

The anionic electron donating group X is a group containing a coordinating atom selected from Group 15 of the periodic table. As said coordination atom, Preferably phosphorus P or nitrogen N is mentioned, More preferably, N is mentioned.

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

-Second polymerization catalyst composition-
Next, the second polymerization catalyst composition (hereinafter, also referred to as “second polymerization catalyst composition”) will be described. As a 2nd polymerization catalyst composition, following formula (IX):

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

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

(Wherein, M represents a lanthanoid element, scandium or yttrium, CpR ′ represents unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl, X represents a hydrogen atom, a halogen atom, an alkoxy group, a thiolate group, An amino group, a silyl group or a monovalent hydrocarbon group having 1 to 20 carbon atoms is shown, L is a neutral Lewis base, w is an integer of 0 to 3, and [B]-is not substituted. And a polymerization catalyst composition comprising at least one complex selected from the group consisting of half metallocene cation complexes represented by
The second polymerization catalyst composition may further contain other components contained in a polymerization catalyst composition containing a conventional metallocene complex, such as a cocatalyst. Here, the metallocene complex is a complex compound in which one or two or more cyclopentadienyls or derivatives thereof are bonded to a central metal, and in particular, only one cyclopentadienyl or a derivative thereof is bonded to the central metal. One metallocene complex may be referred to as a half metallocene complex.
In the polymerization reaction system, the concentration of the complex contained in the second polymerization catalyst composition is preferably in the range of 0.1 to 0.0001 mol / L.

In the metallocene complexes represented by the above formulas (IX) and (X), Cp ^R in the formula is unsubstituted indenyl or substituted indenyl. Cp ^R having an indenyl ring as a basic skeleton can be represented by C ₉ H _7-x _Rx or C ₉ H _11-x _Rx . Here, X is an integer of 0 to 7 or 0 to 11. Further, each R is preferably independently a hydrocarbyl group or a metalloid group. The carbon number of the hydrocarbyl group is preferably 1 to 20, more preferably 1 to 10, and still more preferably 1 to 8. Specifically as a hydrocarbyl group, a methyl group, an ethyl group, a phenyl group, a benzyl group etc. are mentioned suitably. On the other hand, examples of the metalloid of the metalloid group include germyl Ge, stanyl Sn and silyl Si, and the metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group which the metalloid group has is the same as the above hydrocarbyl group. is there. Specific examples of the metalloid group include trimethylsilyl group and the like. Specific examples of the substituted indenyl include 2-phenyl indenyl, 2-methyl indenyl and the like. In addition, two Cp ^R in Formula (IX) and (X) may mutually be same or different, respectively.

In the half metallocene cation complex represented by the above formula (XI), Cp ^{R ′} in the formula is unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl, and among these, unsubstituted or substituted indenyl is preferable. Is preferred. Cp ^{R ′} having a cyclopentadienyl ring as a basic skeleton is represented by C ₅ H _5-x R _x . Here, X is an integer of 0 to 5. Further, each R is preferably independently a hydrocarbyl group or a metalloid group. The carbon number of the hydrocarbyl group is preferably 1 to 20, more preferably 1 to 10, and still more preferably 1 to 8. Specifically as a hydrocarbyl group, a methyl group, an ethyl group, a phenyl group, a benzyl group etc. are mentioned suitably. On the other hand, examples of the metalloid of the metalloid group include germyl Ge, stanyl Sn and silyl Si, and the metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group which the metalloid group has is the same as the above hydrocarbyl group. is there. Specific examples of the metalloid group include trimethylsilyl group and the like. Specific examples of Cp ^{R ′} having a cyclopentadienyl ring as a basic skeleton include the following.

(Wherein R represents a hydrogen atom, a methyl group or an ethyl group)

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

In the formula (XI), Cp ^{R ′} having the above-described fluorenyl ring as a basic skeleton can be represented by C ₁₃ H _9-x R _x or C ₁₃ H _17-x R _x . Here, X is an integer of 0 to 9 or 0 to 17. Further, each R is preferably independently a hydrocarbyl group or a metalloid group. The carbon number of the hydrocarbyl group is preferably 1 to 20, more preferably 1 to 10, and still more preferably 1 to 8. Specifically as a hydrocarbyl group, a methyl group, an ethyl group, a phenyl group, a benzyl group etc. are mentioned suitably. On the other hand, examples of the metalloid of the metalloid group include germyl Ge, stanyl Sn and silyl Si, and the metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group which the metalloid group has is the same as the above hydrocarbyl group. is there. Specific examples of the metalloid group include trimethylsilyl group and the like.

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

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

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

In the formula (XI), X is a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkoxy group, a thiolate group, an amino group, a silyl group and a monovalent hydrocarbon group having 1 to 20 carbon atoms. Here, as the above alkoxy group, aliphatic alkoxy groups such as methoxy group, ethoxy group, propoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group 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, Examples thereof include aryloxy groups such as 2-isopropyl-6-neopentylphenoxy group, and among them, 2,6-di-tert-butylphenoxy group is preferable.

In the formula (XI), as a thiolate group represented by X, aliphatic groups such as thiomethoxy group, thioethoxy group, thiopropoxy group, thio n-butoxy group, thioisobutoxy group, thio sec-butoxy group, thio tert-butoxy group and the like Thiololate group; thiophenoxy group, 2,6-di-tert-butylthiophenoxy group, 2,6-diisopropylthiophenoxy group, 2,6-dineopentylthiophenoxy group, 2-tert-butyl-6-isopropylthio group And arylthiolate groups such as phenoxy group, 2-tert-butyl-6-neopentylthiophenoxy group, 2-isopropyl-6-neopentylthiophenoxy group and 2,4,6-triisopropylthiophenoxy group. Among them, 2,4,6-triisopropylthiophenoxy is preferable. Arbitrariness.

In the formula (XI), as the amino group represented by X, aliphatic amino groups such as dimethylamino, diethylamino and diisopropylamino; phenylamino, 2,6-di-tert-butylphenylamino, 2, 6-diisopropylphenylamino group, 2,6-dineopentylphenylamino group, 2-tert-butyl-6-isopropylphenylamino group, 2-tert-butyl-6-neopentylphenylamino group, 2-isopropyl-6 And arylamino groups such as neopentylphenylamino group and 2,4,6-tri-tert-butylphenylamino group; and bistrialkylsilylamino groups such as bistrimethylsilylamino group. Among them, bistrimethylsilylamino group Is preferred.

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

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

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

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

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

Moreover, the metallocene complex represented by the said Formula (IX) and (X), and the half metallocene cation complex represented by the said Formula (XI) may exist as a monomer, a dimer or it. It may exist as the above multimer.

The metallocene complex represented by the above formula (IX) is, for example, a lanthanoid trishalide, scandium trishalide or yttrium trishalide in a solvent, a salt of indenyl (eg potassium salt or lithium salt) and a bis (trialkylsilyl) amine (For example, potassium salt or lithium salt). The reaction temperature may be about room temperature, so that it can be produced under mild conditions. The reaction time is optional, but is several hours to several tens of hours. The reaction solvent is not particularly limited, but is preferably a solvent that dissolves the raw material and the product. For example, toluene may be used. Below, the reaction example for obtaining the metallocene complex represented by Formula (IX) is shown.

(Wherein, X ′ ′ represents a halide)

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

(Wherein, X ′ ′ represents a halide)

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

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

Examples of the cation represented by [A] ⁺ include a carbonium cation, an oxonium cation, an amine cation, a phosphonium cation, a cycloheptatrienyl cation, and a ferrocenium cation having a transition metal. Examples of the carbonium cation include trisubstituted carbonium cations such as triphenyl carbonium cation and tri (substituted phenyl) carbonium cation, and the like. Specific examples of the tri (substituted phenyl) carbonyl cation include tri (methyl phenyl) ) Carbonium cation etc. are mentioned. Examples of amine cations include trialkyl ammonium cations such as trimethyl ammonium cation, triethyl ammonium cation, tripropyl ammonium cation and tributyl ammonium cation; N, N-dimethylanilinium cation, N, N-diethylanilinium cation, N, N, N, N-dialkylanilinium cations such as 2,4,6-pentamethylanilinium cation; dialkylammonium cations such as diisopropyl ammonium cation and dicyclohexyl ammonium cation. Examples of the phosphonium cation include triaryl phosphonium cations such as triphenyl phosphonium cation, tri (methyl phenyl) phosphonium cation and tri (dimethyl phenyl) phosphonium cation. Among these cations, N, N-dialkylanilinium cations or carbonium cations are preferable, and N, N-dialkylanilinium cations are particularly preferable.

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

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

The cocatalyst which can be used for the second polymerization catalyst composition may be optionally selected from components used as a cocatalyst for a polymerization catalyst composition containing a common metallocene complex. Preferred examples of the cocatalyst include aluminoxane, organic aluminum compounds and the above-mentioned ionic compounds. These co-catalysts may be used alone or in combination of two or more.

As the above-mentioned aluminoxane, alkylaluminoxane is preferable, and, for example, methylaluminoxane (MAO), modified methylaluminoxane and the like can be mentioned. Further, as the modified methylaluminoxane, MMAO-3A (manufactured by Tosoh Finechem Co., Ltd.) and the like are preferable. The content of the aluminoxane in the second polymerization catalyst composition may be such that the element ratio Al / M of the aluminum element Al of the aluminoxane to the central metal M of the metallocene complex is about 10 to 1,000. Preferably, it is more preferably about 100.

On the other hand, as the organoaluminum compound, a compound represented by the general formula AlRR′R ′ ′ (wherein R and R ′ each independently represent a monovalent hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, or a hydrogen atom) And R ′ ′ is a monovalent hydrocarbon group having 1 to 10 carbon atoms. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are illustrated, and a chlorine atom is preferable. Examples of the organic aluminum compound include trialkylaluminum, dialkylaluminum chloride, alkylaluminum dichloride, dialkylaluminum hydride and the like, and among these, trialkylaluminum is preferable. Moreover, as a trialkyl aluminum, a triethyl aluminum, a triisobutyl aluminum etc. are mentioned, for example. The content of the organoaluminum compound in the polymerization catalyst composition is preferably 1 to 50 times mol, and more preferably about 10 times mol, of the metallocene complex.

Furthermore, in the above polymerization catalyst composition, the metallocene complex represented by the above formulas (IX) and (X) and the half metallocene cation complex represented by the above formula (XI) are respectively combined with a suitable cocatalyst. Can increase the cis-1,4 bond content and the molecular weight of the resulting polymer.

-Third polymerization catalyst composition-
Next, the third polymerization catalyst composition (hereinafter, also referred to as "third polymerization catalyst composition") will be described.

As the third polymerization catalyst composition, as a rare earth element-containing compound, the following formula (XIII):
R _a MX _b QY _b (XIII)
(Wherein R each independently represents unsubstituted or substituted indenyl, R is coordinated to M, M is a lanthanoid element, scandium or yttrium, and each X independently represents 1 to 6 carbon atoms. 20 represents a monovalent hydrocarbon group, X is μ-coordinated to M and Q, Q is an element of Group 13 of the periodic table, and Y is independently 1 to 20 carbon atoms And a polymerization catalyst composition containing a metallocene-based composite catalyst represented by the formula: Y is coordinated to Q, and a and b are 2).

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

(Wherein, M ¹ represents a lanthanoid element, scandium or yttrium, CpR each independently represents unsubstituted or substituted indenyl, and R ^A and R ^B each independently have 1 to 20 carbon atoms indicates the valency of the hydrocarbon group, the ^{R a} and ^{R B} are coordinated μ to ^{M 1} and Al, ^{R C} and ^{R D} are each independently a monovalent hydrocarbon of 1 to 20 carbon atoms And a metallocene-based composite catalyst represented by the group or hydrogen atom.

A polymer can be manufactured by using the said metallocene type composite catalyst. Further, by using the above-mentioned metallocene-based composite catalyst, for example, a catalyst which has been composited in advance with an aluminum catalyst, it becomes possible to reduce or eliminate the amount of alkyl aluminum used at the time of multicomponent copolymer synthesis. In addition, when a conventional catalyst system is used, it is necessary to use a large amount of alkylaluminum in multicomponent copolymer synthesis. For example, in the conventional catalyst system, it is necessary to use at least 10 molar equivalents of alkylaluminum with respect to the metal catalyst, but in the case of the above metallocene-based composite catalyst, it is excellent by adding approximately five molar equivalents of alkylaluminum. The catalytic action is exhibited.

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

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

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

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

In the above formula (XIV), Cp ^R is unsubstituted indenyl or substituted indenyl. Cp ^R having an indenyl ring as a basic skeleton can be represented by C ₉ H _{7 -X} R _X or C ₉ H _{11 -X} R _X. Here, X is an integer of 0 to 7 or 0 to 11. Further, each R is preferably independently a hydrocarbyl group or a metalloid group. The carbon number of the hydrocarbyl group is preferably 1 to 20, more preferably 1 to 10, and still more preferably 1 to 8. Specifically as a hydrocarbyl group, a methyl group, an ethyl group, a phenyl group, a benzyl group etc. are mentioned suitably. On the other hand, examples of the metalloid of the metalloid group include germyl Ge, stanyl Sn and silyl Si, and the metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group which the metalloid group has is the same as the above hydrocarbyl group. is there. Specific examples of the metalloid group include trimethylsilyl group and the like.
Specific examples of the substituted indenyl include 2-phenyl indenyl, 2-methyl indenyl and the like. The two Cp ^R 's in formula (XIV) may be identical to or different from one another.

In the above formula (XIV), R ^A and R ^B each independently represent a monovalent hydrocarbon group having 1 to 20 carbon atoms, and R ^A and R ^B are μ-coordinated to M ¹ and Al ing. Here, as the monovalent hydrocarbon group having 1 to 20 carbon atoms, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, a tridecyl group Tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, stearyl group and the like. In addition, (mu) coordination is a coordination mode having a crosslinked structure.
In the above formula (XIV), R ^C and R ^D are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom. Here, as the monovalent hydrocarbon group having 1 to 20 carbon atoms, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, a tridecyl group Tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, stearyl group and the like.
The above metallocene-based composite catalyst may be, for example, a solvent represented by the following formula (XV):

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

In the metallocene complex represented by the above formula (XV), Cp ^R is unsubstituted indenyl or substituted indenyl and has the same meaning as Cp ^R in the above formula (XIV). Further, in the above formula (XV), the metal M ² is a lanthanoid element, scandium or yttrium, and has the same meaning as the metal M ¹ in the above formula (XIV).

The metallocene complex represented by the above formula (XV) contains a silylamide ligand [-N (SiR ₃ ) ₂ ]. The R groups (R ^E to R ^J groups) contained in the silylamide ligand are each independently an alkyl group having 1 to 3 carbon atoms or a hydrogen atom. Preferably, at least one of R ^E to R ^J is a hydrogen atom. Making at least one of R ^E to R ^J a hydrogen atom facilitates the synthesis of the catalyst. Furthermore, as an alkyl group, a methyl group is preferable.

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

Moreover, the metallocene complex represented by the said Formula (XV) may exist as a monomer, and may exist as a dimer or multimer more than that.

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

Specific examples of the above organoaluminum compounds include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, tripentylaluminum and tripentylaluminum. Hexylaluminum, Tricyclohexylaluminum, Trioctylaluminum; Diethylaluminum hydride, Di-n-propylaluminum hydride, Di-n-butylaluminum hydride, Diisobutylaluminum hydride, Dihexylaluminum hydride, Diisohexylaluminum hydride , Hydrogenated dioctylaluminum, hydrogenated diisooctylaluminum; ethylaluminum dihydride, n-propylaluminum Muzi hydride, isobutylaluminum dihydride and the like. Among these, triethylaluminum, triisobutylaluminum, hydrogenated diethylaluminum, hydrogenated diisobutylaluminum are preferred. Moreover, these organoaluminum compounds can be used singly or in combination of two or more. The amount of the organoaluminum compound used to form the above-mentioned metallocene composite catalyst is preferably 1 to 50 times mol, and more preferably about 10 times mol based on the metallocene complex.

The third polymerization catalyst composition may contain the above metallocene-based composite catalyst and a boron anion, and further, other components contained in the polymerization catalyst composition containing a common metallocene-based catalyst, such as a cocatalyst, etc. Is preferred. In addition, the said metallocene type composite catalyst and a boron anion are put together, and it is also called 2 component catalyst. According to the third polymerization catalyst composition, as in the case of the metallocene composite catalyst, the content of each monomer component in the polymer can be arbitrarily controlled because it further contains a boron anion. It becomes.

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

In addition, the said boron anion can be used as an ionic compound combined with the cation. Examples of the cation include a carbonium cation, an oxonium cation, an amine cation, a phosphonium cation, a cycloheptatrienyl cation, and a ferrocenium cation having a transition metal. Examples of the carbonium cation include trisubstituted carbonium cations such as triphenyl carbonium cation and tri (substituted phenyl) carbonium cation, and the like. Specific examples of the tri (substituted phenyl) carbonyl cation include tri (methyl phenyl) ) Carbonium cation etc. are mentioned. Examples of amine cations include trialkyl ammonium cations such as trimethyl ammonium cation, triethyl ammonium cation, tripropyl ammonium cation and tributyl ammonium cation; N, N-dimethylanilinium cation, N, N-diethylanilinium cation, N, N, N, N-dialkylanilinium cations such as 2,4,6-pentamethylanilinium cation; dialkylammonium cations such as diisopropyl ammonium cation and dicyclohexyl ammonium cation. Examples of the phosphonium cation include triaryl phosphonium cations such as triphenyl phosphonium cation, tri (methyl phenyl) phosphonium cation and tri (dimethyl phenyl) phosphonium cation. Among these cations, N, N-dialkylanilinium cations or carbonium cations are preferable, and N, N-dialkylanilinium cations are more preferable. Therefore, as the above ionic compound, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenyl carbonium tetrakis (pentafluorophenyl) borate and the like are preferable. The ionic compound comprising a boron anion and a cation is preferably added in an amount of 0.1 to 10 times mol, more preferably about 1 time mol, with respect to the metallocene composite catalyst.

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

As a co-catalyst which can be used for the said 3rd polymerization catalyst composition, aluminoxane etc. other than the organoaluminum compound represented by above-mentioned AlRKRLRM are mentioned suitably, for example. As the above-mentioned aluminoxane, alkylaluminoxane is preferable, and, for example, methylaluminoxane (MAO), modified methylaluminoxane and the like can be mentioned. Further, as the modified methylaluminoxane, MMAO-3A (manufactured by Tosoh Finechem Co., Ltd.) and the like are preferable. These aluminoxanes may be used alone or in combination of two or more.

-Fourth polymerization catalyst composition-
The fourth polymerization catalyst composition includes a rare earth element compound and a compound having a cyclopentadiene skeleton.

The fourth polymerization catalyst composition is
· Rare earth element compounds (hereinafter, also referred to as "component (A2)"),
・ Compounds selected from the group consisting of substituted or unsubstituted cyclopentadiene, substituted or unsubstituted indene (compound having an indenyl group), and substituted or unsubstituted fluorene (hereinafter also referred to as “component (B2)”) When,
Need to contain.
The fourth polymerization catalyst composition is
-Organometallic compounds (hereinafter, also referred to as "(C2) components")
・ Aluminoxane compound (hereinafter, also referred to as “component (D2)”)
・ Halogen compounds (hereinafter, also referred to as “component (E2)”)
・ Ionic compound (hereinafter, also referred to as “(F2) component”)
May be further included. Among these, the fourth polymerization catalyst composition preferably contains the organometallic compound (component (C2)) and the ionic compound (component (F2)).

The fourth polymerization catalyst composition preferably has high solubility in aliphatic hydrocarbon, and preferably becomes a homogeneous solution in aliphatic hydrocarbon. Here, examples of the aliphatic hydrocarbon include hexane, cyclohexane, pentane and the like.
And it is preferable that a 4th polymerization catalyst composition does not contain an aromatic hydrocarbon. Here, examples of the aromatic hydrocarbon include benzene, toluene, xylene and the like.
In addition, "an aromatic hydrocarbon is not included" means that the ratio of the aromatic hydrocarbon contained in a polymerization catalyst composition is less than 0.1 mass%.

The component (A2) can be a rare earth element-containing compound having a metal-nitrogen bond (M-N bond) or a reaction product of the rare earth element-containing compound and a Lewis base.
Examples of the rare earth element-containing compound include scandium, yttrium, and compounds containing a lanthanoid element formed of an element having an atomic number of 57 to 71, and the like. Specifically, lanthanoid elements are lanthanium, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium.
Further, as the Lewis base, for example, tetrahydrofuran, diethyl ether, dimethyl aniline, trimethyl phosphine, lithium chloride, neutral olefins, neutral diolefins and the like can be mentioned.

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

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

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

According to the above configuration, the component (A2) can be made into a compound having three MN bonds, the bonds become chemically equivalent, the structure of the compound becomes stable, and the handling becomes easy.
Moreover, if it is set as the said structure, the catalyst activity in a reaction system can further be improved. Therefore, the reaction time can be further shortened and the reaction temperature further raised.

When A is oxygen, the component (A2) represented by the formula (1) is not particularly limited, but for example, the following formula (1a)
(RO) ₃ M (1a)
Rare earth alcoholate, represented by
Following formula (1b)
(R-CO ₂ ) ₃ M (1 b)
And rare earth carboxylates represented by and the like. Here, in each of the above formulas (1a) and (1b), R may be the same or different and is an alkyl group having 1 to 10 carbon atoms.
In addition, since it is preferable that it does not have a bond with a rare earth element and carbon as (A2) component, the compound represented by the compound represented by Formula (1a) or Formula (1b) mentioned above can be used conveniently. .

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

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

Examples of the substituted cyclopentadiene include pentamethylcyclopentadiene, tetramethylcyclopentadiene, isopropylcyclopentadiene, trimethylsilyl-tetramethylcyclopentadiene and the like.
As substituted or unsubstituted indene, for example, indene, 2-phenyl-1H-indene, 3-benzyl-1H-indene, 3-methyl-2-phenyl-1H-indene, 3-benzyl-2-phenyl-1H -Indene, 1-benzyl-1H-indene and the like, and in particular, 3-benzyl-1H-indene and 1-benzyl-1H-indene are preferable from the viewpoint of reducing the molecular weight distribution.
Examples of the substituted fluorene include trimethylsilyl fluorene, isopropyl fluorene and the like.

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

The organometallic compound (component (C2)) has a formula (2):
YR ⁴ _a R ⁵ _b R ⁶ _c (2)
(Wherein Y is a metal element selected from the group consisting of elements of Groups 1, 2, 12, and 13 of the periodic table, and R 4 and R 5 each have 1 to 10 carbon atoms) R 6 is a monovalent hydrocarbon group or a hydrogen atom, and R 6 is a monovalent hydrocarbon group having 1 to 10 carbon atoms, provided that R ⁴ , R ⁵ and R ⁶ may be identical to or different from one another, Further, when Y is a metal element of Group 1, a is 1 and b and c are 0, and when Y is a metal element of Group 2 or 12, a and b is 1 and c is 0, and when Y is a metal element of Group 13, a, b and c are 1.
Here, from the viewpoint of enhancing the catalyst activity, it is preferable that in the formula (2), at least one of R ¹ , R ² and R ³ is different.

Specifically, the (C2) component is represented by the formula (3):
AlR ⁷ R ⁸ R ⁹ (3)
(Wherein, R ⁷ and R ^{8 each} represent a monovalent hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom, and R ⁹ represents a monovalent hydrocarbon group having one to 10 carbon atoms, R ⁷ , And R ⁸ and R ⁹ may be the same or different)).
Examples of the organoaluminum compounds include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, tripentylaluminum and trihexyl Aluminum, tricyclohexylaluminum, trioctylaluminum; diethylaluminum hydride, di-n-propylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride, dihexylaluminum hydride, diisohexylaluminum hydride, Hydrogenated dioctylaluminum, hydrogenated diisooctylaluminum; ethylaluminum dihydrate, n-propylaluminum Dihydride, include isobutyl aluminum dihydride, etc., triethylaluminum, triisobutylaluminum, hydrogenated diethylaluminum, preferably diisobutylaluminum hydride, diisobutylaluminum hydride are more preferred.
The organic aluminum compounds may be used alone or in combination of two or more.

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

Here, examples of the organoaluminum compound include trialkylaluminum such as trimethylaluminum, triethylaluminum and triisobutylaluminum, and a mixture thereof, and in particular, a mixture of trimethylaluminum, trimethylaluminum and tributylaluminum is preferable.
As a condensing agent, water etc. are mentioned, for example.

As the component (D2), for example, the formula (4):
-(Al (R ¹⁰ ) O) _n- (4)
(Wherein, R 10 is a monovalent hydrocarbon group having 1 to 10 carbon atoms, wherein part of the hydrocarbon group may be substituted with a halogen and / or an alkoxy group; R ¹⁰ is a repeating group Aluminoxanes represented by units which may be the same or different; n is 5 or more can be mentioned.

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

The aluminoxane preferably has high solubility in aliphatic hydrocarbon, and preferably has low solubility in aromatic hydrocarbon. For example, aluminoxane marketed as a hexane solution is preferred.
Here, as the aliphatic hydrocarbon, hexane, cyclohexane and the like can be mentioned.

The component (D2) is particularly preferably a compound of formula (5):
-(Al (CH ₃ ) _x (i-C ₄ H ₉ ) _y O) _m- (5)
(Wherein, x + y is 1; m is 5 or more) may be a modified aluminoxane (hereinafter also referred to as "TMAO"). As TMAO, for example, a product name: TMAO341 manufactured by Tosoh Finechem Co., Ltd. can be mentioned.

Further, the component (D2) is particularly preferably represented by the formula (6):
-(Al (CH ₃ ) _0.7 (i-C ₄ H ₉ ) _0.3 O) _k- (6)
It may be a modified aluminoxane represented by (wherein k is 5 or more) (hereinafter also referred to as "MMAO"). Examples of MMAO include product name: MMAO-3A manufactured by Tosoh Finechem Co., Ltd.

Furthermore, the component (D2) is particularly preferably a compound of formula (7):
-[(CH ₃ ) AlO] _i ---(7)
(Wherein, i is 5 or more) may be a modified aluminoxane (hereinafter also referred to as “PMAO”). As PMAO, for example, product name: TMAO-211 manufactured by Tosoh Finechem Co., Ltd. can be mentioned.

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

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

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

As the component (E2-1), for example, a halogen-containing compound containing an element of Group 3, Group 4, Group 5, Group 6, Group 8, Group 13, Group 14 or Group 15 or the like And particularly preferred are halides of aluminum or halides of organometallics.
As a halogen-containing compound which is a Lewis acid, for example, titanium tetrachloride, tungsten hexachloride, tri (pentafluorophenyl) borate, methylaluminum dibromide, methylaluminum dichloride, ethylaluminum dibromide, ethylaluminum dichloride, butylaluminum dibromide , Butylaluminum dichloride, dimethylaluminum bromide, dimethylaluminum chloride, diethylaluminum bromide, diethylaluminum chloride, dibutylaluminum bromide, dibutylaluminum chloride, methylaluminum sesquibromide, methylaluminum sesquichloride, ethylaluminum sesquibromide, ethylaluminum sesquichloride, aluminum To Bromide, tri (pentafluorophenyl) aluminum, dibutyltin dichloride, tin tetrachloride, phosphorus trichloride, phosphorus pentachloride, antimony trichloride, antimony pentachloride and the like can be mentioned, and in particular, ethylaluminum dichloride, ethylaluminum dibromide, diethyl Aluminum chloride, diethylaluminum bromide, ethylaluminum sesquichloride and ethylaluminum sesquibromide are preferred.
As the halogen, chlorine or bromine is preferable.
The halogen-containing compounds which are the above-mentioned Lewis acids may be used alone or in combination of two or more.

Examples of the metal halide used for the component (E2-2) include beryllium chloride, beryllium bromide, beryllium iodide, magnesium chloride, magnesium bromide, magnesium iodide, calcium chloride, calcium bromide, calcium iodide, Barium chloride, barium bromide, barium iodide, zinc chloride, zinc bromide, zinc iodide, zinc iodide, cadmium chloride, cadmium bromide, cadmium iodide, mercury iodide, mercury chloride, mercury bromide, mercury iodide, manganese chloride, manganese bromide Manganese iodide, rhenium chloride, rhenium bromide, rhenium iodide, copper chloride, copper bromide, copper iodide, silver chloride, silver bromide, silver iodide, gold chloride, gold iodide, gold bromide, etc. Preferred are magnesium chloride, calcium chloride, barium chloride, zinc chloride, manganese chloride and copper chloride, magnesium chloride and chloride Lead, manganese chloride, copper chloride are more preferable.
The Lewis base used for the component (E2-2) is preferably a phosphorus compound, a carbonyl compound, a nitrogen compound, an ether compound or an alcohol.
For example, tributyl phosphate, tri-2-ethylhexyl phosphate, triphenyl phosphate, tricresyl phosphate, triethyl phosphine, tributyl phosphine, triphenyl phosphine, diethyl phosphino ethane, diphenyl phosphino ethane, acetylacetone, benzoylacetone, propionylacetone , Valerylacetone, ethylacetylacetone, 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 Acid, naphthenic acid, versatic acid, triethylamine, N, N-dimethylacetamide, tetrahydrofuran, diphenyl ether, 2-ethylhexyl alcohol, oleyl acid Coal, stearyl alcohol, phenol, benzyl alcohol, 1-decanol, lauryl alcohol etc., and in particular, tri-2-ethylhexyl phosphate, tricresyl phosphate, acetylacetone, 2-ethylhexanoic acid, versatic acid, 2-ethylhexyl alcohol 1-decanol and lauryl alcohol are preferred.
The number of moles of the Lewis base is preferably 0.01 to 30 moles, more preferably 0.5 to 10 moles with respect to 1 mole of the metal halide. The reaction with this Lewis base can be used to reduce the metal remaining in the polymer.

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

The ionic compound (component (F2)) has the same meaning as the ionic compound (B1-1) described above for the first polymerization catalyst composition.

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

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

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

From the viewpoint of improving the catalyst activity, the ratio of the (E2) component (halogen compound) and the (F2) component (ionic compound) in mole to the (A2) component is preferably 0 or more from the viewpoint of improving the catalyst activity 0.5 From the viewpoint of maintaining the solubility of the component (E2) and the component (F2) and suppressing the decrease of the catalytic activity, it is more preferably 20 or less. Is preferable, and 10 or less is more preferable.
Therefore, according to the above range, the effect of improving the cis-1,4-bond content of the conjugated diene polymer can be enhanced.

<Filler>
The rubber composition of the present embodiment can contain a filler. By containing the filler, the durability of the rubber composition can be improved. The filler is not particularly limited, and examples thereof include carbon black and silica.
The carbon black is not particularly limited, and examples thereof include carbon black of SAF, ISAF, HAF, FF, FEF, GPF, SRF, CF, FT, and MT grade. One type of carbon black may be used alone, or two or more types may be used in combination. The silica is not particularly limited, and examples thereof include wet silica, dry silica, colloidal silica and the like. Among these, the filler used in the present embodiment is preferably carbon black, and more preferably SAF, ISAF, HAF, or FEF grade carbon black.
However, the rubber composition of the present embodiment may not contain a filler.

In addition, the rubber composition of the present embodiment can contain the filler at a ratio of 90 parts by mass or less with respect to 100 parts by mass of the rubber component. When the content of the filler exceeds 90 parts by mass, the vibration damping property may be significantly deteriorated. In addition, the content of the filler in the rubber composition is preferably 70 parts by mass or less and 50 parts by mass or less with respect to 100 parts by mass of the rubber component from the viewpoint of sufficiently suppressing the deterioration of the vibration damping property. It is more preferable that the amount is 30 parts by mass or less.

<Softener and liquid rubber>
The rubber composition of the present embodiment can contain a softener and / or a liquid rubber. By containing the softener and / or the liquid rubber, the vibration damping property can be effectively improved. In addition, in this specification, "liquid rubber" refers to rubber which exhibits a liquid state at 24 degreeC. Further, in the present specification, "liquid rubber" is not included in the above-mentioned rubber component.

Examples of the softener include naphthenic oils, paraffinic oils and aromatic oils. Among these, as a softener, it is preferable to use an aromatic oil. A softening agent may be used individually by 1 type, and may be used in combination of 2 or more type.
Examples of the liquid rubber include, but are not limited to, hydrogenated isoprene rubber, hydrogenated butadiene rubber, liquid ethylene / propylene / diene copolymer, liquid ethylene / propylene copolymer, liquid butadiene / styrene / random copolymer and the like. Be Among these, as the liquid rubber, it is preferable to use a liquid butadiene / styrene / random copolymer. The liquid rubber may be used singly or in combination of two or more.

The rubber composition of the present embodiment preferably contains 20 parts by mass or more of at least one selected from a softener and a liquid rubber with respect to 100 parts by mass of the rubber component. By containing 20 parts by mass or more of the above components, the effect of improving the vibration damping property can be obtained more sufficiently.

<Other ingredients>
In addition, the rubber composition of the present embodiment is a crosslinking agent (including a vulcanizing agent such as sulfur) which is usually used in the rubber industry, if necessary, as long as the effects of the present invention are not impaired. (Vulcanization accelerator), anti-aging agent, zinc white (ZnO), waxes, antioxidant, foaming agent, plasticizer, lubricant, tackifier, petroleum resin, ultraviolet absorber, dispersant, compatibilizer And components such as a homogenizing agent can be suitably contained.

<Production of vibration-proof rubber composition>
It does not restrict | limit especially as a manufacturing method of the rubber composition of this embodiment, For example, the rubber composition of this embodiment can be obtained by mix | blending and knead | mixing each component mentioned above according to a conventional method. In addition, at the time of compounding and kneading, all the components may be compounded and kneaded at once, or each component may be compounded and kneaded in two or three stages. In addition, in the case of kneading | mixing, kneaders, such as a roll, an internal mixer, and a Banbury rotor, can be used. Furthermore, when forming a rubber composition into a sheet form, strip shape, etc., well-known molding machines, such as an extrusion molding machine and a press, can be used.

Further, the rubber composition of the present embodiment may be produced by crosslinking. The crosslinking conditions are not particularly limited, and usually, a temperature of 140 to 180 ° C. and a time of 5 to 120 minutes can be employed.

(Anti-vibration rubber)
The anti-vibration rubber according to an embodiment of the present invention (hereinafter sometimes referred to as "the anti-vibration rubber according to the present embodiment") is characterized by including the rubber composition according to the above-mentioned present embodiment. The anti-vibration rubber according to the present embodiment is excellent in durability and vibration damping property because the rubber composition described above is used. And the vibration-proof rubber of this embodiment can be preferably used, for example, as a vibration-proof member for vehicles, especially for automobiles, for which the required performance is more severe. For example, an engine mount, a torsional damper, a rubber bush, a strut mount, a bound bumper, a helper rubber, a member mount, a stabilizer bush, an air spring, a center support, a rubberized propeller shaft, an antivibration lever. These include compound dampers, damping rubbers, idler arm bushes, steering column bushes, coupling rubbers, body mounts, muffler supports, dynamic dampers and piping rubbers. Among these, the anti-vibration rubber of the present embodiment can be preferably used for an engine mount.

EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples.

(Synthesis of copolymer A)
In a fully dried 1000 mL pressure-resistant stainless steel reactor, 80 g of styrene as an aromatic vinyl compound and 600 mL of toluene were added. On the other hand, mono (bis (1,3-tert-butyldimethylsilyl) indenyl) bis (bis (dimethylsilyl) amide) gadolinium complex (1,3-[(t _{_{_{_{-Bu) Me 2 Si] 2 C}}}} 9 H 5 Gd [N (SiHMe 2) 2] 2) 0.25mmol, dimethylanilinium tetrakis (pentafluorophenyl) borate _{_{_{[Me 2 NHPhB (C 6 F}}} 5) 4] 0 .275 mmol and 1.4 mmol of diisobutylaluminum hydride were charged, and 40 mL of toluene was added to obtain a catalyst solution.
The obtained catalyst solution was added to the above-described pressure resistant stainless steel reactor and heated to 70 ° C. Next, ethylene as a non-conjugated olefin compound is charged at a pressure of 1.5 MPa into this pressure resistant stainless steel reactor, and further 50 mL of a toluene solution containing 5 g of 1,3-butadiene as a conjugated diene compound is loaded over 3 hours And copolymerized at 70 ° C. for a total of 4 hours.
After the copolymerization, 1 mL of 2,2'-methylene-bis (4-ethyl-6-t-butylphenol) (NS-5) in 5% by mass of an isopropanol solution is added to the pressure resistant stainless steel reactor to stop the reaction, The copolymer was separated using a large amount of methanol and vacuum dried at 50 ° C. to obtain copolymer A.

(Synthesis of copolymer B)
In a sufficiently dried 1000 mL pressure-resistant stainless steel reactor, 180 g of styrene as an aromatic vinyl compound and 600 mL of toluene were added. On the other hand, mono (bis (1,3-tert-butyldimethylsilyl) indenyl) bis (bis (dimethylsilyl) amide) gadolinium complex (1,3-[(t _{_{_{_{-Bu) Me 2 Si] 2 C}}}} 9 H 5 Gd [N (SiHMe 2) 2] 2) 0.25mmol, dimethylanilinium tetrakis (pentafluorophenyl) borate _{_{_{[Me 2 NHPhB (C 6 F}}} 5) 4] 0 .275 mmol and 1.1 mmol of diisobutylaluminum hydride were charged, and 40 mL of toluene was added to obtain a catalyst solution.
The obtained catalyst solution was added to the above-described pressure resistant stainless steel reactor and heated to 70 ° C. Next, ethylene as a non-conjugated olefin compound is charged at a pressure of 1.5 MPa into this pressure resistant stainless steel reactor, and 80 mL of a toluene solution containing 15 g of 1,3-butadiene as a conjugated diene compound is further loaded over 8 hours And copolymerized at 70 ° C. for a total of 8.5 hours.
After the copolymerization, 1 mL of 2,2'-methylene-bis (4-ethyl-6-t-butylphenol) (NS-5) in 5% by mass of an isopropanol solution is added to the pressure resistant stainless steel reactor to stop the reaction, The copolymer was separated using a large amount of methanol and vacuum dried at 50 ° C. to obtain copolymer B.

(Synthesis of copolymer C)
In a sufficiently dried 1000 mL pressure-resistant stainless steel reactor, 160 g of styrene as an aromatic vinyl compound and 400 mL of toluene were added. On the other hand, mono (bis (1,3-tert-butyldimethylsilyl) indenyl) bis (bis (dimethylsilyl) amide) gadolinium complex (1,3-[(t _{_{_{_{-Bu) Me 2 Si] 2 C}}}} 9 H 5 Gd [N (SiHMe 2) 2] 2) 0.17mmol, dimethylanilinium tetrakis (pentafluorophenyl) borate _{_{_{[Me 2 NHPhB (C 6 F}}} 5) 4] 0 . 187 mmol and 1.4 mmol of diisobutylaluminum hydride were charged, and 40 mL of toluene was added to obtain a catalyst solution.
The obtained catalyst solution was added to the above-described pressure resistant stainless steel reactor and heated to 70 ° C. Next, ethylene as a non-conjugated olefin compound is charged at a pressure of 1.5 MPa into this pressure resistant stainless steel reactor, and further 150 mL of a toluene solution containing 30 g of 1,3-butadiene as a conjugated diene compound is loaded over 30 minutes And copolymerized at 70 ° C. for 6 hours. Thereafter, 150 mL of a toluene solution containing 30 g of 1,3-butadiene as a conjugated diene compound was further added to the pressure resistant stainless steel reactor over 30 minutes, and copolymerization was performed at 70 ° C. for 1 hour.
After the copolymerization, 1 mL of 2,2'-methylene-bis (4-ethyl-6-t-butylphenol) (NS-5) in 5% by mass of an isopropanol solution is added to the pressure resistant stainless steel reactor to stop the reaction, The copolymer was separated using a large amount of methanol and vacuum dried at 50 ° C. to obtain copolymer C.

(Synthesis of copolymer D)
In a sufficiently dried 1000 mL pressure resistant stainless steel reactor, 240 g of styrene as an aromatic vinyl compound and 600 mL of toluene were added. On the other hand, mono (bis (1,3-tert-butyldimethylsilyl) indenyl) bis (bis (dimethylsilyl) amide) gadolinium complex (1,3-[(t _{_{_{_{-Bu) Me 2 Si] 2 C}}}} 9 H 5 Gd [N (SiHMe 2) 2] 2) 0.5mmol, dimethylanilinium tetrakis (pentafluorophenyl) borate _{_{_{[Me 2 NHPhB (C 6 F}}} 5) 4] 0 .55 mmol and 1.7 mmol of diisobutylaluminum hydride were charged, and 70 mL of toluene was added to obtain a catalyst solution.
The obtained catalyst solution was added to the above-mentioned pressure resistant stainless steel reactor and heated to 80 ° C. Next, ethylene as a non-conjugated olefin compound is charged at a pressure of 1.4 MPa into this pressure resistant stainless steel reactor, and further, 60 mL of a toluene solution containing 5 g of 1,3-butadiene as a conjugated diene compound is charged over 6 hours And copolymerized at 80 ° C. for a total of 6.5 hours.
After the copolymerization, 1 mL of 2,2'-methylene-bis (4-ethyl-6-t-butylphenol) (NS-5) in 5% by mass of an isopropanol solution is added to the pressure resistant stainless steel reactor to stop the reaction, The copolymer was separated using a large amount of methanol and vacuum dried at 50 ° C. to obtain copolymer D.

(Synthesis of copolymer E)
In a sufficiently dried 1000 mL pressure-resistant stainless steel reactor, 160 g of styrene as an aromatic vinyl compound and 600 mL of toluene were added. On the other hand, mono (bis (1,3-tert-butyldimethylsilyl) indenyl) bis (bis (dimethylsilyl) amide) gadolinium complex (1,3-[(t _{_{_{_{-Bu) Me 2 Si] 2 C}}}} 9 H 5 Gd [N (SiHMe 2) 2] 2) 0.25mmol, dimethylanilinium tetrakis (pentafluorophenyl) borate _{_{_{[Me 2 NHPhB (C 6 F}}} 5) 4] 0 .275 mmol and 1.1 mmol of diisobutylaluminum hydride were charged, and 40 mL of toluene was added to obtain a catalyst solution.
The obtained catalyst solution was added to the above-described pressure resistant stainless steel reactor and heated to 70 ° C. Next, ethylene as a non-conjugated olefin compound is charged at a pressure of 1.5 MPa into this pressure resistant stainless steel reactor, and further 50 mL of a toluene solution containing 10 g of isoprene as a conjugated diene compound is charged over 7 hours, 70 ° C. The copolymerization was carried out for a total of 8 hours.
After the copolymerization, 1 mL of 2,2'-methylene-bis (4-ethyl-6-t-butylphenol) (NS-5) in 5% by mass of an isopropanol solution is added to the pressure resistant stainless steel reactor to stop the reaction, The copolymer was separated using a large amount of methanol and vacuum dried at 50 ° C. to obtain copolymer E.

(Synthesis of copolymer F)
A copolymer F was obtained in the same manner as the synthesis of the copolymer A, except that 30 g of styrene was used in the synthesis of the copolymer A.

(Synthesis of copolymer G)
A copolymer G was obtained in the same manner as the synthesis of the copolymer B, except that in the synthesis of the copolymer B, 1,3-butadiene was not added.

(Synthesis of copolymer H)
In a sufficiently dried 1000 mL pressure-resistant stainless steel reactor, 80 g of styrene as an aromatic vinyl compound and 300 mL of toluene were added. On the other hand, mono (bis (1,3-tert-butyldimethylsilyl) indenyl) bis (bis (dimethylsilyl) amide) gadolinium complex (1,3-[(t _{_{_{_{-Bu) Me 2 Si] 2 C}}}} 9 H 5 Gd [N (SiHMe 2) 2] 2) 0.25mmol, dimethylanilinium tetrakis (pentafluorophenyl) borate _{_{_{[Me 2 NHPhB (C 6 F}}} 5) 4] 0 .275 mmol and 1.4 mmol of diisobutylaluminum hydride were charged, and 40 mL of toluene was added to obtain a catalyst solution.
The obtained catalyst solution was added to the above-described pressure resistant stainless steel reactor and heated to 70 ° C. Next, ethylene as a non-conjugated olefin compound is charged at a pressure of 1.5 MPa into this pressure resistant stainless steel reactor, and 500 mL of a toluene solution containing 100 g of 1,3-butadiene as a conjugated diene compound is further loaded over 4 hours And copolymerized at 70 ° C. for a total of 5 hours.
After the copolymerization, 1 mL of 2,2'-methylene-bis (4-ethyl-6-t-butylphenol) (NS-5) in 5% by mass of an isopropanol solution is added to the pressure resistant stainless steel reactor to stop the reaction, The copolymer was separated using a large amount of methanol and vacuum dried at 50 ° C. to obtain copolymer H.

(Synthesis of copolymer I)
In a sufficiently dried 1000 mL pressure-resistant stainless steel reactor, 200 g of styrene as an aromatic vinyl compound and 700 mL of toluene were added. On the other hand, mono (bis (1,3-tert-butyldimethylsilyl) indenyl) bis (bis (dimethylsilyl) amide) gadolinium complex (1,3-[(t _{_{_{_{-Bu) Me 2 Si] 2 C}}}} 9 H 5 Gd [N (SiHMe 2) 2] 2) 0.5mmol, dimethylanilinium tetrakis (pentafluorophenyl) borate _{_{_{[Me 2 NHPhB (C 6 F}}} 5) 4] 0 .55 mmol and 1.7 mmol of diisobutylaluminum hydride were charged, and 70 mL of toluene was added to obtain a catalyst solution.
The obtained catalyst solution was added to the above-described pressure resistant stainless steel reactor and heated to 70 ° C. Next, ethylene as a non-conjugated olefin compound is charged into this pressure resistant stainless steel reactor at a pressure of 1.0 MPa, and further, 50 mL of a toluene solution containing 1 g of 1,3-butadiene as a conjugated diene compound is charged over 4 hours And copolymerized at 70 ° C. for a total of 9 hours.
After the copolymerization, 1 mL of 2,2'-methylene-bis (4-ethyl-6-t-butylphenol) (NS-5) in 5% by mass of an isopropanol solution is added to the pressure resistant stainless steel reactor to stop the reaction, The copolymer was separated using a large amount of methanol and vacuum dried at 50 ° C. to obtain copolymer I.

For each copolymer obtained as described above, using ¹ H-NMR spectrum, the proportion (mol%) of conjugated diene units, the proportion (mol%) of non-conjugated olefin units, and the proportion of aromatic vinyl units The proportion (mol%) was measured.
Moreover, about each copolymer, melting | fusing point, glass transition temperature, and 0 ~ are measured by the differential scanning calorimetry measurement (DSC, the TA Instruments Japan company make, "DSCQ2000") based on JISK7121-1987. The energy of the endothermic peak at 120 ° C. was measured. Specifically, regarding the measurement of the energy of the endothermic peak, first, the temperature is raised from -150 ° C. to 150 ° C. at a temperature rising rate of 10 ° C./min. Then, the energy of the endothermic peak can be measured by determining the endothermic peak (enthalpy relaxation) at 0 to 120 ° C. at that time (1st run).
Further, when the main chain structure of each of the obtained copolymers was examined, no peak was observed at 10 to 24 ppm in the ¹³ C-NMR spectrum chart, and thus each of the obtained copolymers had a main chain Was confirmed to consist only of non-cyclic structure.

From Table 1, it can be seen that the copolymers A to F, H and I are at least multicomponent copolymers having conjugated diene units, nonconjugated olefin units and aromatic vinyl units.

(Preparation of rubber composition and vulcanized rubber)
In each example, a rubber composition was prepared according to the formulation shown in Table 2. Next, this rubber composition was vulcanized at 155 ° C. for 60 minutes to obtain a vulcanized rubber. The obtained vulcanized rubber was subjected to measurement of static spring constant and evaluation of durability according to the following method.

<Measurement of static spring constant>
The prepared rubber composition was press molded (vulcanized) at 155 ° C. for 60 minutes to prepare a cylindrical test piece having a diameter of 8 mm and a height of 6 mm. With respect to this cylindrical test piece, an axial load was applied and 20% compression was made in the axial direction, and after being temporarily unloaded, it was made to compress 20% in the axial direction again. Thereby, the load-deflection characteristics in the second loading process were measured, and a load-deflection curve was created based thereon. From the created curve, read the load value (P: 5%) (unit: N) when deflection is 5% and the load value (P: 15%) (unit: N) when 15%: The static spring constant Ks (N / mm) was calculated by the equation. Here, “0.6” in the formula is a height (mm) of 15% -5% (that is, 10%).
Ks = {(P15%)-(P5%)} / 0.6
In addition, said test was done at the test temperature of 35 degreeC using the dynamic-viscoelasticity tester (The GABO company make, brand name "Eplexor 500N"). The smaller the value of the static spring constant, the better the vibration damping property. The results are shown in Table 2.

<Evaluation of durability>
The prepared rubber composition was press-molded (vulcanized) at 155 ° C. for 60 minutes to prepare a sheet-like test piece having a thickness of 2 mm. Using a constant strain fatigue tester (trade name "FT-3100", manufactured by Shimadzu Corp.), the sheet-like test pieces were subjected to 200%, 250%, 300 at a test temperature of 35 ° C in accordance with JIS K6270. Test strains of% were repeatedly applied to measure the number of times (number of times of breakage) repeated until the test piece broke. Then, from the input energy given to the test piece at each test strain and the number of breaks at each test strain, an energy-breaking number conversion formula was calculated. By this conversion equation, the number of fractures conversion value when the input energy is 1 MPa was determined. The broken number conversion value in each example was indexed with the broken number conversion value determined in Example 11 being 100. It shows that it is excellent in durability, so that this index (durability index) is large. The results are shown in Table 2.

* 1 SBR: manufactured by JSR Corporation "# 1500", Styrene-Butadiene Rubber * 2 EPDM: manufactured by JSR Corporation Trade name "EP 35", Ethylene-Propylene-Diene Rubber * 3 Filler: manufactured by Asahi Carbon Co., Ltd. SAF-class carbon black * 4 Softener: made by Fuji Kosan Co., Ltd., trade name "Aromax # 3, aromatic process oil * 5 Liquid rubber: made by Clay Valley, trade name" Ricon 100 ", butadiene / styrene Random copolymer * 6 Anti-aging agent: SEIKO CHEMICAL CO., LTD., Trade name "Ozonone 6C", N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine * 7 vulcanization accelerator DPG : Made by Ouchi Shinko Chemical Co., Ltd., trade name "Noxceler D", diphenyl guanidine * 8 vulcanization accelerator CZ: made by Ouchi Shinsei Chemical Co., Ltd. Name "Noxceler CZ-G", N-Cyclohexyl-2-benzothiazolylsulfenamide * 9 Vulcanization accelerator DM: made by Ouchi New Chemical Co., Ltd., trade name "Noxcella DM-P", di-2-benzo Thiazolyl disulfide

From Table 2, the rubber component containing a multicomponent copolymer having a conjugated diene unit, a nonconjugated olefin unit, and an aromatic vinyl unit is contained, and the content of the filler is 90 parts by mass with respect to 100 parts by mass of the rubber component It is understood that the rubber composition according to the example which is less than or equal to part is excellent in the durability and the vibration damping property.

Claims

A rubber component containing a multicomponent copolymer having a conjugated diene unit, a nonconjugated olefin unit, and an aromatic vinyl unit, and a filler as an optional component, wherein the content of the filler is the rubber component 100 The vibration-proof rubber composition characterized in that it is 0 to 90 parts by mass with respect to the mass parts.
The multicomponent copolymer is
The ratio of the conjugated diene unit is 1 to 50 mol%,
The proportion of the non-conjugated olefin unit is 40 to 97 mol%,
The proportion of the aromatic vinyl units is 2 to 35 mol%,
The vibration proof rubber composition according to claim 1.
The vibration-proof rubber composition of Claim 1 or 2 whose ratio of the said multicomponent copolymer in the said rubber component is 20 mass% or more.
The anti-vibration rubber composition according to any one of claims 1 to 3, further comprising 20 parts by mass or more based on 100 parts by mass of the rubber component, at least one selected from a softener and a liquid rubber.
The vibration-proof rubber composition according to any one of claims 1 to 4, wherein the multicomponent copolymer has a melting point of 30 to 130 属 C as measured by differential scanning calorimetry (DSC).
The anti-vibration rubber according to any one of claims 1 to 5, wherein the multicomponent copolymer has an endothermic peak energy of 10 to 130 J / g as measured by differential scanning calorimetry (DSC) at 0 to 120 ° C. Composition.
The vibration-proof rubber composition according to any one of claims 1 to 6, wherein the multicomponent copolymer has a glass transition temperature measured by differential scanning calorimetry (DSC) of 0 属 C or less.
The vibration-proof rubber composition according to any one of claims 1 to 7, wherein in the multi-component copolymer, the main chain consists only of a non-cyclic structure.
The vibration-proof rubber composition according to any one of claims 1 to 8, wherein the non-conjugated olefin unit does not have a cyclic structure.
The vibration-proof rubber composition according to any one of claims 1 to 9, wherein the non-conjugated olefin unit comprises only an ethylene unit.
The vibration-proof rubber composition according to any one of claims 1 to 10, wherein the aromatic vinyl unit comprises a styrene unit.
The vibration-proof rubber composition according to any one of claims 1 to 11, wherein the conjugated diene unit contains at least one of 1,3-butadiene unit and isoprene unit.
An anti-vibration rubber comprising the anti-vibration rubber composition according to any one of claims 1 to 12.