JP7134648B2 - Method for producing ethylene/α-olefin/non-conjugated polyene copolymer - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing an ethylene/α-olefin/non-conjugated polyene copolymer, and more particularly, in the presence of an olefin polymerization catalyst containing a bridged metallocene compound having a specific structure, ethylene, α-olefin and The present invention relates to a method for copolymerizing a non-conjugated polyene to produce an ethylene/α-olefin/non-conjugated polyene copolymer.

Ethylene/α-olefin rubber represented by ethylene/propylene/non-conjugated diene copolymer rubber (EPDM) does not have unsaturated bonds in the main chain of its molecular structure, so it is a widely used conjugated diene. It is widely used for automobile parts, electric wire materials, construction and civil engineering materials, industrial material parts, modifiers of various resins, etc.

Conventional ethylene/α-olefin/non-conjugated polyene copolymer rubber such as EPDM generally uses a catalyst system (so-called Ziegler-Natta catalyst system) consisting of a combination of a titanium-based catalyst or a vanadium-based catalyst and an organoaluminum compound. It has been manufactured using The biggest drawback of this catalyst system is its productivity, and because of its low polymerization activity and short catalyst life, it has to be polymerized at a low temperature of 0 to 50°C. For this reason, the high viscosity of the polymerization solution becomes an obstacle, and the concentration of the olefin copolymer in the polymerization vessel cannot be sufficiently increased, resulting in a problem of remarkably low productivity. Furthermore, the polymerization activity is low, so that the amount of catalyst residue contained in the copolymer at the end of the polymerization is large, and there are many cases where the required performance of the product is not satisfied. Therefore, a deashing process is required to remove it, which is extremely disadvantageous in terms of production costs.

On the other hand, ethylene/α-olefin/non-conjugated polyene copolymerization using a polymerization catalyst containing a bridged metallocene compound having a biscyclopentadienyl group or a bisindenyl group as a ligand is disclosed [JP-A-2005-344101. , JP-A-9-151205, JP-A-2000-507635]. Although the obtained ethylene/α-olefin/non-conjugated polyene copolymer has a higher molecular weight than the Ziegler-Natta catalyst system described above, the molecular weight is still insufficient for carrying out high-temperature polymerization. rice field. Generally, in high-temperature solution polymerization, the viscosity of the polymerization solution is lowered, so that the concentration of the olefin copolymer in the polymerization vessel can be kept high, and the productivity per polymerization vessel is improved. On the other hand, however, it is well known to those skilled in the art that the molecular weight of the resulting olefin copolymer decreases as the polymerization temperature increases. Therefore, in order to produce a desired high-molecular-weight olefin copolymer even in high-productivity high-temperature polymerization, a catalyst capable of producing a high-molecular-weight olefin copolymer is required.

In general, EPDM and other ethylene/α-olefin/non-conjugated polyene copolymer rubber products are subject to restrictions on the content of residual polymerization solvent and unreacted olefin monomers due to performance requirements for use. . In production facilities, these impurities are generally removed by performing operations such as heating and pressure reduction in the post-polymerization process. For example, in the production of EPDM, a large load is required to remove unreacted non-conjugated polyene with a high boiling point. A smaller number leads to an improvement in productivity. That is, in the case of continuously producing a certain amount of EPDM in a certain period of time, the smaller the amount of the unreacted non-conjugated polyene, the less the load of the heating and pressure reduction operations, and the lower the production cost. . Conversely, when the load of heating and depressurization operations is kept constant, there is an effect that the smaller the amount of the unreacted non-conjugated polyene, the more the production amount of the production facility per certain time period.

As a method for reducing the amount of unreacted non-conjugated polyene in the polymerization solution for the purpose of obtaining such advantages, there is a method of using a polymerization catalyst having high performance for copolymerizing non-conjugated polyene. By using such a polymerization catalyst, it is possible to reduce the amount of non-conjugated polyene to be added when producing an EPDM having a desired non-conjugated polyene content, resulting in residual unreacted non-conjugated polyene. An effect is obtained that the amount of polyene is also reduced.

As mentioned above, high-molecular-weight ethylene/α-olefin/non-conjugated polyene copolymers are produced to achieve high productivity through high-temperature polymerization, and non-conjugated polyenes are used to improve productivity by reducing the load in the post-polymerization process. A polymerization catalyst with high polyene copolymerization performance is desired. Industrially, in particular, there is a demand for a polymerization catalyst that achieves a good balance between these performances and high polymerization activity that does not require a deashing treatment process at a high level.

The present applicant has disclosed in Patent Document 1 (WO2009/081792) and Patent Document 2 (WO2009/081794) the production of ethylene/α-olefins/nonpolymers using catalysts containing specific bridged cyclopentadienyl-fluorenyl metallocene compounds. A method for producing a conjugated polyene copolymer is proposed. According to the production method of Patent Document 1, an ethylene/α-olefin/non-conjugated polyene copolymer having a high molecular weight can be produced with good polymerization activity, and according to the production method of Patent Document 2, good It is possible to produce an ethylene/α-olefin/non-conjugated polyene copolymer with a high polymerization activity and a high molecular weight, and the polymerization temperature can be set higher.

However, conventional methods for producing ethylene/α-olefin/non-conjugated polyene copolymers, such as the production methods disclosed in Patent Documents 1 and 2, have sufficient There is room for further improvement in producing copolymers with conjugated polyene content.

International publication WO2009/081794 International publication WO2009/081792

By the production methods disclosed in Patent Documents 1 and 2, the molecular weight of the above-mentioned ethylene/α-olefin/non-conjugated polyene copolymer generated during high-temperature polymerization is increased, and ethylene/α-olefin/non-conjugated polyene copolymer is produced with high polymerization activity. Although it was possible to simultaneously produce a non-conjugated polyene copolymer at a high level, even under polymerization conditions where the amount of non-conjugated polyene added was less, a copolymer with a sufficient non-conjugated polyene content was produced. Technology is in demand.

That is, the problem to be solved by the present invention is to increase the molecular weight of the copolymer generated during high-temperature polymerization, and to produce a copolymer with high polymerization activity at a high level at the same time, while at the same time To provide a method for producing an ethylene/α-olefin/non-conjugated polyene copolymer having a sufficient content of non-conjugated polyene even under polymerization conditions where the amount of added is less.

The present invention for solving the above problems is a method for producing an ethylene/α-olefin/non-conjugated polyene copolymer using an olefin polymerization catalyst containing a crosslinked metallocene compound having a specific structure. The gist of the present invention is as follows.

[1]
(A) a bridged metallocene compound represented by the following general formula [I] and (B) (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound and (B-3) a bridged metallocene compound (A) Characterized by copolymerizing ethylene, an α-olefin having 3 or more carbon atoms, and a non-conjugated polyene in the presence of a polymerization catalyst containing at least one compound selected from compounds that form an ion pair by reacting with and

式中、Ｙは、炭素原子、ケイ素原子、ゲルマニウム原子またはスズ原子であり、
Ｍは、チタン原子、ジルコニウム原子またはハフニウム原子であり、
Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷およびＲ⁸は、水素原子、炭素数１から２０の炭化水素基、アリール基、置換アリール基、ケイ素含有基、窒素含有基、酸素含有基、ハロゲン原子およびハロゲン含有基から選ばれる原子または置換基であり、それぞれ同一でも異なっていてもよく、
Ｒ¹からＲ⁶までの隣接した置換基は互いに結合して環を形成していてもよく、
ＡおよびＢは、硫黄原子、酸素原子またはＣＲ⁹であり、Ｒ⁹は、水素原子、炭素数１から２０の炭化水素基、アリール基、置換アリール基、ケイ素含有基、窒素含有基、酸素含有基、ハロゲン原子およびハロゲン含有基から選ばれる原子または置換基であり、Ａが硫黄原子または酸素原子である場合、ＢはＣＲ⁹であり、Ｂが硫黄原子または酸素原子である場合、ＡはＣＲ⁹であり、ＡおよびＢを含む環は可能な位置で二重結合を有し、
Ｑはハロゲン原子、炭素数１から２０の炭化水素基、アニオン配位子および孤立電子対で配位可能な中性配位子から同一のまたは異なる組合せで選ばれ、
ｎは１から４の整数であり、
ｊは１から４の整数である。

wherein Y is a carbon atom, a silicon atom, a germanium atom or a tin atom;
M is a titanium atom, a zirconium atom or a hafnium atom,
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are hydrogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, aryl groups, substituted aryl groups, silicon-containing groups, nitrogen an atom or substituent selected from a containing group, an oxygen-containing group, a halogen atom and a halogen-containing group, each of which may be the same or different;
Adjacent substituents of R ¹ to R ⁶ may be bonded together to form a ring,
A and B are a sulfur atom, an oxygen atom or ^CR9 , and R9 is a hydrogen atom, a hydrocarbon group having ¹ to 20 carbon atoms, an aryl group, a substituted aryl group, a silicon-containing group, a nitrogen-containing group, an oxygen-containing is an atom or substituent selected from a group, a halogen atom and a halogen-containing group, and when A is a sulfur atom or an oxygen atom, B is ^CR9 , and when B is a sulfur atom or an oxygen atom, A is CR ⁹ and the ring containing A and B has a double bond at any possible position;
Q is selected from a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an anionic ligand and a neutral ligand capable of coordinating with a lone electron pair in the same or different combination;
n is an integer from 1 to 4;
j is an integer from 1 to 4;

[2]
The method for producing an ethylene/α-olefin/non-conjugated polyene copolymer according to item [1], wherein n in the general formula [I] is 1.

[3]
The ethylene / α-olefin / non-conjugated polyene copolymer according to item [1] or [2], wherein A or B in the formula [I] is a sulfur atom and the other is CH. Production method.

[4]
Production of the ethylene/α-olefin/non-conjugated polyene copolymer according to item [3], wherein R ¹ , R ² , R ³ and R ⁴ in the formula [I] are all hydrogen atoms. Method.

[5]
The method for producing an ethylene/α-olefin/non-conjugated polyene copolymer according to item [4], wherein Y in the formula [I] is a carbon atom or a silicon atom.

[6]
The ethylene/α-olefin/non-conjugated polyene copolymer according to item [5], wherein R ⁵ and R ⁶ in the general formula [I] are groups selected from aryl groups and substituted aryl groups. Combined manufacturing method.

[7]
R ⁵ and R ⁶ in the above formula [I] are substituted aryl groups in which at least one hydrogen atom of the aryl group is substituted with an electron-donating substituent having a Hammett rule substituent constant σ of −0.2 or less. and in the case of having a plurality of said electron donating substituents, each of said electron donating substituents may be the same or different, and a hydrocarbon group having 1 to 20 carbon atoms other than said electron donating substituents , a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom, and a halogen-containing group. The method for producing an ethylene/α-olefin/non-conjugated polyene copolymer according to item [6], wherein the ethylene/α-olefin/non-conjugated polyene copolymer is an optionally substituted aryl group.

[8]
The ethylene/α ^{- olefin} / A method for producing a non-conjugated polyene copolymer.

[9]
The ethylene/α-olefin/non-conjugated polyene copolymer according to any one of items [1] to [8], wherein M in the formula [I] is a zirconium atom or a hafnium atom. Production method.

[10]
The ethylene/α-olefin/non-conjugated polyene copolymer according to any one of items [1] to [9], wherein the α-olefin is an α-olefin having 3 to 10 carbon atoms. manufacturing method.

[11]
The method for producing an ethylene/α-olefin/non-conjugated polyene copolymer according to any one of items [1] to [10], wherein the α-olefin is propylene.

[12]
The ethylene/α-olefin/non-conjugated polyene copolymer according to any one of items [1] to [11], wherein the non-conjugated polyene is represented by the following general formula [IV]. manufacturing method.

式中、ｎは０から２の整数であり、
Ｒ¹⁰、Ｒ¹¹、Ｒ¹²およびＲ¹³は水素原子、炭素数１から２０の炭化水素基、ケイ素含有基、窒素含有基、酸素含有基、ハロゲン原子およびハロゲン含有基から選ばれる原子または置換基であり、それぞれ同一でも異なっていてもよく、該炭化水素基は二重結合を有していてもよく、
Ｒ¹⁰からＲ¹³までの任意の二つの置換基は互いに結合して環を形成していてもよく、該環は二重結合を含んでいてもよく、Ｒ¹⁰とＲ¹¹とで、またはＲ¹²とＲ¹³とでアルキリデン基を形成していてもよく、Ｒ¹⁰とＲ¹²とが、またはＲ¹¹とＲ¹³とが互いに結合して二重結合を形成していてもよく、
以下の（i）から（iv）の要件の少なくとも一つが満たされる。
（i）Ｒ¹⁰からＲ¹³の少なくとも一つは、二重結合を一つ以上有する炭化水素基である。
（ii）Ｒ¹⁰からＲ¹³までの任意の二つの置換基が互いに結合して環を形成し、該環が二重合を含んでいる。
（iii）Ｒ¹⁰とＲ¹¹とで、またはＲ¹²とＲ¹³とでアルキリデン基を形成している。
（iv）Ｒ¹⁰とＲ¹²とが、またはＲ¹¹とＲ¹³とが互いに結合して二重結合を形成している。

wherein n is an integer from 0 to 2;
R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are atoms or substituents selected from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom and a halogen-containing group; , which may be the same or different, and the hydrocarbon group may have a double bond,
Any two substituents of R ¹⁰ to R ¹³ may be bonded together to form a ring, and the ring may contain a double bond, and R ¹⁰ and R ¹¹ or R ¹² and R ¹³ may form an alkylidene group, R ¹⁰ and R ¹² or R ¹¹ and R ¹³ may bind to each other to form a double bond,
At least one of the following requirements (i) through (iv) is met.
⁽ i) ^At least one of R10 to R13 is a hydrocarbon group having one or more double bonds.
⁽ ii) Any two substituents from R10 to ^R13 are joined together to form a ring, and the ring contains a dimerization.
(iii) R ¹⁰ and R ¹¹ or R ¹² and R ¹³ form an alkylidene group.
(iv) R ¹⁰ and R ¹² or R ¹¹ and R ¹³ are bonded to each other to form a double bond;

[13]
[12], wherein the non-conjugated polyene is 5-ethylidene-2-norbornene (ENB) or 5-vinyl-2-norbornene (VNB); A method for producing an ethylene/α-olefin/non-conjugated polyene copolymer.

[14]
The method for producing an ethylene/α-olefin/non-conjugated polyene copolymer according to any one of items [1] to [13], wherein the polymerization temperature is 80° C. or higher.

According to the present invention, the following effects (1) to (3) are obtained by a method of copolymerizing ethylene, an α-olefin and a non-conjugated polyene in the presence of an olefin polymerization catalyst containing a crosslinked metallocene compound having a specific structure. At the same time, it is possible to achieve a high level of balance in the production of ethylene/α-olefin/non-conjugated polyene copolymers with high productivity and low cost, which have excellent performance as processing materials. The contribution to the

Effect (1): It becomes possible to produce a high-molecular-weight ethylene/α-olefin/non-conjugated polyene copolymer. As a result, the molecular weight of the ethylene/α-olefin/non-conjugated polyene copolymer produced can be maintained at a desired high value even in high-temperature polymerization, so high-temperature polymerization can be carried out. Especially in high-temperature solution polymerization, the viscosity of the polymerization solution containing the produced copolymer decreases, so that the concentration of the copolymer in the polymerization vessel can be increased compared to the case of low-temperature polymerization. productivity is greatly improved. Furthermore, by carrying out high-temperature polymerization, the heat removal cost of the polymerization vessel is greatly reduced.

Effect (2): It becomes possible to produce an ethylene/α-olefin/non-conjugated polyene copolymer with high non-conjugated polyene copolymerization performance. This makes it possible to reduce the amount of non-conjugated polyene to be added when producing an olefin copolymer having a desired non-conjugated polyene content, resulting in residual unreacted non-conjugated polyene in the polymerization solution. Since the amount is reduced, there is an advantage that the load when removing this in the post-polymerization process is reduced, leading to an improvement in productivity.

Effect (3): It becomes possible to produce an ethylene/α-olefin/non-conjugated polyene copolymer with high polymerization activity. This not only reduces the catalyst cost, but also reduces the catalyst residue in the ethylene/α-olefin/non-conjugated polyene copolymer, making the deashing process unnecessary and reducing the production cost. You get the advantage of

The present invention will be described in further detail.
The method for producing an ethylene/α-olefin/non-conjugated polyene copolymer of the present invention comprises an olefin polymerization catalyst containing the bridged metallocene compound (A) represented by the general formula [I] and the compound (B) described above. It is characterized by copolymerizing ethylene, an α-olefin having 3 or more carbon atoms, and a non-conjugated polyene in the presence.

<Bridged metallocene compound (A)>
The bridged metallocene compound (A) is represented by the above general formula [I]. Y, M, R ¹ to R ⁸ , A, B, Q, n and j in formula [I] are explained below.

(Y, M, R ¹ -R ⁸ , A, B, Q, n and j)
Y is selected from carbon atom, silicon atom, germanium atom and tin atom, preferably carbon atom or silicon atom, more preferably carbon atom.
M is a titanium atom, a zirconium atom or a hafnium atom, preferably a zirconium atom or a hafnium atom, more preferably a zirconium atom.
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are hydrogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, aryl groups, substituted aryl groups, silicon-containing groups, nitrogen Atoms or substituents selected from containing groups, oxygen-containing groups, halogen atoms and halogen-containing groups, which may be the same or different. Adjacent substituents of R ¹ to R ⁶ may or may not be bonded to each other to form a ring.

A and B are a sulfur atom, an oxygen atom or ^CR9 , and R9 is a hydrogen atom, a hydrocarbon group having ¹ to 20 carbon atoms, an aryl group, a substituted aryl group, a silicon-containing group, a nitrogen-containing group, an oxygen-containing is an atom or substituent selected from a group, a halogen atom and a halogen-containing group, and when A is a sulfur atom or an oxygen atom, B is ^CR9 , and when B is a sulfur atom or an oxygen atom, A is CR ⁹ , and a preferred embodiment includes an embodiment in which A or B is a sulfur atom and the other is CH. Note that the ring containing A and B has double bonds at possible positions.

Here, the hydrocarbon group having 1 to 20 carbon atoms includes an alkyl group having 1 to 20 carbon atoms, a saturated cyclic hydrocarbon group having 3 to 20 carbon atoms, a chain unsaturated hydrocarbon group having 2 to 20 carbon atoms, A cyclic unsaturated hydrocarbon group having 3 to 20 carbon atoms is exemplified. Further, when adjacent substituents of R ¹ to R ⁶ are bonded to each other to form a ring, examples include an alkylene group having 1 to 20 carbon atoms and an arylene group having 6 to 20 carbon atoms.

Examples of alkyl groups having 1 to 20 carbon atoms include linear saturated hydrocarbon groups such as methyl group, ethyl group, n-propyl group, allyl group, n-butyl group, n-pentyl group and n-hexyl. Branched saturated hydrocarbon groups such as isopropyl group, isobutyl group, s-butyl group, t-butyl group, t-amyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decanyl group group, neopentyl group, 3-methylpentyl group, 1,1-diethylpropyl group, 1,1-dimethylbutyl group, 1-methyl-1-propylbutyl group, 1,1-dipropylbutyl group, 1,1- Examples include dimethyl-2-methylpropyl group, 1-methyl-1-isopropyl-2-methylpropyl group, cyclopropylmethyl group and the like. The number of carbon atoms in the alkyl group is preferably 1-6.

Examples of saturated cyclic hydrocarbon groups having 3 to 20 carbon atoms include cyclic saturated hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornenyl, 1-adamantyl, 3-methylcyclopentyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, 4-methylcyclohexyl group, which is a group in which a hydrogen atom of a cyclic saturated hydrocarbon group is replaced with a hydrocarbon group having 1 to 17 carbon atoms, such as 2-adamantyl group -cyclohexylcyclohexyl group, 4-phenylcyclohexyl group and the like are exemplified. The cyclic saturated hydrocarbon group preferably has 5 to 11 carbon atoms.

Examples of chain unsaturated hydrocarbon groups having 2 to 20 carbon atoms include alkenyl groups such as ethenyl group (vinyl group), 1-propenyl group, 2-propenyl group (allyl group), and 1-methylethenyl group (isopropenyl group). and the like, which are alkynyl groups such as ethynyl group, 1-propynyl group, and 2-propynyl group (propargyl group). The chain unsaturated hydrocarbon group preferably has 2 to 4 carbon atoms.

Examples of cyclic unsaturated hydrocarbon groups having 3 to 20 carbon atoms include cyclic unsaturated hydrocarbon groups such as cyclopentadienyl group, norbornyl group, phenyl group, naphthyl group, indenyl group, azulenyl group, phenanthryl group and anthracenyl group. , 3-methylphenyl group (m-tolyl group), 4-methylphenyl group (p-tolyl group), which are groups in which hydrogen atoms of cyclic unsaturated hydrocarbon groups are replaced with hydrocarbon groups having 1 to 15 carbon atoms , 4-ethylphenyl group, 4-t-butylphenyl group, 4-cyclohexylphenyl group, biphenylyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,4,6-trimethylphenyl group ( a benzyl group, which is a group in which hydrogen atoms of a linear hydrocarbon group or branched saturated hydrocarbon group are replaced with a cyclic saturated hydrocarbon group or a cyclic unsaturated hydrocarbon group having 3 to 19 carbon atoms, such as a mesityl group; A cumyl group and the like are exemplified. The number of carbon atoms in the cyclic unsaturated hydrocarbon group is preferably 6-10.

Examples of the alkylene group having 1 to 20 carbon atoms include methylene group, ethylene group, dimethylmethylene group (isopropylidene group), ethylmethylene group, 1-methylethylene group, 2-methylethylene group, 1,1-dimethylethylene group, Examples include 1,2-dimethylethylene group and n-propylene group. The alkylene group preferably has 1 to 6 carbon atoms.

Examples of arylene groups having 6 to 20 carbon atoms include o-phenylene group, m-phenylene group, p-phenylene group and 4,4'-biphenylylene group. The arylene group preferably has 6 to 12 carbon atoms.

As the aryl group, although it partially overlaps with the examples of the cyclic unsaturated hydrocarbon group having 3 to 20 carbon atoms described above, phenyl group, 1-naphthyl group and 2-naphthyl group, which are substituents derived from aromatic compounds. group, anthracenyl group, phenanthrenyl group, tetracenyl group, chrysenyl group, pyrenyl group, indenyl group, azulenyl group, pyrrolyl group, pyridyl group, furanyl group, thiophenyl group and the like. As the aryl group, a phenyl group or a 2-naphthyl group is preferred.

Examples of the aromatic compounds include aromatic hydrocarbons and heterocyclic aromatic compounds such as benzene, naphthalene, anthracene, phenanthrene, tetracene, chrysene, pyrene, pyrene, indene, azulene, pyrrole, pyridine, furan, and thiophene. be done.

The substituted aryl group partially overlaps with the examples of the cyclic unsaturated hydrocarbon group having 3 to 20 carbon atoms described above, but one or more hydrogen atoms of the aryl group is a hydrocarbon group having 1 to 20 carbon atoms, A group substituted with a substituent selected from an aryl group, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom and a halogen-containing group, specifically a 3-methylphenyl group (m-tolyl group ), 4-methylphenyl group (p-tolyl group), 3-ethylphenyl group, 4-ethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, biphenylyl group, 4-(trimethylsilyl) Phenyl group, 4-aminophenyl group, 4-(dimethylamino)phenyl group, 4-(diethylamino)phenyl group, 4-morpholinylphenyl group, 4-methoxyphenyl group, 4-ethoxyphenyl group, 4-phenoxyphenyl group 3,4-dimethoxyphenyl group, 3,5-dimethoxyphenyl group, 3-methyl-4-methoxyphenyl group, 3,5-dimethyl-4-methoxyphenyl group, 3-(trifluoromethyl)phenyl group, Examples include 4-(trifluoromethyl)phenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 5-methylnaphthyl group, 2-(6-methyl)pyridyl group, etc. be done. Substituted aryl groups also include "electron-donating group-containing substituted aryl groups" described later.

Examples of the silicon-containing group include alkyl groups such as a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, and a triisopropylsilyl group, which are hydrocarbon groups having 1 to 20 carbon atoms in which the carbon atoms are replaced with silicon atoms. Examples include a silyl group, a dimethylphenylsilyl group, a methyldiphenylsilyl group, an arylsilyl group such as a t-butyldiphenylsilyl group, a pentamethyldisilanyl group, and a trimethylsilylmethyl group. The alkylsilyl group preferably has 1 to 10 carbon atoms, and the arylsilyl group preferably has 6 to 18 carbon atoms.

The nitrogen-containing group includes an amino group, a nitro group, an N-morpholinyl group, a hydrocarbon group having 1 to 20 carbon atoms or a silicon-containing group described above in which the =CH- structural unit is replaced with a nitrogen atom, - A group in which the CH ₂ - structural unit is replaced with a nitrogen atom to which a hydrocarbon group having 1 to 20 carbon atoms is bonded, or a nitrogen atom or a nitrile group in which a -CH ₃ structural unit is bonded to a hydrocarbon group having 1 to 20 carbon atoms A dimethylamino group, a diethylamino group, a dimethylaminomethyl group, a cyano group, a pyrrolidinyl group, a piperidinyl group, a pyridinyl group, etc., which are groups substituted with are exemplified. As the nitrogen-containing group, a dimethylamino group and an N-morpholinyl group are preferred.

The oxygen-containing group includes a hydroxyl group, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, or a nitrogen-containing group in which the -CH ₂ - structural unit is replaced with an oxygen atom or a carbonyl group, or - Methoxy group, ethoxy group, t-butoxy group, phenoxy group, trimethylsiloxy group, methoxyethoxy group, hydroxymethyl group in which the _CH3 structural unit is a group substituted with an oxygen atom to which a hydrocarbon group having 1 to 20 carbon atoms is attached group, methoxymethyl group, ethoxymethyl group, t-butoxymethyl group, 1-hydroxyethyl group, 1-methoxyethyl group, 1-ethoxyethyl group, 2-hydroxyethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, n-2-oxabutylene group, n-2-oxapentylene group, n-3-oxapentylene group, aldehyde group, acetyl group, propionyl group, benzoyl group, trimethylsilylcarbonyl group, carbamoyl group, methylaminocarbonyl group, carboxy group, methoxycarbonyl group, carboxymethyl group, ethocarboxymethyl group, carbamoylmethyl group, furanyl group, pyranyl group and the like. A methoxy group is preferred as the oxygen-containing group.

Examples of halogen atoms include Group 17 elements such as fluorine, chlorine, bromine, and iodine.
The halogen-containing group includes a trifluoromethyl group and a tribromo group, which are groups in which hydrogen atoms are substituted by halogen atoms in the above-mentioned hydrocarbon group, silicon-containing group, nitrogen-containing group or oxygen-containing group having 1 to 20 carbon atoms. Examples include a methyl group, a pentafluoroethyl group, a pentafluorophenyl group, and the like.

Q is selected from halogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, anionic ligands and neutral ligands capable of coordinating with lone electron pairs in the same or different combinations.
The details of the halogen atom and the hydrocarbon group having 1 to 20 carbon atoms are as described above. A chlorine atom is preferred when Q is a halogen atom. When Q is a hydrocarbon group having 1 to 20 carbon atoms, the hydrocarbon group preferably has 1 to 7 carbon atoms.

Examples of anionic ligands include alkoxy groups such as methoxy group, t-butoxy group and phenoxy group, carboxylate groups such as acetate and benzoate, and sulfonate groups such as mesylate and tosylate.

Neutral ligands that can be coordinated with a lone pair include organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, and diphenylmethylphosphine; Ether compounds and the like can be exemplified.
n is an integer from 1 to 4;
j is an integer from 1 to 4, preferably 2;
In addition, the above exemplification regarding the formula [I] is similarly applied to the following description of the present invention.

In the bridged metallocene compound (A) represented by the general formula [I], n is preferably 1. Such a bridged metallocene compound (A-1) is represented by the following general formula [V].

式［V］において、Ｙ、Ｍ、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ａ、Ｂ、Ｑおよびｊの定義等は上述のとおりである。

In formula [V], the definitions of Y, M, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , A, B, Q and j are as described above. .

The bridged metallocene compound (A-1) has a simpler production process and a lower production cost than the compound in which n is an integer of 2 to 4 in the above general formula [I], and thus the bridged metallocene compound can be produced. The advantage of using it is that the production cost of the ethylene/α-olefin/non-conjugated polyene copolymer is reduced. Furthermore, when ethylene, an α-olefin having 3 or more carbon atoms, and a non-conjugated polyene are copolymerized in the presence of an olefin polymerization catalyst containing the crosslinked metallocene compound (A-1), the resulting ethylene/α-olefin/ An advantage of increasing the molecular weight of the non-conjugated polyene copolymer is also obtained.

In the bridged metallocene compound (A-1) represented by the general formula [I], R ¹ , R ² , R ³ and R ⁴ are all preferably hydrogen atoms. Such a bridged metallocene compound (A-2) is represented by the following general formula [VI].

式［VI］において、Ｙ、Ｍ、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ａ、Ｂ、Ｑおよびｊの定義等は上述のとおりである。

In formula [VI], the definitions of Y, M, R ⁵ , R ⁶ , R ⁷ , R ⁸ , A, B, Q and j are as described above.

In the bridged metallocene compound (A-2), compared to a compound in which one or more of R ¹ , R ² , R ³ and R ⁴ in the general formula [V] is substituted with a substituent other than a hydrogen atom, The production process is simplified, the production cost is reduced, and the use of this crosslinked metallocene compound provides the advantage of reducing the production cost of the ethylene/α-olefin/non-conjugated polyene copolymer. Furthermore, when ethylene, an α-olefin having 3 or more carbon atoms, and a non-conjugated polyene are copolymerized in the presence of an olefin polymerization catalyst containing the crosslinked metallocene compound (A-2), the polymerization activity is improved and the ethylene produced The advantage of increasing the molecular weight of the /α-olefin/non-conjugated polyene copolymer is also obtained. At the same time, the advantage of improved copolymerization performance of non-conjugated polyenes is obtained.

In the bridged metallocene compound (A-2) represented by the general formula [VI], Y is more preferably a carbon atom. Such a bridged metallocene compound (A-3) is represented by the following general formula [VII].

式［VII］において、Ｍ、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ａ、Ｂ、Ｑおよびｊの定義等は上述のとおりである。

In formula [VII], the definitions of M, R ⁵ , R ⁶ , R ⁷ , R ⁸ , A, B, Q and j are as described above.

In the bridged metallocene compound (A-3) represented by the general formula [VII], A is more preferably a sulfur atom and B is CH. Such a bridged metallocene compound (A-4) is represented by the following general formula [VIII].

式［VIII］において、Ｍ、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｑおよびｊの定義等は上述のとおりである。

In formula [VIII], definitions of M, R ⁵ , R ⁶ , R ⁷ , R ⁸ , Q and j are as described above.

The crosslinked metallocene compound (A-4) has an established production method for the dithiophene moiety compared to the compound represented by the general formula [VII]. The advantage of using a metallocene compound is that the production cost of the ethylene/α-olefin/non-conjugated polyene copolymer is reduced. Furthermore, when ethylene, an α-olefin having 3 or more carbon atoms, and a non-conjugated polyene are copolymerized in the presence of an olefin polymerization catalyst containing the crosslinked metallocene compound (A-4), the compound is thermally stable. Therefore, the advantage of improved polymerization activity at high temperatures can also be obtained. At the same time, the advantage of improved copolymerization performance of non-conjugated polyenes is obtained.

The bridged metallocene compound (A-4) can be synthesized by a simple method such as the following formula [IX].

式［IX］において、Ｍ、Ｒ⁵、Ｒ⁶、Ｒ⁷およびＲ⁸の定義等は上述のとおりである。

In formula [IX], definitions of M, R ⁵ , R ⁶ , R ⁷ and R ⁸ are as described above.

In the above formula [IX], R ⁵ and R ⁶ are a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an aryl group, a substituted aryl group, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom and a halogen-containing are atoms or substituents selected from groups, which may be the same or different, and are substituents which may be combined to form a ring, and which have the general formula R ⁵ —C(═O)—R Since various ketones represented by ⁶ satisfying such conditions are commercially available from general reagent manufacturers, it is easy to obtain raw materials for the bridged metallocene compound (A-4). Moreover, even if such a ketone is not commercially available, it can be easily synthesized by, for example, the method of Olah et al. [Heterocycles, 40, 79 (1995)]. Thus, the bridged metallocene compound (A-4) has a simpler and easier production process than a compound in which Y in the general formula [V] is selected from silicon, germanium and tin atoms, and the production cost is low. Furthermore, the use of this crosslinked metallocene compound has the advantage of reducing the production cost of the ethylene/α-olefin/non-conjugated polyene copolymer. Furthermore, when ethylene, an α-olefin having 3 or more carbon atoms, and a non-conjugated polyene are copolymerized in the presence of an olefin polymerization catalyst containing the crosslinked metallocene compound (A-4), the resulting ethylene/α-olefin/ An advantage of further increasing the molecular weight of the non-conjugated polyene copolymer is also obtained.

In the bridged metallocene compound (A-4) represented by the general formula [VIII], R ⁵ and R ⁶ are preferably groups selected from aryl groups and substituted aryl groups. When ethylene, an α-olefin having 3 or more carbon atoms, and a non-conjugated polyene are copolymerized in the presence of an olefin polymerization catalyst containing the crosslinked metallocene compound, the polymerization activity is further improved and the resulting ethylene/α-olefin/non-conjugated polyene The advantage of further increasing the molecular weight of the conjugated polyene copolymer is obtained. At the same time, the advantage of improved copolymerization performance of non-conjugated polyenes is obtained.

In the bridged metallocene compound (A-4) represented by the general formula [VIII], R ⁵ and R ⁶ are more preferably the same group selected from aryl groups and substituted aryl groups. This selection of R ⁵ and R ⁶ simplifies the process for synthesizing the bridged metallocene compound, further reduces the production cost, and thus the use of the bridged metallocene compound results in an ethylene/α-olefin/unconjugated The advantage is that the production costs of the polyene copolymer are reduced.

In the bridged metallocene compound (A-4) represented by general formula [VIII], R ⁵ and R ⁶ are more preferably the same substituted aryl group. When ethylene, an α-olefin having 3 or more carbon atoms, and a non-conjugated polyene are copolymerized in the presence of an olefin polymerization catalyst containing the crosslinked metallocene compound, the resulting ethylene/α-olefin/non-conjugated polyene copolymer An advantage of higher molecular weight is obtained.

In the bridged metallocene compound (A-4) represented by the above general formula [VIII], R ⁵ and R ⁶ are electrons with a Hammett rule substituent constant σ of −0.2 or less for one or more hydrogen atoms of the aryl group. A substituted aryl group substituted with an electron-donating substituent, and when it has a plurality of electron-donating substituents, each of the electron-donating substituents may be the same or different, and the electron-donating In addition to the substituent, it may have a substituent selected from a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom and a halogen-containing group. When there are a plurality of substituents, each substituent is preferably a substituted aryl group (hereinafter also referred to as an "electron-donating group-containing substituted aryl group") which may be the same or different. When ethylene, an α-olefin having 3 or more carbon atoms, and a non-conjugated polyene are copolymerized in the presence of an olefin polymerization catalyst containing the crosslinked metallocene compound, the resulting ethylene/α-olefin/non-conjugated polyene copolymer An advantage of higher molecular weight is obtained.

An electron-donating group having a Hammett's rule substituent constant σ of −0.2 or less is defined and exemplified below. Hammett's rule is an empirical rule proposed by L. P. Hammett in 1935 to quantitatively discuss the effects of substituents on reactions or equilibria of benzene derivatives, and is widely accepted today. Substituent constants determined by Hammett's rule include σp when substituted at the para-position of the benzene ring and σm when substituted at the meta-position, and these values can be found in many general literatures. For example, the article by Hansch and Taft [Chem. Rev., 91, 165 (1991)] gives a detailed description of a very wide variety of substituents. However, the values of σp and σm described in these documents may be slightly different depending on the documents even if the substituents are the same. In the present invention, in order to avoid confusion caused by this situation, insofar as the substituents listed, Table 1 of Hansch and Taft [Chem. Rev., 91, 165 (1991)] (168-175) page) are defined as the substituent constants σp and σm of Hammett's rule. In the present invention, the electron-donating group having a substituent constant σ of Hammett's rule of −0.2 or less means that, when the electron-donating group is substituted at the para-position (4-position) of the phenyl group, σp is −0.2 or less. It is an electron-donating group, and when substituted at the meta-position (3-position) of a phenyl group, it is an electron-donating group with σm of -0.2 or less. In addition, when the electron-donating group is substituted at the ortho position (2-position) of the phenyl group, or substituted at any position of the aryl group other than the phenyl group, electrons with σp of −0.2 or less It is a donating group.

Electron-donating substituents with a substituent constant σp or σm of Hammett's rule of -0.2 or less include p-amino group (4-amino group), p-dimethylamino group (4-dimethylamino group), and p-diethylamino group. (4-diethylamino group), nitrogen-containing groups such as m-diethylamino group (3-diethylamino group), oxygen-containing groups such as p-methoxy group (4-methoxy group), p-ethoxy group (4-ethoxy group), Examples include tertiary hydrocarbon groups such as p-t-butyl group (4-t-butyl group) and silicon-containing groups such as p-trimethylsiloxy group (4-trimethylsiloxy group). The electron-donating substituents having a substituent constant σp or σm of Hammett's rule defined in the present invention of −0.2 or less are listed in Table 1 of Hansch and Taft [Chem. Rev., 91, 165 (1991)]. (pages 168-175). Even if the substituent is not described in the document, the substituent constant σ or σ when measured based on Hammett's rule will be in the range, the substituent of Hammett's rule defined in the present invention It is included in electron-donating groups with a constant σp or σm of -0.2 or less. Examples of such substituents include p-N-morpholinyl group (4-N-morpholinyl group), m-N-morpholinyl group (3-N-morpholinyl group) and the like.

In the electron-donating group-containing substituted aryl group, when the electron-donating substituents are substituted by a plurality of electron-donating substituents, the respective electron-donating substituents may be the same or different, and in addition to the electron-donating substituents, 1 to 20 substituents selected from a hydrocarbon group, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom and a halogen-containing group may be substituted, and when a plurality of such substituents are substituted Each substituent may be the same or different, but the electron-donating substituent contained in one substituted aryl group and the sum of the Hammett's rule substituent constant σ of each of the substituents is -0.15 or less. is preferred. Examples of such substituted aryl groups include m,p-dimethoxyphenyl group (3,4-dimethoxyphenyl group), p-(dimethylamino)-m-methoxyphenyl group (4-(dimethylamino)-3-methoxyphenyl group), p-(dimethylamino)-m-methylphenyl group (4-(dimethylamino)-3-methylphenyl group), p-methoxy-m-methylphenyl group (4-methoxy-3-methylphenyl group) , p-methoxy-m,m-dimethylphenyl group (4-methoxy-3,5-dimethylphenyl group) and the like.

The hydrocarbon group having 1 to 20 carbon atoms, the silicon-containing group, the nitrogen-containing group, the oxygen-containing group, the halogen atom and the halogen-containing group which the electron-donating group-containing substituted aryl group may have include the above-described atoms Alternatively, specific examples of substituents can be given.

As a result of intensive studies on various bridged metallocene compounds, the present applicant found that in the bridged metallocene compound (A- ⁴ ) represented by the above general formula [VIII], R ⁵ and R When an electron-donating group-containing substituted aryl group substituted with one or more electron-donating substituents having σ of −0.2 or less is used, ethylene and It was found for the first time that the molecular weight of the resulting ethylene/α-olefin/non-conjugated polyene copolymer is further increased when an α-olefin having 3 or more carbon atoms and a non-conjugated polyene are copolymerized.

In the coordination polymerization of olefins using an organometallic complex catalyst such as the crosslinked metallocene compound (A-4) of the present invention, the molecular chains of the olefin polymer produced by repeated polymerization of olefins on the central metal of the catalyst are It is known to grow (propagation reaction) and increase the molecular weight of the olefin polymer. On the other hand, in a reaction called chain transfer, the molecular chain of the olefin polymer dissociates from the central metal of the catalyst, thereby stopping the growth reaction of the molecular chain and thus stopping the increase in the molecular weight of the olefin polymer. Are known. Thus, the molecular weight of an olefin polymer is characterized by the ratio between the propagation reaction frequency and the chain transfer reaction frequency, which is inherent in the organometallic complex catalyst that produces it. That is, the higher the ratio between the frequency of propagation reaction and the frequency of chain transfer reaction, the higher the molecular weight of the olefin polymer produced, and conversely, the smaller the ratio, the lower the molecular weight. Here, the frequency of each reaction can be estimated from the activation energy of each reaction. Reactions with low activation energy are regarded as having high frequency, while reactions with high activation energy are regarded as having low frequency. It is considered possible to Generally, it is known that the frequency of propagation reaction in olefin polymerization is sufficiently higher than the frequency of chain transfer reaction, that is, the activation energy of propagation reaction is sufficiently lower than the activation energy of chain transfer reaction. there is Therefore, the value obtained by subtracting the activation energy of the propagation reaction from the activation energy of the chain transfer reaction (hereinafter referred to as ΔE _C ) is positive, and the larger this value is, the higher the frequency of the propagation reaction is relative to the frequency of the chain transfer reaction. As a result, it is presumed that the resulting olefin polymer has a high molecular weight. The validity of the estimation of the molecular weight of the olefin polymer performed in this way is also supported, for example, by the calculation results of Laine et al. [Organometallics, 30, 1350 (2011)]. In the bridged metallocene compound (A-4) represented by the general formula [VIII], at least one electron-donating substituent having a Hammett rule substituent constant σ of −0.2 or less is used for R ⁵ and R ⁶ . When a substituted aryl group containing a substituted electron-donating group is used, the above _ΔEC increases, and ethylene and an α- It is presumed that the molecular weight of the ethylene/α-olefin/non-conjugated polyene copolymer produced when the olefin and the non-conjugated polyene are copolymerized increases.

In the bridged metallocene compound (A-4) represented by the above general formula [VIII], the electron-donating substituent contained in R ⁵ and R ⁶ is a group selected from a nitrogen-containing group and an oxygen-containing group. More preferably, it is an oxygen-containing group. These substituents have a particularly low value σ in Hammett's rule, and among the problems to be solved by the present invention, they exhibit the effect of increasing the molecular weight of the copolymer formed during high-temperature polymerization.

In the bridged metallocene compound (A-4) represented by the general formula [VIII], R ⁵ and R ⁶ are substituted phenyl containing a group selected from a nitrogen-containing group and an oxygen-containing group as the electron-donating substituent. is more preferably a group, more preferably a substituted phenyl group containing an oxygen-containing group. For example, when synthesizing according to the method of the above formula [IX], various benzophenones as raw materials are commercially available from general reagent manufacturers, so the raw materials are easily available, the production process is simplified, and the production cost is reduced. Therefore, the use of this crosslinked metallocene compound has the advantage of reducing the production cost of the ethylene/α-olefin/non-conjugated polyene copolymer.

Here, the substituted phenyl group containing a group selected from a nitrogen-containing group and an oxygen-containing group as the electron-donating substituent includes an o-aminophenyl group (2-aminophenyl group), a p-aminophenyl group (4 -aminophenyl group), o-(dimethylamino)phenyl group (2-(dimethylamino)phenyl group), p-(dimethylamino)phenyl group (4-(dimethylamino)phenyl group), o-(diethylamino)phenyl group (2-(diethylamino)phenyl group), p-(diethylamino)phenyl group (4-(diethylamino)phenyl group), m-(diethylamino)phenyl group (3-(diethylamino)phenyl group), o-methoxyphenyl group (2-methoxyphenyl group), p-methoxyphenyl group (4-methoxyphenyl group), o-ethoxyphenyl group (2-ethoxyphenyl group), p-ethoxyphenyl group (4-ethoxyphenyl group), o-N-morpho Linylphenyl group (2-N-morpholinylphenyl group), p-N-morpholinylphenyl group (4-N-morpholinylphenyl group), m-N-morpholinylphenyl group (3-N-morpholinylphenyl group) phenyl group), o,p-dimethoxyphenyl group (2,4-dimethoxyphenyl group), m,p-dimethoxyphenyl group (3,4-dimethoxyphenyl group), p-(dimethylamino)-m-methoxyphenyl group (4-(dimethylamino)-3-methoxyphenyl group), p-(dimethylamino)-m-methylphenyl group (4-(dimethylamino)-3-methylphenyl group), p-methoxy-m-methylphenyl group (4-methoxy-3-methylphenyl group), p-methoxy-m,m-dimethylphenyl group (4-methoxy-3,5-dimethylphenyl group) and the like.

In the bridged metallocene compound (A-4) represented by the above general formula [VIII], R ⁵ and R ⁶ are at the meta-position and/or para-position with respect to the bond with the carbon atom as Y above. More preferred are substituted phenyl groups containing oxygen-containing groups as radicals. For example, when synthesized according to a method such as the above formula [IX], the synthesis is easier than when the group is substituted at the ortho position, the production process is simplified, the production cost is reduced, and the bridged metallocene The use of the compound has the advantage of reducing the production cost of the ethylene/α-olefin/non-conjugated polyene copolymer.

In the bridged metallocene compound (A-4) represented by the above general formula [VIII], R ⁵ and R ⁶ are at the meta-position and/or para-position with respect to the bond with the carbon atom as the above electron-donating substitution In the case of a substituted phenyl group containing an oxygen-containing group as a group, the oxygen-containing group is more preferably a group represented by the following general formula [III].
R ¹⁰ -O- ... [III]
(In formula [III], R ¹⁰ is an atom or substituent selected from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a nitrogen-containing group and a halogen-containing group, and is drawn to the right of O A line represents a bond with a phenyl group.)

As R ¹⁰ , the hydrocarbon group having 1 to 20 carbon atoms, the silicon-containing group, the nitrogen-containing group and the halogen-containing group include specific examples of these substituents described above.
Such a bridged metallocene compound (A-5) is represented by the following general formula [X].

式［X］において、Ｍ、Ｒ⁷、Ｒ⁸、Ｑおよびｊの定義等は上述のとおりである。Ｒ¹⁰およびＲ¹¹は水素原子、炭素数１から２０の炭化水素基、ケイ素含有基、窒素含有基、酸素含有基、ハロゲン原子およびハロゲン含有基から選ばれる原子または置換基であり、それぞれ同一でも異なっていてもよく、Ｒ¹⁰の隣接した置換基は互いに結合して環を形成していてもよく、ＯＲ¹⁰はハメット則の置換基定数σ-0.2以下の酸素含有基であり、該酸素含有基が複数個存在する場合にはそれぞれの酸素含有基は互いに同一でも異なっていてもよく、ｎは１から３の整数であり、ｍは０から４の整数である。

In the formula [X], definitions of M, R ⁷ , R ⁸ , Q and j are as described above. R ¹⁰ and R ¹¹ are atoms or substituents selected from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom and a halogen-containing group; Adjacent substituents of R ¹⁰ may be bonded to each other to form a ring, OR ¹⁰ is an oxygen-containing group having a Hammett rule substituent constant σ-0.2 or less, and the oxygen-containing When a plurality of groups are present, each oxygen-containing group may be the same or different, n is an integer of 1 to 3, and m is an integer of 0 to 4.

The bridged metallocene compound (A-5) has a lower σ in Hammett's rule of OR ¹⁰ represented by the above general formula [III], and thus exerts an effect of increasing the molecular weight of the copolymer produced during high-temperature polymerization.

The bridged metallocene compound (A) represented by the general formula [I], the bridged metallocene compound (A-1) represented by the general formula [V], the bridged metallocene compound (A-1) represented by the general formula [VI] A-2), the bridged metallocene compound (A-3) of the present invention represented by the above general formula [VII], the bridged metallocene compound (A-4) of the present invention represented by the above general formula [VIII], or the above In the bridged metallocene compound (A-5) of the present invention represented by general formula [X], M is more preferably a zirconium atom. When ethylene, an α-olefin having 3 or more carbon atoms, and a non-conjugated polyene are copolymerized in the presence of an olefin polymerization catalyst containing the crosslinked metallocene compound where M is a zirconium atom, the resulting ethylene/α-olefin/non- Advantages of higher molecular weight of conjugated polyene copolymer and improvement of copolymerization performance of non-conjugated polyene are obtained.

(Exemplification of Bridged Metallocene Compound (A), etc.)
As such a bridged metallocene compound (A),
[dimethylmethylene(η ⁵ -cyclopentadienyl)(η ⁵ -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride, [diethyl methylene (η ⁵ -cyclopentadienyl)(η ⁵ -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride, [di-n -butylmethylene (η ⁵ -cyclopentadienyl)(η ⁵ -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride, [di Cyclopentylmethylene (η ⁵ -cyclopentadienyl)(η ⁵ -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride, [dicyclohexylmethylene (η ⁵ -cyclopentadienyl)(η ⁵ -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b′]-dithiophene))]zirconium dichloride,
[Cyclopentylidene(η ⁵ -cyclopentadienyl)(η ⁵ -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b′]-dithiophene))]zirconium dichloride, [ cyclohexylidene(η ⁵ -cyclopentadienyl)(η ⁵ -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride,
[Diphenylmethylene(η ⁵ -cyclopentadienyl)(η ⁵ -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride, [di -1-naphthymethylene(η ⁵ -cyclopentadienyl)(η ⁵ -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride, [Di-2-naphthylmethylene(η ⁵ -cyclopentadienyl)(η ⁵ -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride,
[bis(3-methylphenyl)methylene(η ⁵ -cyclopentadienyl)(η ⁵ -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene)) ]zirconium dichloride, [bis(4-methylphenyl)methylene(η ⁵ -cyclopentadienyl)(η ⁵ -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b'] -dithiophene))]zirconium dichloride, [bis(3,4-dimethylphenyl)methylene(η ⁵ -cyclopentadienyl)(η ⁵ -7-(2,5-dimethyl-cyclopenta[1,2-b:4 ,3-b']-dithiophene))]zirconium dichloride, [bis(4-n-hexylphenyl)methylene(η ⁵ -cyclopentadienyl)(η ⁵ -7-(2,5-dimethyl-cyclopenta[1 ,2-b:4,3-b']-dithiophene))]zirconium dichloride, [bis(4-cyclohexylphenyl)methylene(η ⁵ -cyclopentadienyl)(η ⁵ -7-(2,5-dimethyl -cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride, [bis(4-t-butylphenyl)methylene(η ⁵ -cyclopentadienyl)(η ⁵ -7- (2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride,
[bis(3-methoxyphenyl)methylene(η ⁵ -cyclopentadienyl)(η ⁵ -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene)) ]zirconium dichloride, [bis(4-methoxyphenyl)methylene(η ⁵ -cyclopentadienyl)(η ⁵ -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b'] -dithiophene))]zirconium dichloride, [bis(3,4-dimethoxyphenyl)methylene(η ⁵ -cyclopentadienyl)(η ⁵ -7-(2,5-dimethyl-cyclopenta[1,2-b:4 ,3-b']-dithiophene))]zirconium dichloride, [bis(4-methoxy-3-methylphenyl)methylene(η ⁵ -cyclopentadienyl)(η ⁵ -7-(2,5-dimethyl-cyclopenta [1,2-b:4,3-b']-dithiophene))]zirconium dichloride, [bis(4-methoxy-3,4-dimethylphenyl)methylene(η ⁵ -cyclopentadienyl)(η ⁵ - 7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride, [bis(4-ethoxyphenyl)methylene(η ⁵ -cyclopentadienyl) (η ⁵ -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride, [bis(4-phenoxyphenyl)methylene(η ⁵ -cyclo pentadienyl)(η ⁵ -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride, [bis{4-(trimethylsiloxy)phenyl }methylene (η ⁵ -cyclopentadienyl)(η ⁵ -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b′]-dithiophene))]zirconium dichloride,
[bis{3-(dimethylamino)phenyl}methylene(η ⁵ -cyclopentadienyl)(η ⁵ -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']- dithiophene))]zirconium dichloride, [bis{4-(dimethylamino)phenyl}methylene(η ⁵ -cyclopentadienyl)(η ⁵ -7-(2,5-dimethyl-cyclopenta[1,2-b:4 ,3-b']-dithiophene))]zirconium dichloride, [bis(4-N-morpholinylphenyl)(η ⁵ -cyclopentadienyl)(η ⁵ -7-(2,5-dimethyl-cyclopenta[ 1,2-b:4,3-b']-dithiophene))]zirconium dichloride,
[bis{4-(trimethylsilyl)phenyl}methylene(η ⁵ -cyclopentadienyl)(η ⁵ -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene ))] zirconium dichloride,
[bis(3-chlorophenyl)methylene(η ⁵ -cyclopentadienyl)(η ⁵ -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))] Zirconium dichloride, [bis(4-chlorophenyl)methylene(η ⁵ -cyclopentadienyl)(η ⁵ -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene ))]zirconium dichloride, [bis(3-fluorophenyl)methylene(η ⁵ -cyclopentadienyl)(η ⁵ -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b ']-dithiophene))]zirconium dichloride, [bis(4-fluorophenyl)methylene(η ⁵ -cyclopentadienyl)(η ⁵ -7-(2,5-dimethyl-cyclopenta[1,2-b:4 ,3-b']-dithiophene))]zirconium dichloride, [bis{3-(trifluoromethyl)phenyl}methylene(η ⁵ -cyclopentadienyl)(η ⁵ -7-(2,5-dimethyl-cyclopenta [1,2-b:4,3-b']-dithiophene))]zirconium dichloride, [bis{4-(trifluoromethyl)phenyl}methylene(η ⁵ -cyclopentadienyl)(η ⁵ -7- (2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride,
[methylphenylmethylene(η ⁵ -cyclopentadienyl)(η ⁵ -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride, [ Methyl(4-methylphenyl)methylene(η ⁵ -cyclopentadienyl)(η ⁵ -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))] Zirconium dichloride, [methyl(4-methoxyphenyl)methylene(η ⁵ -cyclopentadienyl)(η ⁵ -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']- dithiophene))]zirconium dichloride, [methyl{4-(dimethylamino)phenyl}methylene(η ⁵ -cyclopentadienyl)(η ⁵ -7-(2,5-dimethyl-cyclopenta[1,2-b:4 ,3-b']-dithiophene))]zirconium dichloride, [methyl(4-N-morpholinylphenyl)methylene(η ⁵ -cyclopentadienyl)(η ⁵ -7-(2,5-dimethyl-cyclopenta [1,2-b:4,3-b']-dithiophene))]zirconium dichloride,
[dimethylsilylene(η ⁵ -cyclopentadienyl)(η ⁵ -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride, [diethyl Silylene (η ⁵ -cyclopentadienyl)(η ⁵ -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride, [dicyclohexylsilylene ( η ⁵ -cyclopentadienyl)(η ⁵ -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride, [diphenylsilylene (η ⁵ -cyclopentadienyl)(η ⁵ -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride, [di(4-methylphenyl) silylene (η ⁵ -cyclopentadienyl)(η ⁵ -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride,
[dimethylgermylene (η ⁵ -cyclopentadienyl)(η ⁵ -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride, [ diphenylgermylene (η ⁵ -cyclopentadienyl)(η ⁵ -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride,
[1-(η ⁵ -Cyclopentadienyl)-2-(η ⁵ -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))ethylene]zirconium Dichloride, [1-(η ⁵ -cyclopentadienyl)-3-(η ⁵ -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))propylene ]zirconium dichloride, [1-(η ⁵ -cyclopentadienyl)-2-(η ⁵ -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b′]-dithiophene) )-1,1,2,2-tetramethylsilylene]zirconium dichloride, [1-(η ⁵ -cyclopentadienyl)-2-(η ⁵ -7-(2,5-dimethyl-cyclopenta[1,2 -b:4,3-b']-dithiophene))phenylene]zirconium dichloride, and compounds in which the zirconium atom of these compounds is replaced by a hafnium atom, or compounds in which the chloro ligand is replaced by a methyl group, etc. However, the bridged metallocene compound (A) is not limited to these examples.

<Compound (B)>
The method for producing the ethylene/α-olefin/non-conjugated polyene copolymer of the present invention comprises the above-described crosslinked metallocene compound (A), the organometallic compound (B-1), the organoaluminumoxy compound (B-2), and the crosslinked α having 3 or more carbon atoms with ethylene in the presence of an olefin polymerization catalyst containing at least one compound (B) selected from compounds (B-3) that react with the metallocene compound (A) to form an ion pair. - characterized by the copolymerization of olefins and non-conjugated polyenes;
As the organometallic compound (B-1), specifically, the following organometallic compounds of Groups 1 and 2 and Groups 12 and 13 of the periodic table are used.

(B-1a) general formula R ^a _m Al(OR ^b ) _n H _p X _q
(Wherein, R ^a and R ^b may be the same or different and represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, m is 0<m ≤ 3, n is 0 ≤ n < 3, p is 0 ≤ p < 3, q is a number of 0 ≤ q < 3, and m + n + p + q = 3)
Organoaluminum compound represented by.

Such compounds include tri-n-alkylaluminums such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum,
Tri-branched alkylaluminum such as triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tri-t-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylhexylaluminum, tri-2-ethylhexylaluminum ,
tricycloalkylaluminum such as tricyclohexylaluminum, tricyclooctylaluminum;
triarylaluminum such as triphenylaluminum, tri(4-methylphenyl)aluminum,
dialkylaluminum hydrides such as diisopropylaluminum hydride and diisobutylaluminum hydride;
Alkenyl such as isoprenylaluminum represented by the general formula ( _iC4H9 ) _{xAly ( C5H10} ) _z , where _x , _y , and z are positive numbers and z≤2x aluminum,
alkylaluminum alkoxides such as isobutylaluminum methoxide, isobutylaluminum ethoxide;
dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide, dibutylaluminum butoxide;
alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide, butylaluminum sesquibutoxide,
partially alkoxylated aluminum alkyls having an average composition such as the general formula R ^a _2.5 Al(OR ^b ) _0.5 ;
alkylaluminum aryloxides such as diethylaluminum phenoxide, diethylaluminum (2,6-di-t-butyl-4-methylphenoxide);
dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride;
alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide;
partially halogenated alkylaluminums such as alkylaluminum dihalides such as ethylaluminum dichloride;
dialkylaluminum hydrides such as diethylaluminum hydride, dibutylaluminum hydride;
alkylaluminum dihydrides such as ethylaluminum dihydride, propylaluminum dihydride and other partially hydrogenated alkylaluminums,
Partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxychloride, butylaluminum butoxychloride, and ethylaluminum ethoxybromide can be exemplified. Compounds similar to the compounds represented by the above general formula R am Al _{(OR b ) n H p X q} ^{can also} _{be used ,} for example organic aluminum compounds in which two or more aluminum compounds are bonded via nitrogen atoms. compounds can be mentioned. Specific examples of such compounds include (C ₂ H ₅ ) ₂ AlN(C ₂ H ₅ )Al(C ₂ H ₅ ) ₂ and the like.

(B-1b) General formula M ² AlR ^a ₄
(In the formula, M ² represents Li, Na or K, and R ^a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms.)
A complex alkylate of a Group 1 metal of the periodic table and aluminum represented by
Examples of such compounds include LiAl(C ₂ H ₅ ) ₄ and LiAl(C ₇ H ₁₅ ) ₄ .

(B-1c) general formula R ^a R ^b M ³
(Wherein, R ^a and R ^b may be the same or different and represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and M ³ is Mg, Zn or Cd.)
A dialkyl compound of a Group 2 or Group 12 metal of the periodic table represented by

As the organoaluminumoxy compound (B-2), conventionally known aluminoxanes can be used as they are. Specifically, the following general formula [XI]

および／または下記一般式［XII］

and/or the following general formula [XII]

（式中、Ｒは炭素数１から１０の炭化水素基、nは2以上の整数を示す）
で表わされる化合物を挙げることができ、特にＲがメチル基であるメチルアルミノキサンでnが3以上、好ましくは10以上のものが利用される。これらアルミノキサン類に若干の有機アルミニウム化合物が混入していても差し支えない。本発明においてエチレンと炭素数が３以上のα－オレフィンと非共役ポリエンとの共重合を高温で行う場合には、特開平2-78687号公報に例示されているようなベンゼン不溶性の有機アルミニウムオキシ化合物も適用することができる。また、特開平2-167305号公報に記載されている有機アルミニウムオキシ化合物、特開平2-24701号公報、特開平3-103407号公報に記載されている二種類以上のアルキル基を有するアルミノキサンなども好適に利用できる。なお、本発明のオレフィン重合で用いられることのある「ベンゼン不溶性の有機アルミニウムオキシ化合物」とは、60℃のベンゼンに溶解するAl成分がAl原子換算で通常10%以下、好ましくは5%以下、特に好ましくは2%以下であり、ベンゼンに対して不溶性または難溶性である化合物である。

(Wherein, R is a hydrocarbon group having 1 to 10 carbon atoms, n is an integer of 2 or more)
In particular, methylaluminoxane in which R is a methyl group and n is 3 or more, preferably 10 or more is used. These aluminoxanes may be mixed with a small amount of organoaluminum compounds. In the present invention, when the copolymerization of ethylene, an α-olefin having 3 or more carbon atoms, and a non-conjugated polyene is carried out at a high temperature, a benzene-insoluble organoaluminum oxy group as exemplified in JP-A-2-78687 is used. Compounds can also be applied. In addition, organoaluminum oxy compounds described in JP-A-2-167305, aluminoxanes having two or more types of alkyl groups described in JP-A-2-24701 and JP-A-3-103407. It can be used conveniently. The "benzene-insoluble organoaluminum oxy compound" that may be used in the olefin polymerization of the present invention means that the Al component dissolved in benzene at 60°C is usually 10% or less, preferably 5% or less, in terms of Al atoms. Particularly preferably, the content is 2% or less, and the compound is insoluble or sparingly soluble in benzene.

Specific examples of the organoaluminum compound used in preparing the aluminoxane include the same organoaluminum compounds as those exemplified as the organoaluminum compound (B-1a) above. Among these, trialkylaluminum and tricycloalkylaluminum are preferred, and trimethylaluminum is particularly preferred. These organoaluminum compounds can be used singly or in combination of two or more.

Examples of the organoaluminumoxy compound (B-2) include modified methylaluminoxane represented by the following general formula [XIII].

式中、Ｒは炭素数１から１０の炭化水素基、mおよびnはそれぞれ独立に2以上の整数を示す。

In the formula, R is a hydrocarbon group having 1 to 10 carbon atoms, m and n each independently represent an integer of 2 or more.

The modified methylaluminoxanes are prepared using trimethylaluminum and alkylaluminums other than trimethylaluminum. Such compounds are commonly referred to as MMAO. Such MMAO can be prepared by the methods described in US Pat. No. 4,960,878 and US Pat. No. 5,041,584. In addition, Tosoh Finechem Co., Ltd. and the like also sell products prepared using trimethylaluminum and triisobutylaluminum under the names of MMAO and TMAO, in which R is an isobutyl group. Such MMAO is an aluminoxane with improved solubility in various solvents and storage stability. soluble in aliphatic and alicyclic hydrocarbons.

Furthermore, the organoaluminumoxy compound (B-2) may also include an organoaluminumoxy compound containing boron represented by the following general formula [XIV].

式中、Ｒ^cは炭素数１から１０の炭化水素基を示す。Ｒ^dは、互いに同一でも異なっていてもよく、水素原子、ハロゲン原子または炭素数１から１０の炭化水素基を示す。

In the formula, R ^c represents a hydrocarbon group having 1 to 10 carbon atoms. R ^d may be the same or different and represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 10 carbon atoms.

As the compound (B-3) that reacts with the bridged metallocene compound (A) to form an ion pair (hereinafter sometimes abbreviated as "ionized ionic compound" or simply "ionic compound"), 1-501950, JP-A-1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, USP5321106, etc. Mention may be made of the Lewis acids, ionic compounds, borane compounds and carborane compounds described above. In addition, heteropolycompounds and isopolycompounds may also be mentioned. However, the aforementioned (B-2) organoaluminumoxy compound is not included.

The ionized ionic compound preferably used in the present invention is a boron compound represented by the following general formula [XV].

式中、Ｒ^e+としては、Ｈ⁺、カルベニウムカチオン、オキソニウムカチオン、アンモニウムカチオン、ホスホニウムカチオン、シクロヘプチルトリエニルカチオン、遷移金属を有するフェロセニウムカチオンなどが挙げられる。Ｒ^fからＲⁱは、互いに同一でも異なっていてもよく、炭素数１から２０の炭化水素基、ケイ素含有基、窒素含有基、酸素含有基、ハロゲン原子およびハロゲン含有基から選ばれる置換基であり、好ましくは置換アリール基である。

In the formula, R ^e+ includes H ⁺ , carbenium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, ferrocenium cation having a transition metal, and the like. R ^f to R ⁱ may be the same or different, and are substituents selected from hydrocarbon groups having 1 to 20 carbon atoms, silicon-containing groups, nitrogen-containing groups, oxygen-containing groups, halogen atoms and halogen-containing groups. , preferably a substituted aryl group.

Specific examples of the carbenium cations include triphenylcarbenium cations, tris(4-methylphenyl)carbenium cations, and trisubstituted carbenium cations such as tris(3,5-dimethylphenyl)carbenium cations. .

Specific examples of the ammonium cation include trialkyl-substituted ammonium cations such as trimethylammonium cation, triethylammonium cation, tri(n-propyl)ammonium cation, triisopropylammonium cation, tri(n-butyl)ammonium cation, and triisobutylammonium cation. cations, N,N-dialkylanilinium cations such as N,N-dimethylanilinium cations, N,N-diethylanilinium cations, N,N-2,4,6-pentamethylanilinium cations, diisopropylammonium cations, Examples include dialkylammonium cations such as dicyclohexylammonium cations.

Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tris(4-methylphenyl)phosphonium cation, and tris(3,5-dimethylphenyl)phosphonium cation.

Of the above specific examples, R ^e+ is preferably a carbenium cation or an ammonium cation, and particularly preferably a triphenylcarbenium cation, an N,N-dimethylanilinium cation, or an N,N-diethylanilinium cation.

Among the ionizable ionic compounds preferably used in the present invention, compounds containing carbenium cations include triphenylcarbenium tetraphenylborate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis {3, 5-di-(trifluoromethyl)phenyl}borate, tris(4-methylphenyl)carbeniumtetrakis(pentafluorophenyl)borate, tris(3,5-dimethylphenyl)carbeniumtetrakis(pentafluorophenyl)borate, etc. can be exemplified.

Among the ionizable ionic compounds preferably used in the present invention, compounds containing trialkyl-substituted ammonium cations include triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri(n-butyl)ammonium tetraphenylborate, and trimethylammonium. Tetrakis(4-methylphenyl)borate, Trimethylammoniumtetrakis(2-methylphenyl)borate, Tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate, Triethylammoniumtetrakis(pentafluorophenyl)borate, Tripropylammoniumtetrakis( pentafluorophenyl)borate, tripropylammonium tetrakis(2,4-dimethylphenyl)borate, tri(n-butyl)ammonium tetrakis(3,5-dimethylphenyl)borate, tri(n-butyl)ammonium tetrakis{4-( trifluoromethyl)phenyl}borate, tri(n-butyl)ammonium tetrakis{3,5-di(trifluoromethyl)phenyl}borate, tri(n-butyl)ammonium tetrakis(2-methylphenyl)borate, dioctadecylmethyl ammonium tetraphenylborate, dioctadecylmethylammonium tetrakis(4-methylphenyl)borate, dioctadecylmethylammonium tetrakis(4-methylphenyl)borate, dioctadecylmethylammonium tetrakis(pentafluorophenyl)borate, dioctadecylmethylammonium tetrakis(2) ,4-dimethylphenyl)borate, dioctadecylmethylammonium tetrakis(3,5-dimethylphenyl)borate, dioctadecylmethylammonium tetrakis {4-(trifluoromethyl)phenyl}borate, dioctadecylmethylammonium tetrakis {3,5- Examples include di(trifluoromethyl)phenyl}borate, dioctadecylmethylammonium and the like.

Among the ionizable ionic compounds preferably used in the present invention, compounds containing N,N-dialkylanilinium cations include N,N-dimethylanilinium tetraphenylborate, N,N-dimethylanilinium tetrakis(pentafluorophenyl ) borate, N,N-dimethylanilinium tetrakis {3,5-di(trifluoromethyl)phenyl}borate, N,N-diethylanilinium tetraphenylborate, N,N-diethylanilinium tetrakis(pentafluorophenyl) Borate, N,N-diethylanilinium tetrakis{3,5-di(trifluoromethyl)phenyl}borate, N,N-2,4,6-pentamethylanilinium tetraphenylborate, N,N-2,4 ,6-pentamethylanilinium tetrakis(pentafluorophenyl)borate and the like can be exemplified.

Among the ionizable ionic compounds preferably used in the present invention, di-n-propylammonium tetrakis(pentafluorophenyl)borate, dicyclohexylammonium tetraphenylborate and the like can be exemplified as compounds containing dialkylammonium cations.

In addition, ionic compounds disclosed by the present applicant (Japanese Unexamined Patent Application Publication No. 2004-51676) can also be used without limitation.
The above ionic compound (B-3) may be used alone or in combination of two or more.

As the organometallic compound (B-1), trimethylaluminum, triethylaluminum and triisobutylaluminum, which are commercially available and readily available, are preferred. Among these, triisobutylaluminum is particularly preferable because it is easy to handle.

As the organoaluminumoxy compound (B-2), methylaluminoxane, which is commercially available and readily available, and MMAO prepared using trimethylaluminum and triisobutylaluminum are preferred. Among these, MMAO with improved solubility in various solvents and improved storage stability is particularly preferred.

As the compound (B-3) that forms an ion pair by reacting with the bridged metallocene compound (A), triphenylcarbenium tetrakis is easily available as a commercial product and greatly contributes to the improvement of polymerization activity. (Pentafluorophenyl)borate and N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate are preferred.

As at least one compound (B) selected from compounds (B-1) to (B-3), triisobutylaluminum and triphenylcarbeniumtetrakis(pentafluorophenyl) Combinations with borates and combinations of triisobutylaluminum and N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate are particularly preferred.

<Carrier (C)>
In the present invention, a carrier (C) may optionally be used as a component of the olefin polymerization catalyst.

The carrier (C) that may be used in the present invention is an inorganic or organic compound, and is a granular or particulate solid. Among these inorganic compounds, porous oxides, inorganic chlorides, clays, clay minerals, and ion-exchange layered compounds are preferred.

Examples of porous oxides include SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ and the like, or composites or mixtures containing these, such as Using natural or synthetic zeolite, _SiO2 -MgO, _SiO2 - _Al2O3 , _SiO2 - _TiO2 , _{SiO2 - V2O5} , _{SiO2 - Cr2O3} , _{SiO2 - TiO2} -MgO, etc. can do. Among these, those containing SiO ₂ and/or Al ₂ O ₃ as main components are preferred. The properties of such porous oxides vary depending on the type and production method. to 1000 m ² /g, preferably 100 to 700 m ² /g, with a pore volume in the range 0.3 to 3.0 cm ³ /g. Such a carrier is used after being calcined at 100 to 1000°C, preferably 150 to 700°C, if necessary.

As inorganic chlorides, MgCl ₂ , MgBr ₂ , MnCl ₂ , MnBr ₂ and the like are used. The inorganic chloride may be used as it is, or may be used after pulverizing with a ball mill or vibration mill. Moreover, after dissolving an inorganic chloride in a solvent such as alcohol, the inorganic chloride may be precipitated in the form of fine particles using a precipitating agent.

Clay is usually composed mainly of clay minerals. An ion-exchangeable layered compound is a compound having a crystal structure in which planes are stacked in parallel with a weak bonding force due to ionic bonds or the like, and the ions contained therein can be exchanged. Most clay minerals are ion exchange layered compounds. Moreover, as these clays, clay minerals, and ion-exchangeable layered compounds, not only naturally occurring ones but also artificially synthesized ones can be used. Clays, clay minerals, and ionic crystalline compounds having layered crystal structures such as hexagonal close-packing type, antimony type, _CdCl2 type, and _CdI2 type are used as clays, clay minerals, or ion-exchangeable layered compounds. can be exemplified. Such clays and clay minerals include kaolin, bentonite, kibushi clay, gyrome clay, allophane, hisingerite, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokudite group, palygorskite, kaolinite, nacrite, and dickite. _{and halloysite . _ _ _ _ _} α-Ti(HPO4) ₂ , α _- Ti( _HAsO4 ) _2.H2O , α _- Sn(HPO4) _2.H2O , γ _- Zr ₍ HPO4) ₂ , γ _- Ti ₍ HPO4 ) ₂ and crystalline acid salts of polyvalent metals such as γ-Ti(NH ₄ PO ₄ ) ₂ ·H ₂ O and the like. It is also preferable to chemically treat the clay and clay mineral used in the present invention. Any chemical treatment can be used, such as a surface treatment for removing impurities adhering to the surface, a treatment for affecting the crystal structure of clay, and the like. Specific examples of chemical treatment include acid treatment, alkali treatment, salt treatment, and organic treatment.

The ion-exchangeable layered compound may be a layered compound in which the interlayer spacing is expanded by exchanging the exchangeable ions between the layers with other large bulky ions by utilizing the ion-exchangeability. Such bulky ions play a pillar-like role supporting the layered structure and are usually called pillars. Also, the introduction of another substance (guest compound) between the layers of a layered compound is called intercalation. Guest compounds include cationic inorganic compounds such as TiCl ₄ and ZrCl ₄ , metal alkoxides such as Ti(OR) ₄ , Zr(OR) ₄ , PO(OR) ₃ and B(OR) ₃ (R is a hydrocarbon groups), metal hydroxide ions such as [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH) ₁₄ ] ²⁺ , [Fe ₃ O(OCOCH ₃ ) ₆ ] ⁺ . These compounds are used singly or in combination of two or more. When intercalating these compounds, metal alkoxides (R is a hydrocarbon group, etc.) such as Si(OR) ₄ , Al(OR) ₃ and Ge(OR) ₄ are hydrolyzed and polycondensed. The resulting polymer, a colloidal inorganic compound such as SiO ₂ , etc., can also coexist. Examples of pillars include oxides produced by intercalating the above metal hydroxide ions between layers and then dehydrating them by heating. Among these, preferred are clays or clay minerals, and particularly preferred are montmorillonite, vermiculite, pectolite, taeniolite and synthetic mica.

Examples of the organic compound as the carrier (C) include granular or particulate solids having a particle size in the range of 0.5 to 300 μm. Specifically, (co)polymers produced mainly from α-olefins having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, vinylcyclohexane, and styrene can be exemplified as a (co)polymer produced as a main component, and a modified product thereof.

<Copolymerization of Ethylene, α-Olefin and Non-Conjugated Polyene Using the Olefin Polymerization Catalyst>
The method for producing an ethylene/α-olefin/non-conjugated polyene copolymer of the present invention comprises copolymerizing ethylene, an α-olefin having 3 or more carbon atoms, and a non-conjugated polyene in the presence of the polymerization catalyst. Characterized by

Examples of α-olefins having 3 or more carbon atoms used in the present invention include propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl- C3-C20 linear or branched α such as 1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, vinylcyclohexane, etc. - Olefins can be exemplified. The α-olefin is preferably an α-olefin having 3 to 10 carbon atoms, such as a linear or branched α-olefin having 3 to 10 carbon atoms, such as propylene, 1-butene, 1-hexene and 1-octene. More preferred, propylene is even more preferred. These α-olefins can be used singly or in combination of two or more. Also, the selection thereof can be made so as to provide the most desirable properties of the resulting copolymer. For example, the type of α-olefin is selected so that the ethylene/α-olefin/non-conjugated polyene copolymer obtained in the present invention or the mixture containing the copolymer has desirable physical properties when vulcanized. be able to.

As the non-conjugated polyene used in the present invention, compounds having two or more non-conjugated unsaturated bonds can be used without limitation. or in combination of two or more.

[Non-conjugated cyclic polyene]
Specific examples of the non-conjugated cyclic polyene include compounds represented by the following general formula [IV].

式［IV］において、ｎは０から２の整数であり、
Ｒ¹⁰、Ｒ¹¹、Ｒ¹²およびＲ¹³は水素原子、炭素数１から２０の炭化水素基、ケイ素含有基、窒素含有基、酸素含有基、ハロゲン原子およびハロゲン含有基から選ばれる原子または置換基であり、それぞれ同一でも異なっていてもよく、該炭化水素基は二重結合を有していてもよく、
Ｒ¹⁰からＲ¹³までの任意の二つの置換基は互いに結合して環を形成していてもよく、該環は二重結合を含んでいてもよく、Ｒ¹⁰とＲ¹¹とで、またはＲ¹²とＲ¹³とでアルキリデン基を形成していてもよく、Ｒ¹⁰とＲ¹²とが、またはＲ¹¹とＲ¹³とが互いに結合して二重結合を形成していてもよく、
以下の（i）から（iv）の要件の少なくとも一つが満たされる。
（i）Ｒ¹⁰からＲ¹³の少なくとも一つは、二重結合を一つ以上有する炭化水素基である。
（ii）Ｒ¹⁰からＲ¹³までの任意の二つの置換基が互いに結合して環を形成し、該環が二重結合を含んでいる。
（iii）Ｒ¹⁰とＲ¹¹とで、またはＲ¹²とＲ¹³とでアルキリデン基を形成している。
（iv）Ｒ¹⁰とＲ¹²とが、またはＲ¹¹とＲ¹³とが互いに結合して二重結合を形成している。

In formula [IV], n is an integer from 0 to 2,
R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are atoms or substituents selected from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom and a halogen-containing group; , which may be the same or different, and the hydrocarbon group may have a double bond,
Any two substituents of R ¹⁰ to R ¹³ may be bonded together to form a ring, and the ring may contain a double bond, and R ¹⁰ and R ¹¹ or R ¹² and R ¹³ may form an alkylidene group, R ¹⁰ and R ¹² or R ¹¹ and R ¹³ may bind to each other to form a double bond,
At least one of the following requirements (i) through (iv) is met.
⁽ i) ^At least one of R10 to R13 is a hydrocarbon group having one or more double bonds.
⁽ ii) Any two substituents from R10 to ^R13 are joined together to form a ring, and the ring contains a double bond.
(iii) R ¹⁰ and R ¹¹ or R ¹² and R ¹³ form an alkylidene group.
(iv) R ¹⁰ and R ¹² or R ¹¹ and R ¹³ are bonded to each other to form a double bond;

^Hydrocarbon groups having ¹ to ²⁰ carbon ^atoms , silicon-containing groups, nitrogen-containing groups, oxygen-containing groups, halogen atoms and halogen-containing Specific examples of the group include those atoms and substituents mentioned in the explanation of the general formula [I].

In the above general formula [IV], when any one or more of R ¹⁰ , R ¹¹ , R ¹² and R ¹³ is a hydrocarbon group having one or more double bonds, the hydrocarbon group is an ethenyl group (vinyl group), 1-propenyl group, 2-propenyl group (allyl group), 1-methylethenyl group (isopropenyl group), 1-butenyl group, 2-butenyl group, 3-butenyl group, 1,4-hexadienyl group etc. are exemplified. For example, when R ¹⁰ is an ethenyl group (vinyl group), the compound of the above general formula [IV] can be represented by the following general formula [IV-I].

式［IV-I］において、ｎは０から２の整数であり、
Ｒ¹¹、Ｒ¹²およびＲ¹³は水素原子、炭素数１から２０の炭化水素基、ケイ素含有基、窒素含有基、酸素含有基、ハロゲン原子およびハロゲン含有基から選ばれる原子または置換基であり、それぞれ同一でも異なっていてもよく、該炭化水素基は二重結合を有していてもよく、
Ｒ¹¹からＲ¹³の任意の二つの置換基は互いに結合して環を形成していてもよく、該環は二重結合を含んでいてもよく、Ｒ¹²とＲ¹³とでアルキリデン基を形成していてもよく、Ｒ¹¹とＲ¹³とが互いに結合して二重結合を形成していてもよい。

In formula [IV-I], n is an integer from 0 to 2,
R ¹¹ , R ¹² and R ¹³ are atoms or substituents selected from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom and a halogen-containing group; each may be the same or different, the hydrocarbon group may have a double bond,
Any two substituents of R ¹¹ to R ¹³ may be combined to form a ring, the ring may contain a double bond, and R ¹² and R ¹³ form an alkylidene group. or R ¹¹ and R ¹³ may combine with each other to form a double bond.

In the above general formula [IV], any two substituents of R ¹⁰ to R ¹³ are bonded to each other to form a ring, and when the ring contains a double bond, The compound can be represented, for example, by the following general formula [IV-II] or [IV-III].

式［IV-II］および［IV-III］において、ｎは０から２の整数であり、
Ｒ¹¹、Ｒ¹²およびＲ¹³は水素原子、炭素数１から２０の炭化水素基、ケイ素含有基、窒素含有基、酸素含有基、ハロゲン原子およびハロゲン含有基から選ばれる原子または置換基であり、それぞれ同一でも異なっていてもよく、該炭化水素基は二重結合を有していてもよく、
Ｒ¹¹からＲ¹³の任意の二つの置換基は互いに結合して環を形成していてもよく、該環は二重結合を含んでいてもよく、Ｒ¹²とＲ¹³とでアルキリデン基を形成していてもよく、Ｒ¹¹とＲ¹³とが互いに結合して二重結合を形成していてもよい。

In formulas [IV-II] and [IV-III], n is an integer from 0 to 2,
R ¹¹ , R ¹² and R ¹³ are atoms or substituents selected from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom and a halogen-containing group; each may be the same or different, the hydrocarbon group may have a double bond,
Any two substituents of R ¹¹ to R ¹³ may be combined to form a ring, the ring may contain a double bond, and R ¹² and R ¹³ form an alkylidene group. or R ¹¹ and R ¹³ may combine with each other to form a double bond.

In the above general formula [IV], when R ¹⁰ and R ¹¹ or R ¹² and R ¹³ form an alkylidene group, the alkylidene group is usually an alkylidene group having 1 to 20 carbon atoms, Illustrative examples include the methylene group _{( CH2} =), the ethylidene group (CH3CH=), the propylidene group (CH3CH2CH=) and the isopropylidene group ( _{( CH3} ) _{2C =} ). For example, when R ¹⁰ and R ¹¹ form an ethylidene group, the compound of general formula [IV] can be represented by general formula [IV-IV] below.

式［IV-IV］において、ｎは０から２の整数であり、
Ｒ¹²およびＲ¹³は水素原子、炭素数１から２０の炭化水素基、ケイ素含有基、窒素含有基、酸素含有基、ハロゲン原子およびハロゲン含有基から選ばれる原子または置換基であり、それぞれ同一でも異なっていてもよく、該炭化水素基は二重結合を有していてもよく、
Ｒ¹²とＲ¹³とは互いに結合して環を形成していてもよく、該環は二重結合を含んでいてもよく、Ｒ¹²とＲ¹³とでアルキリデン基を形成していてもよい。

In formula [IV-IV], n is an integer from 0 to 2,
R ¹² and R ¹³ are atoms or substituents selected from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom and a halogen-containing group; may be different, the hydrocarbon group may have a double bond,
R ¹² and R ¹³ may combine with each other to form a ring, the ring may contain a double bond, and R ¹² and R ¹³ may form an alkylidene group.

In the above general formula [IV], when R ¹⁰ and R ¹² or R ¹¹ and R ¹³ are bound to each other to form a double bond, the compound of general formula [IV] is, for example, the following It can be represented by the general formula [IV-V].

式［IV-V］において、ｎは０から２の整数であり、
Ｒ¹¹およびＲ¹³は水素原子、炭素数１から２０の炭化水素基、ケイ素含有基、窒素含有基、酸素含有基、ハロゲン原子およびハロゲン含有基から選ばれる置換基であり、それぞれ同一でも異なっていてもよく、該炭化水素基は二重結合を有していてもよく、
Ｒ¹¹とＲ¹³とは互いに結合して環を形成していてもよく、該環は二重結合を含んでいてもよい。

In formula [IV-V], n is an integer from 0 to 2,
R ¹¹ and R ¹³ are substituents selected from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom and a halogen-containing group, and may be the same or different. may be, the hydrocarbon group may have a double bond,
R ¹¹ and R ¹³ may combine with each other to form a ring, and the ring may contain a double bond.

Among the non-conjugated cyclic polyenes represented by the above general formula [IV], compounds in which at least one of R ¹⁰ to R ¹³ is a hydrocarbon group having one or more double bonds include, for example, 5-vinyl-2-norbornene (VNB) and the following compounds are exemplified. Of these, 5-vinyl-2-norbornene (VNB) is preferred.

上記一般式［IV］で表される非共役環状ポリエンのうち、Ｒ¹⁰からＲ¹³までの任意の二つの置換基が互いに結合して環を形成し、該環が二重結合を含んでいる化合物として、例えばジシクロペンタジエン（ＤＣＰＤ）、ジメチルジシクロペンタジエンおよび下記の化合物などが例示される。これらのうち、ジシクロペンタジエン（ＤＣＰＤ）が好ましい。

Any two substituents of R ¹⁰ to R ¹³ in the non-conjugated cyclic polyene represented by the general formula [IV] are bonded to each other to form a ring, and the ring contains a double bond. Examples of compounds include dicyclopentadiene (DCPD), dimethyldicyclopentadiene, and the following compounds. Among these, dicyclopentadiene (DCPD) is preferred.

上記一般式［IV］で表される非共役環状ポリエンのうち、Ｒ¹⁰とＲ¹¹とで、またはＲ¹²とＲ¹³とでアルキリデン基を形成している化合物として、５－メチレン－２－ノルボルネン、５－エチリデン－２－ノルボルネン（ＥＮＢ）、５－イソプロピリデン－２－ノルボルネンおよび下記の化合物などが例示される。これらのうち、５－エチリデン－２－ノルボルネン（ＥＮＢ）が好ましい。

Among the non-conjugated cyclic polyenes represented by the general formula [IV], 5-methylene-2-norbornene is the compound in which R ¹⁰ and R ¹¹ or R ¹² and R ¹³ form an alkylidene group. , 5-ethylidene-2-norbornene (ENB), 5-isopropylidene-2-norbornene and the following compounds. Of these, 5-ethylidene-2-norbornene (ENB) is preferred.

上記一般式［IV］で表される非共役環状ポリエンのうち、Ｒ¹⁰とＲ¹²とが、またはＲ¹¹とＲ¹³とが互いに結合して二重結合を形成している化合物としては、下記のものが好ましい。

Among the non-conjugated cyclic polyenes represented by the general formula [IV], the compounds in which R ¹⁰ and R ¹² or R ¹¹ and R ¹³ are bonded to each other to form a double bond include the following: is preferred.

上記一般式［IV］で表される非共役環状ポリエンとしては、ｎが０の非共役環状ポリエンが好ましく、特に上記一般式［IV］においてｎが０のアルキリデン基置換非共役環状ポリエン、上記一般式［IV］においてｎが０の二重結合含有環置換非共役環状ポリエン、ｎが０の二重結合含有炭化水素基置換非共役環状ポリエンが好ましい。具体的には、５－エチリデン－２－ノルボルネン（ＥＮＢ）、ジシクロペンタジエン（ＤＣＰＤ）、５－ビニル－２－ノルボルネン（ＶＮＢ）がより好ましい。このうち５－エチリデン－２－ノルボルネン（ＥＮＢ）または５－ビニル－２－ノルボルネン（ＶＮＢ）が特に好ましい。

As the non-conjugated cyclic polyene represented by the general formula [IV], a non-conjugated cyclic polyene in which n is 0 is preferable, and in particular, an alkylidene group-substituted non-conjugated cyclic polyene in which n is 0 in the general formula [IV]. A double bond-containing ring-substituted non-conjugated cyclic polyene in which n is 0 in formula [IV] and a double bond-containing hydrocarbon group-substituted non-conjugated cyclic polyene in which n is 0 are preferred. Specifically, 5-ethylidene-2-norbornene (ENB), dicyclopentadiene (DCPD), and 5-vinyl-2-norbornene (VNB) are more preferred. Of these, 5-ethylidene-2-norbornene (ENB) or 5-vinyl-2-norbornene (VNB) is particularly preferred.

[Non-conjugated linear polyene]
Specific examples of non-conjugated linear polyenes include 1,4-hexadiene, 1,5-heptadiene, 1,6-octadiene, 1,7-nonadiene, 1,8-decadiene, and 1,12-tetradecadiene. , 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4-ethyl-1,4-hexadiene, 3,3-dimethyl-1,4 -hexadiene, 5-methyl-1,4-heptadiene, 5-ethyl-1,4-heptadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene, 5-ethyl-1,5 -heptadiene, 4-methyl-1,4-octadiene, 5-methyl-1,4-octadiene, 4-ethyl-1,4-octadiene, 5-ethyl-1,4-octadiene, 5-methyl-1,5 -octadiene, 6-methyl-1,5-octadiene, 5-ethyl-1,5-octadiene, 6-ethyl-1,5-octadiene, 6-methyl-1,6-octadiene, 7-methyl-1,6 -octadiene, 6-ethyl-1,6-octadiene, 6-propyl-1,6-octadiene, 6-butyl-1,6-octadiene, 7-methyl-1,6-octadiene, 6,7-dimethyl-1 ,6-octadiene, 4-methyl-1,4-nonadiene, 5-methyl-1,4-nonadiene, 4-ethyl-1,4-nonadiene, 5-ethyl-1,4-nonadiene, 5-methyl-1 ,5-nonadiene, 6-methyl-1,5-nonadiene, 5-ethyl-1,5-nonadiene, 6-ethyl-1,5-nonadiene, 6-methyl-1,6-nonadiene, 7-methyl-1 ,6-nonadiene, 6-ethyl-1,6-nonadiene, 7-ethyl-1,6-nonadiene, 7-methyl-1,7-nonadiene, 8-methyl-1,7-nonadiene, 7-ethyl-1 ,7-nonadiene, 6,7-dimethyl-1,6-nonadiene, 5-methyl-1,4-decadiene, 5-ethyl-1,4-decadiene, 5-methyl-1,5-decadiene, 6-methyl -1,5-decadiene, 5-ethyl-1,5-decadiene, 6-ethyl-1,5-decadiene, 6-methyl-1,6-decadiene, 6-ethyl-1,6-decadiene, 7-methyl -1,6-decadiene, 7-ethyl-1,6-decadiene, 7-methyl-1,7-decadiene, 8-methyl-1,7-decadiene, 7-ethyl-1,7-decadiene, 8-ethyl -1,7-deca Diene, 8-methyl-1,8-decadiene, 9-methyl-1,8-decadiene, 8-ethyl-1,8-decadiene, 6-methyl-1,6-undecadiene, 9-methyl-1,8- and undecadiene.

Examples of other non-conjugated chain polyenes include α,ω-dienes such as 1,7-octadiene and 1,9-decadiene. XVI-I] and non-conjugated trienes or tetraenes.

式［XVI-I］において、ｐおよびrは、０または１（ただしｐとrとは同時に０ではない）、
qは０～５の整数（ただしｐとrの両方が１の場合qは０ではない）、
sは１～６の整数、
Ｒ¹⁴、Ｒ¹⁵、Ｒ¹⁶、Ｒ¹⁷、Ｒ¹⁸、Ｒ¹⁹およびＲ²⁰はそれぞれ独立して水素原子または炭素数１～３のアルキル基、
Ｒ²¹は炭素数１～３のアルキル基、
Ｒ²²は水素原子、炭素数１～３のアルキル基または－(ＣＨ₂)_n－ＣＲ²³＝Ｃ(Ｒ²⁴)Ｒ²⁵で表される基（ここでｎは１～５の整数、Ｒ²³およびＲ²⁴はそれぞれ独立して水素原子または炭素数１～３のアルキル基、Ｒ²⁵は炭素数１～３のアルキル基である）
である。ただしｐとrの両方が１の場合、Ｒ²²は水素原子または炭素数１～３のアルキル基である。

In formula [XVI-I], p and r are 0 or 1 (but p and r are not 0 at the same time),
q is an integer from 0 to 5 (however, q is not 0 if both p and r are 1),
s is an integer from 1 to 6;
R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms;
R ²¹ is an alkyl group having 1 to 3 carbon atoms;
R ²² is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a group represented by —(CH ₂ ) _n —CR ²³ ═C(R ²⁴ )R ²⁵ (where n is an integer of 1 to 5, R ²³ and R ²⁴ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ²⁵ is an alkyl group having 1 to 3 carbon atoms.)
is. However, when both p and r are 1, R ²² is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

Among the non-conjugated trienes and tetraenes represented by the above general formula [XVI-I], the non-conjugated trienes represented by the following general formula [XVI-II] are preferred.

式［XVI-II］において、Ｒ¹⁶、Ｒ¹⁷、Ｒ²⁰、Ｒ²¹およびＲ²²はそれぞれ独立して水素原子、メチル基またはエチル基である。ただし、Ｒ²¹とＲ²²とが同時に水素原子になることはない。

In formula [XVI-II], R ¹⁶ , R ¹⁷ , R ²⁰ , R ²¹ and R ²² are each independently a hydrogen atom, a methyl group or an ethyl group. However, R ²¹ and R ²² are not hydrogen atoms at the same time.

The non-conjugated triene represented by the above general formula [XVI-II] is the non-conjugated triene or tetraene represented by the above general formula [XVI-I] where p is 0, q is 0, r is 1, and s is 2. , R ¹⁸ and R ¹⁹ are hydrogen atoms. Furthermore, among the non-conjugated trienes represented by the general formula [XVI-II], compounds in which both R ²⁰ and R ²² are methyl groups are preferred.

Specific examples of the non-conjugated triene or tetraene represented by the above general formula [XVI-I] include the following compounds (excluding compounds contained in the above general formula [XVI-II]).

上記一般式［XVI-II］で表される非共役トリエンとしては、具体的には下記化合物などが挙げられる。

Specific examples of the non-conjugated triene represented by the general formula [XVI-II] include the following compounds.

上記一般式［XVI-I］で表される非共役トリエンまたはテトラエンは公知の方法で製造することができ、その方法は例えば本出願人による特開平９－２３５３２７号公報、特開２００１－１１４８３７号公報などに詳細に記載されている。

The non-conjugated triene or tetraene represented by the above general formula [XVI-I] can be produced by a known method. It is described in detail in publications and the like.

According to the present invention, high-temperature polymerization of an ethylene/α-olefin/non-conjugated polyene copolymer can be achieved by using the polymerization catalyst capable of producing a high-molecular-weight ethylene/α-olefin/non-conjugated polyene copolymer. It becomes possible. That is, by using the olefin polymerization catalyst, the molecular weight of the ethylene/α-olefin/non-conjugated polyene copolymer produced during high-temperature polymerization can be maintained at a desired high value. In solution polymerization, the viscosity of the polymerization solution containing the produced ethylene / α-olefin / non-conjugated polyene copolymer decreases at high temperatures, so the ethylene / α-olefin / non-conjugated polyene in the polymerization vessel is lower than during low-temperature polymerization. It becomes possible to increase the concentration of the copolymer, and as a result, the productivity per polymerization vessel is improved. The copolymerization of ethylene, an α-olefin and a non-conjugated polyene in the present invention can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization (slurry polymerization) or a gas phase polymerization method. Solution polymerization is particularly preferred from the viewpoint of maximizing the effects of the present invention.

The method of use and the order of addition of each component of the polymerization catalyst are arbitrarily selected. Moreover, at least two or more of each component in the catalyst may be contacted in advance.
The bridged metallocene compound (A) (hereinafter also referred to as "component (A)") is generally used in an amount of 10 ^-9 to 10 ^-1 mol, preferably 10 ^-8 to 10 ^-2 mol, per liter of reaction volume. Used in quantity.

The organometallic compound (B-1) (hereinafter also referred to as “component (B-1)”) has a molar ratio between the component (B-1) and the transition metal atom (M) in the component (A) [( B-1)/M] is usually 0.01 to 50,000, preferably 0.05 to 10,000.

The organoaluminumoxy compound (B-2) (hereinafter also referred to as "component (B-2)") is composed of the aluminum atom in component (B-2) and the transition metal atom (M) in component (A). is used in an amount such that the molar ratio of [(B-2)/M] is generally 10 to 5,000, preferably 20 to 2,000.

The compound (B-3) (hereinafter also referred to as “component (B-3)”) that reacts with the bridged metallocene compound (A) to form an ion pair is composed of component (B-3) and component (A). is used in an amount such that the molar ratio of [(B-3)/M] to the transition metal atom (M) is generally 1 to 10,000, preferably 1 to 5,000.

The polymerization temperature is usually 50°C to 300°C, preferably 80°C to 250°C, more preferably 100°C to 200°C. As described above, in the present invention, high-temperature polymerization provides the advantages of improved productivity and reduced production costs. I don't like it because there is In addition, from the viewpoint of the properties of the ethylene/α-olefin/non-conjugated polyene copolymer produced in the present invention, ethylene, which is suitably used in many industrial fields such as films, when the polymerization temperature is in the range of 100 ° C. to 200 ° C. /α-olefin/non-conjugated polyene copolymer can be efficiently produced.

The polymerization pressure is usually normal pressure to 10 MPa gauge pressure (MPa-G), preferably normal pressure to 8 MPa-G.
The polymerization reaction can be carried out in any of a batch system, a semi-continuous system and a continuous system. Furthermore, it is also possible to carry out the polymerization continuously in two or more polymerization vessels having different reaction conditions.

The molecular weight of the obtained ethylene/α-olefin/nonconjugated polyene copolymer can be adjusted by changing the hydrogen concentration in the polymerization system and the polymerization temperature. Furthermore, it can also be adjusted by the amount of component (B) used. When hydrogen is added, the appropriate amount thereof is about 0.001 to 5000 NL per kg of ethylene/α-olefin/non-conjugated polyene copolymer to be produced.

The polymerization solvent used in the liquid phase polymerization method is usually an inert hydrocarbon solvent, preferably a saturated hydrocarbon having a boiling point of 50°C to 200°C under normal pressure. Specific examples of the polymerization solvent include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene, and alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane. and particularly preferably hexane, heptane, octane, decane, and cyclohexane. The α-olefin to be polymerized itself can also be used as a polymerization solvent. Aromatic hydrocarbons such as benzene, toluene, and xylene and halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane can also be used as polymerization solvents. From the viewpoint of minimizing the impact of

The ethylene/α-olefin/non-conjugated polyene copolymer produced by the production method of the present invention comprises (i) a structural unit (ethylene unit) derived from ethylene and (ii) an α-olefin having 3 or more carbon atoms and a structural unit (α-olefin unit) derived from is usually contained in the range of 99/1 to 1/99 in terms of molar ratio [(i)/(ii)], but there is no particular limitation.

The content of structural units derived from ethylene in the ethylene/α-olefin/non-conjugated polyene copolymer produced by the production method of the present invention is usually 50 mol % or more.
The structural unit derived from the non-conjugated polyene compound of the ethylene/α-olefin/non-conjugated polyene copolymer produced by the production method of the present invention is not particularly limited, but usually 0.1 to 49 mol in all structural units. %, preferably 0.2-8 mol %, more preferably 0.3-5 mol %.

The intrinsic viscosity [η] of the ethylene/α-olefin/non-conjugated polyene copolymer produced by the production method of the present invention measured in decalin at 135°C is not particularly limited, but is usually 0.02 to 20 dl/g. , preferably in the range 0.05 to 10 dl/g. When [η] is within this range, it is preferable from the viewpoint of excellent moldability.

The ethylene/α-olefin/non-conjugated polyene copolymer produced by the production method of the present invention preferably has a B value of ≧1.05 as calculated by the following formula [XVII].
B value = (c + d) / [2 x a x (e + f)] ‥‥[XVII]
In formula [XVII], a, e and f are the ethylene mole fraction, α-olefin mole fraction and non-conjugated polyene mole fraction in the ethylene/α-olefin/non-conjugated polyene copolymer, respectively, and c is ethylene - α-olefin diad mole fraction, d is the ethylene-nonconjugated polyene diad mole fraction.

The B value is an index indicating the randomness of the copolymerization monomer chain distribution in the copolymer, and a, c, d, e, and f in the above formula [XVII] are determined by measuring the ¹³ C NMR spectrum, JC Randall [Macromolecules, 15, 353 (1982)], J. Ray [Macromolecules, 10, 773 (1977)].

Ethylene/α-olefin/non-conjugated polyene copolymers with a B value of ≧1.05 have stronger alternating copolymerizability of monomers than ethylene/α-olefin/non-conjugated polyene copolymers with a B value of <1.05, As a result, the average chain length of ethylene is short, and low-temperature properties, which are one of the important physical properties, are good. Also, the larger the B value, the shorter the block-like chain of α-olefin units or non-conjugated polyene units (the stronger the alternating copolymerizability), and the more uniform the distribution of α-olefin units and non-conjugated polyene units. showing. On the other hand, the smaller the B value, the less uniform the distribution of the α-olefin units and the non-conjugated polyene units in the non-conjugated polyene copolymer (weak alternating copolymerizability), and the longer the block chain. The length of this block chain affects the physical properties of the ethylene/α-olefin/non-conjugated polyene copolymer. indicates In addition, the smaller the B value is than 1.00, the wider the composition distribution in the polymer chain of the ethylene / α-olefin / non-conjugated polyene copolymer. For example, when vulcanized, physical properties such as strength may not be sufficiently exhibited.

By the production method of the present invention, an ethylene/α-olefin/non-conjugated polyene copolymer having a B value of ≧1.05 can be obtained. When using the constrained geometry catalyst described, the resulting ethylene/α-olefin/non-conjugated polyene copolymer has a B value of less than 1.05.

The ratio (Mw/Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by GPC of the ethylene/α-olefin/non-conjugated polyene copolymer obtained by the production method of the present invention is usually 1.0 to 4.0, preferably 1.2 to 3.5, more preferably 1.5 to 3.2. When Mw/Mn is within this range, it is preferable in terms of the balance between mechanical strength and workability (kneading, extrusion).

EXAMPLES The present invention will be described in more detail based on examples below, but the present invention is not limited to these examples.
The structure of the bridged metallocene compound and its precursor was determined by measuring ¹ H NMR spectrum (270 MHz, JEOL GSH-270), FD-mass (FD-MS) spectrum (JEOL SX-102A), etc. .
The physical properties/characteristics of the ethylene/α-olefin/non-conjugated polyene copolymer were measured by the following methods.

[Ethylene content, propylene content, 5-ethylidene-2-norbornene (ENB) content]
Using o-dichlorobenzene/benzene-d ₆ (4/1[vol/vol%]) as the measurement solvent, the measurement temperature is 120°C, the spectrum width is 250 ppm, the pulse repetition time is 5.5 seconds, and the pulse width is 4.7 sec (45 ^O pulses). Under measurement conditions (100 MHz, JEOL ^ECX400P ), or under measurement conditions (125 MHz, Bruker Biospin AVANCEIIIcryo -500), the ¹³ C NMR spectrum was measured and calculated.

[B value]
Using o-dichlorobenzene/benzene-d ₆ (4/1[vol/vol%]) as the measurement solvent, the measurement temperature is 120°C, the spectrum width is 250 ppm, the pulse repetition time is 5.5 seconds, and the pulse width is 4.7 sec (45 ^O pulses). Under measurement conditions (100 MHz, JEOL ^ECX400P ), or under measurement conditions (125 MHz, Bruker Biospin AVANCEIIIcryo ^-500 ), and calculated based on the following general formula [XVII].
B value = (c + d) / [2 x a x (e + f)] ‥ [XVII]
In formula [XVII], a, e and f are the ethylene mole fraction, α-olefin mole fraction and non-conjugated polyene mole fraction in the ethylene/α-olefin/non-conjugated polyene copolymer, respectively, and c is ethylene - α-olefin diad mole fraction, d is the ethylene-nonconjugated polyene diad mole fraction.

[Weight average molecular weight (Mw), number average molecular weight (Mn)]
Weight-average molecular weight (Mw) and number-average molecular weight (Mn) were measured using a gel permeation chromatograph Alliance GPC 2000 manufactured by Waters as follows. The separation columns are TSKgel GMH6-HT: 2 and TSKgel GMH6-HTL: 2 (both manufactured by Tosoh Corporation), the column size is 7.5 mm in diameter and 300 mm in length, and the column temperature is 140 ° C. o-Dichlorobenzene (Wako Pure Chemical Industries) and 0.025% by weight of BHT (Takeda Pharmaceutical) as an antioxidant were used as the mobile phase, and the mobile phase was moved at a rate of 1.0 ml/min. , the sample injection volume was 500 μl, and a differential refractometer was used as a detector. Standard polystyrene used was manufactured by Tosoh Corporation for molecular weights Mw<1000 and Mw>4×10 ⁵ , and pressure chemical for molecular weights of 1000≦Mw≦4×10 ⁵ . Various average molecular weights were calculated in terms of polystyrene molecular weight according to the general-purpose calibration procedure.

[Ratio of weight average molecular weight to number average molecular weight (Mw/Mn)]
It was calculated by dividing Mw measured by the above measuring method by Mn similarly measured by the above measuring method.

[Intrinsic viscosity ([η])]
Measured at 135°C using decalin solvent. About 20 mg of the polymer was dissolved in 15 ml of decalin, and the specific viscosity η _sp was measured in an oil bath at 135°C. 5 ml of the decalin solvent was added to the decalin solution to dilute it, and then the specific viscosity η _sp was measured in the same manner. This dilution operation was repeated twice, and the value of η _sp /C when the concentration (C) was extrapolated to 0 was adopted as the intrinsic viscosity.
[η]=lim( _ηsp /C) (C→0)

[Synthesis Example 1]
[bis(4-methoxyphenyl)methylene(η ⁵ -cyclopentadienyl)(η ⁵ -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene)) ] Synthesis of Zirconium Dichloride (i) Bis(4-methoxyphenyl)(cyclopentadienyl)-7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene)methane 30 ml of dehydrated cyclopentyl methyl ether and 2.29 g (11.1 mmol) of 2,5-dimethyl-7H-cyclopenta[1,2-b:4,3-b']-dithiophene were placed in a 100 ml three-necked flask under a nitrogen atmosphere. loaded. To this solution, 7.16 ml (11.1 mmol) of a hexane solution (1.55 M) of n-butyllithium was added dropwise over 5 minutes under an ice water bath. Stirred at room temperature for 1 hour. 2.90 g (10.0 mmol) of 6,6-bis(4-methylphenyl)fulvene was added and stirred at room temperature for 15 hours. A saturated aqueous ammonium chloride solution was added to the reaction solution, the organic layer was separated, the aqueous layer was extracted with 300 ml of methylene chloride, and the organic layer was combined and washed with water and a saturated aqueous sodium chloride solution. After drying with magnesium sulfate, the solvent was distilled off. The resulting solid was washed with diethyl ether to give bis(4-methoxyphenyl)(cyclopentadienyl)-7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b'] -dithiophene)methane was obtained as a white powder. The yield was 1.94 g, a yield of 63%. The identification of bis(4-methoxyphenyl)(cyclopentadienyl)-7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene)methane is based on the FD-MS spectrum. went. The measured values are shown below.
FD-MS spectrum: M/z 497 (M ⁺ )

(ii) [bis(4-methoxyphenyl)methylene(η ⁵ -cyclopentadienyl)(η ⁵ -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']- Synthesis of dithiophene))]zirconium dichloride Bis(4-methoxyphenyl)(cyclopentadienyl)-7-(2,5-dimethyl-cyclopenta[1,2-b:4, 0.497 g (1.00 mmol) of 3-b']-dithiophene)methane, 144 mg (2.00 mmol) of dehydrated tetrahydrofuran, and 30 mL of dehydrated toluene were charged. After cooling with a dry ice/acetone bath, 1.29 ml (2.0 mmol) of 1.55 M n-butyllithium hexane solution was added dropwise over 10 minutes. After warming to room temperature, the mixture was stirred for 4 hours. After cooling with a dry ice/acetone bath, 0.233 g (1.00 mmol) of zirconium tetrachloride was added and reacted at room temperature for 17 hours. After distilling off the solvent, about 15 ml of dehydrated dichloromethane was added to extract the soluble matter. The resulting solution was concentrated, 5 mL of dehydrated diethyl ether and 2 mL of dehydrated hexane were added, the precipitated solid was collected by filtration, and [bis(4-methoxyphenyl)methylene(η ⁵ -cyclopentadienyl) was obtained as an orange powder. (η ⁵ -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b′]-dithiophene))]zirconium dichloride was obtained. Yield was 0.350 g, 53% yield. [bis(4-methoxyphenyl)methylene(η ⁵ -cyclopentadienyl) (η ⁵ -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene)) ] Zirconium dichloride was identified by ¹ H NMR spectrum and FD-MS spectrum. The measured values are shown below.
¹ H NMR spectrum (270 MHz, C ₆ D ₆ ): δ/ppm 7.46 (d, J = 8.9, 4H), 6.81 (d, J = 8.9, Hz, 4H), 6.72 (d, J = 1.3 Hz, 2H), 6.41 (d, J = 2.6 Hz, 2H), 5.89 (d, J = 2.6 Hz, 2H), 3.28 (s, 6H), 2.19 (d, J = 1.3 Hz, 6H)
FD-MS spectrum: M/z 656 (M ⁺ )

[Example 1]
[bis(4-methoxyphenyl)methylene(η ⁵ -cyclopentadienyl) (η ⁵ -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene)) ] Copolymerization of ethylene/propylene/ENB with zirconium dichloride 1030 mL of n-hexane and 4.0 mL of ENB, from which impurities have been removed with activated alumina, are charged at 25°C into a 2-liter stainless steel (SUS) autoclave that has been sufficiently purged with nitrogen. and maintained at 95°C after sealing. Propylene was charged at a partial pressure of 0.90 MPa, and then the pressure was increased to 1.60 MPa-G with ethylene. First, 0.3 mL of a 1 M toluene solution of triisobutylaluminum was injected, and then 0.0001 M of [bis(4-methoxyphenyl)methylene(η ⁵ -cyclopentadienyl) (η ⁵ -7-(2,5- 0.3 mL of a toluene solution of dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene))]zirconium dichloride was injected. Subsequently, 1.2 mL of a toluene solution of 0.0001 M triphenylcarbenium tetrakis(pentafluorophenyl)borate was pressurized to carry out a polymerization reaction for 15 minutes. During the polymerization reaction, the temperature was maintained at 95°C and the pressure was maintained at 1.60 MPa-G by pressurizing ethylene. After 15 minutes from the initiation of the polymerization reaction, 2 mL of methanol was injected with nitrogen to terminate the polymerization reaction.

The resulting polymerization solution was mixed with 1 L of methanol/acetone mixed solution (1/1 [vol/vol%]) containing 5 mL of concentrated hydrochloric acid, and then stirred for 1 hour at room temperature to deash. The precipitated ethylene/propylene/ENB copolymer was collected by filtration and dried at 130°C and -600 mmHg for 10 hours. 9.04 g of an ethylene/propylene/ENB copolymer of 6.1 wt% and [η] = 1.06 dl/g was obtained. Table 1 shows the results.

[Comparative Example 1]
Ethylene/propylene/ENB copolymerization with [bis(4-methylphenyl)silylene(η ⁵ -cyclopentadienyl)(η ⁵ -2,7-di-tert-butyl-fluorenyl)]hafnium dichloride. 1030 mL of n-hexane and 5.0 mL of ENB, from which impurities were removed with activated alumina, were introduced into a stainless steel (SUS) autoclave having an inner volume of 2 L at 25°C, sealed and maintained at 95°C. Propylene was charged at a partial pressure of 0.40 MPa, and then the pressure was increased to 1.60 MPa-G with ethylene. First, 0.3 mL of a 1 M toluene solution of triisobutylaluminum was injected, and then 0.0001 M of [bis(4-methylphenyl)silylene(η ⁵ -cyclopentadienyl)(η ⁵ -2,7-di- 2.5 mL of a toluene solution of tert-butyl-fluorenyl)]hafnium dichloride was injected. Subsequently, 4.0 mL of a toluene solution of 0.001 M triphenylcarbenium tetrakis(pentafluorophenyl)borate was pressurized to carry out a polymerization reaction for 15 minutes. During the polymerization reaction, the temperature was maintained at 95°C and the pressure was maintained at 1.60 MPa-G by pressurizing ethylene. After 15 minutes from the initiation of the polymerization reaction, 2 mL of methanol was injected with nitrogen to terminate the polymerization reaction.

The resulting polymerization solution was mixed with 1 L of methanol/acetone mixed solution (1/1 [vol/vol%]) containing 5 mL of concentrated hydrochloric acid, and then stirred for 1 hour at room temperature to deash. The precipitated ethylene/propylene/ENB copolymer was collected by filtration and dried at 130°C and -600 mmHg for 10 hours. 11.7 g of an ethylene/propylene/ENB copolymer of 3.5 wt% and [η] = 3.29 dl/g was obtained. Table 1 shows the results.

注）成分（Ａ）として以下の架橋メタロセン化合物を使用した。
i : [ビス(4-メトキシフェニル)メチレン(η⁵-シクロペンタジエニル) (η⁵-7-(2,5-ジメチル-シクロペンタ[1,2-b:4,3-b']-ジチオフェン))]ジルコニウムジクロリド
ii : [ビス(4-メチルフェニル)シリレン(η⁵-シクロペンタジエニル)(η⁵-2, 7-ジ-tert-ブチル-フルオレニル)]ハフニウムジクロリド

Note) The following bridged metallocene compounds were used as component (A).
i : [bis(4-methoxyphenyl)methylene(η ⁵ -cyclopentadienyl) (η ⁵ -7-(2,5-dimethyl-cyclopenta[1,2-b:4,3-b']-dithiophene ))] zirconium dichloride
ii : [bis(4-methylphenyl)silylene(η ⁵ -cyclopentadienyl)(η ⁵ -2,7-di-tert-butyl-fluorenyl)]hafnium dichloride

Claims (13)

(A) a bridged metallocene compound represented by the following general formula [I], and
(B) at least one compound selected from (B-1) an organometallic compound, (B-2) an organoaluminumoxy compound, and (B-3) a compound that forms an ion pair by reacting with the bridged metallocene compound (A); A method for producing an ethylene/α-olefin/non-conjugated polyene copolymer, comprising copolymerizing ethylene, an α-olefin having 3 or more carbon atoms, and a conjugated polyene in the presence of an olefin polymerization catalyst containing a compound. .

[wherein Y is a carbon atom, a silicon atom, a germanium atom or a tin atom,
M is a titanium atom, a zirconium atom or a hafnium atom,
R ¹ , R ² , R ³ , R ⁴ , R ⁷ and R ⁸ are a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an aryl group, a substituted aryl group, a silicon-containing group, a nitrogen-containing group or an oxygen-containing group; , an atom or substituent selected from a halogen atom and a halogen-containing group, each of which may be the same or different,
R ⁵ and R ⁶ are aryl groups or substituted aryl groups and may be the same or different;
Adjacent substituents of R ¹ to R ⁶ may be bonded together to form a ring,
A and B are a sulfur atom, an oxygen atom or ^CR9 , and R9 is a hydrogen atom, a hydrocarbon group having ¹ to 20 carbon atoms, an aryl group, a substituted aryl group, a silicon-containing group, a nitrogen-containing group, an oxygen-containing is an atom or substituent selected from a group, a halogen atom and a halogen-containing group, and when A is a sulfur atom or an oxygen atom, B is ^CR9 , and when B is a sulfur atom or an oxygen atom, A is CR ⁹ and the ring containing A and B has a double bond at any possible position;
Q is selected in the same or different combination from a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an anionic ligand and a neutral ligand capable of coordinating with a lone electron pair;
n is an integer from 1 to 4;
j is an integer from 1 to 4; ] 2. The method for producing an ethylene/α-olefin/non-conjugated polyene copolymer according to claim 1, wherein n in the formula [I] is 1. 3. The method for producing an ethylene/α-olefin/non-conjugated polyene copolymer according to claim 1 or 2, wherein A or B in the formula [I] is a sulfur atom and the other is CH. The method for producing an ethylene/α-olefin/non-conjugated polyene copolymer according to claim 3, wherein R ¹ , R ² , R ³ and R ⁴ in the formula [I] are all hydrogen atoms. . 5. The method for producing an ethylene/α-olefin/non-conjugated polyene copolymer according to claim 4, wherein Y in the formula [I] is a carbon atom or a silicon atom. R ⁵ and R ⁶ in the above formula [I] are substituted aryl groups in which at least one hydrogen atom of the aryl group is substituted with an electron-donating substituent having a Hammett rule substituent constant σ of −0.2 or less. and in the case of having a plurality of said electron donating substituents, each of said electron donating substituents may be the same or different, and a hydrocarbon group having 1 to 20 carbon atoms other than said electron donating substituents , a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom, and a halogen-containing group. The method for producing an ethylene/α-olefin/non-conjugated polyene copolymer according to any one of claims 1 to 5 , characterized in that the aryl group is an optionally substituted aryl group. The ethylene / α ^{- olefin} / non A method for producing a conjugated polyene copolymer. The method for producing an ethylene/α-olefin/non-conjugated polyene copolymer according to any one of claims 1 to 7 , wherein M in the formula [I] is a zirconium atom or a hafnium atom. The method for producing an ethylene/α-olefin/non-conjugated polyene copolymer according to any one of claims 1 to 8 , wherein the α-olefin is an α-olefin having 3 to 10 carbon atoms. . The method for producing an ethylene/α-olefin/non-conjugated polyene copolymer according to any one of claims 1 to 9 , wherein the α-olefin is propylene. The method for producing an ethylene/α-olefin/non-conjugated polyene copolymer according to any one of claims 1 to 10 , wherein the non-conjugated polyene is represented by the following general formula [IV]. .

[wherein n is an integer from 0 to 2,
R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are atoms or substituents selected from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom and a halogen-containing group; , which may be the same or different, and the hydrocarbon group may have a double bond,
Any two substituents of R ¹⁰ to R ¹³ may be bonded together to form a ring, and the ring may contain a double bond, and R ¹⁰ and R ¹¹ or R ¹² and R ¹³ may form an alkylidene group, R ¹⁰ and R ¹² or R ¹¹ and R ¹³ may bind to each other to form a double bond,
At least one of the following requirements (i) through (iv) is met.
⁽ i) ^At least one of R10 to R13 is a hydrocarbon group having one or more double bonds.
⁽ ii) Any two substituents from R10 to ^R13 are joined together to form a ring, and the ring contains a dimerization.
(iii) R ¹⁰ and R ¹¹ or R ¹² and R ¹³ form an alkylidene group.
(iv) R ¹⁰ and R ¹² or R ¹¹ and R ¹³ are bonded to each other to form a double bond; ] 12. The ethylene/ A method for producing an α-olefin/non-conjugated polyene copolymer. The method for producing an ethylene/α-olefin/non-conjugated polyene copolymer according to any one of claims 1 to 12 , characterized in that the polymerization temperature is 80°C or higher.