WO2009081794A1 - Method for producing ethylene/α-olefin/nonconjugated polyene copolymer - Google Patents

Abstract

Disclosed is a method for efficiently and economically producing an ethylene/α-olefin/nonconjugated polyene copolymer having various excellent characteristics. In the method for producing an ethylene/α-olefin/nonconjugated polyene copolymer, ethylene, an α-olefin and a nonconjugated polyene are copolymerized in the presence of an olefin polymerization catalyst which contains (A) a specific transition metal compound represented by the general formula [I] or [II] below and (B) at least one compound selected from (B-1) organic metal compounds, (B-2) organic aluminumoxy compounds and (B-3) compounds which form an ion pair by reacting with the transition metal compound (A).

Description

Process for producing ethylene / α-olefin / non-conjugated polyene copolymer

The present invention relates to a novel method for producing an ethylene / α-olefin / non-conjugated polyene copolymer using an olefin polymerization catalyst having a specific structure.

Ethylene / α-olefin rubber represented by ethylene / propylene / non-conjugated diene copolymer rubber (EPDM) does not have an unsaturated bond in the main chain of its molecular structure. Because it is superior in heat resistance and weather resistance compared to rubber, it is widely used in applications such as automotive parts, electric wire materials, building civil engineering materials, industrial material parts, and various resin modifiers.

Conventional ethylene / α-olefin / non-conjugated polyene copolymer rubbers such as EPDM generally use a catalyst system (so-called Ziegler-Natta catalyst system) composed of a titanium catalyst or a combination of a vanadium catalyst and an organoaluminum compound. Has been manufactured.

The biggest drawback of this catalyst system is its productivity, and the polymerization activity is low and the catalyst life is short, so that the polymerization at a low temperature around 0 to 50 ° C. is forced. For this reason, the product concentration in the polymerization system is limited due to the viscosity bottleneck of the polymerization solution, and a process for decatalyzing and deashing the product is indispensable. There is a problem that it is difficult to control polymerization because it is a polymerization, which is disadvantageous in terms of production and cost.

On the other hand, metallocene catalyst systems that have been actively studied since the 1980s show superior polymerization activity and α-α olefin copolymerization ability compared to Ziegler-Natta catalyst systems, and are molecular weight distributions because they are single-site catalysts. It has been reported that a novel olefin copolymer having a narrow composition distribution can be produced, and a novel production method has been made for ethylene / α-olefin / non-conjugated polyene copolymer rubber.

However, even in such metallocene catalyst systems, there are many problems that impede commercialization. Examples of problems related to ethylene / α-olefin / non-conjugated polyene copolymer production include polymerization activity applicable to a deashing-free process, high molecular weight that can withstand high-temperature polymerization, and non-conjugated polyene that does not burden the monomer recovery process There are problems in terms of production, cost, and physical properties such as high monomer alternating copolymerization ability for exhibiting good low temperature characteristics in terms of copolymerization and physical properties.

For example, Patent Document 1, Patent Document 2, Patent Document 3, and Patent Document 4 disclose a production method using a geometrically constrained catalyst, and the geometrically constrained catalyst has an ability to copolymerize α-olefin. Although it produces an excellent high molecular weight product, the average copolymer chain length in the ethylene / α-olefin / non-conjugated polyene copolymer is long due to the low alternating copolymerization of the monomers, and as a result, it is one of the key physical properties. The problem remains that the low-temperature characteristics are not excellent. In addition, in the production method using a geometrically constrained catalyst, there is a problem that it is difficult to control the polymerization heat because it often shows high polymerization activity in the initial stage of polymerization.

Patent Document 5, Patent Document 6, Patent Document 7 and the like disclose a bridged metallocene catalyst having a biscyclopentadienyl group or a bisindenyl group as a ligand. However, the polymerization activity is low, and the molecular weight of the resulting ethylene / α-olefin / non-conjugated polyene copolymer is low.

From such a background, it is desired to develop a polymerization catalyst having the advantages of both the geometrically constrained catalyst and the conventional bridged metallocene catalyst. In other words, it can produce high molecular weight polymers that can withstand high-temperature polymerization, has high polymerization activity that does not require a deashing process, high monomer alternating copolymerization ability that affects low-temperature properties, and high non-conjugated polyene that can reduce the load on the recovery process If a polymerization catalyst system having characteristics such as copolymerization ability can be constructed, it is extremely advantageous in terms of production, cost, and physical properties.
EP0416815A2 WO95 / 00526 WO98 / 27103 Publication JP-T-2001-522398 JP 2005-344101 A JP-A-9-151205 JP 2000-507635 Gazette

Therefore, it is desired to develop a production method for producing an ethylene / α-olefin / non-conjugated polyene copolymer having better characteristics more efficiently and cheaply. For example, if a catalyst system with higher polymerization activity can be developed, the production time can be shortened and the amount of catalyst used can be reduced, so that the process of decatalyzing or deashing the product can be omitted, and the product cost can be reduced. Furthermore, it becomes extremely advantageous in terms of quality. In addition, using a catalyst capable of generating a higher molecular weight can also be performed at a higher temperature, and the product concentration in the polymerization vessel can be increased, leading to an improvement in productivity. Furthermore, if a catalyst system with higher non-conjugated polyene copolymerization capability can be developed, the amount of non-conjugated polyene feed can be reduced, the load on the monomer recovery process is reduced, and more efficient and cost-effective production. Will provide a method.

As a result of intensive studies on a novel method for producing an ethylene / α-olefin / non-conjugated polyene copolymer having desirable characteristics, the present inventors have achieved production costs and costs using a metallocene catalyst having a specific structure. The present inventors have found a novel method for producing an ethylene / α-olefin / non-conjugated polyene copolymer excellent in surface and physical properties, and have completed the present invention.

The present invention includes (A) a transition metal compound represented by the following general formula [I] or [II] (in the following description, it may be abbreviated as “bridged metallocene compound”), and (B) ( B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) at least one compound selected from compounds that react with the transition metal compound (A) to form an ion pair. An ethylene / α-olefin / nonconjugated polyene copolymer production method comprising copolymerizing ethylene, an α-olefin and a nonconjugated polyene in the presence of an olefin polymerization catalyst.

In the formula [I] and the formula [II], R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ is selected from a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom, and a silicon-containing group, and may be the same or different, and R ¹ to R Up to ¹⁴ adjacent substituents may be joined together to form a ring.

Y is a silicon atom or a carbon atom,
M is selected from a titanium atom, a zirconium atom, and a hafnium atom.

However, in the formula [I],
When Y is a silicon atom and R ⁵ to R ¹² are all hydrogen atoms, R ¹³ and R ¹⁴ are from groups other than methyl, butyl, phenyl, silicon-substituted phenyl, cyclohexyl, and benzyl. Chosen;
When Y is a silicon atom, and only R ⁶ and R ¹¹ of R ⁵ to R ¹² are both t-butyl groups, R ¹³ and R ¹⁴ are selected from groups other than benzyl and silicon-substituted phenyl groups;
When Y is a carbon atom and R ⁵ to R ¹² are all hydrogen atoms, R ¹³ and R ¹⁴ are a methyl group, an isopropyl group, a t-butyl group, an isobutyl group, a phenyl group, and a pt-butylphenyl group. , Pn-butylphenyl group, silicon-substituted phenyl group, 4-biphenyl group, p-tolyl group, naphthyl group, benzyl group, cyclopentyl group, cyclohexyl group, and xylyl group;
When Y is a carbon atom and only R ⁶ and R ¹¹ of R ⁵ to R ¹² are t-butyl, methyl, or phenyl, R ¹³ and R ¹⁴ are methyl, phenyl, pt Selected from groups other than -butylphenyl group, pn-butylphenyl group, silicon-substituted phenyl group, benzyl group;
When Y is a carbon atom and only R ⁶ is a dimethylamino group, a methoxy group or a methyl group among R ⁵ to R ¹² , R ¹³ and R ¹⁴ are selected from groups other than a methyl group and a phenyl group;
When Y is a carbon atom, and the moiety composed of a fluorenyl group and R ⁵ to R ¹² is b, h-dibenzofluorenyl or a, i-dibenzofluorenyl, R ¹³ and R ¹⁴ are methyl A group other than a phenyl group.

A in the formula [II] represents a divalent saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms which may contain an aromatic ring, and A represents two or more including a ring formed with Y It may contain a ring structure. However, the ring formed by Y and A is selected from groups other than cyclobutylidene, cyclopentylidene and cyclohexylidene when R ⁵ to R ¹² are all hydrogen atoms.

Q is a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a neutral group having 10 or less carbon atoms, a conjugated or nonconjugated diene, an anionic ligand, and neutral coordination capable of coordination with a lone pair of electrons. Chosen from a child. j is an integer of 1 to 4, and when j is 2 or more, Qs may be the same or different.

In the general formula [I] or [II], M is preferably a zirconium atom or a hafnium atom.

The α-olefin preferably has 3 to 20 carbon atoms, more preferably propylene.

The non-conjugated polyene is preferably a compound represented by the following general formula [III].

[In the formula [III], m is an integer of 0 to 2,
R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represents an atom or group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group, and the hydrocarbon group has a double bond. Well,
Any two of R ¹⁵ to R ¹⁸ may be bonded to each other to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring thus formed has a double bond. Well,
R ¹⁵ and R ¹⁶ , or R ¹⁷ and R ¹⁸ may form an alkylidene group,
R ¹⁵ and R ¹⁷ or R ¹⁶ and R ¹⁸ may be bonded to each other to form a double bond.

Provided that at least one of (i) to (iv) is satisfied;
(I) that any two of R ¹⁵ to R ¹⁸ are bonded to each other, and the monocyclic or polycyclic ring has a double bond (ii) with R ¹⁵ and R ¹⁶ , or R ¹⁷ and R ¹⁸ form an alkylidene group (iii) R ¹⁵ and R ¹⁷ or R ¹⁶ and R ¹⁸ are bonded to each other to form a double bond (iv) At least one of R ¹⁵ to R ¹⁸ is an unsaturated hydrocarbon group having one or more double bonds].

In the production method of the present invention, the polymerization temperature when ethylene, α-olefin and non-conjugated polyene are copolymerized is preferably 80 ° C. or higher.

In addition, the B value calculated by the following formula [IV] based on the ¹³ C-NMR spectrum of the copolymer obtained by the copolymerization is preferably 1.05 or more.

B value = (c + d) / [2 × a × (e + f)] [IV]
(In the formula [IV], a, e and f are the ethylene mole fraction, α-olefin mole fraction and non-conjugated polyene mole fraction in the ethylene / α-olefin / nonconjugated polyene copolymer, respectively, and c is Ethylene-α-olefin dyad mole fraction, d is the ethylene-nonconjugated polyene dyad mole fraction).

By the method for producing an ethylene / α-olefin / nonconjugated polyene copolymer according to the present invention, good polymerization activity, good nonconjugated polyene copolymerization ability, a very high molecular weight, and monomer alternating copolymerizability Strong ethylene / α-olefin / non-conjugated polyene copolymer can be obtained. As a result, the present production method solves the problems of the geometrically constrained catalyst and the existing metallocene catalyst system at the same time in terms of productivity and physical properties. In particular, from the feature of having a very high molecular weight, the polymerization temperature can be set higher, which can greatly contribute to cost reduction.

Hereinafter, examples of the transition metal compound (bridged metallocene compound) represented by the general formula [I] or [II], a preferred bridged metallocene compound, a method for producing the bridged metallocene compound used in the present invention, and the present invention are used. Of the crosslinked metallocene compound to be used for the catalyst for ethylene / α-olefin / non-conjugated polyene copolymer, and finally monomers in the presence of the catalyst for ethylene / α-olefin / non-conjugated polyene copolymer The method of polymerizing the will be sequentially described.

Bridged metallocene compound The bridged metallocene compound used in the present invention is represented by the general formula [I] or [II]. In the general formula [I] or [II], R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ R ¹⁴ is selected from a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom, and a silicon-containing group, and may be the same or different, and R ¹ to R Up to ¹⁴ adjacent substituents may be joined together to form a ring.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the hydrocarbon group include an alkyl group having 1 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a substituted aryl group. For example, methyl group, ethyl group, n-propyl group, isopropyl group, allyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, amyl group, n-pentyl group, neopentyl group N-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decanyl group, 3-methylpentyl group, 1,1-diethylpropyl group, 1,1-dimethylbutyl group, 1- Methyl-1-propylbutyl group, 1,1-propylbutyl group, 1,1-dimethyl-2-methylpropyl group, 1-methyl-1-isopropyl-2-methylpropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl Group, cyclooctyl group, norbornyl group, adamantyl group, phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, xylyl group, isopropyl group Examples include a ruphenyl group, a t-butylphenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a phenanthryl group, an anthracenyl group, a benzyl group, and a cumyl group. An oxygen-containing group such as a methoxy group, an ethoxy group, and a phenoxy group, Nitrogen-containing groups such as nitro group, cyano group, N-methylamino group, N, N-dimethylamino group, N-phenylamino group, boron-containing groups such as boranetriyl group, diboranyl group, sulfonyl group, sulfenyl group, etc. Those containing sulfur-containing groups are also exemplified as hydrocarbon groups.

In the hydrocarbon group, a hydrogen atom may be substituted with a halogen atom, and examples thereof include a trifluoromethyl group, a trifluoromethylphenyl group, a pentafluorophenyl group, and a chlorophenyl group.

Examples of the silicon-containing group include a silyl group, a siloxy group, a hydrocarbon-substituted silyl group, and a hydrocarbon-substituted siloxy group. For example, methylsilyl group, dimethylsilyl group, trimethylsilyl group, ethylsilyl group, diethylsilyl group, triethylsilyl group, diphenylmethylsilyl group, triphenylsilyl group, dimethylphenylsilyl group, dimethyl-t-butylsilyl group, dimethyl (pentafluorophenyl) ) A silyl group etc. can be mentioned.

The cyclopentadienyl group having substituents R ¹ to R ⁴ in the general formulas [I] and [II] is an unsubstituted cyclopentadienyl group in which R ¹ to R ⁴ are hydrogen atoms, 3-t- Butylcyclopentadienyl group, 3-methylcyclopentadienyl group, 3-trimethylsilylcyclopentadienyl group, 3-phenylcyclopentadienyl group, 3-adamantylcyclopentadienyl group, 3-amylcyclopentadienyl group Group, 3-position cyclopentadienyl group such as 3-cyclohexylcyclopentadienyl group, 3-t-butyl-5-methylcyclopentadienyl group, 3-t-butyl-5-ethylcyclopentadienyl Group, 3-phenyl-5-methylcyclopentadienyl group, 3,5-di-t-butylcyclopentadienyl group, 3,5-dimethylcyclopent Examples thereof include a 3,5-disubstituted cyclopentadienyl group such as a tadienyl group, a 3-phenyl-5-methylcyclopentadienyl group, and a 3-trimethylsilyl-5-methylcyclopentadienyl group. is not. From the viewpoint of ease of synthesis of the metallocene compound, production cost, and copolymerization ability of the nonconjugated polyene, a cyclopentadienyl group that is unsubstituted (R ¹ to R ⁴ are hydrogen atoms) is preferable.

As the fluorenyl group having substituents R ⁵ to R ¹² in the general formulas [I] and [II],
An unsubstituted fluorenyl group in which R ⁵ to R ¹² are hydrogen atoms;
2-position 1-substituted fluorenyl group such as 2-methylfluorenyl group, 2-t-butylfluorenyl group, 2-phenylfluorenyl group,
4-position 1-substituted fluorenyl group such as 4-methylfluorenyl group, 4-t-butylfluorenyl group, 4-phenylfluorenyl group,
Or 2,7-di-t-butylfluorenyl group, 3,6-di-t-butylfluorenyl group, etc., 2,7-position or 3,6-position disubstituted fluorenyl group,
2,3,6,7-position 4 such as 2,7-dimethyl-3,6-di-t-butylfluorenyl group, 2,7-diphenyl-3,6-di-t-butylfluorenyl group A substituted fluorenyl group,
Alternatively, R ⁶ and R ⁷ represented by the following general formulas [VI] and [V-II] are bonded to each other to form a ring, and R ¹⁰ and R ¹¹ are bonded to each other to form a ring. Examples include, but are not limited to, a 2,3,6,7-position 4-substituted fluorenyl group.

In the formulas [V-I] and [V-II], R ⁵ , R ⁸ , R ⁹ and R ¹² are the same as defined in the general formula [I] or [II].
R ^a , R ^b , R ^c , R ^d , R ^e , R ^f , R ^g and R ^h are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and are bonded to adjacent substituents. To form a ring. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, an amyl group, and an n-pentyl group. In the formula [V-I], R ^x and R ^y are each independently a hydrocarbon group which may have an unsaturated bond having 1 to 3 carbon atoms, and R ^x is ^a bond to R ^a or R ^c. R ^y may form a double bond with R ^e or R ^g bonded together, and R ^x and R ^y may form a double bond Both are preferably saturated or unsaturated hydrocarbon groups having 1 or 2 carbon atoms.

Specific examples of the compound represented by the general formula [VI] or [V-II] include an octamethyloctahydrodibenzofluorenyl group represented by the formula [V-III], a formula [V- IV] tetramethyldodecahydrodibenzofluorenyl group represented by formula [VV], octamethyltetrahydrodicyclopentafluorenyl group represented by formula [VV], hexamethyldihydro represented by formula [V-VI] Examples thereof include a dicyclopentafluorenyl group and a b, h-dibenzofluorenyl group represented by the formula [V-VII].

Any of the transition metal compounds represented by the above general formulas [I] and [II] containing these fluorenyl groups is excellent in the copolymerization ability of the nonconjugated polyene, but when Y is a silicon atom, the 2,7 position 2 Substituted fluorenyl group, 3,6-position 2-substituted fluorenyl group, 2,3,6,7-position 4-substituted fluorenyl group, 2,3,6,7-position 4-substituted fluorenyl group represented by the above general formula [VI] The transition metal compound having a s is particularly excellent. When Y is a carbon atom, an unsubstituted fluorenyl group in which R ⁵ to R ¹² are hydrogen atoms, a 3,6-positioned 2-substituted fluorenyl group, a 2,3,6,7-positioned 4-substituted fluorenyl group, the above general formula [V A transition metal compound having a 2,3,6,7-position 4-substituted fluorenyl group represented by -I] is particularly excellent.

As for the polymerization activity, when Y is a silicon atom or a carbon atom, the 2,7-position 2-substituted fluorenyl group, the 3,6-position 2-substituted fluorenyl group, the 2,3,6,7-position 4-substituted fluorenyl group, the above general The transition metal compounds represented by the above general formulas [I] and [II] having a 2,3,6,7-positioned 4-substituted fluorenyl group represented by the formula [VI] are particularly excellent.

The molecular weight of the ethylene / α-olefin / non-conjugated polyene copolymer to be produced is as follows: Y is a silicon atom or a carbon atom, and the 2,7-position 2-substituted fluorenyl group, the 3,6-position 2-substituted fluorenyl group A transition metal compound having a 2,3,6,7-position 4-substituted fluorenyl group and a 2,3,6,7-position 4-substituted fluorenyl group represented by the above general formula [VI] has a particularly high molecular weight. A polymer can be produced and is suitable for polymerization at higher temperatures.

In the general formulas [I] and [II], R ¹³ and R ¹⁴ may be the same or different from each other. Among the hydrocarbon groups, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, phenyl group, m-tolyl Group, p-tolyl group, 4-t-butylphenyl group, p-chlorophenyl group, 4-biphenyl group, 2-naphthyl group, xylyl group, benzyl group and m-trifluoromethylphenyl group are preferred, and high molecular weight ethylene Since an / α-olefin / non-conjugated polyene copolymer is produced, it is suitable for polymerization at higher temperatures.

In the present invention, in the bridged metallocene compound represented by the general formula [I],
When Y is a silicon atom and R ⁵ to R ¹² are all hydrogen atoms, R ¹³ and R ¹⁴ are from groups other than methyl, butyl, phenyl, silicon-substituted phenyl, cyclohexyl, and benzyl. Chosen;
When Y is a silicon atom, and only R ⁶ and R ¹¹ of R ⁵ to R ¹² are both t-butyl groups, R ¹³ and R ¹⁴ are selected from groups other than benzyl and silicon-substituted phenyl groups;
When Y is a carbon atom and R ⁵ to R ¹² are all hydrogen atoms, R ¹³ and R ¹⁴ are a methyl group, an isopropyl group, a t-butyl group, an isobutyl group, a phenyl group, and a pt-butylphenyl group. , Pn-butylphenyl group, silicon-substituted phenyl group, 4-biphenyl group, p-tolyl group, naphthyl group, benzyl group, cyclopentyl group, cyclohexyl group, and xylyl group;
When Y is a carbon atom and only R ⁶ and R ¹¹ of R ⁵ to R ¹² are t-butyl, methyl, or phenyl, R ¹³ and R ¹⁴ are methyl, phenyl, pt Selected from groups other than -butylphenyl group, pn-butylphenyl group, silicon-substituted phenyl group, benzyl group;
When Y is a carbon atom and only R ⁶ is a dimethylamino group, a methoxy group or a methyl group among R ⁵ to R ¹² , R ¹³ and R ¹⁴ are selected from groups other than a methyl group and a phenyl group;
When Y is a carbon atom, and the moiety composed of a fluorenyl group and R ⁵ to R ¹² is b, h-dibenzofluorenyl or a, i-dibenzofluorenyl, R ¹³ and R ¹⁴ are methyl A group other than a phenyl group.

In the bridged metallocene compound represented by the general formula [II], A is a divalent saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms which may contain an aromatic ring, and Y is For example, a cycloalkylidene group such as a cyclohexylidene group represented by the following formula [VI-I], a cyclotetramethylenesilylene group represented by the following formula [VI-II] (1
Constituting a cyclomethylenesilylene group such as -silacyclopentylidene group).

(In formulas [VI-I] and [VI-II], ● represents the point of attachment to the (substituted) cyclopentadienyl group and (substituted) fluorenyl group in the above general formula [II].)
A may contain two or more ring structures including a ring formed with Y.

Specifically, in addition to the cyclohexylidene group represented by [VI-I] above, a cyclopropylidene group, cyclobutylidene group, cyclopentylidene group, cycloheptylidene group, cyclooctylidene group, bicyclo [3 3.1] Nonylidene group, norbornylidene group, adamantylidene group, tetrahydronaphthylidene group, dihydroindanilidene group and the like.

In addition to the cyclotetramethylenesilylene group (1-silacyclopentylidene group) represented by [VI-II] above, specifically, a cyclodimethylenesilylene group, a cyclotrimethylenesilylene group, a cyclopentamethylenesilylene group, a cyclohexene group, Examples thereof include a samethylenesilylene group and a cycloheptamethylenesilylene group.

In the present invention, in the bridged metallocene compound represented by the general formula [II], when R ⁵ to R ¹² are all hydrogen atoms, the ring formed by Y and A is cyclobutylidene, It is selected from groups other than cyclopentylidene and cyclohexylidene.

In the above general formulas [I] and [II], Y is a silicon atom or a carbon atom.

M is a titanium atom, a zirconium atom or a hafnium atom, preferably a zirconium atom or a hafnium atom. When it is desired to obtain a higher molecular weight ethylene / α-olefin / non-conjugated polyene copolymer, or when polymerization is desired at a higher temperature, a hafnium atom is more preferable.

Q is a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a neutral group having 10 or less carbon atoms, a conjugated or nonconjugated diene, an anionic ligand, and neutral coordination capable of coordination with a lone pair of electrons. Chosen from a child.

J is an integer of 1 to 4, and when j is 2 or more, Q may be the same or different from each other.

Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and preferably a chlorine atom.

Specific examples of the hydrocarbon group having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, 2-methylpropyl group, 1,1-dimethylpropyl group, and 2,2-dimethylpropyl group. 1,1-diethylpropyl group, 1-ethyl-1-methylpropyl group, 1,1,2,2-tetramethylpropyl group, sec-butyl group, t-butyl group, 1,1-dimethylbutyl group, A 1,1,3-trimethylbutyl group, a neopentyl group, a cyclohexylmethyl group, a cyclohexyl group, a 1-methyl-1-cyclohexyl group, a benzyl group, and the like can be given, and a methyl group, an ethyl group, and a benzyl group are preferable.

Neutral having 10 or less carbon atoms, and specific examples of the conjugated or nonconjugated diene, s- cis - or s- trans eta ^{4-1,3-butadiene,} s- cis - or s- trans eta ⁴ - 1,4-diphenyl-1,3-butadiene, s-cis- or s-trans-η ⁴ -3-methyl-1,3-pentadiene, s-cis- or s-trans-η ⁴ -1,4- Dibenzyl-1,3-butadiene, s-cis- or s-trans-η ⁴ -2,4-hexadiene, s-cis- or s-trans-η ⁴ -1,3-pentadiene, s-cis- or s -Trans-η ⁴ -1,4-ditolyl-1,3-butadiene, s-cis- or s-trans-η ⁴ -1,4-bis (trimethylsilyl) -1,3-butadiene and the like.

Specific examples of the anionic ligand include alkoxy groups such as methoxy, t-butoxy and phenoxy, carboxylate groups such as acetate and benzoate, and sulfonate groups such as mesylate and tosylate.

Specific examples of neutral ligands that can be coordinated by a lone pair include organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, diphenylmethylphosphine, tetrahydrofuran, diethyl ether, dioxane, 1,2- And ethers such as dimethoxyethane.

Specific examples of the transition metal compound represented by the above general formulas [I] and [II] in the present invention are shown below in the bridged metallocene compound and its examples, but the scope of the present invention is not particularly limited thereby. .

As specific examples of the transition metal compound represented by the above general formula [I] in the present invention,
When Y is a silicon atom,
Dimethylsilylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) hafnium dichloride,
Dimethylsilylene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) hafnium dichloride,
Dimethylsilylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-t-butylfluorenyl) hafnium dichloride,
Dimethylsilylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-t-butylfluorenyl) hafnium dichloride,
Dimethylsilylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride,
Dimethylsilylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) hafnium dichloride,
Dimethylsilylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) hafnium dichloride,
Dimethylsilylene (cyclopentadienyl) (hexamethyldihydrodicyclopentafluorenyl) hafnium dichloride,
Dimethylsilylene (cyclopentadienyl) (b, h-dibenzofluorenyl) hafnium dichloride,
Diethylsilylene (cyclopentadienyl) (fluorenyl) hafnium dichloride,
Diethylsilylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) hafnium dichloride,
Diethylsilylene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) hafnium dichloride,
Diethylsilylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-t-butylfluorenyl) hafnium dichloride,
Diethylsilylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-t-butylfluorenyl) hafnium dichloride,
Diethylsilylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride,
Diethylsilylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) hafnium dichloride,
Diethylsilylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) hafnium dichloride,
Diethylsilylene (cyclopentadienyl) (hexamethyldihydrodicyclopentafluorenyl) hafnium dichloride,
Diethylsilylene (cyclopentadienyl) (b, h-dibenzofluorenyl) hafnium dichloride,
Di (n-butyl) silylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) hafnium dichloride,
Di (n-butyl) silylene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) hafnium dichloride,
Di (n-butyl) silylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-t-butylfluorenyl) hafnium dichloride,
Di (n-butyl) silylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-t-butylfluorenyl) hafnium dichloride,
Di (n-butyl) silylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride,
Di (n-butyl) silylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) hafnium dichloride,
Di (n-butyl) silylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) hafnium dichloride,
Di (n-butyl) silylene (cyclopentadienyl) (hexamethyldihydrodicyclopentafluorenyl) hafnium dichloride,
Di (n-butyl) silylene (cyclopentadienyl) (b, h-dibenzofluorenyl) hafnium dichloride,
(Methyl) (phenyl) silylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) hafnium dichloride,
(Methyl) (phenyl) silylene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) hafnium dichloride,
(Methyl) (phenyl) silylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-t-butylfluorenyl) hafnium dichloride,
(Methyl) (phenyl) silylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-t-butylfluorenyl) hafnium dichloride,
(Methyl) (phenyl) silylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride,
(Methyl) (phenyl) silylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) hafnium dichloride,
(Methyl) (phenyl) silylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) hafnium dichloride,
(Methyl) (phenyl) silylene (cyclopentadienyl) (hexamethyldihydrodicyclopentafluorenyl) hafnium dichloride,
(Methyl) (phenyl) silylene (cyclopentadienyl) (b, h-dibenzofluorenyl) hafnium dichloride,
(Methyl) (p-tolyl) silylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) hafnium dichloride,
(Methyl) (p-tolyl) silylene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) hafnium dichloride,
(Methyl) (p-tolyl) silylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-t-butylfluorenyl) hafnium dichloride,
(Methyl) (p-tolyl) silylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-t-butylfluorenyl) hafnium dichloride,
(Methyl) (p-tolyl) silylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride,
(Methyl) (p-tolyl) silylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) hafnium dichloride,
(Methyl) (p-tolyl) silylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) hafnium dichloride,
(Methyl) (p-tolyl) silylene (cyclopentadienyl) (hexamethyldihydrodicyclopentafluorenyl) hafnium dichloride,
(Methyl) (p-tolyl) silylene (cyclopentadienyl) (b, h-dibenzofluorenyl) hafnium dichloride,
Diphenylsilylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) hafnium dichloride,
Diphenylsilylene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) hafnium dichloride,
Diphenylsilylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-t-butylfluorenyl) hafnium dichloride,
Diphenylsilylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-t-butylfluorenyl) hafnium dichloride,
Diphenylsilylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride,
Diphenylsilylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) hafnium dichloride,
Diphenylsilylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) hafnium dichloride,
Diphenylsilylene (cyclopentadienyl) (hexamethyldihydrodicyclopentafluorenyl) hafnium dichloride,
Diphenylsilylene (cyclopentadienyl) (b, h-dibenzofluorenyl) hafnium dichloride,
Di (p-tolyl) silylene (cyclopentadienyl) (fluorenyl) hafnium dichloride,
Di (p-tolyl) silylene (cyclopentadienyl) (2,7-di-t-butylfluorene
Nil) hafnium dichloride,
Di (p-tolyl) silylene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) hafnium dichloride,
Di (p-tolyl) silylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-t-butylfluorenyl) hafnium dichloride,
Di (p-tolyl) silylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-t-butylfluorenyl) hafnium dichloride,
Di (p-tolyl) silylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride,
Di (p-tolyl) silylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) hafnium dichloride,
Di (p-tolyl) silylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) hafnium dichloride,
Di (p-tolyl) silylene (cyclopentadienyl) (hexamethyldihydrodicyclopentafluorenyl) hafnium dichloride,
Di (p-tolyl) silylene (cyclopentadienyl) (b, h-dibenzofluorenyl) hafnium dichloride,
Di (m-tolyl) silylene (cyclopentadienyl) (fluorenyl) hafnium dichloride,
Di (m-tolyl) silylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) hafnium dichloride,
Di (m-tolyl) silylene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) hafnium dichloride,
Di (m-tolyl) silylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-t-butylfluorenyl) hafnium dichloride,
Di (m-tolyl) silylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-t-butylfluorenyl) hafnium dichloride,
Di (m-tolyl) silylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride,
Di (m-tolyl) silylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) hafnium dichloride,
Di (m-tolyl) silylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) hafnium dichloride,
Di (m-tolyl) silylene (cyclopentadienyl) (hexamethyldihydrodicyclopentafluorenyl) hafnium dichloride,
Di (m-tolyl) silylene (cyclopentadienyl) (b, h-dibenzofluorenyl) hafnium dichloride,
Dicyclohexylsilylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) hafnium dichloride,
Dicyclohexylsilylene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) hafnium dichloride,
Dicyclohexylsilylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-t-butylfluorenyl) hafnium dichloride,
Dicyclohexylsilylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-t-butylfluorenyl) hafnium dichloride,
Dicyclohexylsilylene (cyclopentadienyl) (octamethyloctahydrodiben
Zofluorenyl) hafnium dichloride,
Dicyclohexylsilylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) hafnium dichloride,
Dicyclohexylsilylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) hafnium dichloride,
Dicyclohexylsilylene (cyclopentadienyl) (hexamethyldihydrodicyclopentafluorenyl) hafnium dichloride,
Dicyclohexylsilylene (cyclopentadienyl) (b, h-dibenzofluorenyl) hafnium dichloride,
When Y is a carbon atom,
Dimethylmethylene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) hafnium dichloride,
Dimethylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-t-butylfluorenyl) hafnium dichloride,
Dimethylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-t-butylfluorenyl) hafnium dichloride,
Dimethylmethylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride,
Dimethylmethylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) hafnium dichloride,
Dimethylmethylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) hafnium dichloride,
Dimethylmethylene (cyclopentadienyl) (hexamethyldihydrodicyclopentafluorenyl) hafnium dichloride,
Dimethylmethylene (cyclopentadienyl) (b, h-dibenzofluorenyl) hafnium dichloride,
Di (n-butyl) methylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) hafnium dichloride,
Di (n-butyl) methylene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) hafnium dichloride,
Di (n-butyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-t-butylfluorenyl) hafnium dichloride,
Di (n-butyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-t-butylfluorenyl) hafnium dichloride,
Di (n-butyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride,
Di (n-butyl) methylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) hafnium dichloride,
Di (n-butyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) hafnium dichloride,
Di (n-butyl) methylene (cyclopentadienyl) (hexamethyldihydrodicyclopentafluorenyl) hafnium dichloride,
Di (n-butyl) methylene (cyclopentadienyl) (b, h-dibenzofluorenyl) hafnium dichloride,
Dibenzylmethylene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) hafnium dichloride,
Dibenzylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-t-butylfluorenyl) hafnium dichloride,
Dibenzylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-t-butylfluorenyl) hafnium dichloride,
Dibenzylmethylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride,
Dibenzylmethylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) hafnium dichloride,
Dibenzylmethylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) hafnium dichloride,
Dibenzylmethylene (cyclopentadienyl) (hexamethyldihydrodicyclopentafluorenyl) hafnium dichloride,
Dibenzylmethylene (cyclopentadienyl) (b, h-dibenzofluorenyl) hafnium dichloride,
(Methyl) (phenyl) methylene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) hafnium dichloride,
(Methyl) (phenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-t-butylfluorenyl) hafnium dichloride,
(Methyl) (phenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-t-butylfluorenyl) hafnium dichloride,
(Methyl) (phenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride,
(Methyl) (phenyl) methylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) hafnium dichloride,
(Methyl) (phenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) hafnium dichloride,
(Methyl) (phenyl) methylene (cyclopentadienyl) (hexamethyldihydrodicyclopentafluorenyl) hafnium dichloride,
(Methyl) (phenyl) methylene (cyclopentadienyl) (b, h-dibenzofluorenyl) hafnium dichloride,
(Methyl) (p-tolyl) methylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) hafnium dichloride,
(Methyl) (p-tolyl) methylene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) hafnium dichloride,
(Methyl) (p-tolyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-t-butylfluorenyl) hafnium dichloride,
(Methyl) (p-tolyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-t-butylfluorenyl) hafnium dichloride,
(Methyl) (p-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride,
(Methyl) (p-tolyl) methylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) hafnium dichloride,
(Methyl) (p-tolyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) hafnium dichloride,
(Methyl) (p-tolyl) methylene (cyclopentadienyl) (hexamethyldihydrodicyclopentafluorenyl) hafnium dichloride,
(Methyl) (p-tolyl) methylene (cyclopentadienyl) (b, h-dibenzofluorenyl) hafnium dichloride,
Diphenylmethylene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) hafnium dichloride,
Diphenylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-t-butylfluorenyl) hafnium dichloride,
Diphenylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-t-butylfluorenyl) hafnium dichloride,
Diphenylmethylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride,
Diphenylmethylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) hafnium dichloride,
Diphenylmethylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) hafnium dichloride,
Diphenylmethylene (cyclopentadienyl) (hexamethyldihydrodicyclopentafluorenyl) hafnium dichloride,
Diphenylmethylene (cyclopentadienyl) (b, h-dibenzofluorenyl) hafnium dichloride,
Di (p-tolyl) methylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) hafnium dichloride,
Di (p-tolyl) methylene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) hafnium dichloride,
Di (p-tolyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-t-butylfluorenyl) hafnium dichloride,
Di (p-tolyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-t-butylfluorenyl) hafnium dichloride,
Di (p-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride,
Di (p-tolyl) methylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) hafnium dichloride,
Di (p-tolyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) hafnium dichloride,
Di (p-tolyl) methylene (cyclopentadienyl) (hexamethyldihydrodicyclopentafluorenyl) hafnium dichloride,
Di (p-tolyl) methylene (cyclopentadienyl) (b, h-dibenzofluorenyl) hafnium dichloride,
Di (m-tolyl) methylene (cyclopentadienyl) (fluorenyl) hafnium dichloride,
Di (m-tolyl) methylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) hafnium dichloride,
Di (m-tolyl) methylene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) hafnium dichloride,
Di (m-tolyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-t-butylfluorenyl) hafnium dichloride,
Di (m-tolyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-t-butylfluorenyl) hafnium dichloride,
Di (m-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride,
Di (m-tolyl) methylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) hafnium dichloride,
Di (m-tolyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) hafnium dichloride,
Di (m-tolyl) methylene (cyclopentadienyl) (hexamethyldihydrodicyclopentafluorenyl) hafnium dichloride,
Di (m-tolyl) methylene (cyclopentadienyl) (b, h-dibenzofluorenyl) hafnium dichloride,
Di (pt-butylphenyl) methylene (cyclopentadienyl) (3,6-di-tert-butylfluorenyl) hafnium dichloride,
Di (pt-butylphenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-tert-butylfluorenyl) hafnium dichloride,
Di (pt-butylphenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-tert-butylfluorenyl) hafnium dichloride,
Di (pt-butylphenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride,
Di (pt-butylphenyl) methylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) hafnium dichloride,
Di (pt-butylphenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) hafnium dichloride,
Di (pt-butylphenyl) methylene (cyclopentadienyl) (hexamethyldihydrodicyclopentafluorenyl) hafnium dichloride,
Di (pt-butylphenyl) methylene (cyclopentadienyl) (b, h-dibenzofluorenyl) hafnium dichloride,
Di (4-biphenyl) methylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) hafnium dichloride,
Di (4-biphenyl) methylene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) hafnium dichloride,
Di (4-biphenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-t-butylfluorenyl) hafnium dichloride,
Di (4-biphenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-t-butylfluorenyl) hafnium dichloride,
Di (4-biphenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride,
Di (4-biphenyl) methylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) hafnium dichloride,
Di (4-biphenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) hafnium dichloride,
Di (4-biphenyl) methylene (cyclopentadienyl) (hexamethyldihydrodicyclopentafluorenyl) hafnium dichloride,
Di (4-biphenyl) methylene (cyclopentadienyl) (b, h-dibenzofluorenyl) hafnium dichloride,
Di (p-chlorophenyl) methylene (cyclopentadienyl) (fluorenyl) hafnium dichloride,
Di (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) hafnium dichloride,
Di (p-chlorophenyl) methylene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) hafnium dichloride,
Di (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-t-butylfluorenyl) hafnium dichloride,
Di (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-t-butylfluorenyl) hafnium dichloride,
Di (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride,
Di (p-chlorophenyl) methylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) hafnium dichloride,
Di (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) hafnium dichloride,
Di (p-chlorophenyl) methylene (cyclopentadienyl) (hexamethyldihydrodi
Cyclopentafluorenyl) hafnium dichloride,
Di (p-chlorophenyl) methylene
(Cyclopentadienyl) (b, h-dibenzofluorenyl) hafnium dichloride,
Di (m-chlorophenyl) methylene (cyclopentadienyl) (fluorenyl) hafnium dichloride,
Di (m-chlorophenyl) methylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) hafnium dichloride,
Di (m-chlorophenyl) methylene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) hafnium dichloride,
Di (m-chlorophenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-t-butylfluorenyl) hafnium dichloride,
Di (m-chlorophenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-t-butylfluorenyl) hafnium dichloride,
Di (m-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride,
Di (m-chlorophenyl) methylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) hafnium dichloride,
Di (m-chlorophenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) hafnium dichloride,
Di (m-chlorophenyl) methylene (cyclopentadienyl) (hexamethyldihydrodicyclopentafluorenyl) hafnium dichloride,
Di (m-chlorophenyl) methylene (cyclopentadienyl) (b, h-dibenzofluorenyl) hafnium dichloride,
Di (m-trifluoromethylphenyl) methylene (cyclopentadienyl) (fluorenyl) hafnium dichloride,
Di (m-trifluoromethylphenyl) methylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) hafnium dichloride,
Di (m-trifluoromethylphenyl) methylene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) hafnium dichloride,
Di (m-trifluoromethylphenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-t-butylfluorenyl) hafnium dichloride,
Di (m-trifluoromethylphenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-t-butylfluorenyl) hafnium dichloride,
Di (m-trifluoromethylphenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride,
Di (m-trifluoromethylphenyl) methylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) hafnium dichloride,
Di (m-trifluoromethylphenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) hafnium dichloride,
Di (m-trifluoromethylphenyl) methylene (cyclopentadienyl) (hexamethyldihydrodicyclopentafluorenyl) hafnium dichloride,
Di (m-trifluoromethylphenyl) methylene (cyclopentadienyl) (b, h-dibenzofluorenyl) hafnium dichloride,
Di (2-naphthyl) methylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) hafnium dichloride,
Di (2-naphthyl) methylene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) hafnium dichloride,
Di (2-naphthyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-t-butylfluorenyl) hafnium dichloride,
Di (2-naphthyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-t-butylfluorenyl) hafnium dichloride,
Di (2-naphthyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride,
Di (2-naphthyl) methylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) hafnium dichloride,
Di (2-naphthyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) hafnium dichloride,
Di (2-naphthyl) methylene (cyclopentadienyl) (hexamethyldihydrodicyclopentafluorenyl) hafnium dichloride,
Di (2-naphthyl) methylene (cyclopentadienyl) (b, h-dibenzofluorenyl) hafnium dichloride, and a compound in which the hafnium atom of the above compound is replaced by a zirconium atom or a titanium atom, or cyclopentadi of the above compound An enyl group is a 3-methylcyclopentadienyl group, 3-phenylcyclopentadienyl group, 3-t-butylcyclopentadienyl group, 3-t-butyl-5-methylcyclopentadienyl group, 3-t -Butyl-5-ethylcyclopentadienyl group, a compound in which 3,5-dimethylcyclopentadienyl group is replaced, a compound in which the chlorine atom of the above compound is replaced with a methyl group, a benzyl group, or a combination thereof Although it is mentioned, it is not limited to these.

Among the hafnium atoms, zirconium atoms, and titanium atoms, it is preferably a zirconium atom or a hafnium atom, and a compound having a hafnium atom generates a high molecular weight, so that polymerization at a higher temperature is possible. From the viewpoint of improving productivity. Further, the cyclopentadienyl group is preferably a cyclopentadienyl group that is unsubstituted (R ¹ to R ⁴ are hydrogen atoms) from the viewpoint of ease of synthesis, production cost, and copolymerization ability of non-conjugated polyene. .

The above compounds may be used alone or in combination of two or more.

As specific examples of the transition metal compound represented by the general formula [II] in the present invention,
When Y is a silicon atom,
Cyclotetramethylenesilylene (cyclopentadienyl) (fluorenyl) hafnium dichloride,
Cyclotetramethylenesilylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) hafnium dichloride,
Cyclotetramethylenesilylene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) hafnium dichloride,
Cyclotetramethylenesilylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-t-butylfluorenyl) hafnium dichloride,
Cyclotetramethylenesilylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-t-butylfluorenyl) hafnium dichloride,
Cyclotetramethylenesilylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride,
Cyclotetramethylenesilylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) hafnium dichloride,
Cyclotetramethylenesilylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) hafnium dichloride,
Cyclotetramethylenesilylene (cyclopentadienyl) (hexamethyldihydrodicyclopentafluorenyl) hafnium dichloride,
Cyclotetramethylenesilylene (cyclopentadienyl) (b, h-dibenzofluorenyl) hafnium dichloride,
Cyclopentamethylenesilylene (cyclopentadienyl) (fluorenyl) hafnium dichloride,
Cyclopentamethylenesilylene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) hafnium dichloride,
Cyclopentamethylenesilylene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) hafnium dichloride,
Cyclopentamethylenesilylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-t-butylfluorenyl) hafnium dichloride,
Cyclopentamethylenesilylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-t-butylfluorenyl) hafnium dichloride,
Cyclopentamethylenesilylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride,
Cyclopentamethylenesilylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) hafnium dichloride,
Cyclopentamethylenesilylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) hafnium dichloride,
Cyclopentamethylenesilylene (cyclopentadienyl) (hexamethyldihydrodicyclopentafluorenyl) hafnium dichloride,
Cyclopentamethylenesilylene (cyclopentadienyl) (b, h-dibenzofluorenyl) hafnium dichloride,
When Y is a carbon atom,
Cyclopentylidene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) hafnium dichloride,
Cyclopentylidene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) hafnium dichloride,
Cyclopentylidene (cyclopentadienyl) (2,7-dimethyl-3,6-di-t-butylfluorenyl) hafnium dichloride,
Cyclopentylidene (cyclopentadienyl) (2,7-diphenyl-3,6-di-t-butylfluorenyl) hafnium dichloride,
Cyclopentylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride,
Cyclopentylidene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) hafnium dichloride,
Cyclopentylidene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) hafnium dichloride,
Cyclopentylidene (cyclopentadienyl) (hexamethyldihydrodicyclopentafluorenyl) hafnium dichloride,
Cyclopentylidene (cyclopentadienyl) (b, h-dibenzofluorenyl) hafnium dichloride,
Cyclohexylidene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) hafnium dichloride,
Cyclohexylidene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) hafnium dichloride,
Cyclohexylidene (cyclopentadienyl) (2,7-dimethyl-3,6-di-t-butylfluorenyl) hafnium dichloride,
Cyclohexylidene (cyclopentadienyl) (2,7-diphenyl-3,6-di-t-butylfluorenyl) hafnium dichloride,
Cyclohexylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride,
Cyclohexylidene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) hafnium dichloride,
Cyclohexylidene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) hafnium dichloride,
Cyclohexylidene (cyclopentadienyl) (hexamethyldihydrodicyclopentafluorenyl) hafnium dichloride,
Cyclohexylidene (cyclopentadienyl) (b, h-dibenzofluorenyl) hafnium dichloride,
Adamantylidene (cyclopentadienyl) (fluorenyl) hafnium dichloride,
Adamantylidene (cyclopentadienyl) (2,7-di-t-butylfluorenyl) hafnium dichloride,
Adamantylidene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) hafnium dichloride,
Adamantylidene (cyclopentadienyl) (2,7-dimethyl-3,6-di-t-butylfluorenyl) hafnium dichloride,
Adamantylidene (cyclopentadienyl) (2,7-diphenyl-3,6-di-t-butylfluorenyl) hafnium dichloride,
Adamantylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride,
Adamantylidene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) hafnium dichloride,
Adamantylidene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) hafnium dichloride,
Adamantylidene (cyclopentadienyl) (hexamethyldihydrodicyclopentafluorenyl) hafnium dichloride,
Adamantylidene (cyclopentadienyl) (b, h-dibenzofluorenyl) hafnium dichloride and a compound in which the hafnium atom of the above compound is replaced with a zirconium atom or a titanium atom, or the cyclopentadienyl group of the above compound is replaced with 3 -Methylcyclopentadienyl group, 3-phenylcyclopentadienyl group, 3-t-butylcyclopentadienyl group, 3-t-butyl-5-methylcyclopentadienyl group, 3-t-butyl-5 -A compound in which an ethylcyclopentadienyl group or a 3,5-dimethylcyclopentadienyl group is replaced, a compound in which the chlorine atom of the above compound is replaced with a methyl group or a benzyl group, or a combination thereof may be mentioned. It is not limited to.

Among the hafnium atoms, zirconium atoms, and titanium atoms, it is preferably a zirconium atom or a hafnium atom, and a compound having a hafnium atom generates a high molecular weight, so that polymerization at a higher temperature is possible. From the viewpoint of improving productivity. Further, the cyclopentadienyl group is preferably a cyclopentadienyl group that is unsubstituted (R ¹ to R ⁴ are hydrogen atoms) from the viewpoint of ease of synthesis, production cost, and copolymerization ability of non-conjugated polyene. .

The above compounds may be used alone or in combination of two or more.

In the transition metal compound represented by the above general formula [I] or [II] used in the present invention, the hafnium atom is a copolymer of ethylene / α-olefin / non-conjugated polyene compared to a titanium atom or a zirconium atom as a central metal. The molecular weight of the polymer is high. This is because (1) the Lewis acidity of the hafnium atom is low and the reactivity is low compared with the zirconium atom and the titanium atom. (2) The bond energy between the hafnium atom and the carbon atom is compared with the zirconium atom and the titanium atom. This is due to the fact that the chain transfer reaction (including β-hydrogen elimination reaction) of the polymerization active species bound to the generated polymer chain, which is one of the molecular weight determining factors, is suppressed. it is conceivable that.

Production Method of Bridged Metallocene Compound The bridged metallocene compound used in the present invention can be produced by a known method, and the production method is not particularly limited. As a manufacturing method, for example, J. Org. Organomet. Chem. , 63, 509 (1996), WO20023723759, WO01 / 27124, JP2004-168744, JP2004-175759, JP2000-212194, which are publications relating to the application by the present applicant. It can be produced by the method described in the publication.

Preferred Form when Using Crosslinked Metallocene Compound as Catalyst for Ethylene / α-Olefin / Nonconjugated Polyene Copolymer Next, the crosslinked metallocene compound used in the present invention is used for ethylene / α-olefin / nonconjugated polyene copolymer. The preferable form in the case of using as a catalyst (olefin polymerization catalyst) is demonstrated.

When a crosslinked metallocene compound is used as an olefin polymerization catalyst component, the catalyst is
(A) a bridged metallocene compound represented by the general formula [I] or [II],
(B) (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) a compound that reacts with the bridged metallocene compound (A) to form an ion pair. A kind of compound,
If necessary,
(C) It is comprised from a particulate support.
Hereinafter, each component will be specifically described.

(B-1) Organometallic Compound As the (B-1) organometallic compound used in the present invention, specific examples of groups 1 and 2 of the periodic table as shown in the following general formulas [VII] to [IX] Group 12 and 13 organometallic compounds are used.

(B-1a) formula _{^{R a m Al (OR b)}} n H p X q ‥ [VII]
(In the formula [VII], R ^a and R ^b may be the same or different from each other, each represents 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 0 ≦ q <3, and m + n + p + q = 3. Compound.

Examples of such compounds include trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-octylaluminum, tricycloalkylaluminum, isobutylaluminum dichloride, diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, methyl. Examples thereof include aluminum dichloride, dimethylaluminum chloride, and diisobutylaluminum hydride.

(B-1b) General formula M ² AlR ^a ₄ ... [VIII]
(In the formula [VIII], M ² represents Li, Na or K, and R ^a is a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms) Complex alkylated product of Group 1 metal and aluminum.

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 [IX]
(In the formula [IX], R ^a and R ^b may be the same or different and each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and M ³ represents Mg, Zn or A dialkyl compound having a metal of Group 2 or Group 12 of the periodic table represented by Cd.

Among the above organometallic compounds (B-1), organoaluminum compounds such as triethylaluminum, triisobutylaluminum, and tri-n-octylaluminum are preferable. Such organometallic compounds (B-1) may be used alone or in combination of two or more.

(B-2) Organoaluminum Oxy Compound The organoaluminum oxy compound (B-2) used in the present invention may be a conventionally known aluminoxane, or as exemplified in JP-A-2-78687. It may be a benzene-insoluble organoaluminum oxy compound.

A conventionally well-known aluminoxane can be manufactured, for example with the following method, and is normally obtained as a solution of a hydrocarbon solvent.
(1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, first cerium chloride hydrate, etc. A method of reacting adsorbed water or crystal water with an organoaluminum compound by adding an organoaluminum compound such as trialkylaluminum to the suspension of the hydrocarbon.
(2) A method of allowing water, ice or water vapor to act directly on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran.
(3) A method in which an organotin oxide such as dimethyltin oxide or dibutyltin oxide is reacted with an organoaluminum compound such as trialkylaluminum in a medium such as decane, benzene, or toluene.

The aluminoxane may contain a small amount of an organometallic component. Further, after removing the solvent or the unreacted organoaluminum compound from the recovered aluminoxane solution by distillation, it may be redissolved in a solvent or suspended in a poor aluminoxane solvent.

Specific examples of the organoaluminum compound used in preparing the aluminoxane include the same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to the above (B-1a).

Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum and triisobutylaluminum are particularly preferable.

The above organoaluminum compounds are used singly or in combination of two or more.

In addition, the benzene-insoluble organoaluminum oxy compound (B-2) which is an embodiment of the organoaluminum oxy compound used in the present invention has an Al component dissolved in benzene at 60 ° C. based on 100% by weight of benzene in terms of Al atom. Usually, it is preferably 10% by weight or less, preferably 5% by weight or less, particularly preferably 2% by weight or less, that is, one that is insoluble or hardly soluble in benzene.

Examples of (B-2) organoaluminum oxy compounds used in the present invention include organoaluminum oxy compounds containing boron represented by the following general formula [X].

[In the formula [X], R ¹ represents a hydrocarbon group having 1 to 10 carbon atoms, and R ² to R ⁵ may be the same or different from each other, and have a hydrogen atom, a halogen atom or a carbon atom number. 1 to 10 hydrocarbon groups are shown. ]
The organoaluminum oxy compound containing boron represented by the general formula [X] is an alkyl boronic acid represented by the following general formula [XI],
R ¹ -B (OH) ₂ ... [XI]
(In the formula [XI], R ¹ represents the same group as R ¹ in the general formula [X].)
It can be produced by reacting an organoaluminum compound with an organoaluminum compound in an inert solvent under an inert gas atmosphere at a temperature of −80 ° C. to room temperature for 1 minute to 24 hours.

Specific examples of the alkyl boronic acid represented by the general formula [XI] include methyl boronic acid, ethyl boronic acid, isopropyl boronic acid, n-propyl boronic acid, n-butyl boronic acid, isobutyl boronic acid, n-hexyl boron. Examples include acid, cyclohexyl boronic acid, phenyl boronic acid, 3,5-difluorophenyl boronic acid, pentafluorophenyl boronic acid, 3,5-bis (trifluoromethyl) phenyl boronic acid and the like.

Of these, methyl boronic acid, n-butyl boronic acid, isobutyl boronic acid, 3,5-difluorophenyl boronic acid, and pentafluorophenyl boronic acid are preferable. These may be used alone or in combination of two or more.

Specific examples of the organoaluminum compound to be reacted with the alkylboronic acid include the same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to the above (B-1a).

Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum, triethylaluminum, and triisobutylaluminum are particularly preferable. These may be used alone or in combination of two or more. The (B-2) organoaluminum oxy compounds as described above are used singly or in combination of two or more.

(B-3) Compound which forms an ion pair by reacting with transition metal compound (A) Compound (B-3) which reacts with bridged metallocene compound (A) used in the present invention to form an ion pair (hereinafter referred to as “B”) Are referred to as “ionized ionic compounds”), as disclosed in JP-A-1-501950, JP-A-1-502036, JP-A-3-179005, JP-A-3-179006, and JP-A-3-207703. And Lewis acids, ionic compounds, borane compounds and carborane compounds described in JP-A-3-207704, USP-5321106 and the like. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned. Such ionized ionic compounds (B-3) are used singly or in combination of two or more.

Specifically, as the Lewis acid, a compound represented by BR ₃ (R is a phenyl group or fluorine which may have a substituent such as fluorine, methyl group or trifluoromethyl group) can be mentioned. For example, trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron, tris ( and p-tolyl) boron, tris (o-tolyl) boron, and tris (3,5-dimethylphenyl) boron.

Examples of the ionic compound include compounds represented by the following general formula [XII].

(In the formula [XII], ^examples of R ¹⁺ include H ⁺ , carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, and ferrocenium cation having a transition metal. ² to R ⁵ may be the same or different from each other, and are an organic group, preferably an aryl group or a substituted aryl group.
Specific examples of the carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation, tri (methylphenyl) carbonium cation, and tri (dimethylphenyl) carbonium cation.

Specific examples of the ammonium cation include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation, and tri (n-butyl) ammonium cation;
N, N-dialkylanilinium cations such as N, N-dimethylanilinium cation, N, N-diethylanilinium cation, N, N, 2,4,6-pentamethylanilinium cation;
And dialkylammonium cations such as di (isopropyl) ammonium cation and dicyclohexylammonium cation.

Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation.

R ¹⁺ is preferably a carbonium cation, an ammonium cation or the like, and particularly preferably a triphenylcarbonium cation, an N, N-dimethylanilinium cation or an N, N-diethylanilinium cation.

Examples of the ionic compound include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts.

Specific examples of trialkyl-substituted ammonium salts include triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron, and trimethylammonium tetra (p-tolyl). Boron, trimethylammonium tetra (o-tolyl) boron, tri (n-butyl) ammonium tetra (pentafluorophenyl) boron, tripropylammonium tetra (o, p-dimethylphenyl) boron, tri (n-butyl) ammonium tetra ( N, N-dimethylphenyl) boron, tri (n-butyl) ammonium tetra (p-trifluoromethylphenyl) boron, tri (n-butyl) ammonium tetra (3,5-ditrifluoromethylphenyl) Yl) boron, tri (n- butyl) ammonium tetra (o-tolyl) and boron and the like.

Specific examples of the N, N-dialkylanilinium salt include N, N-dimethylanilinium tetra (phenyl) boron, N, N-diethylanilinium tetra (phenyl) boron, N, N, 2,4,6. -Pentamethylanilinium tetra (phenyl) boron and the like.

Specific examples of the dialkylammonium salt include di (1-propyl) ammonium tetra (pentafluorophenyl) boron and dicyclohexylammonium tetra (phenyl) boron.

Further, as ionic compounds, triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) borate, triphenylcarbenium pentaphenyl Examples thereof include a cyclopentadienyl complex, an N, N-diethylanilinium pentaphenylcyclopentadienyl complex, and a boron compound represented by the following formula [XIII] or [XIV].

(In the formula, Et represents an ethyl group.)

(In the formula, Et represents an ethyl group.)
Specific examples of borane compounds include decaborane;
Bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium] undecaborate, bis [tri (n-butyl) ammonium] dodecaborate Salts of anions such as bis [tri (n-butyl) ammonium] decachlorodecaborate and bis [tri (n-butyl) ammonium] dodecachlorododecaborate;
Of metal borane anions such as tri (n-butyl) ammonium bis (dodecahydridododecaborate) cobaltate (III) and bis [tri (n-butyl) ammonium] bis (dodecahydridododecaborate) nickelate (III) Examples include salt.

Specific examples of the carborane compound include 4-carbanonaborane, 1,3-dicarbanonaborane, 6,9-dicarbadecarborane, dodecahydride-1-phenyl-1,3-dicarbanonaborane, dodecahydride- 1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarbaundecaborane, 2,7-dicarbaundecaborane, Undecahydride-7,8-dimethyl-7,8-dicarboundecarborane, dodecahydride-11-methyl-2,7-dicarboundeaborane, tri (n-butyl) ammonium 1-carbadecarborate, tri ( n-butyl) ammonium-1-carbaundecaborate, tri (n-butyl) ammonium-1-carba Decaborate, tri (n-butyl) ammonium-1-trimethylsilyl-1-carbadecaborate, tri (n-butyl) ammonium bromo-1-carbadodecaborate, tri (n-butyl) ammonium-6-carbadecaborate, tri (N-butyl) ammonium-7-carbaundecaborate, tri (n-butyl) ammonium-7,8-dicarboundeborate, tri (n-butyl) ammonium-2,9-dicarboundeborate, tri ( n-butyl) ammonium dodecahydride-8-methyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-ethyl-7,9-dicarbaundecaborate, tri (n-butyl) Ammonium undecahydride-8-butyl-7, 9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-allyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,8- A salt of an anion such as dicarboundeborate, tri (n-butyl) ammonium undecahydride-4,6-dibromo-7-carboundeborate;
Tri (n-butyl) ammonium bis (nonahydride-1,3-dicarbanonaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) Ferrate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7) , 8-Dicarbaundecaborate) nickelate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) cuprate (III), tri (n-butyl) Ammonium bis (undecahydride-7,8-dicarbaundecaborate) goldate (III), tri (n-butyl) ammonium Bis (nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate) ferrate (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicar (Boundecaborate) chromate (III), tri (n-butyl) ammonium bis (tribromooctahydride-7,8-dicarboundecaborate) cobaltate (III), tris [tri (n-butyl) ammonium Bis (undecahydride-7-carbaundecaborate) chromate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) manganate (IV) Bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) cobaltate (II And salts of metal carborane anions such as bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) nickelate (IV).

The heteropoly compound is composed of atoms selected from silicon, phosphorus, titanium, germanium, arsenic and tin, and one or more atoms selected from vanadium, niobium, molybdenum and tungsten. Specifically, phosphovanadic acid, germanovanadic acid, arsenic vanadic acid, phosphoniobic acid, germanoniobic acid, siliconomolybdic acid, phosphomolybdic acid, titanium molybdic acid, germanomolybdic acid, arsenic molybdic acid, tin molybdic acid, phosphorus Tungstic acid, germanotungstic acid, tin tungstic acid, phosphomolybdovanadic acid, lintongost vanadic acid, germano-tungstovanadic acid, phosphomolybdo-tungstovanadic acid, germano-molybdo-tangostanodic acid, phosphomolybdotungstic acid , Phosphomolybniobic acid, and salts of these acids, such as metals of Groups 1 or 2 of the periodic table, specifically lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium Etc. Salts, and organic salts such as triphenylethyl salts can be used, not limited thereto.

(B-3) Among the ionized ionic compounds, the above-mentioned ionic compounds are preferable. Among them, triphenylcarbenium tetrakis (pentafluorophenyl) borate and N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate are preferable. More preferred.

(B-3) The ionized ionic compounds are used singly or in combination of two or more.

When the transition metal compound (A) represented by the general formula [I] or [II] is used as a catalyst, an organometallic compound (B-1) such as triisobutylaluminum, an organoaluminum oxy compound such as methylaluminoxane ( When an ionized ionic compound (B-3) such as B-2) or triphenylcarbenium tetrakis (pentafluorophenyl) borate is used in combination, an extremely high polymerization activity is produced in the production of an ethylene / α-olefin / nonconjugated polyene copolymer. Indicates.

The olefin polymerization catalyst used in the present invention comprises the transition metal compound (A), (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) an ionized ion. A carrier (C) may be used as necessary together with at least one compound (B) selected from the active compounds.

(C) Carrier The carrier (C) used as necessary in the present invention is an inorganic compound or an organic compound, and is a granular or particulate solid.

Among these, as the inorganic compound, porous oxides, inorganic halides, clays, clay minerals or ion-exchangeable layered compounds are preferable.

As the porous oxide, specifically, SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ or the like, or a composite or mixture containing these is used. For example, natural or synthetic zeolite, SiO ₂ —MgO, SiO ₂ —Al ₂ O ₃ , SiO ₂ —TiO ₂ , SiO ₂ —V ₂ O ₅ , SiO ₂ —Cr ₂ O ₃ , SiO ₂ —TiO ₂ —MgO, etc. Can be used. Of these, those containing SiO ₂ and / or Al ₂ O ₃ as main components are preferred. Such porous oxides have different properties depending on the type and production method, but the carrier preferably used in the present invention has a particle size of 10 to 300 μm, preferably 20 to 200 μm, and a specific surface area of 50 to 1000 m. ² / g, preferably in the range of 100 to 700 m ² / g, and the pore volume is in the range of 0.3 to 3.0 cm ³ / g. Such a carrier is used after calcining at 100 to 1000 ° C., preferably 150 to 700 ° C., if necessary.

As the inorganic halide, MgCl ₂ , MgBr ₂ , MnCl ₂ , MnBr ₂ or the like is used. The inorganic halide may be used as it is or after being pulverized by a ball mill or a vibration mill. Further, it is also possible to use a material in which an inorganic halide is dissolved in a solvent such as alcohol and then precipitated into fine particles with a precipitating agent.

The clay used in the present invention is usually composed mainly of clay minerals. The ion-exchangeable layered compound used in the present invention is a compound having a crystal structure in which surfaces formed by ionic bonds and the like are stacked in parallel with each other with a weak binding force, and the contained ions can be exchanged. . Most clay minerals are ion-exchangeable layered compounds. In addition, these clays, clay minerals, and ion-exchange layered compounds are not limited to natural products, and artificial synthetic products can also be used.

In addition, as clay, clay mineral, or ion-exchangeable layered compound, clay, clay mineral, ionic crystalline compound having a layered crystal structure such as hexagonal fine packing type, antimony type, CdCl ₂ type, CdI ₂ type, etc. It can be illustrated. Examples of such clays and clay minerals include kaolin, bentonite, kibushi clay, gyrome clay, allophane, hysinger gel, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokdeite group, palygorskite, kaolinite, nacrite, dickite Examples of ion-exchangeable layered compounds include α-Zr (HAsO ₄ ) ₂ .H ₂ O, α-Zr (HPO ₄ ) ₂ , α-Zr (KPO ₄ ) ₂ .3H ₂ O, α-Ti (HPO ₄ ) ₂ , α-Ti (HAsO ₄ ) ₂ .H ₂ O, α-Sn (HPO ₄ ) ₂ .H ₂ O, γ-Zr (HPO ₄ ) ₂ , γ-Ti (HPO ₄ ) ₂ and crystalline acidic salts of polyvalent metals such as γ-Ti (NH ₄ PO ₄ ) ₂ .H ₂ O.

Such a clay, clay mineral or ion exchange layered compound preferably has a pore volume of not less than 0.1 cc / g having a radius of 20 mm or more as measured by a mercury intrusion method, and is preferably from 0.3 to 5 cc / g. Particularly preferred. Here, the pore volume is measured in a pore radius range of 20 to 30000 mm by a mercury intrusion method using a mercury porosimeter.

When using a carrier having a pore volume smaller than 0.1 cc / g having a radius of 20 mm or more as a carrier, it tends to be difficult to obtain high polymerization activity.

It is also preferable to subject the clay and clay mineral used in the present invention to chemical treatment. As the chemical treatment, any of a surface treatment that removes impurities adhering to the surface and a treatment that affects the crystal structure of clay can be used. Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, and organic matter treatment. In addition to removing impurities on the surface, the acid treatment increases the surface area by eluting cations such as Al, Fe, and Mg in the crystal structure. Alkali treatment destroys the crystal structure of the clay, resulting in a change in the structure of the clay. In the salt treatment and the organic matter treatment, an ion complex, a molecular complex, an organic derivative, and the like can be formed, and the surface area and interlayer distance can be changed.

The ion-exchangeable layered compound used in the present invention may be a layered compound in a state where the layers are expanded by exchanging the exchangeable ions between the layers with other large and bulky ions using the ion-exchange property. . Such bulky ions play a role of supporting pillars to support the layered structure and are usually called pillars. Moreover, introducing another substance between the layers of the layered compound in this way is called intercalation. Examples of guest compounds to be intercalated 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 group), metal hydroxide ions such as [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH) ₁₄ ] ²⁺ , [Fe ₃ O (OCOCH ₃ ) ₆ ] ⁺ Etc. These compounds are used alone or in combination of two or more. Further, when these compounds were intercalated, they were obtained by hydrolyzing metal alkoxides such as Si (OR) ₄ , Al (OR) ₃ , Ge (OR) ₄ (R is a hydrocarbon group, etc.). Polymers, colloidal inorganic compounds such as SiO _2, and the like can also coexist. Examples of the pillar include oxides generated by heat dehydration after intercalation of the metal hydroxide ions between layers.

The clay, clay mineral, and ion-exchangeable layered compound used in the present invention may be used as they are, or may be used after processing such as ball milling and sieving. Further, it may be used after newly adsorbing and adsorbing water or after heat dehydration treatment. Furthermore, you may use individually or in combination of 2 or more types.

Of these, clay or clay mineral is preferable, and montmorillonite, vermiculite, hectorite, teniolite, and synthetic mica are particularly preferable.

Examples of the organic compound include granular or particulate solids having a particle size in the range of 10 to 300 μm. Specifically, a (co) polymer produced mainly from an α-olefin having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, vinylcyclohexane, styrene (Co) polymers produced by the main component, and their modified products.

The olefin polymerization catalyst used in the present invention comprises a bridged metallocene compound (A), (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) an ionized ionic compound. Along with at least one selected compound (B) and a carrier (C) used as necessary, it may contain a specific organic compound component (D) as described later, if necessary.

(D) Organic Compound Component In the present invention, the (D) organic compound component is used for the purpose of improving the polymerization performance and the physical properties of the produced polymer as necessary. Examples of such organic compounds include, but are not limited to, alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, and sulfonates.

In the method for producing an ethylene / α-olefin / non-conjugated polyene copolymer according to the present invention, ethylene, α-olefin, non-polymer in the presence of the ethylene / α-olefin / non-conjugated polyene copolymer catalyst as described above. An ethylene / α-olefin / non-conjugated polyene copolymer is obtained by copolymerizing the conjugated polyene.

The α-olefin usable in the present invention is not particularly limited, but those having 3 to 20 carbon atoms can be used. For example, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1 -Pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicocene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3-ethyl -1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 9 -Methyl-1-decene, 11-methyl-1-dodecene, 12-ethyl-1-tetradodecene and the like. Among these, α-olefins having 3 to 8 carbon atoms are preferable, particularly preferably propylene, 1-butene, 1-hexene, 1-octene and 4-methyl-1-pentene, and most preferably propylene. is there.

Furthermore, these α-olefins can be used alone or in combination of two or more. The α-olefin can be appropriately selected so as to be most desirable in terms of the properties of the copolymer to be produced. An example of the selection is that the physical properties when the copolymer or a mixture containing the copolymer is vulcanized are desirable.

As the non-conjugated polyene constituting the ethylene / α-olefin / non-conjugated polyene copolymer of the present invention, a compound having two or more non-conjugated unsaturated bonds can be used without limitation. For example, the following non-conjugated cyclic polyene, Examples thereof include non-conjugated chain polyenes, which can be used alone 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 [III].

(In the formula [III], m is an integer of 0 to 2, and R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are each independently an atom selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group, or Represents a group.)
Regarding R ¹⁵ to R ¹⁸ in the general formula [III], examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the hydrocarbon group include an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms and a double group. And an unsaturated hydrocarbon group having one or more bonds. More specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, and an octadecyl group. Examples of the halogenated alkyl group include groups in which at least a part of the hydrogen atoms forming the alkyl group as described above are substituted with a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Examples of the cycloalkyl group include a cyclohexyl group. Examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group. Examples of the unsaturated hydrocarbon group include a vinyl group and an allyl group.

In the general formula [III], any two of R ¹⁵ to R ¹⁸ , that is, R ¹⁵ and R ¹⁷ , R ¹⁷ and R ¹⁸ , R ¹⁵ and R ¹⁶ are R ¹⁶ and R ¹⁸ may be combined with R ¹⁵ and R ¹⁸ or R ¹⁶ and R ¹⁷ (in combination with each other) to form a monocyclic or polycyclic ring. The formed monocycle or polycycle may have a double bond.

In the general formula [III], R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group (R =). Such an alkylidene group is usually an alkylidene group having 1 to 20 carbon atoms. Specific examples thereof include a methylene group (CH ₂ =), an ethylidene group (CH ₃ CH =), and a propylidene group (CH ₃ CH ₂ CH =) and an isopropylidene group ((CH ₃ ) ₂ C =).

In the general formula [III], R ¹⁵ and R ¹⁷ or R ¹⁶ and R ¹⁸ may be bonded to each other to form a double bond.

For example, when R ¹⁵ and R ¹⁷ are bonded to each other to form a double bond, the compound of the general formula [III] has the following structure.

The non-conjugated cyclic polyene represented by the general formula [III] satisfies any one or more of the following (i) to (iv):
(I) The monocyclic or polycyclic ring formed by bonding any two of R ¹⁵ to R ¹⁸ to each other has a double bond.
(Ii) R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ form an alkylidene group.
(Iii) R ¹⁵ and R ¹⁷ or R ¹⁶ and R ¹⁸ are bonded to each other to form a double bond.
(Iv) At least one of R ¹⁵ to R ¹⁸ is an unsaturated hydrocarbon group having one or more double bonds.

Specific examples of the non-conjugated cyclic polyene represented by the general formula [III] include
An alkylidene group-containing non-conjugated cyclic polyene having an alkylidene group formed by R ¹⁵ and R ¹⁶ or an alkylidene group of R ¹⁷ and R ¹⁸ ;
A polycyclic non-conjugated cyclic polyene in which any two of R ¹⁵ to R ¹⁸ are bonded to each other to form a monocyclic or polycyclic ring having one or more double bonds,
An unsaturated hydrocarbon group-containing nonconjugated cyclic polyene in which at least one of R ¹⁵ to R ^{18 is} a monovalent unsaturated hydrocarbon group having one or more double bonds,
R ¹⁵ and R ¹⁷ , or R ¹⁶ and R ¹⁸ are bonded to each other to form a double bond, and bridge head carbon atoms or carbon atoms in the condensed ring when m is 1 are connected. Examples thereof include a ring-symmetric non-conjugated cyclic polyene in which the ring has symmetry when the line is the axis of symmetry.

Specific examples of the alkylidene group-containing non-conjugated cyclic polyene include compounds represented by the following general formula [III-I].

(In the formula [III-I], s is an integer of 0 to 2, R ¹⁹ is an alkylidene group, R ²⁰ and R ²¹ are each independently an atom selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group. Or represents a group, and R ²⁰ and R ²¹ may form an alkylidene group.)
Specific examples of the alkylidene group represented by R ¹⁹ in the general formula [III-I] include alkylidene groups having 1 to 20 carbon atoms such as a methylene group, an ethylidene group, a propylidene group, and an isopropylidene group.

In the general formula [III-I], s is preferably 0. Examples of the halogen atom represented by R ²⁰ and R ²¹ are the same as described above. Examples of the hydrocarbon group include an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms. Can be mentioned.

Specific examples of the alkylidene group-containing non-conjugated cyclic polyene represented by the general formula [III-I] include 5-methylene-2-norbornene, 5-ethylidene-2-norbornene (ENB), 5-isopropylidene. Examples thereof include lidene-2-norbornene and the following compounds. Of these, 5-ethylidene-2-norbornene (ENB) is preferred.

Specific examples of the polycyclic non-conjugated cyclic polyene include dicyclopentadiene (DCPD), dimethyldicyclopentadiene, and the following compounds.

Specific examples of the unsaturated hydrocarbon group-containing nonconjugated cyclic polyene include 5-vinyl-2-norbornene (VNB) and the following compounds. Of these, 5-vinyl-2-norbornene (VNB) is preferred.

Specific examples of the ring-symmetric non-conjugated cyclic polyene include the following compounds.

As the non-conjugated cyclic polyene represented by the general formula [III], a non-conjugated cyclic polyene having m of 0 is preferable. In particular, in the general formula [III], an alkylidene group-containing non-conjugated cyclic polyene having m of 0, An alkylidene group-containing non-conjugated cyclic polyene in which s is 0 in the general formula [III-I], or a polycyclic non-conjugated cyclic polyene in which m is 0 in the general formula [III], an unsaturated hydrocarbon group in which m is 0 Nonconjugated cyclic polyenes are preferred. Specifically, 5-ethylidene-2-norbornene (ENB), dicyclopentadiene (DCPD), and 5-vinyl-2-norbornene (VNB) are more preferable.

(Non-conjugated chain polyene)
Specific examples of the non-conjugated chain polyene include 1,4-hexadiene, 1,5-heptadiene, 1,6-octadiene, 1,7-nonadiene, 1,8-decadiene, 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- Examples include undecadiene.

Examples of other non-conjugated chain polyenes include α, ω-dienes such as 1,7-octadiene and 1,9-decadiene.

Further, other non-conjugated chain polyenes include, for example, non-conjugated trienes or tetraenes represented by the following general formula [III-II].

[In the formula [III-II], p and q are 0 or 1 (provided that p and q are not 0 at the same time),
f is an integer of 0 to 5 (where f is not 0 when both p and q are 1), g is an integer of 1 to 6, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ And R ⁷ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ⁸ is an alkyl group having 1 to 3 carbon atoms, R ⁹ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or — (CH ₂ ) a group represented by _n— CR ¹⁰ ═C (R ¹¹ ) R ¹² (where n is an integer of 1 to 5, R ¹⁰ and R ¹¹ are each independently a hydrogen atom or an alkyl having 1 to 3 carbon atoms) Group R ¹² is an alkyl group having 1 to 3 carbon atoms). However, when both p and q are 1, R ⁹ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ]
Among the non-conjugated trienes or tetraenes represented by the general formula [III-II], non-conjugated trienes represented by the following general formula [III-III] are preferable.

(In the formula [III-III], R ¹ to R ⁵ each independently represents a hydrogen atom, a methyl group or an ethyl group. However, R ⁴ and R ⁵ do not simultaneously become a hydrogen atom.)
The non-conjugated triene represented by the general formula [III-III] is a non-conjugated triene or tetraene represented by the general formula [III-II], wherein f is 0, g is 2, p is 0, and q is 1 , R ⁵ and R ⁶ are non-conjugated trienes which are hydrogen atoms. Further, among the non-conjugated trienes represented by the above general formula [III-III], compounds in which R ³ and R ⁵ are both methyl groups are preferred.

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

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

The non-conjugated triene or tetraene represented by the general formula [III-II] can be produced by a known method, for example, Japanese Patent Application Laid-Open Nos. 9-235327 and 2001-114837 by the present applicant. Are described in detail.

The ethylene / α-olefin / non-conjugated polyene copolymer produced by the production method according to the present invention comprises (i) a structural unit derived from ethylene (ethylene unit) and (ii) an α having 3 to 20 carbon atoms. -Containing structural units derived from olefins (α-olefin units) in a molar ratio [(i) / (ii)] and usually in the range of 99/1 to 1/99, but there is no particular limitation .

The structural unit derived from the non-conjugated polyene compound of the ethylene / α-olefin / non-conjugated polyene copolymer is not particularly limited, but is generally 0.1 to 50 mol%, preferably 0.2 to It is in the range of 8 mol%, more preferably 0.3-5 mol%.

The intrinsic viscosity [η] of the ethylene / α-olefin / nonconjugated 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 of 0.05 to 10 dl / g.

The iodine value (IV) of the ethylene / α-olefin / non-conjugated polyene copolymer is not particularly limited, but is usually 55 g / 100 g or less, preferably 1 to 40 g / 100 g.

The ethylene / α-olefin / non-conjugated polyene copolymer produced by the production method of the present invention usually has a content of structural units derived from ethylene of 50 mol% or more, and the B value calculated by the following formula [IV] However, the ethylene / α-olefin / nonconjugated polyene copolymer having a B value ≧ 1.05 and a B value ≧ 1.05 is preferably an ethylene / α-olefin / B / B copolymer having a B value <1.05. Compared with a non-conjugated polyene copolymer, the alternating copolymerization property of the monomer is strong, and as a result, the ethylene average chain length is shortened, and the low temperature characteristic which is one of the important physical properties is excellent.

B value = (c + d) / [2 × a × (e + f)] [IV]
(In the formula [IV], a, e and f are the ethylene mole fraction, α-olefin mole fraction and non-conjugated polyene mole fraction in the ethylene / α-olefin / nonconjugated polyene copolymer, respectively, and c is Ethylene-α-olefin dyad mole fraction, d is the ethylene-nonconjugated polyene dyad mole fraction).

The B value is an index indicating the randomness of the copolymer monomer chain distribution in the copolymer, and a, c, d, e, and f in the above formula [IV] measure the ¹³ C-NMR spectrum, JCRandall (Macromolecules, 15, 353 (1982)), J. Ray (Macromolecules, 10, 773 (1977)) et al.

The larger the B value, the shorter the block chain of α-olefin units or non-conjugated polyene units (stronger alternating copolymerization), and the distribution of α-olefin units and non-conjugated polyene units is more uniform. Is shown. The smaller the B value, the more uneven the distribution of α-olefin units and non-conjugated polyene units of the non-conjugated polyene copolymer (the weaker alternate copolymerization becomes) and the longer the block chain. Yes. The length of this block chain affects the physical properties of the ethylene / α-olefin / non-conjugated polyene copolymer. For example, the larger the B value, the shorter the block chain and the better low-temperature properties. Indicates. Further, as the B value becomes smaller than 1.00, the composition distribution in the polymer chain of the ethylene / α-olefin / nonconjugated polyene copolymer becomes wider, and such a copolymer is a copolymer having a narrow composition distribution. In contrast, for example, when vulcanized, physical properties such as strength may not be sufficiently exhibited.

An ethylene / α-olefin / nonconjugated polyene copolymer rubber having a B value ≧ 1.05 can be obtained by the method for producing an ethylene / α-olefin / nonconjugated polyene copolymer of the present invention. B-value of the resulting ethylene / α-olefin / non-conjugated polyene copolymer is less than 1.05 when a non-metallocene catalyst or a geometrically constrained catalyst described in JP-T-2001-522398 is used. Indicates.

Method for polymerizing monomers in the presence of a catalyst for ethylene / α-olefin / non-conjugated polyene copolymer Each component constituting the polymerization catalyst when copolymerizing ethylene, α-olefin and non-conjugated polyene in the present invention The method of use and the order of addition are arbitrarily selected, and the following methods are exemplified.
(1) A method of adding the component (A) alone to the polymerization vessel.
(2) A method of adding the component (A) and the component (B) to the polymerization vessel in an arbitrary order.
(3) A method in which the catalyst component having component (A) supported on carrier (C) and component (B) are added to the polymerization vessel in any order.
(4) A method in which the catalyst component having component (B) supported on carrier (C) and component (A) are added to the polymerization vessel in any order.
(5) A method in which a catalyst component in which the component (A) and the component (B) are supported on the carrier (C) is added to the polymerization vessel.

In each of the above methods (2) to (5), at least two of the catalyst components (A), (B), and (C) may be contacted in advance.

In the above methods (4) and (5) in which the component (B) is supported, the unsupported component (B) may be added in any order as necessary. In this case, the component (B) may be the same as or different from the component (B) supported on the carrier (C).

The solid catalyst component in which the component (A) is supported on the component (C) and the solid catalyst component in which the component (A) and the component (B) are supported on the component (C) are prepolymerized with olefin. Alternatively, a catalyst component may be further supported on the prepolymerized solid catalyst component.

In the method for producing an ethylene / α-olefin / non-conjugated polyene copolymer according to the present invention, ethylene, α-olefin, non-polymer in the presence of the ethylene / α-olefin / non-conjugated polyene copolymer catalyst as described above. An ethylene / α-olefin / non-conjugated polyene copolymer is obtained by copolymerizing the conjugated polyene.

In the present invention, any of a liquid phase polymerization method such as solution (dissolution) polymerization and suspension polymerization, or a gas phase polymerization method can be used.

Specific examples of the inert hydrocarbon medium used in the liquid phase polymerization include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene, cyclopentane, cyclohexane, and methylcyclopentane. Alicyclic hydrocarbons such as benzene, toluene, xylene and other aromatic hydrocarbons, ethylene chloride, chlorobenzene, dichloromethane and other halogenated hydrocarbons are mentioned, and these may be used alone or in combination of two or more. Can do. Moreover, olefin itself can also be used as a solvent.

When the olefin polymerization is carried out using the above olefin polymerization catalyst, the component (A) is usually 10 ⁻¹² to 10 ⁻² mol, preferably 10 ⁻¹⁰ to 10 ⁻⁸ mol per liter of reaction volume. It is used in such an amount that it becomes a mole.

Component (B-1) generally has a molar ratio [(B-1) / M] of component (B-1) to all transition metal atoms (M) in component (A) of 0.01 to 50000, The amount is preferably 0.05 to 10,000. Component (B-2) has a molar ratio [(B-2) / M] of the aluminum atoms in component (B-2) to the total transition metals (M) in component (A) usually from 10 to The amount used is 50000, preferably 20 to 10,000. Component (B-3) has a molar ratio [(B-3) / M] of component (B-3) to transition metal atom (M) in component (A) of usually 1 to 20, preferably The amount used is 1 to 15.

The olefin polymerization temperature using such an olefin polymerization catalyst is usually in the range of −50 to + 200 ° C., preferably in the range of 0 to + 200 ° C., more preferably in the range of +80 to + 200 ° C. Depending on the ultimate molecular weight of the system and the polymerization activity, a higher temperature (+ 80 ° C. or higher) is desirable from the viewpoint of productivity.

The polymerization pressure is usually from normal pressure to 10 MPa gauge pressure, preferably from normal pressure to 5 MPa gauge pressure, and the polymerization reaction can be carried out by any of batch, semi-continuous and continuous methods. Furthermore, the polymerization can be performed in two or more stages having different reaction conditions.

The molecular weight of the obtained olefin polymer can be adjusted by allowing hydrogen to exist in the polymerization system or changing the polymerization temperature. Furthermore, it can also adjust with the quantity of the component (B) to be used. Specific examples include triisobutylaluminum, methylaluminoxane, diethylzinc and the like. When hydrogen is added, the amount is suitably about 0.001 to 100 NL per kg of olefin.

Next, a method for measuring physical properties and properties of the ethylene / α-olefin / non-conjugated polyene copolymer obtained by the production method of the present invention in the following examples will be described. The measuring method is as follows.

[Intrinsic viscosity ([η])]
It measured at 135 degreeC using the decalin solvent.

[Iodine number (IV)]
It was determined based on the composition of non-conjugated polyene calculated from infrared spectroscopy (apparatus: manufactured by JASCO, FT-IR610).

[Ethylene content, propylene content, non-conjugated polyene content]
¹³ C-NMR spectrum (100 MHz, JEOL ECX400P) was measured at a measurement temperature of 120 ° C. using o-dichlorobenzene-d ₄ / benzene-d ₆ (4/1 [v / v]) as a measurement solvent. Calculated.

[B value]
¹³ C-NMR spectrum (100 MHz, JEOL ECX400P) was measured at a measurement temperature of 120 ° C. using o-dichlorobenzene-d ₄ / benzene-d ₆ (4/1 [v / v]) as a measurement solvent. Based on the following general formula [IV].

B value = (c + d) / [2 × a × (e + f)] [IV]
(In the formula [IV], a, e and f are the ethylene mole fraction, α-olefin mole fraction and non-conjugated polyene mole fraction in the ethylene / α-olefin / nonconjugated polyene copolymer, respectively, and c is Ethylene-α-olefin dyad mole fraction, d is the ethylene-nonconjugated polyene dyad mole fraction).

Hereinafter, the present description will be described more specifically based on examples, but the present invention is not limited to these examples.

The catalysts used in Examples 1 to 28 and Comparative Examples 4 to 6 are described in J. Org. Organomet. Chem. 63, 509 (1996), the methods described by the present applicants in WO200006123759, WO01 / 27124, JP2004-168744, JP2004-175759, JP2000-212194, and the like. The structure of the synthesized compound was determined using 270 MHz ¹ H-NMR (JEOL GSH-270), FD-mass spectrometry (JEOL SX-102A) and the like.

[Example 1]
A 1-liter stainless steel (SUS) autoclave thoroughly purged with nitrogen was charged with 470 ml of n-heptane and impurities, 4.0 ml of 5-ethylidene-2-norbornene (hereinafter abbreviated as ENB) at 25 ° C. The liquid phase and gas phase were saturated for 15 minutes at an ethylene feed rate of 100 L / hr, sealed, and maintained at 80 ° C. Propylene was charged at a partial pressure of 0.20 MPa, and then increased to 0.80 MPaG with ethylene. First, 0.1 ml of a toluene solution of 1 mmol / ml triisobutylaluminum was injected, and then 0.0015 mmol / ml diphenylsilylene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) hafnium. 0.1 ml of a toluene solution of dichloride was injected under pressure. Subsequently, 0.0075 mmol / ml triphenylcarbenium tetrakis (pentafluorophenyl) borate toluene solution was injected under a pressure of 0.375 ml, and a polymerization reaction was performed for 15 minutes. During the polymerization reaction, the temperature was maintained at 80 ° C., and the pressure was maintained at 0.80 MPaG by ethylene pressurization. 15 minutes after the start of the polymerization reaction, 2 ml of methanol was injected with nitrogen to stop the polymerization reaction.

The obtained polymerization solution was mixed in 1 L of a 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 for 10 hours under the conditions of 130 ° C. and −600 mmHg. The ethylene content was 70.8 mol%, the propylene content was 27.2 mol%, and the ENB content was 2.0 mol. %, Iodine value (IV) 15.2 g / 100 g, intrinsic viscosity [η] 8.07 dl / g, B value 1.13 ethylene / propylene / ENB copolymer 2.414 g was obtained. The polymerization activity was 64.4 kg / mmol-Hf / h.

[Examples 2 to 27]
In Example 1, it carried out like Example 1 except having set to the propylene partial pressure of Table 1 using the catalyst and co-catalyst of Table 1, and setting it. The polymerization results are shown in Table 1.

[Comparative Example 1]
A 1 L stainless steel (SUS) autoclave thoroughly purged with nitrogen was charged with 470 ml of n-heptane and 4.0 ml of ENB from which impurities had been removed with activated alumina at 25 ° C., and the liquid was supplied for 15 minutes at an ethylene feed rate of 100 L / hr. The phase and gas phase were saturated and sealed and maintained at 80 ° C. Propylene was charged at a partial pressure of 0.15 MPa, and then increased to 0.80 MPaG with ethylene. First, 0.1 ml of a toluene solution of 1 mmol / ml triisobutylaluminum was injected, and then 0.001 mmol / ml (t-butylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silane titanium dichloride (special 0.1 ml of a toluene solution synthesized according to the method described in Kaihei 3-163088 was press-fitted. Subsequently, 0.25 ml of a toluene solution of 0.004 mmol / ml triphenylcarbenium tetrakis (pentafluorophenyl) borate was injected, and a polymerization reaction was performed for 15 minutes. During the polymerization reaction, the temperature was maintained at 80 ° C., and the pressure was maintained at 0.80 MPaG by ethylene pressurization. 15 minutes after the start of the polymerization reaction, 2 ml of methanol was injected with nitrogen to stop the polymerization reaction.

The obtained polymerization solution was mixed in 1 L of a 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 for 10 hours under the conditions of 130 ° C. and −600 mmHg. The ethylene content was 73.3 mol%, the propylene content was 25.3 mol%, and the ENB content was 1.4 mol. %, Iodine value (IV) 11.4 g / 100 g, intrinsic viscosity [η] 4.23 dl / g, B value 0.94 ethylene / propylene / ENB copolymer was obtained 1.294 g. The polymerization activity was 51.8 kg / mmol-Ti / h.

[Comparative Example 2]
A 1 L stainless steel (SUS) autoclave thoroughly purged with nitrogen was charged with 470 ml of n-heptane and 4.0 ml of ENB from which impurities had been removed with activated alumina at 25 ° C., and the liquid was supplied for 15 minutes at an ethylene feed rate of 100 L / hr. The phase and gas phase were saturated and sealed and maintained at 80 ° C. Propylene was charged at a partial pressure of 0.70 MPa, and then pressurized with ethylene to 0.8 MPaG. First, 0.5 ml of a toluene solution of 1 mmol / ml triisobutylaluminum was injected, and then bis (1,3-dimethylcyclopentadienyl) zirconium dichloride (manufactured by Kanto Chemical Co.) and methylaluminoxane (manufactured by Albemarle, 10 wt. % Toluene solution) at a zirconium: aluminum ratio of 1: 300, 0.1 ml of a toluene solution having a Zr concentration of 0.015 mmol / ml, which had been pre-contacted in advance, was injected, and a polymerization reaction was carried out for 15 minutes. During the polymerization reaction, the temperature was maintained at 80 ° C., and the pressure was maintained at 0.80 MPaG by ethylene pressurization. 15 minutes after the start of the polymerization reaction, 2 ml of methanol was injected with nitrogen to stop the polymerization reaction.

The obtained polymerization solution was mixed with 500 ml of water containing 5 ml of concentrated hydrochloric acid and washed. Thereafter, liquid separation was performed, and the organic layer was further washed with 500 ml of water three times, and the solvent of the obtained organic layer was distilled off. The obtained ethylene / propylene / ENB copolymer was dried at 130 ° C. and −600 mmHg for 10 hours, and had an ethylene content of 71.4 mol%, a propylene content of 26.7 mol%, an ENB content of 1.9 mol%, an iodine value ( IV) 11.174 g of an ethylene / propylene / ENB copolymer having 17.1 g / 100 g, intrinsic viscosity [η] of 0.59 dl / g and B value of 1.15 was obtained. The polymerization activity was 29.8 kg / mmol-Zr / h.

[Comparative Example 3]
A 1 L stainless steel (SUS) autoclave thoroughly purged with nitrogen was charged with 470 ml of n-heptane and 4.0 ml of ENB from which impurities had been removed with activated alumina at 25 ° C., and the liquid was supplied for 15 minutes at an ethylene feed rate of 100 L / hr. The phase and gas phase were saturated and sealed and maintained at 80 ° C. Propylene was charged at a partial pressure of 0.45 MPa, and then pressurized with ethylene to 0.80 MPaG. First, 0.5 ml of a toluene solution of 1 mmol / ml triisobutylaluminum was injected, and then dimethylsilylene bis (indenyl) zirconium dichloride (synthesized according to the method described in JP-A-4-268307) and methylaluminoxane (manufactured by Albemarle). A 10 wt% toluene solution) was injected in advance with 0.1 ml of a Zr concentration of 0.010 mmol / ml preliminarily contacted at a zirconium: aluminum ratio of 1: 300, and a polymerization reaction was carried out for 15 minutes. During the polymerization reaction, the temperature was maintained at 80 ° C., and the pressure was maintained at 0.80 MPaG by ethylene pressurization. 15 minutes after the start of the polymerization reaction, 2 ml of methanol was injected with nitrogen to stop the polymerization reaction.

The obtained polymerization solution was mixed with 500 ml of water containing 5 ml of concentrated hydrochloric acid and washed. Thereafter, liquid separation was performed, and the organic layer was further washed with 500 ml of water three times, and the solvent of the obtained organic layer was distilled off. The obtained ethylene / propylene / ENB copolymer was dried at 130 ° C. and −600 mmHg for 10 hours, and had an ethylene content of 66.0 mol%, a propylene content of 29.9 mol%, an ENB content of 4.1 mol%, an iodine value ( IV) An ethylene / propylene / ENB copolymer having an intrinsic viscosity of 33.6 g / 100 g, an intrinsic viscosity [η] of 0.82 dl / g, and a B value of 1.15 was obtained. The polymerization activity was 18.9 kg / mmol-Zr / h.

[Comparative Examples 4 to 6]
In Example 1, it carried out like Example 1 except having set to the propylene partial pressure of Table 1 using the catalyst and co-catalyst of Table 1, and setting it. The polymerization results are shown in Table 1.

[Example 28]
The same procedure as in Example 1 was conducted, except that 4.0 ml of ENB, which was the non-conjugated polyene of Example 1, was changed to 4.0 ml of ENB and 1.0 ml of 5-vinyl-2-norbornene (VNB). The polymerization results are shown in Table 2.

By the method for producing an ethylene / α-olefin / nonconjugated polyene copolymer according to the present invention, good polymerization activity, good nonconjugated polyene copolymerization ability, a very high molecular weight, and monomer alternating copolymerizability Strong ethylene / α-olefin / non-conjugated polyene copolymer can be obtained. As a result, the present production method solves the problems of the geometrically constrained catalyst and the existing metallocene catalyst system at the same time in terms of productivity and physical properties. In particular, from the feature of having a very high molecular weight, the polymerization temperature can be set higher, which can greatly contribute to cost reduction.

Claims (8)

(A) a transition metal compound represented by the following general formula [I] or [II]:
(B) (B-1) organometallic compound,
In the presence of an olefin polymerization catalyst comprising (B-2) an organoaluminum oxy compound, and (B-3) at least one compound selected from compounds that react with the transition metal compound (A) to form an ion pair. A process for producing an ethylene / α-olefin / non-conjugated polyene copolymer, comprising copolymerizing ethylene, an α-olefin and a non-conjugated polyene:

(In the formula [I] and formula ^{[II], R 1, R} 2, R 3, R 4, R 5, R 6, R 7, R 8, R 9, R 10, R 11, R 12, R 13 , R ¹⁴ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to even better carbon atoms substituted with a halogen atom 20, and are selected from silicon-containing group, each may be the same or different, from R ¹ Adjacent substituents up to R ¹⁴ may combine with each other to form a ring.
Y is a silicon atom or a carbon atom,
M is selected from a titanium atom, a zirconium atom, and a hafnium atom.
However, in the formula [I],
When Y is a silicon atom and R ⁵ to R ¹² are all hydrogen atoms, R ¹³ and R ¹⁴ are from groups other than methyl, butyl, phenyl, silicon-substituted phenyl, cyclohexyl, and benzyl. Chosen;
When Y is a silicon atom, and only R ⁶ and R ¹¹ of R ⁵ to R ¹² are both t-butyl groups, R ¹³ and R ¹⁴ are selected from groups other than benzyl and silicon-substituted phenyl groups;
When Y is a carbon atom and R ⁵ to R ¹² are all hydrogen atoms, R ¹³ and R ¹⁴ are a methyl group, an isopropyl group, a t-butyl group, an isobutyl group, a phenyl group, and a pt-butylphenyl group. , Pn-butylphenyl group, silicon-substituted phenyl group, 4-biphenyl group, p-tolyl group, naphthyl group, benzyl group, cyclopentyl group, cyclohexyl group, and xylyl group;
When Y is a carbon atom and only R ⁶ and R ¹¹ of R ⁵ to R ¹² are t-butyl, methyl, or phenyl, R ¹³ and R ¹⁴ are methyl, phenyl, pt Selected from groups other than -butylphenyl group, pn-butylphenyl group, silicon-substituted phenyl group, benzyl group;
When Y is a carbon atom and only R ⁶ is a dimethylamino group, a methoxy group or a methyl group among R ⁵ to R ¹² , R ¹³ and R ¹⁴ are selected from groups other than a methyl group and a phenyl group;
When Y is a carbon atom, and the moiety composed of a fluorenyl group and R ⁵ to R ¹² is b, h-dibenzofluorenyl or a, i-dibenzofluorenyl, R ¹³ and R ¹⁴ are methyl A group other than a phenyl group.
A in the formula [II] represents a divalent saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms which may contain an aromatic ring, and A represents two or more including a ring formed with Y It may contain a ring structure. However, the ring formed by Y and A is selected from groups other than cyclobutylidene, cyclopentylidene, and cyclohexylidene when R ⁵ to R ¹² are simultaneously hydrogen atoms.
Q is a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a neutral group having 10 or less carbon atoms, a conjugated or nonconjugated diene, an anionic ligand, and neutral coordination capable of coordination with a lone pair of electrons. Chosen from a child. j is an integer of 1 to 4, and when j is 2 or more, Qs may be the same or different. ) The process for producing an ethylene / α-olefin / non-conjugated polyene copolymer according to claim 1, wherein M in the general formula [I] or [II] is a hafnium atom. The process for producing an ethylene / α-olefin / nonconjugated polyene copolymer according to claim 1, wherein M in the general formula [I] or [II] is a zirconium atom. The method for producing an ethylene / α-olefin / non-conjugated polyene copolymer according to any one of claims 1 to 3, wherein the α-olefin has 3 to 20 carbon atoms. The method for producing an ethylene / α-olefin / non-conjugated polyene copolymer according to any one of claims 1 to 3, wherein the α-olefin is propylene. 4. The method for producing an ethylene / α-olefin / non-conjugated polyene copolymer according to claim 1, wherein the non-conjugated polyene is a compound represented by the following general formula [III]: :

[In the formula [III], m is an integer of 0 to 2,
R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represents an atom or group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group, and the hydrocarbon group has a double bond. Well,
Any two of R ¹⁵ to R ¹⁸ may be bonded to each other to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring thus formed has a double bond. Well,
R ¹⁵ and R ¹⁶ , or R ¹⁷ and R ¹⁸ may form an alkylidene group,
R ¹⁵ and R ¹⁷ or R ¹⁶ and R ¹⁸ may be bonded to each other to form a double bond.
Provided that at least one of (i) to (iv) is satisfied;
(I) that any two of R ¹⁵ to R ¹⁸ are bonded to each other, and the monocyclic or polycyclic ring has a double bond (ii) with R ¹⁵ and R ¹⁶ , or R ¹⁷ and R ¹⁸ form an alkylidene group (iii) R ¹⁵ and R ¹⁷ or R ¹⁶ and R ¹⁸ are bonded to each other to form a double bond (iv) At least one of R ¹⁵ to R ¹⁸ is an unsaturated hydrocarbon group having one or more double bonds]. The method for producing an ethylene / α-olefin / non-conjugated polyene copolymer according to any one of claims 1 to 3, wherein a polymerization temperature in the copolymerization is 80 ° C or higher. The B value calculated by the following formula [IV] based on the ¹³ C-NMR spectrum of the copolymer obtained by the copolymerization is 1.05 or more, A process for producing an ethylene / α-olefin / non-conjugated polyene copolymer as described in:
B value = (c + d) / [2 × a × (e + f)] [IV]
(In the formula [IV], a, e and f are the ethylene mole fraction, α-olefin mole fraction and non-conjugated polyene mole fraction in the ethylene / α-olefin / nonconjugated polyene copolymer, respectively, and c is (The ethylene-α-olefin dyad mole fraction, d is the ethylene-nonconjugated polyene dyad mole fraction.)