JP2024048362A - TRANSITION METAL COMPOUND, CATALYST FOR OLEFIN POLYMERIZATION, AND METHOD FOR PRODUCING ETHYLENE-α-OLEFIN-NONCONJUGATED POLYENE COPOLYMER - Google Patents

Abstract

To provide a transition metal compound that yields an ethylene-α-olefin-nonconjugated polyene copolymer, enriched with nonconjugated diene and with α-olefin content appropriately suppressed.SOLUTION: The present invention provides a transition metal compound represented by formula (I), a catalyst for olefin polymerization comprising the transition metal compound, and a method for producing an ethylene-α-olefin-nonconjugated polyene copolymer including the step [P] for polymerizing an ethylene-α-olefin-nonconjugated polyene in the presence of this catalyst.SELECTED DRAWING: None

Description

The present invention relates to a transition metal compound, an olefin polymerization catalyst, and a method for producing an ethylene-α-olefin-non-conjugated polyene copolymer.

Ethylene-α-olefin rubber, typified by ethylene-propylene-non-conjugated diene copolymer (EPDM), has no unsaturated bonds in the main chain of its molecular structure, and therefore has superior heat resistance and weather resistance compared to commonly used conjugated diene rubber. Therefore, it is widely used in applications such as automobile parts, electric wire materials, construction and civil engineering materials, industrial parts, and modifiers for various resins.

Conventionally, ethylene-α-olefin-non-conjugated polyene copolymers such as EPDM have generally been produced using a catalyst system (so-called Ziegler-Natta catalyst system) consisting of a combination of a titanium-based catalyst or a vanadium-based catalyst with an organoaluminum compound.
The biggest drawback of this catalyst system is its productivity. The Ziegler-Natta catalyst system has low polymerization activity and a short catalyst life, so it is necessary to carry out polymerization under low temperature conditions of around 0 to 50°C. When polymerization is carried out at such low temperatures, the viscosity generally increases as the temperature decreases, so 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 essential. Furthermore, it is known that polymerization control is difficult in terms of removing the heat of polymerization due to the low-temperature polymerization. There has been a demand for improvement in the Ziegler-Natta catalyst system in terms of production and cost.

Meanwhile, metallocene catalyst systems, which have been the subject of active research since the 1980s, show superior polymerization activity and excellent copolymerization performance with α-olefins compared to Ziegler-Natta catalyst systems, and because they are single-site catalysts, they have made it possible to produce new olefin copolymers with narrow molecular weight and composition distributions. In addition, there have been reports on methods for producing ethylene-α-olefin-non-conjugated polyene copolymers using metallocene catalyst systems.

For example, Patent Documents 1, 2, 3, and 4 disclose manufacturing methods using geometrically constrained catalysts.

In addition, Patent Documents 5, 6, and 7 disclose bridged metallocene catalysts having biscyclopentadienyl and bisindenyl groups in the ligand. In addition, Patent Document 8 discloses a method for preparing particulate ultra-high molecular weight polyethylene (pUHMWPE) by copolymerization of ethylene and an olefin comonomer.

European Patent Application Publication No. 416815 International Publication No. WO 95/00526 WO 98/27103 JP 2001-522398 A JP 2005-344101 A Japanese Patent Application Laid-Open No. 9-151205 JP 2000-507635 A

However, even with such metallocene catalyst systems, there are many issues that prevent commercial practical use. Examples of issues related to the production of ethylene-α-olefin-non-conjugated polyene copolymers include issues in terms of production, cost, and physical properties, such as polymerization activity that can be adapted to a non-decalcifying process, high molecular weight that can withstand high-temperature polymerization, non-conjugated polyene copolymerization ability that does not place a burden on the monomer recovery process, and high monomer alternating copolymerization ability to exhibit good low-temperature properties in terms of physical properties.

Patent Documents 1 to 4 disclose geometrically constrained catalysts. Although these geometrically constrained catalysts have excellent copolymerizability with α-olefins and produce high molecular weight products, they have low alternating copolymerizability with monomers, which results in a long average ethylene chain length in the ethylene-α-olefin-non-conjugated polyene copolymer, and as a result, the low-temperature properties, which are one of the important physical properties, are insufficient. In addition, production methods using geometrically constrained catalysts often show high polymerization activity in the early stages of polymerization, which makes it difficult to control the polymerization heat.

Although the monomers described in Patent Documents 5 to 7 have relatively high alternating copolymerizability, they all have problems in that the polymerization activity is low and the molecular weight of the obtained ethylene/α-olefin/non-conjugated polyene copolymer is low.
Therefore, there is a demand for the development of a manufacturing method for more efficiently and cheaply producing ethylene-α-olefin-non-conjugated polyene copolymers with excellent heat resistance, weather resistance, and low-temperature properties. In particular, ethylene-α-olefin-non-conjugated polyene copolymers rich in non-conjugated polyene content are in wide demand. In addition, if a manufacturing method can be developed that appropriately suppresses the α-olefin content, it will be possible to increase the crystalline ethylene chain segments, and it will also be possible to design brands that specialize in tensile strength, another important physical property.

In view of these problems, an object of one embodiment of the present invention is to provide a transition metal compound which, when used as a component of an olefin polymerization catalyst, gives an ethylene/α-olefin/non-conjugated polyene copolymer having a rich non-conjugated polyene content and an appropriately suppressed α-olefin content.
Another problem to be solved by one embodiment of the present invention is to provide an olefin polymerization catalyst that gives an ethylene-α-olefin-non-conjugated polyene copolymer having a rich non-conjugated polyene content and an appropriately suppressed α-olefin content, and a method for producing an ethylene-α-olefin-non-conjugated polyene copolymer using the same.

After extensive research, the inventors discovered that the above problems could be solved by using a transition metal compound having a geometrically constrained ligand of a specific structure as a component of an olefin polymerization catalyst, and thus completed the present invention.

The gist of the present invention is as follows.
<1> [A] A transition metal compound represented by the following general formula (I):

[In the formula (I),
M represents a transition metal atom of Groups 3 to 11 of the periodic table;
n represents an integer from 1 to 6;
R ^1a , R ^1b and R ^N each independently represent a substituent selected from the group consisting of an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aryl group, an aliphatic heterocyclic group, an oxygen atom-containing group, a nitrogen atom-containing group, a boron atom-containing group, a sulfur atom-containing group, a phosphorus atom-containing group, a silicon atom-containing group, a germanium atom-containing group and a tin atom-containing group, and two or more groups among R ^1a , R ^1b and R ^N may be bonded to each other to form a ring,
R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently represent an atom or substituent selected from the group consisting of a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aryl group, an oxygen atom-containing group, a nitrogen atom-containing group, a boron atom-containing group, a sulfur atom-containing group, a phosphorus atom-containing group, a silicon atom-containing group, a germanium atom-containing group and a tin atom-containing group, adjacent substituents of R ³ to R ⁷ may be bonded to each other to form a ring,
R ² is a substituent represented by *-ZR (* represents a bonding site with the indene ring, Z represents an oxygen atom or a sulfur atom, R is a substituent selected from the group consisting of an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aryl group, an oxygen atom-containing group, a nitrogen atom-containing group, a boron atom-containing group, a sulfur atom-containing group, a phosphorus atom-containing group, a silicon atom-containing group, a germanium atom-containing group and a tin atom-containing group, and R may bond with R ^1a or R ^1b to form a ring),
X represents a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen atom-containing group, a sulfur atom-containing group, a nitrogen atom-containing group, a boron atom-containing group, an aluminum atom-containing group, a phosphorus atom-containing group, a halogen atom-containing group, a heterocyclic group, a silicon atom-containing group, a germanium atom-containing group, or a tin atom-containing group, and when n is 2 or more, the multiple groups represented by X may be the same or different from one another, and the multiple groups represented by X may be bonded to one another to form a ring.

<2> The transition metal compound according to <1>, wherein R ⁵ and R ⁶ in the general formula (I) are bonded to each other to form a ring.
<3> The transition metal compound according to <1> or <2>, wherein in *-ZR represented by R ² in the general formula (I), Z is an oxygen atom.
<4> The transition metal compound according to any one of <1> to <3>, wherein R ³ , R ⁴ and R ⁷ in the general formula (I) are hydrogen atoms.
<5> The transition metal compound according to any one of <1> to <4>, wherein *-ZR represented by R ² in the general formula (I) is any one of a methoxy group, an ethoxy group, and a silyloxy group.
<6> The transition metal compound according to any one of <1> to <5>, wherein R ^1a and R ^1b in the general formula (I) are each independently any one of a methyl group and a phenyl group.
<7> The transition metal compound according to any one of <1> to <6>, wherein R ^N in the general formula (I) is a tert-butyl group.
<8> The transition metal compound according to any one of <1> to <7>, wherein M in the general formula (I) is any one of an atom of titanium, zirconium, and hafnium.
<9> The transition metal compound according to any one of <1> to <8>, wherein M in the general formula (I) is titanium.
<10> An olefin polymerization catalyst comprising the transition metal compound according to any one of <1> to <9>.
<11> [B] [B-1] an organometallic compound, [B-2] an organoaluminum oxy compound, and
[B-3] A compound that reacts with the transition metal compound to form an ion pair.
<12> A method for producing an ethylene-α-olefin-non-conjugated polyene copolymer, comprising a step [P] of copolymerizing ethylene, an α-olefin, and a non-conjugated polyene in the presence of the olefin polymerization catalyst according to <10>.
<13> The method for producing an ethylene/α-olefin/non-conjugated polyene copolymer according to <12>, wherein the non-conjugated polyene is a compound represented by the following general formula (II):

[In the formula (II),
m is an integer from 0 to 2;
R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ each independently represent an atom or a substituent selected from the group consisting of a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon atom-containing group, a nitrogen atom-containing group, an oxygen atom-containing group, a halogen atom and a halogen atom-containing group, the hydrocarbon group optionally having a double bond;
Any two of the substituents among R ⁸ to R ¹¹ may be bonded to each other to form a ring, and the ring may contain a double bond; R ⁸ and R ⁹ , or R ¹⁰ and R ¹¹ may be bonded to each other to form an alkylidene group; R ⁸ and R ¹⁰ , or R ⁹ and R ¹¹ may be bonded to each other to form a double bond;
At least one of the following requirements (i) to (iv) is met:
(i) at least one of R ⁸ to R ¹¹ is a hydrocarbon group having one or more double bonds;
(ii) any two of the substituents R ⁸ to R ¹¹ are bonded to each other to form a ring, and the ring contains a double bond;
(iii) R ⁸ and R ⁹ together, or R ¹⁰ and R ¹¹ together form an alkylidene group;
(iv) R ⁸ and R ¹⁰ , or R ⁹ and R ¹¹ , are bonded to each other to form a double bond.
<14> The method for producing an ethylene/α-olefin/non-conjugated polyene copolymer according to <12> or <13>, wherein the non-conjugated polyene is 5-ethylidene-2-norbornene (ENB) or 5-vinyl-2-norbornene (VNB).
<15> The method for producing an ethylene-α-olefin-non-conjugated polyene copolymer according to any one of <12> to <14>, wherein the step [P] is a step of copolymerizing ethylene, an α-olefin having 3 to 10 carbon atoms, and a non-conjugated polyene.
<16> The method for producing an ethylene/α-olefin/non-conjugated polyene copolymer according to any one of <12> to <15>, wherein the α-olefin is propylene.
<17> The method for producing an ethylene/α-olefin/non-conjugated polyene copolymer according to any one of <12> to <16>, wherein the polymerization temperature in the step [P] is 80° C. or higher.

According to one embodiment of the present invention, there is provided a transition metal compound which, when used as a component of an olefin polymerization catalyst, gives an ethylene/α-olefin/non-conjugated polyene copolymer having a rich non-conjugated polyene content and an appropriately suppressed α-olefin content.
Furthermore, according to one embodiment of the present invention, there are provided an olefin polymerization catalyst that gives an ethylene-α-olefin-non-conjugated polyene copolymer having a rich non-conjugated polyene content and an appropriately suppressed α-olefin content, and a method for producing an ethylene-α-olefin-non-conjugated polyene copolymer using the same.

In this specification, organic groups that are not specified as having or not having a substituent include both substituted and unsubstituted ones. For example, when simply describing an "alkyl group", it includes both an alkyl group in which one or more hydrogen atoms are substituted with a substituent and an unsubstituted alkyl group, and when describing a "substituted alkyl group", it refers only to an alkyl group in which one or more hydrogen atoms are substituted with a substituent.

Two or more oxygen atom-containing groups, nitrogen atom-containing groups, sulfur atom-containing groups, and phosphorus atom-containing groups may be contained in one substituent.

[Transition metal compound [A]]
The transition metal compound according to the present invention (hereinafter, sometimes referred to as "transition metal compound [A]") is represented by the following general formula (I). When the transition metal compound [A] is used as a component of an olefin polymerization catalyst, it is possible to obtain an ethylene/α-olefin/non-conjugated polyene copolymer that is rich in non-conjugated polyene content and has an appropriately suppressed α-olefin content. The reason for this is not clear, but is presumed to be as follows.

When the transition metal compound according to the present invention is used as a component of an olefin polymerization catalyst, if the substituent R ² is a substituent represented by *-ZR (* represents a bonding site with an indene ring, and Z represents an oxygen atom or a sulfur atom), the partial charge of the transition metal atom in the polymerization active species increases, and the interaction between the polymerization active species and the non-conjugated polyene becomes more dominant. On the other hand, the unshared electron pair on the oxygen or sulfur atom represented by Z is conjugated with the indene ring, and the lowest unoccupied molecular orbital (LUMO) of the polymerization active species increases. As a result, the energy difference with the highest occupied molecular orbital (HOMO) of the α-olefin increases, making the interaction between the polymerization active species and the α-olefin more unfavorable, and the copolymerizability of the α-olefin is suppressed. Due to the above effects, when the transition metal compound [A] is used as a component of an olefin polymerization catalyst, ethylene-α-olefin-non-conjugated polyene copolymerization is performed, and an ethylene-α-olefin-non-conjugated polyene copolymer rich in non-conjugated polyene content and moderately suppressed in α-olefin content is obtained.
Each of the substituents possessed by the transition metal compound [A] according to the present invention will be described in detail below.

<M>
In the above general formula (I), M represents a transition metal atom of Groups 3 to 11 of the periodic table (Group 3 also includes lanthanoids), preferably a metal atom of Groups 3 to 9, more preferably a transition metal atom selected from Groups 3 to 5, still more preferably a transition metal atom selected from Group 4 or Group 5, and particularly preferably a transition metal atom of Group 4.
Specific examples of M include scandium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, cobalt, rhodium, yttrium, chromium, molybdenum, tungsten, manganese, rhenium, iron, ruthenium, etc. Among these, from the viewpoint of excellent copolymerizability of comonomers, M is preferably scandium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, cobalt, and rhodium, more preferably titanium, zirconium, hafnium, cobalt, rhodium, vanadium, niobium, and tantalum, more preferably titanium, zirconium, and hafnium, and particularly preferably titanium.

<n>
In the above general formula (I), n represents an integer of 1 to 6, preferably an integer of 1 to 4, more preferably an integer of 1 to 3, and further preferably 2. When n is 2 or more, the multiple X's may be the same or different. Furthermore, the multiple groups represented by X may be bonded to each other to form a ring.

<R ^1a , R ^1b and R ^N >
In the above general formula (I), R ^1a , R ^1b and R ^N each independently represent a substituent selected from the group consisting of an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aryl group, an aliphatic heterocyclic group, an oxygen atom-containing group, a nitrogen atom-containing group, a boron atom-containing group, a sulfur atom-containing group, a phosphorus atom-containing group, a silicon atom-containing group, a germanium atom-containing group, or a tin atom-containing group, and two or more of R ^1a , R ^1b and R ^N may be linked to each other to form a ring.

<<Aliphatic Hydrocarbon Group Having 1 to 20 Carbon Atoms>>
The aliphatic hydrocarbon group having 1 to 20 carbon atoms may be a linear or branched aliphatic hydrocarbon group having 1 to 20 carbon atoms, or a cyclic hydrocarbon group having 3 to 20 carbon atoms.
The aliphatic hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group.

The saturated aliphatic hydrocarbon group is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms. Specific examples of such saturated aliphatic hydrocarbon groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, neopentyl, and n-hexyl groups.

The unsaturated aliphatic hydrocarbon group is a linear or branched alkenyl group having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, such as a vinyl group, an allyl group, or an isopropenyl group; or a linear or branched alkynyl group having 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, such as an ethynyl group or a 2-propynyl group.

The cyclic hydrocarbon group may be a cyclic saturated hydrocarbon group or a cyclic unsaturated hydrocarbon group. The cyclic hydrocarbon group having 3 to 20 carbon atoms is preferably a cyclic saturated hydrocarbon group having 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and an adamantyl group. Other examples include cyclic unsaturated hydrocarbon groups having 5 to 20 carbon atoms, such as a cyclopentadienyl group, an indenyl group, and a fluorenyl group.

The hydrogen atoms in the above hydrocarbon groups may be substituted with halogen atoms. The halogen atoms used for the halogen substitution are not particularly limited, and examples thereof include the halogen atoms in R ³ to R ⁷ described below.
Examples of hydrocarbon groups in which hydrogen atoms are substituted with halogens (hereinafter also referred to as "halogen-substituted hydrocarbon groups") include halogenated hydrocarbon groups having 1 to 30, preferably 1 to 20, carbon atoms, such as a trifluoromethyl group, a pentafluorophenyl group, and a chlorophenyl group.

The hydrocarbon group may be unsubstituted or may have a substituent.
Examples of the substituent on the hydrocarbon group include aliphatic heterocyclic groups, oxygen atom-containing groups, nitrogen atom-containing groups, sulfur atom-containing groups, phosphorus atom-containing groups, silicon atom-containing groups, germanium atom-containing groups and tin atom-containing groups, which will be described later.

<<Aryl Group>>
The aryl group is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms. Examples of the aryl group include a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a phenanthryl group, and an anthracenyl group.

The aryl group may also be a heteroaryl group, such as a thienyl group, a pyridyl group, or an indolyl group.
The aryl group may be a substituted aryl group. The substituted aryl group is preferably an alkyl-substituted aryl group, more preferably an alkyl-substituted aryl group having a total of 7 to 20 carbon atoms.
Examples of the alkyl-substituted aryl group include a tolyl group, an iso-propylphenyl group, a t-butylphenyl group, a dimethylphenyl group, and a di-t-butylphenyl group.

<<Aliphatic Heterocyclic Group>>
Examples of the aliphatic heterocyclic group include nitrogen-containing heterocyclic groups such as pyrrolyl, pyridyl, pyrimidyl, quinolyl, and triazinyl groups, acid-containing heterocyclic groups such as fulleryl and pin, and sulfur-containing heterocyclic groups such as thienyl.
The aliphatic heterocyclic group preferably has 1 to 30 carbon atoms.
The heterocyclic group may have a substituent, and preferred examples of the substituent include an alkyl group having 1 to 20 carbon atoms, and an alkoxy group.

<<Oxygen Atom-Containing Group>>
The oxygen atom-containing group may contain only one oxygen atom, or may contain two or more oxygen atoms.
In addition, at least one of the oxygen atoms contained in the oxygen atom-containing group is preferably an oxygen atom that is not included as a ring member in a cyclic structure.
Examples of the oxygen atom-containing group include an alkoxy group, an aryloxy group, an ester group, an ether group, an acyl group, a carboxyl group, a carbonate group, a hydroxy group, a peroxy group, and a carboxylic anhydride group.

Specific examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and a t-butoxy group.
Specific examples of the aryloxy group include a phenoxy group, a 2,6-dimethylphenoxy group, and a 2,4,6-trimethylphenoxy group.
Specific examples of the acyl group include a formyl group, an acetyl group, a benzoyl group, a p-chlorobenzoyl group, and a p-methoxybenzoyl group.
Specific examples of the ester group include an acetyloxy group, a benzoyloxy group, a methoxycarbonyl group, a phenoxycarbonyl group, and a p-chlorophenoxycarbonyl group.

<<Nitrogen Atom-Containing Group>>
The nitrogen atom-containing group is not particularly limited and may contain only one nitrogen atom or two or more nitrogen atoms.
In addition, at least one of the nitrogen atoms contained in the nitrogen-atom-containing group is preferably a nitrogen atom that is not included as a ring member in a cyclic structure.
Examples of such a nitrogen atom-containing group include an amino group, an imino group, an amido group, an imido group, a hydrazino group, a hydrazono group, a nitro group, a nitroso group, a cyano group, an isocyano group, a cyanate ester group, an amidino group, a diazo group, and an amino group that has become an ammonium salt.

The amino group is not particularly limited, and examples thereof include alkylamino groups such as a methylamino group, a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group, an ethylmethylamino group, and a dicyclohexylamino group; arylamino groups such as a phenylamino group, a diphenylamino group, a ditolylamino group, a dinaphthylamino group, and a methylphenylamino group, or alkylarylamino groups.
Specific examples of the imino group include a methylimino group, an ethylimino group, a propylimino group, a butylimino group, and a phenylimino group.
Specific examples of the amide group include an acetamide group, an N-methylacetamide group, and an N-methylbenzamide group.
Specific examples of the imido group include an acetimido group and a benzimido group.

<<Boron Atom-Containing Group>>
The boron atom-containing group is not particularly limited, and specific examples include _BR4 (R represents a hydrogen atom, an alkyl group, an aryl group which may have a substituent, a halogen atom, etc.). Examples of the halogen atom include the halogen atoms in ^R3 to ^R7 described below.

<<Sulfur Atom-Containing Group>>
The sulfur atom-containing group is not particularly limited and may contain only one sulfur atom or may contain two or more sulfur atoms.
In addition, at least one of the sulfur atoms contained in the sulfur atom-containing group is preferably a sulfur atom that is not contained as a ring member in a cyclic structure.

Examples of sulfur atom-containing groups include mercapto groups, thioester groups, dithioester groups, alkylthio groups, arylthio groups, thioacyl groups, thioether groups, thiocyanate ester groups, isocyanate ester groups, sulfone ester groups, sulfonamide groups, thiocarboxyl groups, dithiocarboxyl groups, sulfo groups, sulfonyl groups, sulfinyl groups, sulfenyl groups, and sulfino groups.

Specific examples of the sulfonyl (sulfonate) group include a methylsulfonyl (sulfonate) group, a trifluoromethanesulfonyl (sulfonate) group, a phenylsulfonate group, a benzylsulfonyl (sulfonate) group, a p-toluenebenzylsulfonyl group, a trimethylbenzenesulfonyl (sulfonate) group, a triisobutylbenzenesulfonyl (sulfonate) group, a p-chlorobenzenesulfonyl (sulfonate) group, and a pentafluorobenzenesulfonyl (sulfonate) group.
Examples of the sulfinate (sulfinyl) group include a methylsulfinate group, a phenylsulfinate group, a benzylsulfinate group, a p-toluenesulfinate group, a trimethylbenzenesulfinate group, and a pentafluorobenzenesulfinate group.

Specific examples of the thioester group include an acetylthio group, a benzoylthio group, a methylthiocarbonyl group, and a phenylthiocarbonyl group.
Specific examples of the alkylthio group include a methylthio group and an ethylthio group.
Specific examples of the arylthio group include a phenylthio group, a methylphenylthio group, and a naphthylthio group.
Specific examples of the sulfonate group include a methyl sulfonate group, an ethyl sulfonate group, and a phenyl sulfonate group.
Specific examples of the sulfonamide group include a phenylsulfonamide group, an N-methylsulfonamide group, and an N-methyl-p-toluenesulfonamide group.

<<Phosphorus Atom-Containing Group>>
The phosphorus atom-containing group is not particularly limited, and may contain only one phosphorus atom or may contain two or more phosphorus atoms.
In addition, at least one of the phosphorus atoms contained in the phosphorus atom-containing group is preferably a phosphorus atom that is not included as a ring member in a cyclic structure.
Examples of the phosphorus atom-containing group include a phosphite group (phosphido group), a phosphoryl group, a thiophosphoryl group, a phosphate group, etc. For example, a trialkylphosphine group such as a trimethylphosphine group, a tributylphosphine group, or a tricyclohexylphosphine group;
triarylphosphine groups such as a triphenylphosphine group and a tritolylphosphine group;
Examples of the phosphite group (phosphido group) include a methyl phosphite group, an ethyl phosphite group, a phenyl phosphite group, etc.; a phosphonic acid group; and a phosphinic acid group, but are not limited to these.

<<Silicon Atom-Containing Group>>
Examples of the silicon atom-containing group include a silyl group, a siloxy group, a hydrocarbon-substituted silyl group, and a hydrocarbon-substituted siloxy group. More specific examples include a methylsilyl group, a dimethylsilyl group, a trimethylsilyl group, an ethylsilyl group, a diethylsilyl group, a triethylsilyl group, a diphenylmethylsilyl group, a triphenylsilyl group, a dimethylphenylsilyl group, a dimethyl-t-butylsilyl group, and a dimethyl(pentafluorophenyl)silyl group.

Among these, a methylsilyl group, a dimethylsilyl group, a trimethylsilyl group, an ethylsilyl group, a diethylsilyl group, a triethylsilyl group, a dimethylphenylsilyl group, and a triphenylsilyl group are preferred, and a trimethylsilyl group, a triethylsilyl group, a triphenylsilyl group, and a dimethylphenylsilyl group are particularly preferred.
Specific examples of the hydrocarbon-substituted siloxy group include a trimethylsiloxy group.

Examples of the hydrocarbon substituent in the silicon atom-containing group include linear or branched alkyl groups having 1 to 30, preferably 1 to 20, carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, neopentyl, and n-hexyl.
Examples of the hydrocarbon substituent include a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a phenanthryl group, an anthracenyl group, and the like, and preferably an aryl group having 6 to 20 carbon atoms.

The aryl group may be substituted with a halogen atom, preferably with 1 to 20 alkyl or alkoxy groups, and preferably with 6 to 20 aryl or aryloxy groups. The aryl group is preferably a substituted aryl group having 1 to 5 substituents.

<<Germanium Atom-Containing Group and Tin Atom-Containing Group>>
The germanium atom-containing group or the tin atom-containing group includes groups in which the silicon atom of the silicon atom-containing group is substituted with a germanium atom or a tin atom.

As described above, two or more of R ^1a , R ^1b and R ^N in the above general formula (I) may be linked to each other to form a ring.
More specifically, the ring formed by combining two or more groups, preferably adjacent groups, among R ^1a , R ^1b and R ^N may be an alicyclic ring or an aromatic ring. These rings may further have a substituent.
The alicyclic ring and aromatic ring may be a monocyclic ring or a polycyclic ring. The number of ring members of the alicyclic ring and aromatic ring is not particularly limited, but is preferably, for example, 3 to 8.

- Alicyclic -
The alicyclic ring may be an aliphatic hydrocarbon ring composed only of carbon atoms (hereinafter also simply referred to as a "carbocyclic ring"), or may be an aliphatic heterocyclic ring containing a heteroatom (hereinafter also referred to as a "non-aromatic heterocyclic ring").
The alicyclic ring (carbocyclic ring) composed only of carbon atoms is preferably an alicyclic ring having 3 to 7 carbon atoms, and more preferably an alicyclic ring having 4 to 7 carbon atoms.
Examples of the alicyclic ring having 3 to 7 carbon atoms include a cyclopropane ring, a cyclopentane ring, a cyclohexane ring, and a cycloheptane ring.

-Non-aromatic heterocycle-
The heteroatom contained in the non-aromatic heterocycle is preferably a nitrogen atom, an oxygen atom, or a sulfur atom. These heteroatoms may be one type or two or more types, and the non-aromatic heterocycle may contain a plurality of the same heteroatoms.
The non-aromatic heterocycle is preferably a 4- to 7-membered non-aromatic heterocycle containing at least one nitrogen atom, oxygen atom or sulfur atom, and more preferably a 4- to 6-membered non-aromatic heterocycle containing at least one nitrogen atom, oxygen atom or sulfur atom.

The non-aromatic heterocycle is preferably a heterocycle having 3 to 14 carbon atoms containing at least one nitrogen atom, oxygen atom or sulfur atom, more preferably a heterocycle having 3 to 10 carbon atoms containing at least one nitrogen atom, oxygen atom or sulfur atom, and even more preferably a heterocycle having 3 to 8 carbon atoms containing at least one nitrogen atom, oxygen atom or sulfur atom.
Examples of the non-aromatic heterocycle include an oxolane ring, a dioxolane ring, a piperidine ring, and a pyrrolidine ring.

-Aromatic ring-
The aromatic ring is not particularly limited, and may be an aromatic ring composed only of carbon atoms, or an aromatic ring containing a heteroatom (hereinafter also referred to as an "aromatic heterocycle").
When the aromatic ring is polycyclic, it may be a condensed ring of two or more aromatic rings, or a condensed ring of an aromatic ring and an alicyclic ring. Examples of the alicyclic ring condensed with the aromatic ring include the above-mentioned alicyclic rings.

The aromatic ring is preferably an aromatic ring having 6 to 14 carbon atoms, and more preferably an aromatic ring having 6 to 10 carbon atoms.
Examples of the aromatic ring include a benzene ring, a naphthalene ring, and an anthracene ring.

- Aromatic heterocycle -
The aromatic heterocycle is preferably an aromatic heterocycle having 3 to 14 carbon atoms containing at least one nitrogen atom, oxygen atom or sulfur atom, more preferably an aromatic heterocycle having 3 to 10 carbon atoms containing at least one nitrogen atom, oxygen atom or sulfur atom, and even more preferably an aromatic heterocycle having 3 to 8 carbon atoms containing at least one nitrogen atom, oxygen atom or sulfur atom.
Examples of the aromatic heterocycle include a pyridine ring, a piperazine ring group, a pyrrolidine ring group, a pyrrole ring, a piperidine ring, a pyran ring, a thiopyran ring, and a thiophene ring.

The alicyclic ring and aromatic ring may have a substituent.
Examples of the substituent include an alkyl group having 1 to 20 carbon atoms and an alkoxy group.

Of R ^1a , R ^1b and R ^N in the above general formula (I), from the viewpoint of polymerization activity, R ^N is preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aryl group, and more preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms.
From the above viewpoint, R ^1a and R ^1b in the above general formula (I) are each preferably independently an alkyl group having 1 to 5 carbon atoms or a phenyl group, more preferably a methyl group or a phenyl group.
From the above viewpoint, R ^N in general formula (I) is preferably a tertiary alkyl group having 4 to 10 carbon atoms, and particularly preferably a tert-butyl group.

< ^R3 , ^R4 , ^R5 , ^R6 and ^R7 >
In the above general formula (I), R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently an atom or substituent selected from the group consisting of a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aryl group, an oxygen atom-containing group, a nitrogen atom-containing group, a boron atom-containing group, a sulfur atom-containing group, a phosphorus atom-containing group, a silicon atom-containing group, a germanium atom-containing group and a tin atom-containing group, and adjacent substituents of R ³ to R ⁷ may be bonded to each other to form a ring.
The aliphatic hydrocarbon group having ¹ to 20 carbon atoms, aryl group, oxygen atom-containing group, nitrogen atom-containing group, boron atom ^- containing group, sulfur atom-containing group, phosphorus atom-containing group, silicon atom-containing group, germanium atom-containing group, and tin atom-containing group in R ³ to R ⁷ are synonymous with the aliphatic hydrocarbon group having 1 to 20 ^carbon atoms, aryl group, oxygen atom-containing group, nitrogen atom-containing group, boron atom-containing group, sulfur atom-containing group, phosphorus atom-containing group, silicon atom-containing group, germanium atom-containing group, and tin atom-containing group in R 1a, R 1b, and R N, and examples thereof include the same as those exemplified above.

<<Halogen atoms>>
The halogen atom includes fluorine, chlorine, bromine, iodine, and the like.

The ring formed by bonding adjacent substituents of R to ^{R to} each other has the same meaning as the ring formed by bonding adjacent substituents of ^R , R and ^R. Among the above rings, an alicyclic ring is preferred, and an alicyclic ring having ³ to 7 carbon atoms is more preferred.

From the viewpoint of excellent copolymerizability of comonomers, it is preferable that ^R5 and ^R6 are bonded to ^each other to form a ring ^{and R3} , ^R4 and ^R7 are hydrogen atoms in the above general formula (I), and it is more preferable that ^R5 and ^R6 are bonded ^{to each} other to form ^a cyclopentane ring and ^R3 , ^R4 and ^R7 are hydrogen atoms.

^<R2>
In the general formula (I), ^R2 is a substituent represented by *-ZR, in which * represents a bonding site with the indene ring, Z is an oxygen atom or a sulfur atom, R is a substituent selected from the group consisting of an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aryl group, an oxygen atom-containing group, a nitrogen atom-containing group, a boron atom-containing group, a sulfur atom-containing group, a phosphorus atom-containing group, a silicon atom-containing group, a germanium atom-containing group, and a tin atom-containing group, and R may bond with ^R1a or ^R1b to form a ring.

Examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms, the oxygen atom-containing group, the nitrogen atom-containing group, the boron atom-containing group, the sulfur atom-containing group, the phosphorus atom ^- containing group, the silicon atom-containing group, the germanium atom-containing group, and the tin atom-containing group include the same groups as those exemplified in the explanation of the ^aliphatic hydrocarbon group having ¹ to 20 carbon atoms, the oxygen atom-containing group, the nitrogen atom-containing group, the boron atom-containing group, the sulfur atom-containing group, the phosphorus atom-containing group, the silicon atom-containing group, the germanium atom-containing group, and the tin atom-containing group for R 1a, R 1b, and R N.

From the viewpoint of excellent polymerization activity and copolymerizability with comonomers, *-ZR represented by ^R2 in general formula (I) is preferably such that Z is an oxygen atom and R is an aliphatic hydrocarbon group having 1 to 10 carbon atoms or a silicon atom-containing group, and more preferably such that Z is an oxygen atom and R is an alkyl group or silyl group having 1 to 4 carbon atoms.
From the above viewpoints, the substituent represented by *-ZR is preferably any one of an alkyl group having 1 to 4 carbon atoms and a silyloxy group, and more preferably any one of a methoxy group, an ethoxy group, and a silyloxy group.

＜X＞
In the above general formula (I), X represents a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen atom-containing group, a sulfur atom-containing group, a nitrogen atom-containing group, a boron atom-containing group, an aluminum atom-containing group, a phosphorus atom-containing group, a halogen atom-containing group, a heterocyclic group, a silicon atom-containing group, a germanium atom-containing group, or a tin atom-containing group. The groups represented by X may be the same or different from each other, and the groups represented by X may be bonded to each other to form a ring.
The halogen atom includes fluorine, chlorine, bromine, iodine, and the like.

The hydrocarbon group may, for example, be a hydrocarbon group having 1 to 20 carbon atoms, and may be the same as the hydrocarbon group having 1 to 20 carbon atoms in R ^1a , R ^1b and R ^N described above.

The oxygen atom-containing group, sulfur atom-containing group, nitrogen atom ^- containing group, boron atom-containing group, phosphorus atom-containing group, silicon atom-containing group, germanium atom-containing group, and tin atom ^- containing group have the same meanings as the oxygen atom-containing group, sulfur atom-containing group, nitrogen atom-containing group, boron atom-containing group, phosphorus atom ^- containing group, silicon atom-containing group, germanium atom-containing group, and tin atom-containing group in R 1a, R 1b, and R N, and preferred embodiments are also the same.

Specific examples of the aluminum-containing group include AlR ₄ (R represents hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, etc.), but are not limited thereto.

The heterocyclic group for X is not particularly limited, and may be an aromatic heterocyclic group or an aliphatic heterocyclic group.
The aromatic heterocyclic group has the same meaning as the heteroaryl group described above, and the preferred embodiments are also the same. The aliphatic heterocyclic group has the same meaning as the aliphatic heterocyclic group in R ^1a , R ^1b , and R ^N described above, and the preferred embodiments are also the same.

The halogen atom contained in the halogen atom-containing group is not particularly limited, and may be fluorine, chlorine, bromine, or iodine. Specific examples of the halogen atom-containing group include, but are not limited to, fluorine atom-containing groups such as _PF6 and _BF4 , chlorine atom-containing groups such as _ClO4 and _SbCl6 , and iodine atom-containing groups such as _IO4 .

Specific examples of the transition metal compound [A] represented by the above general formula (I) are shown below, but the transition metal compound [A] of the present invention is not limited to these.

In the above examples, Ph represents a phenyl group, and TBS represents a tert-butyldimethylsilyl group. In the above examples, transition metal compounds in which at least one of the two chlorine atoms on the metal is replaced with a substituent exemplified as X in general formula (I) are also examples of transition metal compound [A].

<<Method of producing transition metal compound [A]>>
The method for producing such a transition metal compound [A] is not particularly limited, and it can be produced, for example, as follows.

First, the ligand can be synthesized by a method previously reported (Organometallics, 2001, 20, 2663.). The resulting ligand can then be reacted with a compound of a transition metal atom to synthesize the corresponding transition metal compound. Specifically, the ligand is dissolved in a solvent and lithiated with two equivalents of n-butyllithium at a temperature range of 0°C to room temperature, and then a compound having a transition metal atom M, such as a metal halide or metal alkyl compound, is mixed at a temperature range of 0°C to room temperature and stirred overnight. As the solvent, any solvent commonly used for such reactions can be used, but it is particularly preferable to use a polar solvent such as tetrahydrofuran (THF) added in a small amount to a hydrocarbon solvent such as toluene.

In addition, the transition metal compound obtained by this production method can be used directly in the polymerization of olefins as a reaction solution of the ligand and the metal compound without isolation.

[Olefin Polymerization Catalyst]
The olefin polymerization catalyst according to the present invention contains the above-mentioned transition metal compound [A], and preferably contains the transition metal compound [A] and at least one compound selected from the group consisting of the compound [B] group: [B-1] organometallic compounds, [B-2] organoaluminum oxy compounds, and [B-3] compounds that react with the transition metal compound [A] to form an ion pair.
The olefin polymerization catalyst according to the present invention can produce an ethylene-α-olefin-non-conjugated polyene copolymer with higher comonomer copolymerizability while maintaining the copolymerizability of α-olefin, and therefore can produce an ethylene-α-olefin-non-conjugated polyene copolymer of the same composition with a smaller amount of comonomer used. This is expected to streamline the process for producing an ethylene-α-olefin-non-conjugated polyene copolymer, such as reducing the load of the demonomerization step.
The compound [B] group, which is a constituent element of the olefin polymerization catalyst of the present invention, and other components that can be used as required will be specifically described below.

<Compound [B] Group>
It is preferable that the olefin polymerization catalyst according to the present invention further contains, in addition to the above-mentioned olefin polymerization catalyst, at least one compound selected from the group consisting of [B-1] organometallic compounds, [B-2] organoaluminum oxy compounds, and [B-3] compounds that react with the above-mentioned transition metal compounds to form ion pairs (hereinafter, [B-1] organometallic compounds, [B-2] organoaluminum oxy compounds, and [B-3] may be collectively referred to as the "compound [B] group").

<<[B-1] Organometallic Compound>>
Specific examples of the organometallic compound [B-1] include organoaluminum compounds represented by the following general formula (B-1a), complex alkyl compounds of metals of Group 1 of the periodic table and aluminum represented by the general formula (B-1b), and dialkyl compounds of metals of Group 2 or Group 12 of the periodic table represented by the general formula (B-1c).
The organometallic compound [B-1] does not include the organoaluminum oxy compound [B-2] described later.

R ^a _p Al(OR ^b ) _q H _r Y _s ... general formula (B-1a)
In general formula (B-1a), R ^a and R ^b each independently represent a hydrocarbon group having 1 to 15 carbon atoms, and preferably a hydrocarbon group having 1 to 4 carbon atoms, Y represents a halogen atom, p represents a number that satisfies 0<p≦3, q represents a number that satisfies 0≦q<3, r represents a number that satisfies 0≦r<3, s represents a number that satisfies 0≦s<3, and p+q+r+s=3.

M ³ AlR ^c ₄ ... general formula (B-1b)
In formula (B-1b), M ³ represents Li, Na or K, and R ^c represents a hydrocarbon group having 1 to 15 carbon atoms, preferably a hydrocarbon group having 1 to 4 carbon atoms.

R ^d R ^e M ⁴ ... General formula (B-1c)
In general formula (B-1c), R ^d and R ^e each independently represent a hydrocarbon group having 1 to 15 carbon atoms, preferably a hydrocarbon group having 1 to 4 carbon atoms, and M ⁴ represents Mg, Zn or Cd.

Examples of the organoaluminum compound represented by the general formula (B-1a) include the following organoaluminum compounds (1) to (3).
(1): R ^a _p Al(OR ^b ) _3-p (wherein R ^a and R ^b may be the same or different and each represent a hydrocarbon group having 1 to 15, preferably 1 to 4, carbon atoms, and p is preferably a number satisfying 1.5≦p≦3.)

(2): An organoaluminum compound represented by R ^a _p AlY _3-p (wherein R ^a represents a hydrocarbon group having 1 to 15, preferably 1 to 4, carbon atoms, Y represents a halogen atom, and p is preferably a number satisfying 0<p<3); and R ^a _p AlH _3-p (wherein R ^a represents a hydrocarbon group having 1 to 15, preferably 1 to 4, carbon atoms, and p is preferably a number satisfying 2≦p<3).

(3): R ^a _p Al(OR ^b ) _q Y _s (wherein R ^a and R ^b may be the same or different and each represents a hydrocarbon group having 1 to 15, preferably 1 to 4, carbon atoms; Y represents a halogen atom; p represents a number satisfying 0<p≦3, q represents a number satisfying 0≦q<3, s represents a number satisfying 0≦s<3, and p+q+s=3).

More specific examples of the organoaluminum compound belonging to the general formula (B-1a) include tri-n-alkylaluminums such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, and tridecylaluminum;
tri-branched alkylaluminums such as triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylbutylaluminum, tri-2-methylpentylaluminum, tri-3-methylpentylaluminum, tri-4-methylpentylaluminum, tri-2-methylhexylaluminum, tri-3-methylhexylaluminum, and tri-2-ethylhexylaluminum;
Tricycloalkylaluminums such as tricyclohexylaluminum and tricyclooctylaluminum;
Triarylaluminum such as triphenylaluminum and tritolylaluminum;
dialkylaluminum hydrides such as diisobutylaluminum hydride; trialkenylaluminums such as triisoprenylaluminum represented by the formula (iC ₄ H ₉ ) _x Al _y (C ₅ H ₁₀ ) _z (wherein x, y and z are positive numbers and z≧2x);
alkylaluminum alkoxides such as isobutylaluminum methoxide, isobutylaluminum ethoxide, and isobutylaluminum isopropoxide;
Dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide, and dibutylaluminum butoxide;
Alkyl aluminum sesquialkoxides such as ethyl aluminum sesquiethoxide and butyl aluminum sesquibutoxide;
partially alkoxylated alkylaluminum having an average composition represented by R ^a _2.5 Al(OR ^b ) _0.5 (wherein R ^a and R ^b may be the same or different and each represents a hydrocarbon group having 1 to 15, preferably 1 to 4, carbon atoms);
dialkylaluminum aryloxides such as diethylaluminum phenoxide, diethylaluminum (2,6-di-t-butyl-4-methylphenoxide), ethylaluminum bis(2,6-di-t-butyl-4-methylphenoxide), diisobutylaluminum (2,6-di-t-butyl-4-methylphenoxide), and isobutylaluminum bis(2,6-di-t-butyl-4-methylphenoxide);
Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, and diisobutylaluminum chloride;
Alkyl aluminum sesquihalides such as ethyl aluminum sesquichloride, butyl aluminum sesquichloride, and ethyl aluminum sesquibromide;
partially halogenated alkylaluminums, such as alkylaluminum dihalides, such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide, and the like;
Dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride;
Other partially hydrogenated alkylaluminums, such as alkylaluminum dihydrides, such as ethylaluminum dihydride, propylaluminum dihydride, etc.;
Examples of the aluminum compounds include partially alkoxylated and halogenated alkylaluminum compounds such as ethylaluminum ethoxy chloride, butylaluminum butoxy chloride, and ethylaluminum ethoxy bromide.

The organometallic compound [B-1] may also be a compound similar to (B-1a), such as an organoaluminum compound in which two or more aluminum compounds are bonded via nitrogen atoms.
Specific examples of such compounds include ( _C2H5 ) _2AlN ( _{C2H5 )} Al( _{C2H5 ) 2 .}

Examples of the compound represented by the general formula (B-1b) include LiAl(C ₂ H ₅ ) ₄ and LiAl(C ₇ H ₁₅ ) ₄ .

Examples of the compound represented by the general formula (B-1c) include dimethylmagnesium, diethylmagnesium, dibutylmagnesium, butylethylmagnesium, dimethylzinc, diethylzinc, diphenylzinc, di-n-propylzinc, diisopropylzinc, di-n-butylzinc, diisobutylzinc, bis(pentafluorophenyl)zinc, dimethylcadmium, and diethylcadmium.

Other examples of the organometallic compound [B-1] include methyl lithium, ethyl lithium, propyl lithium, butyl lithium, methyl magnesium bromide, methyl magnesium chloride, ethyl magnesium bromide, ethyl magnesium chloride, propyl magnesium bromide, propyl magnesium chloride, butyl magnesium bromide, and butyl magnesium chloride.

The organometallic compound [B-1] may also be a compound that forms the above-mentioned organoaluminum compound in the polymerization system, such as a combination of an aluminum halide and an alkyllithium, or a combination of an aluminum halide and an alkylmagnesium.
The organometallic compounds [B-1] as described above may be used singly or in combination of two or more kinds.

<<[B-2] Organoaluminum oxy compound>>
The organoaluminum oxy compound [B-2] is not particularly limited and may be a conventionally known aluminoxane or a benzene-insoluble organoaluminum oxy compound such as those exemplified in JP-A-2-78687. Specific examples of the organoaluminum oxy compound [B-2] include methylaluminoxane, ethylaluminoxane, and isobutylaluminoxane.

Conventionally known aluminoxanes can be produced, for example, by the following methods (1) to (3), and are usually obtained as a solution in a hydrocarbon solvent.
(1) A method in which an organoaluminum compound such as trialkylaluminum is added to a hydrocarbon medium suspension of a compound containing adsorbed water or a salt containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, or cerous chloride hydrate, to react the adsorbed water or the water of crystallization with the organoaluminum compound.
(2) A method in which water, ice or water vapor is allowed to directly act on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran.
(3) A method in which an organoaluminum compound such as trialkylaluminum is reacted with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

The aluminoxane may contain a small amount of an organometallic component. After the solvent or unreacted organoaluminum compound is removed by distillation from the recovered aluminoxane solution, the resulting aluminoxane may be redissolved in a solvent or suspended in a poor solvent for the aluminoxane.

Specific examples of organoaluminum compounds that can be used to prepare aluminoxane include the same organoaluminum compounds as those exemplified as the organoaluminum compounds represented by the general formula (B-1a) above.

Of these, the organoaluminum compound is preferably a trialkylaluminum or a tricycloalkylaluminum, and particularly preferably trimethylaluminum.
The above organoaluminum compounds may be used alone or in combination of two or more.

Examples of solvents used in the preparation of aluminoxane include hydrocarbon solvents such as aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane; aliphatic hydrocarbon rings such as cyclopentane, cyclohexane, cyclooctane, and methylcyclopentane; petroleum fractions such as gasoline, kerosene, and diesel; and halides of the above-mentioned aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic aliphatic hydrocarbon rings, particularly chlorides and brominated products.
As the solvent, ethers such as ethyl ether, tetrahydrofuran, etc. can also be used. Among these, aromatic hydrocarbons or aliphatic hydrocarbons are particularly preferred as the solvent.

The organoaluminum compound may be insoluble in benzene, and the benzene-insoluble organoaluminum oxy-compound is preferably one in which the Al component dissolved in benzene at 60°C is usually 10% or less, preferably 5% or less, and particularly preferably 2% or less, calculated as Al atoms, i.e., it is preferably insoluble or poorly soluble in benzene.

[B-2] Examples of organoaluminum oxy compounds include boron-containing organoaluminum oxy compounds represented by the following general formula (V):

In formula (V), R ¹¹ represents a hydrocarbon group having 1 to 10 carbon atoms, and the four R ¹² each independently represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 10 carbon atoms.

The boron-containing organoaluminum oxy compound represented by the general formula (V) can be produced by reacting an alkylboronic acid represented by the following general formula (VI) with an organoaluminum compound in an inert gas atmosphere in an inert solvent at a temperature between -80°C and room temperature for 1 minute to 24 hours.

^R12 -B(OH) ₂ ... (VI)
(In formula (VI), R ¹² represents the same group as R ¹² in formula (V).)

Specific examples of the alkylboronic acid represented by the general formula (V) include methylboronic acid, ethylboronic acid, isopropylboronic acid, n-propylboronic acid, n-butylboronic acid, isobutylboronic acid, n-hexylboronic acid, cyclohexylboronic acid, phenylboronic acid, 3,5-difluoroboronic acid, pentafluorophenylboronic acid, and 3,5-bis(trifluoromethyl)phenylboronic acid.
Among these, preferred alkylboronic acids are methylboronic acid, n-butylboronic acid, isobutylboronic acid, 3,5-difluorophenylboronic acid, and pentafluorophenylboronic acid.
These may be used alone or in combination of two or more.

Specific examples of the organoaluminum compound to be reacted with such an alkylboronic acid include the same organoaluminum compounds as those exemplified as the organoaluminum compound represented by the above general formula (B-1a).
As the organoaluminum compound, trialkylaluminum and tricycloalkylaluminum are preferred, and trimethylaluminum, triethylaluminum and triisobutylaluminum are particularly preferred. These may be used alone or in combination of two or more.
The organoaluminum oxy compound (B-2) may be used alone or in combination of two or more kinds.

<<[B-3] Compound that reacts with transition metal compound [A] to form an ion pair>>
The compound [B-3] that reacts with the transition metal compound [A] to form an ion pair (hereinafter, may be referred to as "ionizing ionic compound [B-3]") is not particularly limited, and examples thereof include Lewis acids, ionic compounds, borane compounds, and carborane compounds described in JP-T-1-501950, JP-T-1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, U.S. Pat. No. 5,321,106, and the like.
[B-3] The ionizing ionic compounds further include heteropoly compounds and isopoly compounds.

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

The ionic compound may, for example, be a compound represented by the following general formula (VII):

In general formula (VII), R ¹³ is H ⁺ , a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptyltrienyl cation, or a ferrocenium cation having a transition metal atom, and R ¹⁴ to R ¹⁷ are each independently a hydrocarbon group having 1 to 10 carbon atoms, preferably an aryl group or a substituted aryl group having 6 to 10 carbon atoms.

Specific examples of the carbonium cation include tri-substituted 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, and 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.

In formula (VII), R ¹³⁺ is preferably a carbonium cation or an ammonium cation, and particularly preferably a triphenylcarbonium cation, an N,N-dimethylanilinium cation, or an N,N-diethylanilinium cation.

In formula (VII), R ¹⁴ to R ¹⁷ are each independently a hydrocarbon group having 1 to 10 carbon atoms, preferably an aryl group or substituted aryl group having 6 to 10 carbon atoms.
The aryl group and the substituted aryl group specifically include a phenyl group, a tolyl group, a dimethylphenyl group, a trifluoromethylphenyl group, a ditrifluoromethylphenyl group, a pentafluorophenyl group, and a tolylpentafluorophenyl group. Among these, the trifluoromethylphenyl group, the ditrifluoromethylphenyl group, and the pentafluorophenyl group are preferred, and the pentafluorophenyl group is particularly preferred.

Other examples of ionic compounds include trialkyl-substituted ammonium salts, N,N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts.

Specific examples of the trialkyl-substituted ammonium salt include triethylammonium tetra(phenyl)boron, tripropylammonium tetra(phenyl)boron, tri(n-butyl)ammonium tetra(phenyl)boron, 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(m,m-dimethylphenyl)boron, tri(n-butyl)ammonium tetra(p-trifluoromethylphenyl)boron, tri(n-butyl)ammonium tetra(3,5-ditrifluoromethylphenyl)boron, and tri(n-butyl)ammonium tetra(o-tolyl)boron.

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

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

Further examples of ionic compounds include triphenylcarbenium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, ferrocenium tetra(pentafluorophenyl)borate, triphenylcarbenium pentaphenylcyclopentadienyl complex, N,N-diethylanilinium pentaphenylcyclopentadienyl complex, and boron compounds represented by the following formula (VIII) or (IX).

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

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

[B-3] Specific examples of the borane compound, which is an example of the ionized ionic compound (compound [B-3]), include decaborane;
Salts of anions such as bis[tri(n-butyl)ammonium]nonaborate, bis[tri(n-butyl)ammonium]decaborate, bis[tri(n-butyl)ammonium]undecaborate, bis[tri(n-butyl)ammonium]dodecaborate, bis[tri(n-butyl)ammonium]decachlorodecaborate, and bis[tri(n-butyl)ammonium]dodecachlorododecaborate;
Examples of the salt include salts of metal borane anions such as tri(n-butyl)ammonium bis(dodecahydride dodecaborate) cobaltate (III) and bis[tri(n-butyl)ammonium]bis(dodecahydride dodecaborate) nickelate (III).

[B-3] Specific examples of carborane compounds, which are examples of ionized ionic compounds, include 4-carbanonaborane, 1,3-dicarbanonaborane, 6,9-dicarbadecaborane, 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, and undecahydride-7,8. -dimethyl-7,8-dicarboxadecaborane, dodecahydride-11-methyl-2,7-dicarboxadecaborane, tri(n-butyl)ammonium 1-carbadecaborate, tri(n-butyl)ammonium 1-carbaundecaborate, tri(n-butyl)ammonium 1-carbadodecaborate, tri(n-butyl)ammonium 1-trimethylsilyl-1-carbadecaborate, tri(n-butyl)ammonium bromo-1-carbadodecaborate, tri(n-butyl)ammonium ammonium 6-carbadecaborate, tri(n-butyl)ammonium 6-carbadecaborate, tri(n-butyl)ammonium 7-carboundecaborate, tri(n-butyl)ammonium 7,8-dicarboxaundecaborate, tri(n-butyl)ammonium 2,9-dicarboxaundecaborate, tri(n-butyl)ammonium dodecahydride-8-methyl-7,9-dicarboxaundecaborate, tri(n-butyl)ammonium undecahydride-8-ethyl-7,9-dicarboxaundecaborate Salts of anions such as carbowndecaborate, tri(n-butyl)ammonium undecahydride-8-butyl-7,9-dicarboxaborate, tri(n-butyl)ammonium undecahydride-8-allyl-7,9-dicarboxaborate, tri(n-butyl)ammonium undecahydride-9-trimethylsilyl-7,8-dicarboxaborate, and tri(n-butyl)ammonium undecahydride-4,6-dibromo-7-carbowndecaborate;
Tri(n-butyl)ammonium bis(nonahydride-1,3-dicarbanonaborate)cobaltate(III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbandecaborate)ferrate(III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbandecaborate)cobaltate(III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbandecaborate)nickelate(III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbandecaborate)cuprate(III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbandecaborate)aurate(III), tri(n-butyl)ammonium bis(nonahydride-7,8-dimethyl-7,8-dicarbandecaborate)ferrate salt (III), tri(n-butyl)ammonium bis(nonahydride-7,8-dimethyl-7,8-dicarboxecaporate)chromate (III), tri(n-butyl)ammonium bis(tribromooctahydride-7,8-dicarboxecaporate)cobaltate (III), tris[tri(n-butyl)ammonium]bis(undecahydride-7-carbowndecaborate)chromate (III), bis[tri(n-butyl)ammonium]bis(undecahydride-7-carbowndecaborate)manganate (IV), bis[tri(n-butyl)ammonium]bis(undecahydride-7-carbowndecaborate)cobaltate (III), and bis[tri(n-butyl)ammonium]bis(undecahydride-7-carbowndecaborate)nickelate (IV).

[B-3] The heteropoly compound, which is an example of the ionized ionic compound, is a compound containing an atom selected from silicon, phosphorus, titanium, germanium, arsenic, and tin, and one or more atoms selected from vanadium, niobium, molybdenum, and tungsten.Specific examples include, but are not limited to, phosphovanadic acid, germanovanadic acid, arsenic vanadic acid, phosphoniobic acid, germanoniobic acid, siliconomolybdic acid, phosphomolybdic acid, titaniummolybdic acid, germanomolybdic acid, arsenic molybdic acid, tinmolybdic acid, phosphotungstic acid, germanotungstic acid, tintungstic acid, phosphomolybdovanadic acid, phosphotungstovanadic acid, germanotungstovanadic acid, phosphomolybdotungstovanadic acid, germanomolybdotungstovanadic acid, phosphomolybdotungstic acid, phosphomolybdoniobic acid, and salts of these acids.
Examples of the salt include salts of the acids with metals of Group 1 or 2 of the periodic table, specifically, lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, etc., and organic salts such as triphenylethyl salts.

[B-3] The isopoly compound, which is an example of the ionized ionic compound, is a compound composed of a metal ion of one type of atom selected from vanadium, niobium, molybdenum, and tungsten, and can be considered to be a molecular ion species of a metal oxide. Specific examples include, but are not limited to, vanadic acid, niobic acid, molybdic acid, tungstic acid, and salts of these acids. In addition, examples of the salts include salts of the acids with metals of Group 1 or 2 of the periodic table, specifically lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, etc., and organic salts such as triphenylethyl salts.
The above-mentioned ionizing ionic compound [B-3] (a compound that reacts with the transition metal compound [A] [B-3] to form an ion pair) may be used alone or in combination of two or more kinds.

The organometallic compound [B-1], the organoaluminum oxy compound [B-2], and the compound [B-3] which reacts with the transition metal compound [A] to form an ion pair, which have been described above in detail, can also be used in combination with each other.
In particular, it has been revealed that the olefin polymerization catalyst according to the present invention exhibits high polymerization activity and high copolymerizability when it contains a combination of an organometallic compound [B-1] and a compound [B-3] that reacts with the transition metal compound [A] to form an ion pair. Up until now, examples have been reported in which high polymerization activity has been demonstrated by using an organoaluminum oxy compound [B-2] such as methylaluminoxane as a cocatalyst component in combination with a known transition metal compound, but the organoaluminum oxy compound (B-2) such as methylaluminoxane is generally expensive, and depending on the amount used, this has led to high costs for the obtained olefin polymer.

On the other hand, as described above, the olefin polymerization catalyst according to the present invention exhibits high polymerization activity and high copolymerizability even when used in combination with the cocatalyst components [B-1], an organometallic compound, and [B-3], a compound that reacts with the transition metal compound [A] to form an ion pair, and these cocatalyst components are very inexpensively available, which has the advantage that it is possible to produce olefin polymers at low cost.

The olefin polymerization catalyst according to the present invention may contain the above-mentioned transition metal compound [A], at least one compound [B] selected from the group consisting of [B-1] organometallic compounds, [B-2] organoaluminum oxy compounds, and [B-3] ionizing ionic compounds, and may also contain the following carrier [C] as necessary.

[Carrier [C]]
The olefin polymerization catalyst according to the present invention may use a carrier [C], if necessary.
The carrier [C] is preferably an inorganic or organic compound, and is a granular or fine particle solid. By supporting the transition metal compound [A] and the compound [B] on the carrier [C], a polymer with good morphology can be obtained.
The inorganic compound is preferably a porous oxide, an inorganic halide, a clay, a clay mineral, or an ion-exchangeable layered compound.

Specific examples of the porous oxide include _SiO2 , _Al2O3 , _MgO , ZrO, _TiO2 , _B2O3 , _CaO , ZnO, BaO, _ThO2 , and the like, as well as composites or mixtures containing these.
Further examples of the porous oxide include natural or synthetic zeolites, _{SiO2 - MgO} , _SiO2 - _{Al2O3 , SiO2-TiO2, SiO2-V2O5, SiO2-Cr2O3 , SiO2 - TiO2 - MgO , etc. Among} these, the porous oxides mainly composed of _SiO2 and/or _Al2O3 are preferred.

In addition, the above-mentioned porous oxide may contain small amounts of _{carbonates , sulfates, nitrates, and oxide components such as Na2CO3, K2CO3, CaCO3, MgCO3, Na2SO4 , Al2 ( SO4 ) 3 , BaSO4 , KNO3 ,} Mg( _NO3 ) ₂ , Al( _NO3 ) ₃ , _Na2O , _K2O , and _Li2O .

Although the properties of such porous oxides vary depending on the type and production method, the porous oxides preferably used in the present invention have a particle size of preferably 10 to 300 μm, more preferably 20 to 200 μm, a specific surface area of preferably 50 to 1000 m ² /g, more preferably 100 to 700 m ² /g, and a pore volume of preferably 0.3 to 3.0 cm ³ /g. Such porous oxides may be calcined at 100 to 1000° C., preferably 150 to 700° C., if necessary.

Examples of the inorganic halide include _MgCl2 , _MgBr2 , _MnCl2 , and _MnBr2 . The inorganic halide may be used as it is, or may be used after being pulverized by a ball mill or a vibration mill. In addition, the inorganic halide may be dissolved in a solvent such as alcohol, and then precipitated into fine particles by a precipitating agent.

The clay is usually composed mainly of clay minerals. The ion-exchangeable layered compounds are compounds with a crystal structure in which planes formed by ionic bonds or the like are stacked in parallel with weak bonding forces, and the ions they contain are exchangeable. Most clay minerals are ion-exchangeable layered compounds. These clays, clay minerals, and ion-exchangeable layered compounds are not limited to natural products, and may be artificially synthesized products.

Examples of the clay, clay mineral, or ion-exchangeable layered compound include ionic crystalline compounds having layered crystal structures such as hexagonal close packing type, antimony type, CdCl ₂ type, and CdI ₂ type.

Furthermore, examples of clay and clay minerals include kaolin, bentonite, kibushi clay, gairome clay, allophane, hisingerite, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokudeite group, palygorskite, kaolinite, nacrite, dickite, halloysite, and the like.
Examples of the ion-exchangeable layered compound include _{crystalline acid} salts of polyvalent metals such as α-Zr( _HAsO4 ) _{2.H2O ,} α-Zr _{( HPO4 ) 2} , α-Zr( _KPO4 )2.3H2O, α- _Ti (HPO4) ₂ , α-Ti( _HAsO4 ) _2.H2O , α-Sn( _HPO4 ) _2.H2O , _γ -Zr( _HPO4 ) ₂ , γ-Ti( _HPO4 ) ₂ , and γ _- Ti( _NH4PO4 ) _2.H2O .

Such clays, clay minerals, or ion-exchangeable layered compounds preferably have a pore volume of 0.1 cc/g or more, particularly preferably 0.3 to 5 cc/g, having a radius of 20 Å or more, as measured by mercury intrusion porosimetry. Here, the pore volume is measured for a pore radius range of 20 to 30,000 Å by mercury intrusion porosimetry using a mercury porosimeter.
When a carrier having a pore volume of less than 0.1 cc/g and a radius of 20 Å or more is used, it tends to be difficult to obtain high polymerization activity.

It is also preferable to subject the clay or clay mineral used as the carrier [C] to a chemical treatment. Any of the following chemical treatments can be used: surface treatment to remove impurities adhering to the surface, and treatment to affect the clay's crystal structure. Specific examples of chemical treatments include acid treatment, alkali treatment, salt treatment, and organic treatment. Acid treatment removes surface impurities and increases the surface area by dissolving cations such as Al, Fe, and Mg in the crystal structure. Alkaline treatment destroys the clay's crystal structure, resulting in a change in the clay's structure. Salt treatment and organic treatment form ion complexes, molecular complexes, and organic derivatives, which can change the surface area and interlayer distance.

The ion-exchangeable layered compound used as the carrier [C] may be a layered compound in which the space between the layers is expanded by exchanging the exchangeable ions between the layers with other large bulky ions by utilizing the ion exchangeability. Such bulky ions play a role of supporting the layered structure and are usually called pillars. The introduction of 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, etc.), and metal hydroxide ions such as [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH) ₁₄ ] ²⁺ and [Fe ₃ O(OCOCH ₃ ) ₆ ] ⁺ . These compounds may be used alone or in combination of two or more. In addition, when intercalating these compounds, polymers obtained by hydrolysis of metal alkoxides (R represents a hydrocarbon group, etc.) such as Si(OR) ₄ , Al(OR) ₃ , and Ge(OR) ₄ , and colloidal inorganic compounds such as SiO ₂ can be coexisted. Examples of pillars include oxides generated by intercalating the above metal hydroxide ions between layers and then dehydrating them with heat.

The above clays, clay minerals, and ion-exchangeable layered compounds may be used as they are, or after treatment such as ball milling or sieving. They may also be used after adding and adsorbing new water or after heat dehydration treatment. Furthermore, they may be used alone or in combination of two or more kinds.
Among these, preferred as the carrier [C] are clays or clay minerals, and particularly preferred are montmorillonite, vermiculite, pectolite, taeniolite and synthetic mica.

As described above, the carrier [C] is an inorganic compound or an organic compound. The organic compound may be a granular or fine particle solid having a particle size in the range of 10 to 300 μm.
Specific examples include (co)polymers produced mainly from an α-olefin having 2 to 14 carbon atoms, such as ethylene, propylene, 1-butene, and 4-methyl-1-pentene, and (co)polymers produced mainly from vinylcyclohexane and styrene, and modified products thereof.

The olefin polymerization catalyst according to the present invention contains the above-mentioned transition metal compound [A], preferably the above-mentioned compound [B] group, and, if necessary, a carrier [C], and may further contain the following specific organic compound component [D] together with these, if necessary.

[Organic Compound Component [D]]
The organic compound component [D] is used, if necessary, for the purpose of improving the polymerization performance (e.g., catalytic activity) of the olefin polymerization catalyst according to the present invention and the physical properties of the produced polymer (e.g., increasing the molecular weight of the produced polymer). Examples of such organic compounds include, but are not limited to, alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, and sulfonates.

The alcohols and phenolic compounds typically used are those represented by ^R18 -OH, where ^R18 represents a hydrocarbon group having 1 to 50 carbon atoms (in the case of phenols, the number of carbon atoms is 6 to 50) or a halogenated hydrocarbon group having 1 to 50 carbon atoms (in the case of phenols, the number of carbon atoms is 6 to 50).

As the alcohols, those in which R ¹⁸ is a halogenated hydrocarbon group are preferred, and as the phenolic compounds, those in which the α,α'-positions of the hydroxyl group are substituted with a hydrocarbon having 1 to 20 carbon atoms are preferred.

The carboxylic acid is usually represented by R ¹⁹ -COOH, where R ¹⁹ represents a hydrocarbon group having 1 to 50 carbon atoms or a halogenated hydrocarbon group having 1 to 50 carbon atoms, and is particularly preferably a halogenated hydrocarbon group having 1 to 50 carbon atoms.

As the phosphorus compound, phosphoric acids having a P--O--H bond, phosphates having a P--OR or P=O bond, and phosphine oxide compounds are preferred.
The sulfonate may be represented by the following general formula (X).

In general formula (X), ^M5 is an element of Groups 1 to 14 of the periodic table, ^R20 is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms, Z is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms, t is an integer from 1 to 7, and u is an integer that satisfies 1≦u≦7. In addition, t-u is an integer that satisfies t-u≧1.

[Method for producing ethylene-α-olefin-non-conjugated polyene copolymer]
The production method of the ethylene-α-olefin-non-conjugated polyene copolymer according to the present invention (hereinafter, may be simply referred to as the "production method according to the present invention") includes a step [P] of copolymerizing ethylene, an α-olefin, and a non-conjugated polyene in the presence of the above-mentioned olefin polymerization catalyst, thereby making it possible to obtain the ethylene-α-olefin-non-conjugated polyene copolymer.

The above step [P] is preferably a step of copolymerizing ethylene, an α-olefin having 3 to 10 carbon atoms, and a non-conjugated polyene.
In the present invention, when ethylene, an α-olefin (preferably an α-olefin having 3 to 10 carbon atoms), and a non-conjugated polyene are copolymerized, the method of using and the order of adding each component constituting the olefin polymerization catalyst are not particularly limited and may be arbitrarily selected, and examples thereof include the following methods.

(1) A method in which the transition metal compound [A] is added alone to a polymerization reactor.
(2) A method in which the transition metal compound [A] and the compound [B] group are added to a polymerization vessel in any order.
(3) A method in which a catalyst component in which a transition metal compound [A] is supported on a carrier [C] and a group of compounds [B] are added to a polymerization vessel in any order.
(4) A method in which a catalyst component in which the compound [B] group is supported on a carrier [C] and a transition metal compound [A] are added to a polymerization vessel in any order.
(5) A method in which a catalyst component in which the transition metal compound [A] and the compound [B] group are supported on a carrier [C] is added to a polymerization vessel.
(6) A method in which a catalyst component in which a transition metal compound [A] and a compound [B] group are supported on a carrier [C], and the compound [B] group are added to a polymerization vessel in any order. In this case, the compounds [B] group may be the same or different.
(7) A method in which a catalyst component in which the compound [B] group is supported on a carrier [C], and a transition metal compound [A] are added to a polymerization vessel in any order.
(8) A method in which a catalyst component in which the compound [B] group is supported on a carrier [C], a transition metal compound [A], and a compound [B] are added to a polymerization vessel in any order. In this case, the compounds [B] group may be the same or different.
(9) A method in which a component in which the transition metal compound [A] is supported on a carrier [C] and a component in which the compound [B] group is supported on a carrier [C] are added to a polymerization vessel in any order.
(10) A method in which a component in which a transition metal compound [A] is supported on a carrier [C], a component in which a compound [B] group is supported on a carrier [C], and a compound [B] group are added to a polymerization vessel in any order. In this case, the compounds [B] group may be the same or different.
(11) A method in which the transition metal compound [A], the compound [B] group, and the organic compound component [D] are added to a polymerization reactor in any order.
(12) A method in which a component in which the compound [B] group and the organic compound component [D] are contacted in advance, and the transition metal compound [A] are added to a polymerization vessel in any order.
(13) A method in which the compound [B] group, the organic compound component [D] supported on the carrier [C], and the transition metal compound [A] are added to a polymerization vessel in any order.
(14) A method in which a catalyst component in which a transition metal compound [A] and a compound [B] group have been contacted in advance, and an organic compound component [D] are added to a polymerization vessel in any order.
(15) A method in which a catalyst component in which a transition metal compound [A] and a compound [B] group have been contacted in advance, a compound [B] group, and an organic compound component [D] are added to a polymerization vessel in any order. In this case, the compounds [B] group may be the same or different.
(16) A method of adding a catalyst component in which a transition metal compound [A] is previously contacted with a compound [B] group, and a component in which a compound [B] group is previously contacted with an organic compound component [D] to a polymerization vessel in any order. In this case, the compounds [B] group may be the same or different.
(17) A method in which a transition metal compound [A] supported on a carrier [C], a compound [B] group, and an organic compound component [D] are added to a polymerization reactor in any order.
(18) A method in which a component in which a transition metal compound [A] is supported on a carrier [C] and a component in which a compound [B] group is contacted with an organic compound component [D] in advance are added to a polymerization vessel in any order.
(19) A method in which a catalyst component obtained by previously contacting a transition metal compound [A], a compound [B] group, and an organic compound component [D] in any order is added to a polymerization vessel.
(20) A method in which a catalyst component obtained by previously contacting a transition metal compound [A], a compound [B] group, and an organic compound component [D] in any order, and the compound [B] group are added to a polymerization vessel in any order. In this case, the compounds [B] group may be the same or different.
(21) A method in which a catalyst comprising a transition metal compound [A], a compound [B] group, and an organic compound component [D] supported on a carrier [C] is added to a polymerization reactor.
(22) A method in which a catalyst component in which a transition metal compound [A], a compound [B] group, and an organic compound component [D] are supported on a carrier [C], and a compound [B] group are added to a polymerization vessel in any order. In this case, the compounds [B] group may be the same or different.

In the solid catalyst component in which the transition metal compound [A] is supported on the support [C], and in the solid catalyst component in which the transition metal compound [A] and the compound [B] group are supported on the support [C], an olefin may be prepolymerized, or the transition metal compound [A] and the compound [B] group may be further supported on the prepolymerized solid catalyst component.
In each of the above methods (2) to (5), at least two of the transition metal compound [A], the compound [B] group, and the support [C] may be contacted in advance.

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

In addition, the solid catalyst component in which the transition metal compound [A] is supported on the above-mentioned carrier [C], and the solid catalyst component in which the transition metal compound [A] and the compound [B] group are supported on the carrier [C] may be prepolymerized with an olefin, or a catalyst component may be further supported on the prepolymerized solid catalyst component.

The prepolymerization is preferably a substantially homopolymerization in which the α-olefin is 95 mol % or more. The α-olefin used in the prepolymerization is preferably the same as that used in the main polymerization.
Specifically, they are ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 4,4-dimethyl-1-pentene, 1-heptene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 3-ethyl-1-hexene, 4-ethyl-1-hexene, 1-octene, 1-decene, cyclopentene, and vinylcyclohexane, and particularly preferred are ethylene, propylene, 1-butene, 1-heptene, 3-methyl-1-butene, 1-hexene, and 4-methyl-1-pentene.

The amount of α-olefin polymerized in the prepolymerization is in the range of 0.1 to 1000 g, preferably 1 to 50 g, per gram of the solid catalyst component.
The above prepolymerization is usually preferably carried out by slurry polymerization, and as a solvent, saturated aliphatic or aromatic hydrocarbons such as hexane, heptane, cyclohexane, benzene, toluene, etc. can be used alone or in combination.

The prepolymerization temperature is preferably in the range of -50 to +100°C, particularly preferably -20 to +80°C, and further preferably 0 to +40°C.
The prepolymerization time may be appropriately determined depending on the prepolymerization temperature and the amount of polymerization in the prepolymerization. The pressure in the prepolymerization is not limited, but in the case of slurry polymerization, it is generally from normal pressure to about 50 kg/cm ² .

Each prepolymerization may be carried out in a batch, semi-batch, or continuous manner. After each prepolymerization is completed, it is preferable to wash the mixture with saturated aliphatic or aromatic hydrocarbons such as hexane, heptane, cyclohexane, benzene, or toluene, either alone or in a mixture of these, and the number of washes is usually preferably 5 to 6 times.

When olefins are polymerized using the above-mentioned olefin polymerization catalyst, the transition metal compound [A] is used in an amount of usually 10 ^-12 to 10 ^-2 mol, preferably 10 ^-10 to 10 ^-8 mol, per liter of reaction volume.

The organometallic compound [B-1] is used in an amount such that the molar ratio [[B-1]/[M]] of the organometallic compound [B-1] to the total transition metal atoms [M] in the transition metal compound [A] is usually 0.01 to 100,000, preferably 0.05 to 50,000.
The organoaluminum oxy compound [B-2] is used in such an amount that the molar ratio [[B-2]/[M]] of the aluminum atoms in the organoaluminum oxy compound [B-2] to the total transition metal atoms [M] in the transition metal compound [A] is usually 10 to 500,000, preferably 20 to 100,000.
The ionizing ionic compound [B-3] is used in an amount such that the molar ratio [[B-3]/[M]] of the ionizing ionic compound [B-3] to the total transition metal atoms [M] in the transition metal compound [A] is usually 1 to 10, preferably 1 to 5.

When the compound [B] group is an organometallic compound [B-1], the organic compound component [D] is used in an amount such that the molar ratio [[D]/[B-1]] is usually 0.01 to 10, preferably 0.1 to 5. When the compound [B] group is an organoaluminum oxy compound [B-2], the organic compound component [D] is used in an amount such that the molar ratio [[D]/[B-2]] is usually 0.01 to 2, preferably 0.005 to 1. When the compound [B] group is an ionized ionic compound [B-3], the organic compound component [D] is used in an amount such that the molar ratio [[D]/[B-3]] is usually 0.01 to 10, preferably 0.1 to 5.

The method for producing the ethylene-α-olefin-non-conjugated polyene copolymer according to the present invention is not particularly limited and can be carried out by any of liquid phase polymerization methods such as solution (dissolution) polymerization and suspension polymerization, or gas phase polymerization methods, but it is preferable to further include a step of obtaining the polymerization reaction liquid described below.

The process for obtaining a polymerization reaction liquid is a process for copolymerizing ethylene, the α-olefin, and the non-conjugated polyene in the presence of an olefin polymerization catalyst containing the transition metal compound [A] according to the present invention using an aliphatic hydrocarbon as a polymerization solvent, to obtain a polymerization reaction liquid of an ethylene-α-olefin-non-conjugated polyene copolymer.

If the concentration of the ethylene-α-olefin-non-conjugated polyene copolymer in the polymerization solvent exceeds the above range, the viscosity of the polymerization solution will be too high, and the solution will not be stirred uniformly, which may make the polymerization reaction difficult.

Examples of the polymerization solvent include aliphatic hydrocarbons and aromatic hydrocarbons.Specific examples include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene, aliphatic hydrocarbon rings such as cyclopentane, cyclohexane, and methylcyclopentane, aromatic hydrocarbons such as benzene, toluene, and xylene, and halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane.These solvents can be used alone or in combination of two or more.Furthermore, olefins themselves can be used as the solvent.
Among these, hexane is preferred from the viewpoint of separation and purification from the resulting ethylene-α-olefin-non-conjugated polyene copolymer.

In step [P], in which ethylene, an α-olefin, and a non-conjugated diene are copolymerized in the presence of an olefin polymerization catalyst, the polymerization temperature is usually in the range of -50 to +200°C, preferably 0 to +200°C, and more preferably +80 to +200°C. Although it depends on the molecular weight attained and the polymerization activity of the metallocene catalyst system used, a higher temperature (+80°C or higher) is preferable from the viewpoints of catalyst activity, copolymerizability, and productivity.

The polymerization pressure is usually between normal pressure and 10 MPa gauge pressure, preferably between normal pressure and 5 MPa gauge pressure, and the polymerization reaction can be carried out in any of batch, semi-continuous, and continuous systems. Furthermore, the polymerization can be carried out in two or more stages with different reaction conditions.

The reaction time (average residence time when copolymerization is carried out by a continuous method) varies depending on conditions such as catalyst concentration and polymerization temperature, but is usually 0.5 minutes to 5 hours, preferably 5 minutes to 3 hours.

The molecular weight of the resulting ethylene/α-olefin/non-conjugated polyene copolymer can also be adjusted by making hydrogen present in the polymerization system or by changing the polymerization temperature.
Furthermore, the amount of the compound [B] group used can also be adjusted. Specific examples of the compound [B] group include triisobutylaluminum, methylaluminoxane, diethylzinc, etc. When hydrogen is added, the amount is suitably about 0.001 to 100 NL per kg of olefin.

The molar ratio of ethylene to the above α-olefin (ethylene/α-olefin) is preferably 25/75 to 80/20, more preferably 30/70 to 70/30.
The molar ratio of the ethylene to the non-conjugated polyene (ethylene/non-conjugated polyene) is preferably 70/30 to 99/1, more preferably 80/20 to 98/2.

The components used in the method for producing the ethylene-α-olefin-non-conjugated polyene copolymer according to the present invention are described below.

[α-Olefin]
The α-olefin used in the production method according to the present invention is usually an α-olefin having 3 to 20 carbon atoms, and examples thereof include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-eicosene.

Among these, α-olefins having 3 to 8 carbon atoms, such as propylene, 1-butene, 1-hexene, and 1-octene, are preferred, with propylene being particularly preferred. Such α-olefins are preferred because the raw material costs are relatively low, ethylene-α-olefin-non-conjugated polyene copolymers exhibit excellent mechanical properties, and molded articles having rubber elasticity can be obtained. These α-olefins may be used alone or in combination of two or more.

The ethylene-α-olefin-non-conjugated polyene copolymer obtained by the production method according to the present invention contains structural units derived from at least one type of α-olefin having 3 to 20 carbon atoms, and may contain structural units derived from two or more types of α-olefins having 3 to 20 carbon atoms.

[Non-conjugated polyenes]
The non-conjugated polyene used in the production method according to the present invention is not particularly limited as long as it is a compound having two or more non-conjugated unsaturated bonds, and examples thereof include the non-conjugated cyclic polyenes and non-conjugated chain polyenes described below.
The non-conjugated polyenes may be used alone or in combination of two or more kinds.
In the production method according to the present invention, the non-conjugated polyene is preferably a compound represented by the following general formula (II).

In formula (II),
m is an integer from 0 to 2;
R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ each independently represent an atom or a substituent selected from the group consisting of a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon atom-containing group, a nitrogen atom-containing group, an oxygen atom-containing group, a halogen atom and a halogen atom-containing group, the hydrocarbon group optionally having a double bond;
Any two of the substituents among R ⁸ to R ¹¹ may be bonded to each other to form a ring, and the ring may contain a double bond; R ⁸ and R ⁹ , or R ¹⁰ and R ¹¹ may be bonded to each other to form an alkylidene group; R ⁸ and R ¹⁰ , or R ⁹ and R ¹¹ may be bonded to each other to form a double bond;
At least one of the following requirements (i) to (iv) is met:
(i) at least one of R ⁸ to R ¹¹ is a hydrocarbon group having one or more double bonds;
(ii) any two of the substituents R ⁸ to R ¹¹ are bonded to each other to form a ring, and the ring contains a double bond;
(iii) R ⁸ and R ⁹ together, or R ¹⁰ and R ¹¹ together form an alkylidene group;
(iv) R ⁸ and R ¹⁰ , or R ⁹ and R ¹¹ are bonded to each other to form a double bond.

In the above general formula [II], specific ^examples of the hydrocarbon groups having ¹ to 20 carbon atoms, silicon atom-containing groups, nitrogen atom-containing groups, oxygen atom-containing groups, halogen atoms and halogen atom-containing groups given as R 8 to R 11 include the specific examples of these atoms and substituents given in the explanation of the above general formula (I).

In the above general formula [II], when any one or more of R ⁸ to R ¹¹ is a hydrocarbon group having one or more double bonds, examples of the hydrocarbon group include an ethenyl group (vinyl group), a 1-propenyl group, a 2-propenyl group (allyl group), a 1-methylethenyl group (isopropenyl group), a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, and a 1,4-hexadienyl group.
For example, when R ⁸ is an ethenyl group (vinyl group), the compound of the above general formula [II] can be represented by the following general formula [II-I].

In formula [II-I], m is an integer of 0 to 2,
R ⁹ , R ¹⁰ and R ¹¹ each independently represent an atom or a substituent selected from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon atom-containing group, a nitrogen atom-containing group, an oxygen atom-containing group, a halogen atom and a halogen atom-containing group, the hydrocarbon group optionally having a double bond;
Any two of the substituents R ⁹ to R ¹¹ may be bonded to each other to form a ring, the ring structure formed may contain a double bond, R ¹⁰ and R ¹¹ may be bonded to each other to form an alkylidene group, or R ⁹ and R ¹¹ may be bonded to each other to form a double bond.

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

In the general formulas [II-II] and [II-III], m is an integer of 0 to 2,
R ⁸ , R ¹⁰ and R ¹¹ each independently represent an atom or a substituent selected from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon atom-containing group, a nitrogen atom-containing group, an oxygen atom-containing group, a halogen atom and a halogen atom-containing group, the hydrocarbon group optionally having a double bond;
Any two of the substituents R ⁸ to R ¹¹ may be bonded to each other to form a ring, the ring formed may contain a double bond, R ¹⁰ and R ¹¹ may be bonded to each other to form an alkylidene group, or R ⁸ and R ¹¹ may be bonded to each other to form a double bond.

In the above general formula [II], when R ⁸ and R ⁹ or R ¹⁰ and R ¹¹ combine to form an alkylidene group, the formed alkylidene group is usually an alkylidene group having 1 to 20 carbon atoms, and specific examples include a methylene group (CH ₂ =), an ethylidene group (CH ₃ CH =), a propylidene group (CH ₃ CH ₂ CH =), and an isopropylidene group ((CH ₃ ) ₂ C =). Among the alkylidene groups, an ethylidene group (CH ₃ CH =) is preferred.
For example, when R ⁸ and R ⁹ combine to form an ethylidene group, the compound of the above general formula [II] can be represented by the following general formula [II-IV].

In formula [II-IV], m is an integer of 0 to 2,
R ¹⁰ and R ¹¹ each independently represent an atom or a substituent selected from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon atom-containing group, a nitrogen atom-containing group, an oxygen atom-containing group, a halogen atom, and a halogen atom-containing group, the hydrocarbon group optionally having a double bond;
R ¹⁰ and R ¹¹ may be bonded to each other to form a ring, and the ring formed may contain a double bond, or R ¹⁰ and R ¹¹ may be bonded to each other to form an alkylidene group.
In formula [II-IV], preferably, m is 0 or 1, and R ¹⁰ and R ¹¹ are each independently preferably a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, more preferably, m is 0, and R ¹⁰ and R ¹¹ are each independently preferably a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and even more preferably, m is 0, and R ¹⁰ and R ¹¹ are each independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.

In the above general formula [II], when R ⁸ and R ¹⁰ , or R ⁹ and R ¹¹ are bonded to each other to form a double bond, the compound of the above general formula [II] can be represented, for example, by the following general formula [II-V].

In the general formula [II-V], m is an integer of 0 to 2,
R ⁹ and R ¹¹ each independently represent a substituent selected from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon atom-containing group, a nitrogen atom-containing group, an oxygen atom-containing group, a halogen atom, and a halogen atom-containing group, the hydrocarbon group optionally having a double bond;
R ⁹ and R ¹¹ may be bonded to each other to form a ring, and the ring formed may contain a double bond.

Among the above general formulas [II-I] to [II-V], the general formula [II] is preferably the general formula [II-I], the general formula [II-III], or the general formula [II-IV], and more preferably the general formula [II-IV].

Among the non-conjugated cyclic polyenes represented by the above general formula [II], examples of the compound in which at least one of the groups R ⁸ to R ¹¹ (preferably R ⁸ or R ⁹ ) is a hydrocarbon group having one or more double bonds include the following 5-vinyl-2-norbornene (VNB) and the following compounds, etc. Of these, 5-vinyl-2-norbornene (VNB) is preferred.

Among the non-conjugated cyclic polyenes represented by the above general formula [II], examples of compounds in which any two of the substituents R ⁸ to R ¹¹ are bonded to each other to form a ring and the formed ring contains a double bond include dicyclopentadiene (DCPD), dimethyldicyclopentadiene, and the following compounds, etc. Of these, dicyclopentadiene (DCPD) is preferred.

Among the non-conjugated cyclic polyenes represented by the above general formula [II], examples of compounds in which R ⁸ and R ⁹ , or R ¹⁰ and R ¹¹ , form an alkylidene group include 5-methylene-2-norbornene, 5-ethylidene-2-norbornene (ENB), 5-isopropylidene-2-norbornene, and the tetracyclo[6.2.1.13,6.02,7]dodec-4-ene derivative represented by the following compound. Among these, 5-ethylidene-2-norbornene (ENB) is preferred.

Among the non-conjugated cyclic polyenes represented by the above general formula [II], the following are preferred as compounds in which R ⁸ and R ¹⁰ or R ⁹ and R ¹¹ are bonded to each other to form a double bond.

As the non-conjugated cyclic polyene represented by the above general formula [II] (preferably the non-conjugated polyene represented by the general formula [II-I], the general formula [II-III] and the general formula [II-IV]), a non-conjugated cyclic polyene in which m is 0 is preferred, and in particular, an alkylidene group-substituted non-conjugated cyclic polyene in which m is 0 in the above general formula [II], a double bond-containing ring-substituted non-conjugated cyclic polyene in which m is 0 in the above general formula [II], and a double bond-containing hydrocarbon group-substituted non-conjugated cyclic polyene in which m is 0 are preferred.
As the non-conjugated cyclic polyene in which m is 0 in the above general formula [II] (preferably the non-conjugated polyenes represented by general formulas [II-I], [II-III] and [II-IV]), 5-ethylidene-2-norbornene (ENB), dicyclopentadiene (DCPD) and 5-vinyl-2-norbornene (VNB) are more preferable, and 5-ethylidene-2-norbornene (ENB) and 5-vinyl-2-norbornene (VNB) are particularly preferable.

Specific examples of the general formula [II-I] and general formula [II-III] representing ENB, DCPD, and VNB and the non-conjugated dienes include cyclic conjugated dienes such as 5-ethylidene-2-norbornene (ENB), 5-propylidene-5-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene (VNB), 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, and norbornadiene; and linear non-conjugated dienes such as 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene, 6-methyl-1,7-octadiene, and 7-methyl-1,6-octadiene.
Examples of non-conjugated trienes include 2,3-diisopropylidene-5-norbornene and 4-ethylidene-8-methyl-1,7-nonadiene.

Among these, the non-conjugated polyenes are preferably cyclic non-conjugated dienes and linear non-conjugated dienes, more preferably 5-ethylidene-2-norbornene (ENB), 5-vinyl-2-norbornene (VNB), 5-methylene-2-norbornene, 7-methyl-1,6-octadiene, 1,4-hexadiene and dicyclopentadiene, and more preferably 5-ethylidene-2-norbornene (ENB), 5-vinyl-2-norbornene (VNB) and 7-methyl-1,6-octadiene.

Furthermore, when a composition containing an ethylene-α-olefin-non-conjugated polyene copolymer is crosslinked with sulfur, preferred non-conjugated polyenes are ENB, 1,4-hexadiene, and dicyclopentadiene, which are excellent in mechanical strength, and when a composition containing an ethylene-α-olefin-non-conjugated polyene copolymer is crosslinked with an organic peroxide, preferred non-conjugated polyenes are VNB, 5-methylene-2-norbornene, which are excellent in crosslinking efficiency and heat aging resistance.
These non-conjugated polyenes may be used alone or in combination of two or more.

The ethylene-α-olefin-non-conjugated polyene copolymer obtained by the production method according to the present invention usually has a content of structural units derived from non-conjugated polyene of 0.1 to 5 mol %, preferably 2.5 to 4 mol %, where the total of the structural units derived from ethylene, the structural units derived from α-olefin, and the structural units derived from non-conjugated polyene is taken as 100 mol %.
Within the above range, a molded article obtained from the composition containing the ethylene-α-olefin-non-conjugated polyene copolymer has excellent strength, rubber elasticity, compression set, etc., and when the composition containing the ethylene-α-olefin-non-conjugated polyene copolymer contains a crosslinking agent and a foaming agent, it has excellent foamability, dimensional stability, etc., and is therefore preferred.
The content of the structural units derived from ethylene can be determined by ¹³ C NMR.

The ethylene-α-olefin-non-conjugated polyene copolymer obtained by the production method according to the present invention usually has an intrinsic viscosity [η] measured in decalin at 135°C of 0.1 to 10 dL/g, preferably 4 to 6 dL/g.

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

The structure of the transition metal compound [A] was determined by measuring the ¹ H NMR spectrum (400 MHz, ECZ-400 manufactured by JEOL Ltd.), FD-mass (hereinafter referred to as FD-MS) spectrum (SX-102A manufactured by JEOL Ltd.), and the like.

The physical properties of the ethylene-α-olefin-non-conjugated polyene copolymers synthesized in the examples and comparative examples were measured using the following methods.

[Ethylene content, propylene content, and 5-ethylidene-2-norbornene (ENB) content]
The 13C NMR spectrum was measured using o-dichlorobenzene/benzene- _d (4/1 {vol/vol%}) as the measurement solvent under the measurement conditions of a measurement temperature of 120°C, a spectral width of 250 ppm, a pulse repetition time of 5.5 seconds, and a pulse width of 4.7 μsec (45° pulse) using a nuclear magnetic resonance apparatus (100 MHz, manufactured by JEOL Ltd., product name: ECX400P) or under the measurement conditions of a measurement temperature of 120°C, a spectral width of 250 ppm, a pulse repetition time of 5.5 seconds, and a pulse width of 5.0 μsec (45 ^° pulse) using a nuclear magnetic resonance apparatus (125 MHz, manufactured by Bruker Biospin, product name: AVANCEIII cryo-500), and the values were calculated.

[Intrinsic viscosity ([η])]
The measurement was performed at 135°C using decalin solvent. Approximately 20 mg of the polymer was dissolved in 15 mL of decalin, and the specific viscosity η _sp was measured in an oil bath at 135°C. After diluting the decalin solution by adding 5 mL of decalin solvent, the specific viscosity η _sp was measured in the same manner. This dilution operation was repeated two more times, and the value of η _sp /C when the concentration (C) was extrapolated to 0 was adopted as the limiting viscosity.
[η] = lim (η _sp / C) (C → 0)

[Synthesis of transition metal compound [A]]
[Synthesis Example 1]
Under a nitrogen atmosphere, tert-butylamino(1,5,6,7-tetrahydro-2-methoxy-s-indacen-1-yl)dimethylsilane (685 mg, 2.17 mmol) was dissolved in a mixed solvent of 20 mL of toluene and 1 mL of tetrahydrofuran in a 100 mL two-diameter eggplant flask. n-Butyllithium (1.58 M, 2.8 mL, 4.42 mmol) was added dropwise in an ice bath and stirred at room temperature for 3 hours. Separately, in a 100 mL two-diameter eggplant flask, a mixed solution of titanium tetrachloride-tetrahydrofuran adduct (745 mg, 2.16 mmol) in 20 mL of toluene and 1 mL of tetrahydrofuran was prepared, and the dark reddish brown dilithium solution was transferred and charged. Stirring was continued overnight. The reaction solution was concentrated using a vacuum pump, then brought into a glove box, and the residue was extracted with toluene. The solution was desalted by filtration through Celite, and the filtrate was concentrated. The residue was washed with hexane to obtain 330 mg of the target compound shown below (hereinafter referred to as transition metal compound [A-1]) (yield: 35% by mass).

^1H NMR (270MHz, _CDCl3 ) δ = 7.43 (1H,s,Ar-H), 7.36 (1H,s,Ar-H), 6.43 (1H,s,Alkenyl-H), 3.95 (3H,s,-OMe), 3.05-2.88 (4H,m,Ar- _CH2- ), 2.11-2.02 (2H,m,Ar- _CH2 - _CH2- ), 1.36 (9H,s,tert-Bu), 0.84 (3H,s,Si-Me), 0.69 (3H,s,Si-Me). FD-MS M ⁺ = 431.0.

[Synthesis Example 2]
Under a nitrogen atmosphere, tert-butylamino(1,5,6,7-tetrahydro-2-methoxy-s-indacen-1-yl)di(p-tolyl)silane (838 mg, 1.49 mmol) was dissolved in 30 mL of hexane in a 100 mL two-diameter eggplant flask. n-Butyllithium (1.56 M, 2.05 mL, 3.20 mmol) was added dropwise in an ice bath to obtain a pale beige slurry. After stirring at room temperature for 2 hours, the solution was concentrated to 10 mL with a vacuum pump. An additional 20 mL of tetrahydrofuran was added to obtain a black-brown solution, which was transferred to a mixed slurry of titanium tetrachloride-tetrahydrofuran adduct (510 mg, 1.48 mmol) in 20 mL of toluene and 1 mL of tetrahydrofuran in an ice bath. After stirring overnight at room temperature, the solution was concentrated with a vacuum pump, and the residue was extracted with toluene in a glove box. The filtrate from the Celite filtration was concentrated using a vacuum pump, and the residue was washed with pentane to obtain 78 mg of the target product shown below (hereinafter referred to as transition metal compound [A-2]) (yield: 9% by mass).

^1H NMR (400MHz, _CDCl3 ) δ = 8.03 (2H, d, J = 7.6Hz, Ar-H), 7.90 (2H, d, J = 7.6Hz, Ar-H), 7.14 (1H, s, Ar-H), 7.11 (2H, d, J = 8.0Hz, Ar-H), 7.09 (2H, d, J = 8.0Hz), 6.98 (1H, s, Ar-H), 6.08 (1H, s, Alkenyl-H), 3.47 (3H, s, -OMe), 2.82-2.75 (1H, m, Ar- _CH2- ), 2.64-2.56 (1H, m, Ar- _CH2- ), 2.54-2.46 (1H, m, Ar- _CH2- CH _2- ), 2.41-2.34 (1H,m,Ar- _CH2 - _CH2- ), 2.14 (3H,s,Ar-Me), 2.11 (3H,s,Ar-Me),
1.65 (9H,s,tert-Bu). FD-MS M ⁺ = 583.1

[Synthesis Example 3]
Under a nitrogen atmosphere, tert-butylamino(1,5,6,7-tetrahydro-2-methoxy-s-indacen-1-yl)diphenylsilane (1120 mg, 2.16 mmol) was dissolved in 20 mL of toluene in a 100 mL two-diameter eggplant flask, and tetrahydrofuran (0.38 mL, 4.68 mmol) was added. n-Butyllithium (1.56 M, 2.95 mL, 4.60 mmol) was added dropwise in an ice bath, and the mixture was stirred at room temperature for 5 hours to obtain an ochre slurry. Separately, in a 100 mL two-diameter eggplant flask, a 20 mL toluene solution of titanium tetrachloride-tetrahydrofuran adduct (745 mg, 2.16 mmol) was prepared, and the di-lithio compound slurry was transferred and charged in an ice bath. Stirring was continued overnight to raise the temperature to room temperature. After concentration with a vacuum pump, the mixture was brought into a glove box, and the residue was extracted with methylcyclohexane. After desalting by filtration through Celite, the filtrate was concentrated using a vacuum pump and further azeotroped with hexane. The resulting residue was washed with pentane to obtain 792 mg of the target product shown below (hereinafter referred to as transition metal compound [A-3]) (yield: 66% by mass).

^1H NMR (400MHz, _CDCl3 ) δ = 7.98-7.95 (2H, m, Ar-H), 7.68-7.66 (2H, m, Ar-H), 7.61-7.57 (1H, m, Ar-H), 7.55-7.51 (2H, m, Ar-H), 7.44-7.40 (1H, m, Ar-H), 7.37 (1H, s, Ar-H), 7.37-7.33 (2H, m, Ar-H), 6.58 (1H, s, Ar-H), 6.50 (1H, s, Alkenyl-H), 3.87 (3H, s, -OMe), 2.99-2.89 (2H, m, Ar- _CH2 -), 2.99-2.89 (2H, m, Ar-CH ₂ -), 2.70-2.60 (1H, m, Ar-CH ₂ -CH ₂ -), 2.01-1.94 (1H, m, Ar-CH ₂ -CH ₂ -), 1.46 (9H, s, tert-Bu) FD-MS M ⁺ = 555.1

[Synthesis Example 4]
Under a nitrogen atmosphere, tert-butylamino(1,5,6,7-tetrahydro-2-ethoxy-s-indacen-1-yl)dimethylsilane (700 mg, 1.81 mmol) was dissolved in 20 mL of toluene in a 100 mL two-diameter eggplant flask, and tetrahydrofuran (0.32 mL, 3.94 mmol) was added. n-Butyllithium (1.56 M, 2.60 mL, 4.06 mmol) was added dropwise in an ice bath, and the mixture was stirred at room temperature for 3 hours. Separately, in a 100 mL two-diameter eggplant flask, a 20 mL toluene solution of titanium tetrachloride-tetrahydrofuran adduct (650 mg, 1.89 mmol) was prepared, and the di-lithio compound slurry was transferred and charged. The mixture was stirred overnight and concentrated with a vacuum pump, then brought into a glove box, and the residue was extracted with methylcyclohexane. The mixture was desalted by filtration through Celite, and the filtrate was concentrated with a vacuum pump. The residue was washed with cold pentane to obtain 60 mg of the target compound shown below (hereinafter referred to as transition metal compound [A-4]) (yield: 7% by mass).

^1H NMR (400MHz, _CDCl3 ) δ = 7.42 (1H, s, Ar-H), 7.35 (1H, s, Ar-H), 6.39 (1H, s, Alkenyl-H _{) ,} 4.43-4.36 (1H, m, _-OCH2CH3 ), 4.15-4.07 (1H, s, _-OCH2CH3 ), 3.06-2.89 (4H, m, Ar- _CH2- ), 2.11-1.99 (2H, m, Ar- _{CH2 - CH2-} ), 1.37 (9H, s, tert-Bu), 1.36 (3H, t, J = 6.8Hz, _-OCH2CH3 ), 0.84 (3H,s,Si-Me), 0.70 (3H,s,Si-Me) FD-MS M ⁺ =445.1.

[Synthesis Example 5]
In a nitrogen atmosphere, isopropylamino(1,5,6,7-tetrahydro-2-methoxy-s-indacen-1-yl)di(p-tolyl)silane (838 mg, 1.49 mmol) was dissolved in a mixed solvent of 14 mL of toluene and 0.7 mL of tetrahydrofuran in a 100 mL two-diameter eggplant flask. n-Butyllithium (1.58 M, 1.80 mL, 2.81 mmol) was added dropwise in an ice bath, and the mixture was stirred at room temperature for 2 hours to obtain an ocher-colored slurry. Separately, in a 100 mL two-diameter eggplant flask, a mixed solution of titanium tetrachloride-tetrahydrofuran adduct (480 mg, 1.39 mmol) in 14 mL of toluene and 0.7 mL of tetrahydrofuran was prepared, and transferred to the ocher-colored slurry in an ice bath. Stirring was continued overnight to raise the liquid temperature to room temperature. After concentrating with a vacuum pump, the mixture was brought into a glove box and the residue was extracted with toluene. The mixture was desalted by celite filtration, and the filtrate was concentrated with a vacuum pump. The residual hexane extract was concentrated again and washed with pentane to obtain 61 mg of the target product shown below (hereinafter referred to as transition metal compound [A-5]) (yield 8%).

^1H NMR (400MHz, _CDCl3 ) δ = 7.72 (2H, d, J = 7.6Hz, Ar-H), 7.49 (2H, d, J = 7.6Hz, Ar-H), 7.40 (1H, s, Ar-H), 7.33 (2H, d, J = 7.6Hz, Ar-H), 7.16 (2H, d, J = 7.6Hz, Ar-H), 6.82 (1H, s, Ar-H), 6.42 (1H, s, Alkenyl-H), 4.91 (1H, sep, J = 6.0Hz, -N-CH), 3.84 (3H, s, -OMe), 3.01-2.85 (2H, m, Ar- _CH2 -), 2.74-2.64 (2H, m, Ar-CH2-), 2.47 (3H, s, Ar-Me), 2.37 (3H, s, Ar-Me), 2.04-1.94 (2H, m, Ar- _CH2 - _CH2- ), 1.23 (3H, d, J = 6.0 Hz, -N- _CHMe2 ), 1.18 (3H, d, J = 6.0 Hz, -N- _CHMe2 ).
FD-MS M ⁺ was not observable due to fragmentation.

[Synthesis Example 6]
Under a nitrogen atmosphere, cyclohexylamino(1,5,6,7-tetrahydro-2-methoxy-s-indacen-1-yl)diphenylsilane (1256 mg, 2.16 mmol) was dissolved in 24 mL of toluene in a 100 mL two-diameter eggplant flask, and tetrahydrofuran (0.41 mL, 5.05 mmol) was added. n-Butyllithium (1.56 M, 3.20 mL, 4.99 mmol) was added dropwise in an ice bath, and the mixture was stirred at room temperature for 3 hours to obtain a slurry. Separately, in a 100 mL two-diameter eggplant flask, a 20 mL toluene solution of titanium tetrachloride-tetrahydrofuran adduct (825 mg, 2.40 mmol) was prepared, and the above slurry was transferred and charged in an ice bath. Stirring was continued overnight to raise the liquid temperature to room temperature. After concentrating with a vacuum pump, the mixture was brought into a glove box and the residue was extracted with cyclohexane. After desalting by celite filtration, the filtrate was concentrated with a vacuum pump, and the residue was washed with pentane. The precipitate was further washed with hexane to obtain 539 mg of the target compound shown below (hereinafter referred to as transition metal compound [A-6]) (yield: 40%).

^1H NMR (400MHz, CDCl3) δ = 7.86-7.84 (2H, m, Ar-H), 7.62-7.49 (5H, m, Ar-H), 7.45-7.31 (3H, m, Ar-H), 7.37-7.33 (5H, m, Ar-H), 6.77 (1H, s, Alkenyl-H), 4.51 (1H, m, -N-CH), 3.83 (3H, s, -OMe), 3.00-2.87 (2H, m, Ar- _CH2- ), 2.70-2.65 (2H, m, Ar- _CH2- ), 2.01-1.95 (2H, m, Ar- _CH2 - _CH2 -), 1.70-1.00 (10H,m,-N-CH( _CH2 ) ₅ ).
FD-MS M ⁺ 581.1

[Comparative Synthesis Example 1]
According to the description in US Pat. No. 5,965,756, the transition metal compound [B-1] shown below was synthesized.

[Production of ethylene-propylene-ENB copolymer]
[Example 1]
1030 mL of hexane and 8 mL of 5-ethylidene-2-norbornene (ENB) were charged into a 2 L stainless steel autoclave that had been thoroughly purged with nitrogen, and the temperature inside the system was raised to 95°C. After charging propylene at a partial pressure of 0.40 MPa-G, ethylene was fed to adjust the total pressure to 1.6 MPa-G, and 0.3 mmol of triisobutylaluminum was injected. After 15 minutes, a mixed solution obtained by stirring 0.1 μmol of the transition metal compound [A-1] synthesized above and 2.0 μmol of triisobutylaluminum at room temperature for 6 minutes was injected. Subsequently, 0.4 μmol of triphenylcarbenium tetrakis(pentafluorophenyl)borate was injected with nitrogen, and polymerization was initiated by changing the stirring speed to 250 rpm.

Thereafter, the total pressure was maintained at 1.6 MPa-G by continuously supplying only ethylene, and polymerization was carried out at 95°C for 15 minutes. A small amount of ethanol was added to the system to terminate the polymerization, and then unreacted ethylene was purged. The resulting polymer solution was poured into a large excess of a mixed solution of methanol/acetone to precipitate the polymer. The polymer was recovered by filtration and dried overnight under reduced pressure at 120°C to obtain an ethylene-propylene-ENB copolymer.
As a result, 3.81 g of an ethylene-propylene-ENB copolymer having an intrinsic viscosity of 4.24, an ethylene content of 74.7 mass%, a propylene content of 18.3 mass%, and an ENB content of 7.0 mass% was obtained. The polymerization activity was 152 kg/mmol-Ti/h.

[Example 2]
The same procedure as in Example 1-1 was carried out, except that 0.1 μmol of the transition metal compound [A-1] was changed to 0.1 μmol of the transition metal compound [A-2].
As a result, 2.86 g of an ethylene/propylene/ENB copolymer having an intrinsic viscosity of 5.89, an ethylene content of 72.2 mass%, a propylene content of 20.9 mass%, and an ENB content of 6.9 mass% was obtained. The polymerization activity was 114 kg/mmol-Ti/h.

[Example 3]
The same procedure as in Example 1-1 was carried out, except that 0.1 μmol of the transition metal compound [A-1] was changed to 0.15 μmol of the transition metal compound [A-3].
As a result, 5.25 g of an ethylene/propylene/ENB copolymer having an intrinsic viscosity of 5.38, an ethylene content of 71.7 mass%, a propylene content of 20.9 mass%, and an ENB content of 7.4 mass% was obtained. The polymerization activity was 140 kg/mmol-Ti/h.

[Example 4]
The same procedure as in Example 1-1 was carried out, except that 0.1 μmol of the transition metal compound [A-1] was changed to 0.15 μmol of the transition metal compound [A-4].
As a result, 13.1 g of an ethylene/propylene/ENB copolymer having an intrinsic viscosity of 4.19, an ethylene content of 73.4 mass%, a propylene content of 19.8 mass%, and an ENB content of 6.8 mass% was obtained. The polymerization activity was 349 kg/mmol-Ti/h.

[Example 5]
The same procedure as in Example 1-1 was carried out, except that 0.1 μmol of the transition metal compound [A-1] was changed to 0.15 μmol of the transition metal compound [A-6].
As a result, 2.4 g of an ethylene/propylene/ENB copolymer having an intrinsic viscosity of 2.46, an ethylene content of 59.9 mass%, a propylene content of 31.0 mass%, and an ENB content of 9.1 mass% was obtained. The polymerization activity was 9.6 kg/mmol-Ti/h.

[Example 6]
The same procedure as in Example 1-1 was carried out, except that 0.1 μmol of the transition metal compound [A-1] was changed to 0.6 μmol of the transition metal compound [A-5].
As a result, 5.64 g of an ethylene/propylene/ENB copolymer having an intrinsic viscosity of 4.15, an ethylene content of 66.5 mass%, a propylene content of 25.2 mass%, and an ENB content of 7.3 mass% was obtained. The polymerization activity was 37.6 kg/mmol-Ti/h.

[Comparative Example 1]
The same procedure as in Example 1-1 was carried out, except that 0.1 μmol of the transition metal compound [A-1] was changed to 0.1 μmol of the transition metal compound [B-1].
As a result, 6.29 g of an ethylene/propylene/ENB copolymer having an intrinsic viscosity of 5.45, an ethylene content of 64.6 mass%, a propylene content of 29.8 mass%, and an ENB content of 5.6 mass% was obtained. The polymerization activity was 315 kg/mmol-Ti/h.

It can be seen that the method for producing an ethylene-α-olefin-non-conjugated polyene copolymer using the olefin polymerization catalysts of Examples 1 to 6 as components of the olefin polymerization catalyst produces an ethylene-α-olefin-non-conjugated polyene copolymer with a richer non-conjugated polyene content and an appropriately suppressed α-olefin content than the method for producing an ethylene-α-olefin-non-conjugated polyene copolymer using the olefin polymerization catalyst of Comparative Example 1.

Claims (17)

[A] A transition metal compound represented by the following general formula (I):

[In the formula (I),
M represents a transition metal atom of Groups 3 to 11 of the periodic table;
n represents an integer from 1 to 6;
R ^1a , R ^1b and R ^N each independently represent a substituent selected from the group consisting of an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aryl group, an aliphatic heterocyclic group, an oxygen atom-containing group, a nitrogen atom-containing group, a boron atom-containing group, a sulfur atom-containing group, a phosphorus atom-containing group, a silicon atom-containing group, a germanium atom-containing group and a tin atom-containing group, and two or more groups among R ^1a , R ^1b and R ^N may be bonded to each other to form a ring,
R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently represent an atom or substituent selected from the group consisting of a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aryl group, an oxygen atom-containing group, a nitrogen atom-containing group, a boron atom-containing group, a sulfur atom-containing group, a phosphorus atom-containing group, a silicon atom-containing group, a germanium atom-containing group and a tin atom-containing group, adjacent substituents of R ³ to R ⁷ may be bonded to each other to form a ring,
R ² is a substituent represented by *-ZR (* represents a bonding site with the indene ring, Z represents an oxygen atom or a sulfur atom, R is a substituent selected from the group consisting of an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aryl group, an oxygen atom-containing group, a nitrogen atom-containing group, a boron atom-containing group, a sulfur atom-containing group, a phosphorus atom-containing group, a silicon atom-containing group, a germanium atom-containing group, and a tin atom-containing group, and R may bond to R ^1a or R ^1b to form a ring),
X represents a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen atom-containing group, a sulfur atom-containing group, a nitrogen atom-containing group, a boron atom-containing group, an aluminum atom-containing group, a phosphorus atom-containing group, a halogen atom-containing group, a heterocyclic group, a silicon atom-containing group, a germanium atom-containing group, or a tin atom-containing group, and when n is 2 or more, the multiple groups represented by X may be the same or different from one another, and the multiple groups represented by X may be bonded to one another to form a ring. The transition metal compound according to claim 1 , wherein R ⁵ and R ⁶ in the general formula (I) are bonded to each other to form a ring. 2. The transition metal compound according to claim 1, wherein in *-ZR represented by R ² in the general formula (I), Z is an oxygen atom. 2. The transition metal compound according to claim 1, wherein ^R3 , ^R4 and ^R7 in the general formula (I) are hydrogen atoms. 2. The transition metal compound according to claim 1, wherein *-ZR represented by R ² in the general formula (I) is any one of a methoxy group, an ethoxy group, and a silyloxy group. 2. The transition metal compound according to claim 1, wherein R ^1a and R ^1b in the general formula (I) are each independently any one of a methyl group and a phenyl group. 2. The transition metal compound according to claim 1, wherein R ^N in the general formula (I) is a tert-butyl group. The transition metal compound according to claim 1, wherein M in the general formula (I) is an atom of titanium, zirconium, or hafnium. The transition metal compound according to claim 1, wherein M in the general formula (I) is titanium. An olefin polymerization catalyst containing the transition metal compound according to any one of claims 1 to 9. [B] [B-1] An organometallic compound [B-2] An organoaluminum oxy compound, and
[B-3] A compound that reacts with the transition metal compound to form an ion pair. The olefin polymerization catalyst according to claim 10, further comprising at least one compound selected from the group consisting of: A method for producing an ethylene-α-olefin-non-conjugated polyene copolymer, comprising step [P] of copolymerizing ethylene, an α-olefin, and a non-conjugated polyene in the presence of the olefin polymerization catalyst according to claim 10. The method for producing an ethylene/α-olefin/non-conjugated polyene copolymer according to claim 12, wherein the non-conjugated polyene is a compound represented by the following general formula (II):

[In the formula (II),
m is an integer from 0 to 2;
R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ each independently represent an atom or a substituent selected from the group consisting of a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon atom-containing group, a nitrogen atom-containing group, an oxygen atom-containing group, a halogen atom and a halogen atom-containing group, the hydrocarbon group optionally having a double bond;
Any two of the substituents among R ⁸ to R ¹¹ may be bonded to each other to form a ring, and the ring may contain a double bond; R ⁸ and R ⁹ , or R ¹⁰ and R ¹¹ may be bonded to each other to form an alkylidene group; R ⁸ and R ¹⁰ , or R ⁹ and R ¹¹ may be bonded to each other to form a double bond;
At least one of the following requirements (i) to (iv) is met:
(i) at least one of R ⁸ to R ¹¹ is a hydrocarbon group having one or more double bonds;
(ii) any two of the substituents R ⁸ to R ¹¹ are bonded to each other to form a ring, and the ring contains a double bond;
(iii) R ⁸ and R ⁹ together, or R ¹⁰ and R ¹¹ together form an alkylidene group;
(iv) R ⁸ and R ¹⁰ , or R ⁹ and R ¹¹ , are bonded to each other to form a double bond. The method for producing an ethylene-α-olefin-non-conjugated polyene copolymer according to claim 12, wherein the non-conjugated polyene is 5-ethylidene-2-norbornene (ENB) or 5-vinyl-2-norbornene (VNB). The method for producing an ethylene-α-olefin-non-conjugated polyene copolymer according to claim 12, wherein the step [P] is a step of copolymerizing ethylene, an α-olefin having 3 to 10 carbon atoms, and a non-conjugated polyene. The method for producing an ethylene-α-olefin-non-conjugated polyene copolymer according to claim 12, wherein the α-olefin is propylene. The method for producing an ethylene-α-olefin-non-conjugated polyene copolymer according to claim 12, wherein the polymerization temperature in step [P] is 80°C or higher.