JP2004331966A - METHOD FOR PRODUCING alpha-OLEFIN/CYCLOOLEFIN COPOLYMER - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a copolymer of an α-olefin/cycloolefin in high polymerization activity and effectively incorporating the cycloolefin. <P>SOLUTION: The copolymer is obtained by copolymerizing (A) a straight-chain or branched 2-30C α-olefin with (B) a cycloolefin in the presence of the catalyst for polymerization of olefin comprising (C) a transition metal compound expressed by general formula (IV) and (D) at least a compound selected from (D-1) an organometallic compound, (D-2) an organic aluminumoxy compound, and (D-3) a compound forming an ionic pair by reacting with the transition metal compound (C). <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an α-olefin / cyclic olefin copolymer and a method for producing the same, and more particularly, to a method for producing an α-olefin / cyclic olefin that efficiently incorporates a cyclic olefin.

  Cyclic olefin copolymers obtained by copolymerizing α-olefins and specific cyclic olefins are excellent in optical properties, mechanical properties, thermal properties, etc., and have a good balance between them. It is used as an optical material such as a fiber.

  Such a cyclic olefin-based copolymer is conventionally used in the presence of a vanadium-based catalyst formed from a soluble vanadium compound and an organoaluminum compound, in a hydrocarbon solvent such as toluene, cyclohexane, hexane, and heptane, or in a cyclic olefin. It is produced by copolymerizing an α-olefin with a specific cyclic olefin using itself as a solvent. However, such a vanadium-based catalyst has low polymerization activity, and it has been difficult to obtain a cyclic olefin-based copolymer in a high yield. In addition, the obtained cyclic olefin-based copolymer had problems such as a wide molecular weight distribution, a nonuniform composition distribution, and a large amount of high-molecular-weight α-olefin components.

  On the other hand, a catalyst comprising a metallocene and an aluminoxane has excellent polymerization activity for cyclic olefins, as disclosed in JP-A-61-221206, JP-A-5-9223, JP-A-5-320258 and JP-A-8-320258. No. 3230, for example. However, such a catalyst comprising a zirconium compound and an aluminoxane is a single-site catalyst, and the obtained polymer has a narrow molecular weight distribution, and a polymer having a more uniform composition distribution than that obtained with a vanadium-based catalyst is used. However, there is a problem in that the cyclic olefin incorporation efficiency is poor and a large amount of cyclic olefin must be charged in order to obtain the desired cyclic olefin copolymer. Further, there is a problem that this catalyst is very expensive.

  For this reason, there has been a demand for an inexpensive catalyst capable of copolymerizing an α-olefin and a specific cyclic olefin with high polymerization activity and a method for producing a cyclic olefin copolymer.

  Recently, as a novel olefin polymerization catalyst, the present applicant has proposed a transition metal compound having a salicylaldimine ligand represented by the general formula (IV) in JP-A-11-315109.

  This complex can improve the polymerization performance by converting the ligand structure. For example, in Japanese Patent Application Laid-Open No. 2000-119315, in the copolymerization of ethylene with a comonomer such as an -olefin, the relative reactivity with the comonomer (hereinafter referred to as copolymerization Described in Japanese Patent Application Laid-Open No. 2000-239312, a compound having higher polymerization activity at high temperature is proposed. However, in the copolymerization of ethylene with a comonomer such as a cyclic olefin using these complexes, further improvement in polymerization activity and copolymerizability is desired.

Under such circumstances, development of an olefin polymerization catalyst excellent in copolymerizability with a cyclic olefin or the like without impairing high polymerization activity is desired.
JP-A-11-315109 JP 2000-119315 A JP-A-2000-2391212 WO9623010 SUMMARY OF THE INVENTION The present inventors have conducted studies in view of the above-described conventional techniques, and as a result, have found that a specific transition metal compound reacts with an organometallic compound, an organoaluminumoxy compound or a transition metal compound to form an ion. The inventors have found that a catalyst comprising at least one compound selected from compounds forming a pair has excellent copolymerization activity between an α-olefin and a cyclic olefin, and have completed the present invention.

  An object of the present invention is to provide a method for efficiently incorporating an α-olefin / cyclic olefin copolymer with high polymerization activity and a cyclic olefin.

The method for producing the α-olefin / cyclic olefin copolymer according to the present invention includes:
(A) a linear or branched α-olefin having 2 to 30 carbon atoms,
(B) The following general formula (I)

(In the formula (I), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, R ^{61 to} R ⁷⁸ and R ^a1 and R ^b1 are the same or different. A hydrogen atom, a halogen atom or a hydrocarbon group; R ^{75 to} R ⁷⁸ may be combined with each other to form a monocyclic or polycyclic ring; it may have a double bond, or may form a R ⁷⁵ and between R ^76, or alkylidene group and R ⁷⁷ and R ^78.)
A cyclic olefin represented by the following general formula (II)

(In the formula (II), x and d are 0 or an integer of 1 or more; y and z are 0, 1 or 2; R ^{81 to} R ⁹⁹ may be the same or different from each other; , A halogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group or an alkoxy group, wherein the carbon atom to which R ⁸⁹ and R ⁹⁰ are bonded and the carbon atom to which R ⁹³ is bonded or R ⁹¹ are bonded. May be bonded directly or via an alkylene group having 1 to 3 carbon atoms, and when y = z = 0, R ⁹⁵ and R ⁹² or R ⁹⁵ and R ⁹⁹ They may combine with each other to form a monocyclic or polycyclic aromatic ring.)
And a cyclic olefin represented by the following general formula (III)

(In the formula (III), R ¹⁰⁰ and R ¹⁰¹ may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and f is 1 ≦ f ≦ 18.)
And at least one cyclic olefin selected from the group consisting of cyclic olefins represented by
(C) a transition metal compound represented by the following general formula (IV),

(Wherein, M represents a transition metal atom belonging to Groups 4 to 5 of the periodic table, m represents an integer of 1 to 4, and R ¹ represents a fluorine atom or a fluorine-containing hydrocarbon group having 1 to 30 carbon atoms. And R ^{2 to} R ⁵ may be the same or different from each other, and represent a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group. , A phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, two or more of which may be connected to each other to form a ring, and R ⁶ is hydrogen, primary, or C1-C4 hydrocarbon groups consisting of only secondary carbons, C5 or more aliphatic hydrocarbon groups, aryl-substituted alkyl groups, monocyclic or bicyclic alicyclic hydrocarbon groups and aromatics And n represents a number that satisfies the valency of M. X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, Represents a silicon-containing group, a germanium-containing group, or a tin-containing group, and when n is 2 or more, a plurality of groups represented by X may be the same or different from each other; It may combine to form a ring.)
(D) (D-1) an organometallic compound,
(D-2) an organic aluminum oxy compound, and
(D-3) copolymerization in the presence of an olefin polymerization catalyst comprising at least one compound selected from compounds which form an ion pair by reacting with the transition metal compound (C). This is a method for producing an olefin / cyclic olefin copolymer.

In the method for producing an α-olefin / cyclic olefin according to the present invention, the α-olefin is ethylene, and the cyclic olefin is bicyclo [2.2.1] hept-2-ene and / or tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene.

  The present invention provides a method for efficiently incorporating an α-olefin / cyclic olefin copolymer with high polymerization activity and a cyclic olefin.

  Hereinafter, the method for producing the α-olefin / cyclic olefin copolymer in the present invention will be specifically described.

The method for producing the α-olefin / cyclic olefin copolymer according to the present invention includes:
(A) a linear or branched α-olefin having 2 to 30 carbon atoms,
(B) at least one selected from the group consisting of a cyclic olefin represented by the following general formula (I), a cyclic olefin represented by the following general formula (II), and a cyclic olefin represented by the following general formula (III) The starting material is a kind of cyclic olefin.

  First, these α-olefins and cyclic olefins will be described.

(A) α-Olefin The α-olefin (A) according to the present invention is a structural unit derived from a linear or branched α-olefin having 2 to 30 carbon atoms as described below.

  Specific examples of the linear or branched α-olefin having 2 to 30 carbon atoms include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, Methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like. Of these, ethylene and propylene are preferred, and ethylene is particularly preferred. Two or more structural units derived from these α-olefins may be contained.

(B) Structural unit derived from cyclic olefin The cyclic olefin (B) according to the present invention is represented by the following general formula (I), (II) or (III).

  First, the cyclic olefin represented by the general formula (I) will be described.

  In the formula (I), u is 0 or 1, v is 0 or a positive integer, and w is 0 or 1. When w is 1, the ring represented by w is a 6-membered ring, and when w is 0, the ring is a 5-membered ring.

R ^{61 to} R ⁷⁸ and R ^a1 and R ^b1 may be the same or different and are a hydrogen atom, a halogen atom or a hydrocarbon group.

  Here, the halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

  Examples of the hydrocarbon group include an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, and an aromatic hydrocarbon group. .

  More specifically, examples of the alkyl group include methyl, ethyl, propyl, isopropyl, amyl, hexyl, octyl, decyl, dodecyl, octadecyl and the like.

  Examples of the halogenated alkyl group include a group in which one or more halogen atoms are substituted for the above alkyl group having 1 to 20 carbon atoms.

  Examples of the cycloalkyl group include cyclohexyl, and examples of the aromatic hydrocarbon group include phenyl and naphthyl.

Further, in the above general formula (I), R ⁷⁵ and R ⁷⁶ , R ⁷⁷ and R ⁷⁸ , R ⁷⁵ and R ⁷⁷ , R ⁷⁶ and R ⁷⁸ , R ⁷⁵ and R ⁷⁸ , or R ⁷⁶ and R ⁷⁷ may be bonded to each other (in cooperation with each other) to form a monocyclic or polycyclic group, and the monocyclic or polycyclic ring thus formed is a double bond. May be provided. Specific examples of the monocyclic or polycyclic ring formed here include the following.

In the above examples, the carbon atoms numbered 1 or 2 represent the carbon atoms to which R ⁷⁵ (R ⁷⁶ ) or R ⁷⁷ (R ⁷⁸ ) are bonded in the general formula (I), respectively.

Also, R ⁷⁵ and R ⁷⁶ or R ⁷⁷ and R ⁷⁸ may form an alkylidene group. Such an alkylidene group is usually an alkylidene group having 2 to 20 carbon atoms, and specific examples of such an alkylidene group include ethylidene, propylidene, and isopropylidene.

  Next, the cyclic olefin represented by the general formula (II) will be described.

  In the formula (II), x and d are 0 or a positive integer, and y and z are 0, 1 or 2.

R ^{81 to} R ⁹⁹ may be the same or different and are a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group or an alkoxy group.

  Examples of the halogen atom include the same as the halogen atom in the above formula (I).

  Examples of the aliphatic hydrocarbon group include an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 15 carbon atoms.

  More specifically, examples of the alkyl group include methyl, ethyl, propyl, isopropyl, amyl, hexyl, octyl, decyl, dodecyl, octadecyl and the like.

  Examples of the cycloalkyl group include cyclohexyl.

  Examples of the aromatic hydrocarbon group include an aryl group and an aralkyl group, and specific examples include phenyl, tolyl, naphthyl, benzyl, and phenylethyl.

  Examples of the alkoxy group include methoxy, ethoxy, and propoxy.

Here, the carbon atom to which R ⁸⁹ and R ⁹⁰ are bonded and the carbon atom to which R ⁹³ is bonded or the carbon atom to which R ⁹¹ is bonded are directly or an alkylene group having 1 to 3 carbon atoms. And may be bonded via That is, when the two carbon atoms are bonded via an alkylene group, R ⁸⁹ and R ⁹³ or R ⁹⁰ and R ⁹¹ cooperate with each other to form a methylene group (—CH ₂ -), ethylene group (-CH ₂ CH ₂ -) or propylene group _{(-CH 2 CH 2 CH 2 -} ) to form one alkylene group of the.

Further, when y = z = 0, R ⁹⁵ and R ⁹² or R ⁹⁵ and R ⁹⁹ may combine with each other to form a monocyclic or polycyclic aromatic ring. Specifically, when y = z = 0, the following aromatic rings formed by R ⁹⁵ and R ⁹² can be mentioned.

ここで、ｌは上記一般式（II）におけるｄと同じである。

Here, l is the same as d in the general formula (II).

  Next, the cyclic olefin represented by the general formula (III) will be described.

In the formula (III), R ¹⁰⁰ and R ¹⁰¹ may be the same or different and each is a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and f is 1 ≦ f ≦ 18.

The hydrocarbon group having 1 to 5 carbon atoms preferably includes an alkyl group, a halogenated alkyl group and a cycloalkyl group. These specific examples will be apparent from the specific examples of R ^{61 to} R ^{78 in} the above formula (I).

As the cyclic olefin represented by the above general formula (I), (II) or (III), specifically,
Bicyclo-2-heptene derivatives (bicyclohept-2-ene derivatives), tricyclo-3-decene derivatives, tricyclo-3-undecene derivatives, tetracyclo-3-dodecene derivatives, pentacyclo-4-pentadecene derivatives, pentacyclopentadecadienes, Pentacyclo-3-pentadecene derivative, pentacyclo-4-hexadecene derivative, pentacyclo-3-hexadecene derivative, hexacyclo-4-heptacene derivative, heptacyclo-5-eicosene derivative, heptacyclo-4-eicosene derivative, heptacyclo-5-heneicosene derivative, octacyclo -5-docosene derivative, nonacyclo-5-pentacosene derivative, nonacyclo-6-hexacocene derivative, cyclopentadiene-acenaphthylene adduct, 1,4-methano-1,4,4a, 9a-tetrahydrofluorene derivative, 1,4-methanol -1,4,4a, 5,10,10a-Hexahydroant Helix derivatives, cycloalkylene derivatives having 3 to 20 carbon atoms, and the like are included.

  Hereinafter, specific examples of the cyclic olefin represented by the above formula (I), (II) or (III) are shown.

  Cyclobutene, cyclopentene, cyclohexene, 3-methylcyclohexene, cycloheptene, cyclooctene, cyclodecene, cyclododecene, cycloeicosene and the like.

Among these, bicyclo [2.2.1] -2-heptene derivatives, tetracyclo [4.4.0. ^12,5 .1 ^7,10] -3-dodecene derivatives and hexacyclo [6.6.1.1 ^{3, 6} .1 ^{10, 13} .0 ^{2,7. 09,14]} -4-heptadecene derivative are preferred, particularly bicyclo [2.2.1] -2-heptene, is tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene preferred .

  The cyclic olefin represented by the general formula (I) or (II) as described above can be produced by subjecting cyclopentadiene and an olefin having a corresponding structure to a Diels-Alder reaction.

  Polymerization may be carried out by including two or more of these cyclic olefins represented by the general formulas (I), (II) or (III).

The method for producing the α-olefin / cyclic olefin copolymer according to the present invention, the method for producing the α-olefin / cyclic olefin copolymer,
A linear or branched α-olefin having 2 to 30 carbon atoms,
At least one cyclic olefin selected from the group consisting of the cyclic olefin represented by the general formula (I), the cyclic olefin represented by the general formula (II), and the cyclic olefin represented by the general formula (III) And (C) a transition metal compound represented by the following general formula (IV),
(D) (D-1) an organometallic compound,
(D-2) an organic aluminum oxy compound, and
(D-3) Copolymerize in the presence of an olefin polymerization catalyst comprising at least one compound selected from the compounds forming an ion pair by reacting with the transition metal compound (C).

  Hereinafter, each component forming the olefin polymerization catalyst used in the present invention will be described.

(C) Transition metal compound The transition metal compound used in the present invention is a compound represented by the general formula (IV). These transition metal compounds can be used alone or in combination of two or more.

  The transition metal compound (C) used in the present invention is a compound represented by the following general formula (IV).

  In addition, although N ... M generally shows coordination, in the present invention, coordination may or may not be performed.

  Hereinafter, specific examples of the transition metal compound represented by the general formula (IV) are shown, but the invention is not limited thereto.

In the general formula (IV), M represents a transition metal atom of Groups 4 to 5 of the periodic table, specifically, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or the like. Yes, specifically, titanium, zirconium and hafnium, more preferably titanium.
m represents an integer of 1 to 4, and is preferably 2.

As a hydrocarbon group having 1 to 30 carbon atoms having one or more fluorine atoms for R ¹ , specifically, trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluorobutyl, perfluoropentyl, perfluorohexyl, Monofluorophenyl, difluorophenyl, trifluorophenyl, tetrafluorophenyl, pentafluorophenyl, (trifluoromethyl) fluorophenyl, bis (trifluoromethyl) phenyl, tris (trifluoromethyl) phenyl, tetrakis (trifluoromethyl) phenyl , Pantakis (trifluoromethyl) phenyl, perfluoroethylphenyl, bis (perfluoroethyl) phenyl, perfluoropropylphenyl, perfluorobutylphenyl, perfluoropentylphenyl, Fluorohexyl phenyl, bis (perfluorohexyl) phenyl, perfluoronaphthyl, perfluoro phenanthrenyl, perfluoro anthracenyl, and the like.

R ^{2 to} R ⁵ may be the same or different from each other and include a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, A containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of these may be connected to each other to form a ring.
Examples of the halogen atom include fluorine, chlorine, bromine, and iodine.

  Specific examples of the hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, n-hexyl, and the like. A linear or branched alkyl group having 1 to 20 carbon atoms; a linear or branched alkenyl group having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, such as vinyl, allyl and isopropenyl; ethynyl, propargyl and the like A linear or branched alkynyl group having 2 to 30, preferably 2 to 20 carbon atoms; having 3 to 30, preferably 3 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl and adamantyl; To 20 cyclic saturated hydrocarbon groups; C5 to C30 cyclic unsaturated such as cyclopentadienyl, indenyl and fluorenyl Hydrocarbon group; aryl group having 6 to 30, preferably 6 to 20 carbon atoms, such as phenyl, benzyl, naphthyl, biphenyl, terphenyl, phenanthryl and anthracenyl; tolyl, iso-propylphenyl, t-butylphenyl, dimethyl And alkyl-substituted aryl groups such as phenyl and di-t-butylphenyl.

  The hydrocarbon group may have a hydrogen atom substituted with a halogen atom. For example, the number of carbon atoms such as monotrifluoromethyl, ditrifluoromethyl, monofluorophenyl, difluorophenyl, trifluorophenyl, pentafluorophenyl, and chlorophenyl There may be mentioned 1 to 30, preferably 1 to 20, halogenated hydrocarbon groups.

  The hydrocarbon group may be substituted with another hydrocarbon group, and examples thereof include an aryl-substituted alkyl group such as benzyl and cumyl.

  Furthermore, the hydrocarbon group may be a heterocyclic compound residue; such as 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. Oxygen-containing group; amino group, imino group, amide group, imide group, hydrazino group, hydrazono group, nitro group, nitroso group, cyano group, isocyano group, cyanate ester group, amidino group, diazo group, and amino group are ammonium salts Nitrogen-containing groups such as those described below; boron-containing groups such as borandiyl, borantoriyl, and diboranyl groups; mercapto, thioester, dithioester, alkylthio, arylthio, thioacyl, thioether, and thiocyanate groups , Isocyanate ester group, sulfone ester group, Sulfur-containing groups such as a sulfonamide group, a thiocarboxyl group, a dithiocarboxyl group, a sulfo group, a sulfonyl group, a sulfinyl group, and a sulfenyl group; phosphorus-containing groups such as a phosphide group, a phosphoryl group, a thiophosphoryl group, and a phosphato group; , A germanium-containing group, or a tin-containing group.

  Among them, in particular, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, neopentyl, n-hexyl and the like having 1 to 30, preferably 1 to 20 carbon atoms. A linear or branched alkyl group; a cyclic hydrocarbon having 3 to 50, preferably 3 to 30 carbon atoms such as cyclopropyl, cyclobutyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantyl, norbornyl, and tetracyclododecyl; Aryl groups having 6 to 30, preferably 6 to 20 carbon atoms, such as phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, anthracenyl; halogen atoms, 1 to 30 carbon atoms, preferably 1 to 20 An alkyl or alkoxy group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms And substituted aryl groups the substituents is one to five substituents such as aryl group or an aryloxy group.

  Examples of the oxygen-containing group, the nitrogen-containing group, the boron-containing group, the sulfur-containing group, and the phosphorus-containing group include the same as those exemplified above.

  Heterocyclic compound residues include pyrrole, pyridine, pyrimidine, quinoline, nitrogen-containing compounds such as triazines, furans, oxygen-containing compounds such as pyran, residues such as sulfur-containing compounds such as thiophene, and heterocyclic compounds thereof. Examples thereof include groups in which a compound residue is further substituted with a substituent such as an alkyl group or an alkoxy group having 1 to 30, preferably 1 to 20 carbon atoms.

  Examples of the silicon-containing group include a silyl group, a siloxy group, a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxy group, and specifically, methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, diphenylmethylsilyl, triphenyl Examples include phenylsilyl, dimethylphenylsilyl, dimethyl-t-butylsilyl, dimethyl (pentafluorophenyl) silyl, and the like. Among them, methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, dimethylphenylsilyl, triphenylsilyl and the like are preferable. Particularly, trimethylsilyl, triethylsilyl, triphenylsilyl and dimethylphenylsilyl are preferred. Specific examples of the hydrocarbon-substituted siloxy group include trimethylsiloxy.

  Examples of the germanium-containing group and the tin-containing group include those obtained by substituting silicon in the silicon-containing group with germanium and tin.

Next, the examples of R ^{2 to} R ⁵ described above will be described more specifically.

  Among the oxygen-containing groups, alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy and the like, and aryloxy groups include phenoxy, 2,6-dimethylphenoxy, 2, As acyl groups, formyl group, acetyl group, benzoyl group, p-chlorobenzoyl group, p-methoxybenzoyl group, etc., and as ester groups, acetyloxy, benzoyloxy, methoxycarbonyl. Phenoxycarbonyl, p-chlorophenoxycarbonyl and the like.

  Among the nitrogen-containing groups, amide groups include acetamido, N-methylacetamido, N-methylbenzamide, etc., amino groups include dimethylamino, ethylmethylamino, diphenylamino, etc., and imide groups include acetimido, benzimide Preferred examples of the imino group include methylimino, ethylimino, propylimino, butylimino, and phenylimino.

  Among the sulfur-containing groups, alkylthio groups include methylthio, ethylthio, and the like; arylthio groups include phenylthio, methylphenylthio, and nartylthio; and thioester groups include acetylthio, benzoylthio, methylthiocarbonyl, and phenylthiocarbonyl. Preferred examples of the sulfone ester group include methyl sulfonate, ethyl sulfonate, and phenyl sulfonate. Examples of the sulfonamide group include phenyl sulfonamide, N-methyl sulfonamide, and N-methyl-p-toluene sulfonamide. Can be

In R ^{2 to} R ⁵ , two or more of these groups, preferably, adjacent groups may be linked to each other to form an aliphatic ring, an aromatic ring, or a hydrocarbon ring containing a hetero atom such as a nitrogen atom. And these rings may further have a substituent.

When m is 2 or more, two of the groups represented by R ^{2 to} R ⁵ may be linked. Furthermore, R ¹ each other when m is 2 or more, R ² together, R ³ together, R ⁴ together, R ⁵ each other, they may be the same or different from each other.

The primary or secondary only hydrocarbon group having 4 or less carbon atoms consisting of carbon of R ^6, carbon directly connected to the phenoxy ring in the carbon of R ⁶ is a primary or carbon atoms are secondary carbon 4 or less carbon It is a hydrogen group. Specifically, a linear or branched C1-C4, preferably 1-3, carbon atom such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl or s-butyl. Alkyl group.

The aliphatic hydrocarbon group having 5 or more carbon atoms of R ^6, and that of the hydrocarbon group in which the carbon directly connected to the phenoxy ring in the carbon of R ⁶ is not included in the ring structure, for example, 5 carbon atoms 30. Specifically, the carbon number of n-pentyl, i-pentyl, s-pentyl, t-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl and the like is 5 to 30, preferably 5 to 30 carbon atoms. And 5-20 linear or branched alkyl groups.

Examples of the aryl-substituted alkyl group for R ⁶ include benzyl, cumyl, 1-diphenylethyl, triphenylmethyl and the like.

Examples of the monocyclic or bicyclic alicyclic hydrocarbon group for R ⁶ include those having 3 to 30 carbon atoms. Specifically, a hydrocarbon group having a monocyclic alicyclic skeleton having 3 to 30, preferably 3 or 3 to 20 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl; .1.0] butyl, bicyclo [2.1.0] pentyl, norbornyl, bicyclo [2.2.2] octyl, spiro [2.2] pentyl, spiro [2.3] hexyl and the like. 5 to 30, preferably 5 to 20 hydrocarbon groups having a bicyclic alicyclic skeleton; and the like.

Examples of the aromatic group represented by R6 include those having 6 to 30 carbon atoms. Specifically, phenyl, naphthyl, biphenyl, terphenyl, fluorenyl, anthracenyl, phenanthryl and the like can be mentioned.

  A hydrocarbon group having 4 or less carbon atoms, an aliphatic hydrocarbon group having 5 or more carbon atoms, an aryl-substituted alkyl group, a monocyclic or bicyclic alicyclic hydrocarbon group consisting of only the above primary or secondary carbon In the aromatic group, the hydrogen atom may be substituted with another hydrocarbon group or halogen, and for example, the number of carbon atoms such as 3,5-dimethylphenyl, 2,6-dimethylphenyl, and 4-tert-butylphenyl 1 to 30, preferably 1 to 20 hydrocarbon groups or carbon atoms such as trifluoromethyl, difluoromethyl, monofluorophenyl, difluorophenyl, trifluorophenyl, pentafluorophenyl, bis (trifluoromethyl) phenyl, chlorophenyl and the like Halogenated hydrocarbon groups of numbers 1 to 30, preferably 1 to 20 are mentioned.

  R6 is particularly preferably an aryl group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, such as phenyl, benzyl, naphthyl and anthracenyl, and methyl, ethyl, isopropyl, isobutyl, sec-butyl, neopentyl and the like. Has 1 to 30, preferably 1 to 20 linear or branched (secondary) alkyl groups, cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 2,6-dimethylcyclohexyl, 3,5 -Dimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, cyclododecyl and the like are also preferably groups selected from cyclic saturated hydrocarbon groups having 3 to 30, preferably 3 to 20 carbon atoms. .

  Further, R6 is particularly preferably an aromatic group such as phenyl, benzyl or naphthyl, and 3,5-difluorophenyl or 3,5-bis (trifluoromethyl) phenyl in which these hydrogen atoms are substituted.

R ^{1 to} R ⁵ are two or more of these groups, preferably adjacent groups are linked to each other to form an aliphatic ring, an aromatic ring, or a hydrocarbon ring containing a hetero atom such as a nitrogen atom. And these rings may further have a substituent.

  n is a number that satisfies the valence of M, and is specifically an integer of 2 to 4, and is preferably 2.

  X represents a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, and a silicon-containing residue. Group, germanium-containing group, or tin-containing group. When n is 2 or more, a plurality of groups represented by X may be the same or different, and a plurality of groups represented by X are bonded to each other to form a ring. Is also good.

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

  Specific examples of the hydrocarbon group include alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, octyl, nonyl, dodecyl, and eicosyl; and those having 3 to 30 carbon atoms such as cyclopentyl, cyclohexyl, norbornyl, and adamantyl. Cycloalkyl groups; alkenyl groups such as vinyl, propenyl and cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl and phenylpropyl; phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, naphthyl, methylnaphthyl , Anthryl, phenanthryl and the like, but are not limited thereto. These hydrocarbon groups also include halogenated hydrocarbons, specifically, groups in which at least one hydrogen of a hydrocarbon group having 1 to 20 carbon atoms has been replaced by halogen.

  Heterocyclic compound residues include pyrrole, pyridine, pyrimidine, quinoline, nitrogen-containing compounds such as triazines, furans, oxygen-containing compounds such as pyran, residues such as sulfur-containing compounds such as thiophene, and heterocyclic compounds thereof. Examples thereof include groups in which a compound residue is further substituted with a substituent such as an alkyl group or an alkoxy group having 1 to 30, preferably 1 to 20 carbon atoms.

  Specific examples of the oxygen-containing group include a hydroxy group; an alkoxy group such as methoxy, ethoxy, propoxy and butoxy; an aryloxy group such as phenoxy, methylphenoxy, dimethylphenoxy and naphthoxy; and an arylalkoxy group such as phenylmethoxy and phenylethoxy. An acetoxy group; a carbonyl group, and the like, but are not limited thereto.

  Specific examples of the sulfur-containing group include methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, p-toluene sulfonate, trimethylbenzene sulfonate, and triisobutylbenzene sulfonate. Sulfonate groups such as benzoate, p-chlorobenzenesulfonate and pentafluorobenzenesulfonate; methylsulfinate, phenylsulfinate, benzylsulfinate, p-toluenesulfinate, trimethylbenzenesulfinate, penta Examples include, but are not limited to, sulfinate groups such as fluorobenzenesulfinate; alkylthio groups; arylthio groups.

  Specifically, as the nitrogen-containing group, specifically, an amino group; an alkylamino group such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, dicyclohexylamino; phenylamino, diphenylamino, ditolylamino, dinaphthyl Examples include, but are not limited to, arylamino groups such as amino and methylphenylamino or alkylarylamino groups.

Specific examples of the boron-containing group include BR ₄ (R represents hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, or the like).

  Specific examples of the phosphorus-containing group include trialkyl phosphine groups such as trimethyl phosphine, tributyl phosphine, and tricyclohexyl phosphine; triaryl phosphine groups such as triphenyl phosphine and tolyl phosphine; methyl phosphite, ethyl phosphite, and phenyl phosphite Phosphite groups (phosphide groups); phosphonic acid groups; phosphinic acid groups, and the like, but are not limited thereto.

  Specific examples of the silicon-containing group include hydrocarbon-substituted silyl groups such as phenylsilyl, diphenylsilyl, trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, methyldiphenylsilyl, tritolylsilyl, and trinaphthylsilyl. Hydrocarbon-substituted silyl ether groups such as trimethylsilyl ether; silicon-substituted alkyl groups such as trimethylsilylmethyl; and silicon-substituted aryl groups such as trimethylsilylphenyl.

  Specific examples of the germanium-containing group include groups in which silicon of the silicon-containing group is replaced with germanium.

  Specific examples of the tin-containing group include a group in which silicon of the silicon-containing group is substituted with tin.

Specific examples of the halogen-containing group include a fluorine-containing group such as PF ₆ and BF ₄ , a chlorine-containing group such as ClO ₄ and SbCl ₆ , and an iodine-containing group such as IO ₄ , but are not limited thereto. Absent.

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

  Hereinafter, specific examples of the transition metal compound represented by the general formula (IV) are shown, but the invention is not limited thereto. Titanium in the examples may be replaced by a transition metal element of Groups 4 to 5 of the periodic table, such as zirconium, hafnium, vanadium, niobium, tantalum, and the like. X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, It may be replaced with a silicon-containing group, a germanium-containing group, or a tin-containing group. M may replace 2 with 1 accordingly. Accordingly, the number n may be replaced with a changed number.

In the above examples, Me represents a methyl group, Et represents an ethyl group, ⁿ Pr represents an n-propyl group, ⁱ Pr represents an isopropyl group, ⁿ Bu represents an n-butyl group, and ^t Bu represents a t-butyl group. ^N C ₅ H ₁₁ represents an n-pentyl group, ⁱ C ₅ H ₁₁ represents an isopentyl group, ^s C ₅ H ₁₁ represents an s-pentyl group, ^neo C ₅ H ₁₁ represents a neopentyl group, and Ph represents a phenyl group.

  The method for producing such a transition metal compound (C) is not particularly limited, and can be produced, for example, as follows.

First, the ligand constituting the transition metal compound (C) is a salicylaldehyde compound, a primary amine compound of the formula R ¹ —NH ₂ (R ¹ is as defined above), for example, an alkylamine. It is obtained by reacting with a similar compound. Specifically, both starting compounds are dissolved in a solvent. As the solvent, those commonly used for such a reaction can be used, and among them, alcohol solvents such as methanol and ethanol, and hydrocarbon solvents such as toluene are preferable. Then, the obtained solution is stirred under a reflux condition from room temperature for about 1 to 48 hours to obtain a corresponding ligand in a good yield.

  When synthesizing the ligand compound, an acid catalyst such as formic acid, acetic acid, or toluenesulfonic acid may be used as a catalyst. Further, when molecular sieves, magnesium sulfate or sodium sulfate are used as a dehydrating agent, or when dehydration is performed by Dean-Stark, it is effective for the progress of the reaction.

  Next, by reacting the ligand thus obtained with a transition metal M-containing compound, a corresponding transition metal compound can be synthesized. Specifically, the synthesized ligand is dissolved in a solvent, and if necessary, contacted with a base to prepare a phenoxide salt, and then mixed with a metal compound such as a metal halide or a metal alkylate at a low temperature. The mixture is stirred at -78 ° C to room temperature or under reflux for about 1 to 48 hours. As the solvent, those which are commonly used in such reactions can be used, and among them, polar solvents such as ether and tetrahydrofuran (THF), and hydrocarbon solvents such as toluene are preferably used. Further, as a base used when preparing a phenoxide salt, a lithium salt such as n-butyllithium, a metal salt such as a sodium salt such as sodium hydride, and an organic base such as triethylamine and pyridine are preferable. Not as long.

  Further, depending on the properties of the compound, the corresponding transition metal compound can be synthesized by directly reacting the ligand with the metal compound without going through the preparation of the phenoxide salt.

Further, the metal M in the synthesized transition metal compound can be exchanged for another transition metal by a conventional method. Further, for example, when any of R ^{1 to} R ⁵ is H, a substituent other than H can be introduced at any stage of the synthesis.

  Alternatively, the reaction solution of the ligand and the metal compound can be used as it is for the polymerization without isolating the transition metal compound.

  The transition metal compounds (C) as described above are used alone or in combination of two or more.

(Other transition metal compounds)
As the transition metal compound other than the transition metal compound (C), specifically, the following transition metal compounds can be used, but not limited thereto.

  (c-1) a transition metal imide compound represented by the following general formula (IV-c)

  In the formula, M represents a transition metal atom selected from Groups 8 to 10 of the periodic table, and is preferably nickel, palladium or platinum.

R ^{31 to} R ³⁴ may be the same or different from each other, and may be a hydrocarbon group having 1 to 50 carbon atoms, a halogenated hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon-substituted silyl group, or nitrogen, oxygen, And a hydrocarbon group substituted with a substituent containing at least one atom selected from phosphorus, sulfur and silicon.

In the groups represented by R ^{31 to} R ³⁴ , two or more of these groups, preferably adjacent groups, may be connected to each other to form a ring.
q shows the integer of 0-4.

  X represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group or a nitrogen-containing group. , Q is 2 or more, the plurality of groups represented by X may be the same or different.

  (c-2) a transition metal amide compound represented by the following general formula (IV-d)

  In the formula, M represents a transition metal atom selected from Groups 3 to 6 of the periodic table, and is preferably titanium, zirconium, or hafnium.

R ′ and R ″ may be the same or different from each other, and represent a hydrogen atom, a hydrocarbon group having 1 to 50 carbon atoms, a halogenated hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon-substituted silyl group, Or a substituent having at least one atom selected from nitrogen, oxygen, phosphorus, sulfur and silicon.
m is an integer of 0 to 2.
n is an integer of 1 to 5.

  A represents an atom selected from Groups 13 to 16 of the periodic table, and specific examples include boron, carbon, nitrogen, oxygen, silicon, phosphorus, sulfur, germanium, selenium, and tin. Preferably, there is. When n is 2 or more, a plurality of A may be the same or different from each other.

E is a substituent having at least one atom selected from carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron and silicon. When m is 2, two Es may be the same or different from each other, or may be linked to each other to form a ring.
p is an integer of 0 to 4.

  X represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group or a nitrogen-containing group. Is shown. When p is 2 or more, a plurality of groups represented by X may be the same or different from each other. Among them, X is preferably a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a sulfonate group.

  (C-3) Transition metal diphenoxy compound represented by the following general formula (IV-e)

  In the formula, M represents a transition metal atom selected from Groups 3 to 11 of the periodic table, l and m are each an integer of 0 or 1, A and A ′ are a hydrocarbon group having 1 to 50 carbon atoms, A halogenated hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having a substituent containing oxygen, sulfur or silicon, or a halogenated hydrocarbon group having 1 to 50 carbon atoms; May be the same or different.

B is a hydrocarbon group having 1 to 50 carbon atoms, a halogenated hydrocarbon group having 1 to 50 carbon atoms, a group represented by R ¹ R ² Z, oxygen or sulfur, wherein R ¹ and R ² is a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having 1 to 20 carbon atoms containing at least one heteroatom, and Z represents carbon, nitrogen, sulfur, phosphorus or silicon.
p is a number that satisfies the valence of M.

  X represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group or a nitrogen-containing group. , P is 2 or more, the plurality of groups represented by X may be the same or different from each other, or may be bonded to each other to form a ring.

  (c-4) a transition metal compound containing a ligand having a cyclopentadienyl skeleton containing at least one heteroatom represented by the following formula (IV-f)

式中、Ｍは周期表第３〜１１族から選ばれる遷移金属原子を示す。

In the formula, M represents a transition metal atom selected from Groups 3 to 11 of the periodic table.

X represents an atom selected from Groups 13, 14 and 15 of the periodic table, and at least one of X is other than carbon.
a represents 0 or 1.

  R may be the same or different, and represents a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a hydrocarbon-substituted silyl group, or is selected from nitrogen, oxygen, phosphorus, sulfur and silicon. And represents a hydrocarbon group having a substituent containing at least one atom, and two or more Rs may be connected to each other to form a ring.

b is an integer of 1 to 4, and when b is 2 or more, each [((R) _a ) ₅ -X ₅ ] group may be the same or different, and even if Rs are cross-linked, Good.
c is a number that satisfies the valence of M.

  Y represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group or a nitrogen-containing group. .

  When c is 2 or more, a plurality of groups represented by Y may be the same or different from each other, and a plurality of groups represented by Y may be bonded to each other to form a ring.

(C-5) general formula RB (Pz) ₃ transition metal compound formula represented by MX _n, M indicates the periodic table 3 to 11 group transition metal compound.

R represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms.
Pz represents a pyrazoyl group or a substituted pyrazoyl group.
n is a number that satisfies the valence of M.

  X represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group or a nitrogen-containing group. . When n is 2 or more, a plurality of groups represented by X may be the same or different from each other, or may be bonded to each other to form a ring.

  (C-6) a transition metal compound represented by the following formula (IV-g)

In the formula, Y ¹ and Y ³ may be the same or different and are atoms selected from Group 15 of the periodic table, and Y ² is an atom selected from Group 16 of the periodic table.

R ^{41 to} R ⁴⁸ may be the same or different from each other, and represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, It represents a sulfur-containing group or a silicon-containing group, and two or more of these may be linked to each other to form a ring.

  (C-7) a compound of a compound represented by the following general formula (IV-h) and a transition metal atom selected from Groups 8 to 10 of the periodic table

In the formula, R ^{51 to} R ⁵⁴ may be the same or different and each 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. And two or more of these may be connected to each other to form a ring.

  (C-8) a transition metal compound represented by the following formula (IV-i)

In the formula, M represents a transition metal atom selected from Groups 3 to 11 of the periodic table.
m is an integer of 0 to 3,
n is an integer of 0 or 1,
p is an integer of 1 to 3,
q is a number that satisfies the valence of M.

R ^{61 to} R ⁶⁸ may be the same or different from each other, and include a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, It represents a sulfur-containing group, a silicon-containing group or a nitrogen-containing group, and two or more of these may be connected to each other to form a ring.

  X represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group or a nitrogen-containing group. , Q is 2 or more, the plurality of groups represented by X may be the same or different from each other, or the plurality of groups represented by X may be bonded to each other to form a ring.

  Y is a group that bridges the borata benzene ring, and represents carbon, silicon or germanium.

A represents an atom selected from Group 14, 15, or 16 of the periodic table.
(C-9) a transition metal compound represented by the following general formula (IV-j)

In the formula, M represents a transition metal atom selected from Groups 3 to 11 of the periodic table.
m shows the integer of 1-3.
A represents an oxygen atom, a sulfur atom, a selenium atom or a nitrogen atom having a substituent R ^77,.

R ^{71 to} R ⁷⁷ may be the same or different, and each represents a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, Represents a containing group, a silicon-containing group, a germanium-containing group or a tin-containing group, and two or more of these may be linked to form a ring. and one group of R ⁷¹ to R ⁷⁷ contained, may be bonded with each one of the radicals R ⁷¹ to R ⁷⁷ contained in other ligands, R ⁷¹ together, R ⁷² each other, R ⁷³ to each other, R ⁷⁴ to each other, R ⁷⁵ to each other, R ⁷⁶ to each other, each other R ⁷⁷ may be the same or different from each other.
n is an integer satisfying the valence of M.

X represents a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, and a silicon-containing residue. A group, a germanium-containing group or a tin-containing group, and when n is 2 or more, a plurality of groups represented by X may be the same or different.
Further, a plurality of groups represented by X may be bonded to each other to form a ring.

(C-10) Transition metal compound containing a ligand having a cyclopentadienyl skeleton (c-11) Vanadium compound represented by VO (OR) _n X _{3-n In the} formula, R represents an aliphatic hydrocarbon residue Represents a group.
X represents a halogen atom.
n is 0 <n ≦ 3.

((D-1) organometallic compound)
As the (D-1) organometallic compound used as required in the present invention, specifically, an organometallic compound selected from the first, second and twelfth and thirteenth groups of the periodic table is used.

(D-1a) formula _{^{R a m Al (OR b)}} n H p X q
(Wherein, R ^a and R ^b may be the same or different and each represent a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms, X represents a halogen atom, and m represents 0 <M ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is a number 0 ≦ q <3, and m + n + p + q = 3.)
An organoaluminum compound represented by the formula:

(D-1b) General formula M ² AlR ^a ₄
(Wherein, M ² represents a Li, Na or K, R ^a is the number of carbon atoms 1 to 15, preferably a 1-4 hydrocarbon group.)
A complex alkylated product of a metal of Group 1 of the periodic table and aluminum represented by the formula:

(D-1c) Formula R ^a R ^b M ³
(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 M ³ is Mg, Zn or Cd. .)
A dialkyl compound of a metal of Group 2 or 12 of the periodic table represented by

  Examples of the organoaluminum compound belonging to (D-1a) include the following compounds.

Formula _{^{R a m Al (OR b)}} 3-m
(Wherein, R ^a and R ^b may be the same or different from each other, and represent a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms, and m is preferably 1.5 ≦ m ≦ This is the number 3.)
An organoaluminum compound represented by
In the general formula R ^a _m AlX _3-m (wherein, R ^a is from 1 to 15 carbon atoms, preferably an 1-4 hydrocarbon group, X represents a halogen atom, m is preferably 0 <m <3), an organoaluminum compound represented by the formula:
(Wherein, R ^a is from 1 to 15 carbon atoms, preferably an 1-4 hydrocarbon group, m is preferably 2 ≦ m <3.) The general formula R ^a _m AlH _3-m in An organoaluminum compound represented by:

Formula _{^{R a m Al (OR b)}} n X q
(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, X represents a halogen atom, and m represents 0 <M ≦ 3, n is a number satisfying 0 ≦ n <3, q is a number satisfying 0 ≦ q <3, and m + n + q = 3).

More specifically, as the organoaluminum compound belonging to (D-1a),
Tri-n-alkylaluminum such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum; triisopropylaluminum, triisobutylaluminum, trisec- Butylaluminum, tri-tert-butylaluminum, tri2-methylbutylaluminum, tri3-methylbutylaluminum, tri2-methylpentylaluminum, tri3-methylpentylaluminum, tri4-methylpentylaluminum, tri2-methylhexylaluminum Tri-branched alkyl aluminum such as tri-methylhexyl aluminum and tri 2-ethylhexyl aluminum; tricyclohexyla Miniumu, tricycloalkyl aluminum such as tri-cyclooctyl aluminum; dialkyl aluminum hydride such as diisobutyl aluminum hydride; triphenyl aluminum, triaryl aluminum such as tri tolyl aluminum _{(i-C 4 H 9)} x Al y (C 5 H ₁₀ ) Trialkenyl aluminum such as triisoprenyl aluminum represented by _z (where x, y, and z are positive numbers and z ≧ 2x); isobutylaluminum methoxide, isobutylaluminum ethoxide Aluminum alkoxides such as butyl, isobutyl aluminum isopropoxide; dialkyl aluminum alkoxides such as dimethyl aluminum methoxide, diethyl aluminum ethoxide, dibutyl aluminum butoxide Arm alkoxide; ethylaluminum sesquichloride ethoxide, alkyl sesquichloride such as butyl sesquichloride butoxide ^{_{alkoxide; R a 2.5 Al (OR b}} ) partially alkoxylated alkyl aluminum having an average composition represented by like _0.5; diethylaluminum Phenoxide, diethylaluminum (2,6-di-t-butyl-4-methylphenoxide), ethylaluminum bis (2,6-di-t-butyl-4-methylphenoxide), diisobutylaluminum (2,6-di- dialkyl aluminum aryloxides such as t-butyl-4-methylphenoxide) and isobutylaluminum bis (2,6-di-t-butyl-4-methylphenoxide); dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethyl Alminium Dialkyl aluminum halides such as mbromide and diisobutyl aluminum chloride; alkyl aluminum sesquihalides such as ethyl aluminum sesquichloride, butyl aluminum sesquichloride and ethyl aluminum sesquibromide; alkyl aluminum dihalides such as ethyl aluminum dichloride, propyl aluminum dichloride and butyl aluminum dibromide Partially halogenated alkylaluminums such as; dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride; and other partially hydrogenated such as alkylaluminum dihydrides such as ethylaluminum dihydride and propylaluminum dihydride Alkyl aluminum; ethyl aluminum Partially alkoxylated and halogenated alkyl aluminums such as muethoxycyclolide, butylaluminum butoxycyclolide, ethylaluminum ethoxybromide and the like can be mentioned.

Further, a compound similar to (D-1a) can also be used, and examples thereof include an organic aluminum compound in which two or more aluminum compounds are bonded via a nitrogen atom. Specific examples of such compounds, and the like _{(C 2 H 5) 2 AlN} (C 2 H 5) Al (C 2 H 5) 2.

As the compound belonging to (D-1b),
LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ can be exemplified.

  In addition, as the (B-1) organometallic compound, 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, butylmagnesium bromide, butylmagnesium chloride, dimethylmagnesium, diethylmagnesium, dibutylmagnesium, butylethylmagnesium and the like can also be used.

  Further, a compound that forms the above-mentioned organoaluminum compound in the polymerization system, for example, a combination of aluminum halide and alkyllithium, or a combination of aluminum halide and alkylmagnesium can also be used.

  (D-1) Among the organometallic compounds, an organoaluminum compound is preferred.

  The (D-1) organometallic compound as described above is used alone or in combination of two or more.

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

A conventionally known aluminoxane can be produced, for example, by the following method, and is usually obtained as a solution of a hydrocarbon solvent.
(1) Compounds containing water of adsorption or salts containing water of crystallization, for example, magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, cerous chloride hydrate and the like A method of adding an organoaluminum compound such as a trialkylaluminum to a suspension of a hydrocarbon medium of the above, and reacting the water of adsorption or 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 organic metal component. The solvent or the unreacted organoaluminum compound may be removed from the recovered solution of aluminoxane by distillation, and then redissolved in a solvent or suspended in a poor solvent for aluminoxane.

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

  Of these, trialkyl aluminum and tricycloalkyl aluminum are preferred, and trimethyl aluminum is particularly preferred.

  The above-mentioned organoaluminum compounds are used alone or in combination of two or more.

  Solvents used in the preparation of aluminoxane include aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane, and cyclopentane , Cyclohexane, cyclooctane, alicyclic hydrocarbons such as methylcyclopentane, gasoline, kerosene, petroleum fractions such as light oil, and halides of the above aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons (chlorinated products) , Bromides, etc.). Further, ethers such as ethyl ether and tetrahydrofuran can also be used. Among these solvents, aromatic hydrocarbons and aliphatic hydrocarbons are particularly preferred.

  The benzene-insoluble organic aluminum oxy compound used in the present invention has an Al component soluble in benzene at 60 ° C. of usually 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atom. That is, those which are insoluble or hardly soluble in benzene are preferred.

  As the organoaluminum oxy compound used in the present invention, an organoaluminum oxy compound containing boron represented by the following general formula (V) can also be mentioned.

式中、Ｒ²⁰は、炭素原子数が１〜１０の炭化水素基を示す。
Ｒ²¹は、互いに同一でも異なっていてもよく、水素原子、ハロゲン原子、炭素原子数が１〜１０の炭化水素基を示す。

In the formula, R ²⁰ represents a hydrocarbon group having 1 to 10 carbon atoms.
R ²¹ may be the same or different and each represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 10 carbon atoms.

The organoaluminum oxy compound containing boron represented by the general formula (V) includes an alkylboronic acid represented by the following general formula (VI) and R ²⁰ -B- (OH) ₂ ... (VI)
(In the formula, R ²⁰ represents the same group as described above.)
It can be produced by reacting an organoaluminum compound in an inert solvent under an inert gas atmosphere at a temperature of -80C to room temperature for 1 minute to 24 hours.

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

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

  Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum, triethylaluminum and triisobutylaluminum are particularly preferable. These may be used alone or in combination of two or more.

  The above-mentioned (B-2) organoaluminum oxy compounds are used alone or in combination of two or more.

(D-3) Compound forming an ion pair by reacting with a transition metal compound Compound (D-3) (hereinafter referred to as a compound forming an ion pair by reacting with a transition metal compound (C) used as required in the present invention) , "Ionized ionic compound") described in JP-A-1-501950, JP-A-1-502036, JP-A-3-179905, JP-A-3-179006, and JP-A-3-207703. And Lewis acids, ionic compounds, borane compounds and carborane compounds described in JP-A No. 3-207704 and US Pat. No. 5,321,106. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned.

Specifically, as the Lewis acid, BR ₃ (R is a phenyl group or a fluorine which may have a substituent such as a fluorine, a methyl group, a trifluoromethyl group or the like.
), 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.

  Examples of the ionic compound include a compound represented by the following general formula (VII).

In the formula, R ²²⁺ includes H ⁺ , a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptyltrienyl cation, and a ferrocenium cation having a transition metal.

R ^{23 to} R ²⁶ may be the same or different and are an organic group, preferably an aryl group or a substituted aryl group.

  Specific examples of the carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation, tri (methylphenyl) carbonium cation, and tri (dimethylphenyl) carbonium cation.

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

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

The R ^22, is preferably such as carbonium cation, ammonium cation, particularly triphenyl carbonium cation, N, N- dimethylanilinium cation, N, is N- diethylanilinium cation.

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

  Specific examples of the trialkyl-substituted ammonium salt include, for example, triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron, and trimethylammonium tetra (p-tolyl) Boron, trimethylammonium tetra (o-tolyl) boron, tri (n-butyl) ammonium tetra (pentafluorophenyl) boron, tripropylammonium tetra (o, p-dimethylphenyl) boron, tri (n-butyl) ammonium tetra ( m, m-dimethylphenyl) boron, tri (n-butyl) ammonium tetra (p-trifluoromethylphenyl) boron, tri (n-butyl) ammonium tetra (3,5-ditrifluoromethylphenyl) boron, tri (n -Butyl) ammonium Such as tetra (o- tolyl) boron and the like.

  Specific examples of the N, N-dialkylanilinium salt include, for example, N, N-dimethylaniliniumtetra (phenyl) boron, N, N-diethylaniliniumtetra (phenyl) boron, N, N-2,4,6 -Pentamethylanilinium tetra (phenyl) boron and the like.

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

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

（式中、Ｅｔはエチル基を示す。）

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

Specific examples of the borane compound include, for example, decaborane (14);
Bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium] undecaborate, bis [tri (n-butyl) ammonium] dodecaborate Salts of anions such as bis [tri (n-butyl) ammonium] decachlorodecaborate and bis [tri (n-butyl) ammonium] dodecachlorododecaborate; tri (n-butyl) ammonium bis (dodecahydride dodecaborate) Metal borane anion salts such as cobaltate (III) and bis [tri (n-butyl) ammonium] bis (dodecahydride dodecaborate) nickelate (III).

Specific examples of the carborane compound include, for example,
4-carbanonaborane (14), 1,3-dicarbanonaborane (13), 6,9-dicarbadecaborane (14), dodeca hydride-1-phenyl-1,3-dicarbanona borane, dodeca hydride- 1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarboundecaborane (13), 2,7-dicarbane Decaborane (13), undecahydride-7,8-dimethyl-7,8-dicarboundecaborane, dodecahydride-11-methyl-2,7-dicarboundecaborane, tri (n-butyl) ammonium 1- Carbadecaborate, tri (n-butyl) ammonium 1-carboundecaborate, tri (n-butyl) ammonium 1-carbadodecaborate, tri (n-butyl) ammonium 1-trimethylsilyl-1-carbadecaborate, tri ( n-butyl) ammo Umbromo-1-carbadodecaborate, tri (n-butyl) ammonium 6-carbadecaborate (14), tri (n-butyl) ammonium 6-carbadecaborate (12), tri (n-butyl) ammonium 7-carb Bound decaborate (13), tri (n-butyl) ammonium 7,8-dicarboundecaborate (12), tri (n-butyl) ammonium 2,9-dicarboundecaborate (12), tri (n-butyl) ) Ammonium dodecahydride-8-methyl-7,9-dicarboundecaborate, tri (n-butyl) ammonium undecahydride-8-ethyl-7,9-dicarboundecaborate, tri (n-butyl) ammonium Decahydride-8-butyl-7,9-dicarboundecaborate, tri (n-butyl) ammonium undecahydride-8-allyl-7,9-dicarboundecabo , Tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,8-dicarboundecaborate, tri (n-butyl) ammonium undecahydride-4,6-dibromo-7-carboundecaborate Salts of anions such as; tri (n-butyl) ammonium bis (nonahydride-1,3-dicarbanonaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8) -Dicarboundecaborate) ferrate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) cobaltate (III), tri (n-butyl) ammonium bis (Undecahydride-7,8-dicarbaundecaborate) nickelate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbamate) Undecaborate) cuprate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) aurate (III), tri (n-butyl) ammonium bis (nona Hydride-7,8-dimethyl-7,8-dicarboundecaborate) ferrate (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarboundecaborate) ) Chromate (III), tri (n-butyl) ammonium bis (tribromooctahydride-7,8-dicarboundecaborate) cobaltate (III), tris [tri (n-butyl) ammonium] bis ( Undecahydride-7-carboundecaborate) chromate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) manganate (IV), Bis (tri (n-butyl) ammonium) bis (undecahydride-7-carboundecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaun) And salts of metal carborane anions such as (decaborate) nickelate (IV).

  The heteropoly compound is composed of atoms selected from silicon, phosphorus, titanium, germanium, arsenic, and tin, and one or more atoms selected from vanadium, niobium, molybdenum, and tungsten. Specifically, phosphorus vanadic acid, germanovanadate, arsenic vanadate, phosphorus niobate, germanoniobate, siliconomolybdate, phosphomolybdate, titanium molybdate, germanomolybdate, arsenic molybdate, tin molybdate, phosphorus molybdate, phosphorus Tungstic acid, germanotoungstic acid, tin tungstic acid, phosphomolybdovanadic acid, phosphorus tungstovanadic acid, germanotangostovanadate acid, phosphomolybdo tongue vanadate acid, germano molybdo tungstovanadate acid, phosphomolybdine Tungstic acid, phosphomolybdniobic acid, and salts of these acids, such as metals of Group 1 or 2 of the Periodic Table, specifically lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium ,barium Salts with organic salts of triphenyl ethyl salts, and the like can be used.

  The above (D-3) ionized ionic compound is used alone or in combination of two or more.

  When the transition metal compound according to the present invention uses an organoaluminum oxy compound (D-2) such as methylaluminoxane as a catalyst or a co-catalyst component, it exhibits good activity and high copolymerizability with respect to an olefin compound. When an ionized ionic compound (D-3) such as triphenylcarbonium tetrakis (pentafluorophenyl) borate is used as a co-catalyst component, an olefin polymer having good activity and a high molecular weight can be obtained.

  Further, the olefin polymerization catalyst according to the present invention comprises the above transition metal compound (C), (D-1) an organometallic compound, (D-2) an organoaluminum oxy compound, and (D-3) an ionized ionic compound. A carrier (E) as described later can be used together with at least one compound (D) selected, if necessary.

((E) carrier)
The carrier (E) used as required in the present invention is an inorganic or organic compound, and is a granular or fine solid.

  Among them, the inorganic compound is preferably a porous oxide, an inorganic halide, a clay, a clay mineral or an ion-exchange layered compound.

As the porous oxide, specifically, SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO _{2 and the} like, or a composite or a mixture containing these, for example, Use natural or synthetic zeolite, SiO ₂ -MgO, SiO ₂ -Al ₂ O ₃ , SiO ₂ -TiO ₂ , SiO ₂ -V ₂ O ₅ , SiO ₂ -Cr ₂ O ₃ , SiO ₂ -TiO ₂ -MgO can do. Among them, those containing SiO ₂ and / or Al ₂ O ₃ as a main component are preferable.

In addition, the above inorganic oxide contains a small amount of Na ₂ CO ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ ) ₂ , carbonates such as Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, and Li ₂ O, sulfates, nitrates, and oxide components may be contained.

Such porous oxides have different properties depending on the kind and the production method, but the carrier preferably used in the present invention has a particle size of 10 to 300 μm, preferably 20 to 200 μm, and a specific surface area of 50 to 1000 m. ² / g, preferably in the range of 100 to 700 m ² / g, and the pore volume is desirably in the range of 0.3 to 3.0 cm ³ / g. Such a carrier is used by firing at 100 to 1000 ° C, preferably 150 to 700 ° C, if necessary.

As the inorganic halide, MgCl ₂ , MgBr ₂ , MnCl ₂ , MnBr ₂ or the like is used. The inorganic halide may be used as it is, or may be used after being pulverized by a ball mill or a vibration mill. In addition, a material obtained by dissolving an inorganic halide in a solvent such as alcohol, and then precipitating the fine particles with a precipitant can also be used.

  Clay is usually composed mainly of clay minerals. Further, the ion-exchangeable layered compound used in the present invention is a compound having a crystal structure in which a plurality of layers are stacked in parallel with a weak bonding force by ionic bonding or the like, and the contained ions are exchangeable. Most clay minerals are ion-exchangeable layered compounds. In addition, as these clays, clay minerals, and ion-exchangeable layered compounds, not only natural ones but also artificially synthesized ones can be used.

Further, as the clay, clay mineral or ion-exchangeable layered compound, clay, clay mineral, ionic crystalline compound having a layered crystal structure such as hexagonal dense packing type, antimony type, CdCl ₂ type, CdI ₂ type and the like. Examples can be given.

Examples of such clays and clay minerals include kaolin, bentonite, kibushi clay, gairome clay, allophane, hysingelite, pyrophyllite, plum group, montmorillonite group, vermiculite, ryokudeite group, palygorskite, kaolinite, nacrite, dickite. , Halloysite, and the like, and examples of the ion-exchangeable layered compound include α-Zr (HAsO ₄ ) ₂ .H ₂ O, α-Zr (HPO _{4) 2} , α-Zr (KPO ₄ ) ₂ .3H ₂ O, α-Ti (HPO ₄ ) ₂ , α-Ti (HAsO ₄ ) ₂ · H ₂ O, α-Sn (HPO ₄ ) ₂ · H ₂ O, γ-Zr (HPO ₄ ) ₂ , γ-Ti (HPO ₄ ) ₂ , crystalline acidic salts of polyvalent metals such as γ-Ti (NH ₄ PO ₄ ) ₂ .H ₂ O, and the like.

Such clays, clay minerals or ion-exchangeable layered compounds preferably have a pore volume of 0.1 cc / g or more as measured by mercury intrusion at a radius of 20 ° or more, and preferably 0.3 to 5 cc / g. Particularly preferred. Here, the pore volume is measured by a mercury intrusion method using a mercury porosimeter in a range of a pore radius of 20 to 3 × 10 ⁴ Å.

  When a pore having a radius of 20 ° or more and a pore volume of less than 0.1 cc / g is used as a carrier, high polymerization activity tends to be hardly obtained.

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

The ion-exchange layered compound may be a layered compound in which the layers are expanded by utilizing ion-exchangeability and exchanging exchangeable ions between layers with another large bulky ion. Such bulky ions play a pillar-like role for supporting the layered structure, and are usually called pillars. Introducing another substance between layers of the layered compound in this way is called intercalation. Examples of the guest compound to be intercalated include cationic inorganic compounds such as TiCl ₄ and ZrCl _4, and metal alkoxides such as Ti (OR) ₄ , Zr (OR) ₄ , PO (OR) ₃ and B (OR) ₃ ( R is a hydrocarbon group, etc.), metal hydroxide ions such as [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH) ₁₄ ] ²⁺ , [Fe ₃ O (OCOCH ₃ ) ₆ ] ⁺ And the like. These compounds are used alone or in combination of two or more. When intercalating these compounds, they were obtained by hydrolyzing metal alkoxides (R is a hydrocarbon group, etc.) such as Si (OR) ₄ , Al (OR) ₃ , and Ge (OR) ₄ . A polymer, a colloidal inorganic compound such as SiO _2, and the like can also coexist. Examples of the pillar include oxides formed by intercalating the metal hydroxide ions between layers and then heating and dehydrating the layers.

  The clay, the clay mineral, and the ion-exchangeable layered compound may be used as they are, or may be used after performing a treatment such as ball milling or sieving. Further, it may be used after newly adding and adsorbing water or performing a heat dehydration treatment. Furthermore, they may be used alone or in combination of two or more.

  Of these, preferred are clays or clay minerals, and particularly preferred are montmorillonite, vermiculite, pectolite, teniolite and synthetic mica.

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

  The olefin polymerization catalyst according to the present invention is selected from the above transition metal compounds (C), (D-1) organometallic compounds, (D-2) organoaluminum oxy compounds, and (D-3) ionized ionic compounds. At least one compound (D) and, if necessary, a specific organic compound component (F) as described later can be contained together with the carrier (E).

((F) Organic compound component)
The (F) organic compound component used as necessary in the present invention is used, if necessary, for the purpose of improving polymerization performance and physical properties of the produced polymer. Such organic compounds include alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, sulfonates and the like.

As the alcohols and phenolic compounds, those represented by R ³¹ —OH are usually used, wherein R ³¹ is a hydrocarbon group having 1 to 50 carbon atoms or a halogenated group having 1 to 50 carbon atoms. Shows a hydrocarbon group.

As the alcohols, those in which R ³¹ is a halogenated hydrocarbon are preferred. As the phenolic compound, a compound in which the α, α′-position of the hydroxyl group is substituted with a hydrocarbon having 1 to 20 carbon atoms is preferable.

As the carboxylic acid, one represented by R ³² —COOH is usually used. R ³² represents a hydrocarbon group having 1 to 50 carbon atoms or a halogenated hydrocarbon group having 1 to 50 carbon atoms, particularly preferably a halogenated hydrocarbon group having 1 to 50 carbon atoms.

As the phosphorus compound, a phosphoric acid having a P—O—H bond, a P-OR, a phosphate having a P ＝ O bond, and a phosphine oxide compound are preferably used.
As the sulfonate, those represented by the following general formula (X) are used.

式中、Ｍは周期表１〜１４族から選ばれる原子である。

In the formula, M is an atom selected from Groups 1 to 14 of the periodic table.

R ³³ is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms.

X 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.
m is an integer of 1 to 7, and n is 1 ≦ n ≦ 7.

At the time of polymerization, the method of use and the order of addition of each component are arbitrarily selected, and the following methods are exemplified.
(1) A method in which the component (C) and the component (D) are added to the polymerization vessel in an arbitrary order.
(2) A method in which the catalyst component in which the component (C) is supported on the carrier (E) and the component (D) are added to the polymerization reactor in any order.
(3) A method in which the catalyst component in which the component (D) is supported on the carrier (E) and the component (C) are added to the polymerization reactor in any order.
(4) A method in which a catalyst component in which the component (C) is supported on the carrier (E) and a catalyst component in which the component (D) is supported on the carrier (E) are added to the polymerization reactor in any order.
(5) A method in which a catalyst component in which the component (C) and the component (D) are supported on a carrier (E) is added to a polymerization reactor.

  In each of the above methods (1) to (5), at least two or more of the respective catalyst components may be brought into contact in advance.

  The solid catalyst component in which the component (C) and the component (D) are supported on the component (E) may have an olefin preliminarily polymerized. Components may be supported.

  In the α-olefin / cyclic olefin copolymerization method according to the present invention, the α-olefin and the cyclic olefin are copolymerized in the presence of the above-mentioned α-olefin / cyclic olefin copolymerization catalyst to form the α-olefin / cyclic olefin. A cyclic olefin copolymer is obtained.

  In the present invention, the polymerization can be carried out by any of a liquid phase polymerization method such as a solution polymerization and a suspension polymerization or a gas phase polymerization method.

(Polymerization solvent)
Specific examples of the inert hydrocarbon medium used in the liquid phase polymerization include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, and methylcyclopentane Alicyclic hydrocarbons such as benzene, toluene, xylene and the like; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, dichloromethane and the like and mixtures thereof, and α-olefins and / or The cyclic olefin itself can be used as a solvent.

(Catalyst concentration)
When the α-olefin / cyclic olefin copolymerization is carried out using the α-olefin / cyclic olefin copolymerization catalyst as described above, the component (C) usually contains 10 ⁻¹² to 10 ⁻² per liter of polymerization volume. Mol, preferably 10 ^-10 to 10 ^-3 mol.

  Component (D-1) has a molar ratio [(D-1) / M] of component (D-1) to transition metal atom (M) in component (C) of usually 0.01 to 100, 000, preferably 0.05 to 50,000. Component (D-2) has a molar ratio [(D-2) / M] of aluminum atom in component (D-2) to transition metal atom (M) in component (C) of usually 10 to 10. It is used in an amount of 500,000, preferably 20-100,000. The component (D-3) has a molar ratio [(D-3) / M] of the component (D-3) to the transition metal atom (M) in the component (C) of usually 1 to 10, preferably 1 to 10. It is used in such an amount as to be 1 to 5.

  Component (F) has a molar ratio [(F) / (D-1)] of usually 0.01 to 10, preferably 0.1 to 5, when component (D) is component (D-1). When the component (D) is the component (D-2), the molar ratio [(F) / (D-2)] is usually 0.001 to 2, preferably 0.005 to 2. When the component (D) is the component (D-3) in such an amount as to be 1, the molar ratio [(F) / (D-3)] is usually 0.01 to 10, preferably 0.1. It is used as needed in such an amount as to be ５5.

(Polymerization temperature and polymerization pressure)
The olefin polymerization temperature using such an olefin polymerization catalyst is usually in the range of −50 to + 200 ° C., preferably 0 to 170 ° C. The polymerization pressure is usually from normal pressure to 9.8 MPa (100 kg / cm ² ), preferably from normal pressure to 4.9 MPa (50 kg / cm ² ), and the polymerization reaction is a batch type, semi-continuous type, continuous type. This can be done by any of the formulas. Further, the polymerization can be performed in two or more stages having different reaction conditions.

(Adjustment of molecular weight)
The molecular weight of the resulting olefin polymer can be adjusted by the presence of hydrogen in the polymerization system or by changing the polymerization temperature. Furthermore, it can be adjusted by the difference of the component (B) used.

(Other monomers)
If necessary, a polar monomer may be copolymerized in addition to the α-olefin and the cyclic olefin. As the polar monomer, for example, acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, bicyclo (2,2,1) -5-heptene-2,3-dicarboxylic anhydride and the like α, β-unsaturated carboxylic acids and metal salts of α, β-unsaturated carboxylic acids such as sodium salt, potassium salt, lithium salt, zinc salt, magnesium salt, calcium salt thereof; methyl acrylate, ethyl acrylate, N-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, Α, β-unsaturated carboxylic esters such as n-butyl methacrylate and isobutyl methacrylate; vinyl acetate, propio Vinyl esters such as vinyl acrylate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate, and vinyl trifluoroacetate; unsaturated glycidyls such as glycidyl acrylate, glycidyl methacrylate, and monoglycidyl itaconate; Examples include halogen-containing olefins such as vinyl chloride and vinyl fluoride.

  Further, vinylcyclohexane, diene, polyene, or the like can be used. As the diene or polyene, a cyclic or chain compound having 4 to 30, preferably 4 to 20 carbon atoms and having two or more double bonds is used. Specifically, butadiene, isoprene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,3-hexadiene, 1 7,3-octadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, ethylidene norbornene, vinylnorbornene, dicyclopentadiene; 7-methyl-1,6-octadiene, 4 -Ethylidene-8-methyl-1,7-nonadiene, 5,9-dimethyl-1,4,8-decatriene; further, aromatic vinyl compounds such as styrene, o-methylstyrene, m-methylstyrene, p-methyl Mono- or polyalkylstyrenes such as styrene, o, p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene; methoxystyrene, ethoxystyrene, vinylbenzoic acid, methylvinylbenzoate, Benzyl acetate, hydroxystyrene, o- chlorostyrene, p- chlorostyrene, functional group-containing styrene derivatives such as divinylbenzene; and 3-phenylpropylene, 4-phenylpropylene, etc. α- methyl styrene. These olefins can be used alone or in combination of two or more.

(Molecular weight of α-olefin / cyclic olefin copolymer)
The weight average molecular weight (Mw) of the α-olefin / cyclic olefin copolymer obtained by the present invention determined by GPC is 1,000 ≦ Mw ≦ 5,000,000, preferably 3,000 ≦ Mw ≦ 3,000. 0,000, more preferably 5,000 ≦ Mw ≦ 2,000,000, and even more preferably 5,000 ≦ Mw ≦ 1,000,000.

When the weight average molecular weight (Mw) of the α-olefin / cyclic olefin copolymer is within the above range, a molded article tends to have excellent strength and excellent moldability.
Mw in the present specification is a value when measurement is performed under the above-described GPC conditions.

(Structural unit of α-olefin / cyclic olefin copolymer)
The molar ratio (α-olefin / cyclic olefin) of the structural unit (A) derived from α-olefin to the structural unit derived from cyclic olefin in the α-olefin / cyclic olefin copolymer according to the present invention is 20. / 80 to 99/1, preferably 30/70 to 90/10, more preferably 40/60 to 80/20, even more preferably 50/50 to 70/30.

  When the molar ratio of the structural unit derived from α-olefin and the structural unit derived from cyclic olefin in the α-olefin / cyclic olefin copolymer is within the above range, the characteristic of the α-olefin / cyclic olefin copolymer is as follows. Certain optical properties, mechanical properties, thermal properties, etc. tend to be excellent, and manufacturing is not difficult.

The cyclic olefin content in the polymer is determined in advance by calculating the correlation equation between the cyclic olefin content of the polymer by ¹³ C-NMR analysis and the Tg by DSC measurement, and using this correlation equation from the DSC measurement of the produced polymer-Tg. To calculate the cyclic olefin content.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.
Examples of the synthesis of the transition metal compound used for the polymerization are shown below.

The obtained compound is analyzed by ICP method after 270 MHz ¹ H-NMR (JEOL GSH-270), FD-mass spectrometry (JEOL SX-102A), metal content analysis (dry ashing and dissolution of diluted nitric acid); The structure was determined using SHIMADZU ICPS-8000).

[ Synthesis Example 1 ]
In a 100 ml reactor sufficiently purged with nitrogen, 50 ml of toluene, 3.06 g (19.0 mmol) of p-trifluoromethylaniline, 2.38 g (12.0 mmol) of 3-phenylsalicylaldehyde and a small amount of p-toluene as a catalyst Sulfonic acid was added, and the mixture was stirred under reflux for 12 hours. After cooling to room temperature, the catalyst was removed by filtration, and the mixture was concentrated under reduced pressure. The residue was purified by recrystallization using hexane to obtain 3.26 g (yield: 80%) of a yellow solid represented by the following formula (a).

1.365 g (4.00 mmol) of the compound (a) obtained in the above Synthesis Example and anhydrous diethyl ether were charged into a 100 ml reactor sufficiently purged with nitrogen, and cooled to -78 ° C. To this, 2.56 ml of n-butyllithium (n-hexane solution, 1.59 M, 4.00 mmol) was added dropwise over 5 minutes, and then the temperature was slowly raised to room temperature. After stirring at room temperature for 2.5 hours, the mixture was slowly added to a slurry of 2.00 ml (1.00 M, 2.00 mmol) of a titanium tetrachloride toluene solution cooled to -78 ° C in anhydrous diethyl ether. After the addition, the mixture was stirred for 17 hours while slowly raising the temperature to room temperature. The slurry was concentrated under reduced pressure, 30 ml of methylene chloride was added, the slurry was filtered, and the filtrate was concentrated. The residue was dissolved in 10 ml of ether, and the precipitated solid was collected and washed with n-hexane. The obtained solid was dried under reduced pressure to obtain 0.981 g (yield: 61%) of a yellow compound represented by the following formula (1). In addition, the result of FD-mass spectrometry of the transition metal compound (1) was 798 (M ⁺ ).

[ Synthesis Example 2 ]
In a 100 ml reactor sufficiently purged with nitrogen, 10 ml of toluene, 1.64 g (7.16 mmol) of 3,5-bis (trifluoromethyl) aniline, 0.92 g (4.64 mmol) of 3-phenylsalicylaldehyde and a small amount of p-toluene as a catalyst Sulfonic acid was added, and the mixture was stirred under reflux for 12 hours. After cooling to room temperature, the catalyst was removed by filtration, and the mixture was concentrated under reduced pressure. The residue was purified using a silica gel column to obtain 1.87 g (yield 98%) of a yellow solid represented by the following formula (b).

1.68 g (4.11 mmol) of the compound (b) and 25 ml of diethyl ether were charged into a 100 ml reactor which was sufficiently dried and purged with argon, cooled to −78 ° C., and stirred. To this, 2.75 ml of n-butyllithium (n-hexane solution, 1.58 M, 4.35 mmol) was added dropwise over 5 minutes, and the mixture was stirred at the same temperature for 2 hours, then slowly warmed to room temperature, and further cooled to room temperature for 3 hours. Stir for hours to adjust the lithium salt. This solution was added dropwise to 25 ml of a diethyl ether solution containing 2.0 ml of TiCl ₄ (toluene solution, 1.0 M, 2.05 mmol) cooled to −78 ° C. After completion of the dropwise addition, stirring was continued while slowly raising the temperature to room temperature. After further stirring at room temperature for 12 hours, the reaction solution was evaporated. The obtained solid was dissolved in 25 ml of methylene chloride, and insolubles were removed with a glass filter. The filtrate was concentrated under reduced pressure, the precipitated solid was reprecipitated with diethyl ether, and dried under reduced pressure to obtain 0.56 g (yield 30%) of a transition metal compound as a red-brown powder represented by the following formula (2).

[ Synthesis Example 3 ]
In a 100 ml reactor sufficiently purged with nitrogen, 50 ml of toluene, 3.78 g (16.5 mmol) of 3,5-bis (trifluoromethyl) aniline, 1.50 g (11.0 mmol) of 3-methylsalicylaldehyde and a catalyst A small amount of p-toluenesulfonic acid was added, and the mixture was stirred under reflux for 12 hours. After cooling to room temperature, the catalyst was removed by filtration, and the mixture was concentrated under reduced pressure. The residue was purified by recrystallization using hexane to obtain 2.80 g (yield 73%) of a yellow solid represented by the following formula (c).

0.800 g (2.30 mmol) of the compound (c) obtained in the above Synthesis Example and anhydrous diethyl ether were charged into a 100 ml reactor sufficiently purged with nitrogen, and cooled to -78 ° C. To this, 1.45 ml of n-butyllithium (n-hexane solution, 1.59 M, 2.31 mmol) was added dropwise over 5 minutes, and then the temperature was slowly raised to room temperature. After stirring at room temperature for 2.5 hours, the mixture was gradually added to a slurry of 1.15 ml (1.00 M, 1.15 mmol) of a titanium tetrachloride toluene solution cooled to -78 ° C in anhydrous diethyl ether. After the addition, the mixture was stirred for 18 hours while slowly warming to room temperature. The slurry was concentrated under reduced pressure, 30 ml of methylene chloride was added, the slurry was filtered, and the filtrate was concentrated. A small amount of dichloromethane was added to the residue to dissolve it, n-hexane was added with stirring, and the precipitated solid was collected and washed with n-hexane. The obtained solid was dried under reduced pressure to obtain 0.511 g (55% yield) of a yellow compound represented by the following formula (3). In addition, the result of FD-mass spectrometry of the transition metal compound (3) was 810 (M ⁺ ).

[ Synthesis Example 4 ]
To a 300 ml reactor purged with nitrogen were charged 55.2 g (655 mmol) of 3,4-dihydro-2H-pyran and 60 ml of methylene chloride, and 0.2 ml of concentrated hydrochloric acid was added. A solution of 42.1 g (260 mmol) of trifluoromethylphenol in 80 ml of methylene chloride was added dropwise. After the dropwise addition, the mixture was stirred at room temperature for 10 hours, and then the reaction solution was washed with an aqueous sodium hydrogen carbonate solution, and the solvent was removed to obtain a pale yellow oil (d1). 41.78 g (360 mmol) of tetramethylethylenediamine was charged into a 1-liter reactor sufficiently purged with nitrogen, and 231.6 ml of n-butyllithium (n-hexane solution, 1.58N, 366 mmol) was added while maintaining the temperature at -20 ° C. It was added dropwise over 10 minutes. To this solution, a 60 ml hexane solution of a pale yellow oil (d1) was added dropwise over 40 minutes. After stirring was continued for 3 hours, 27.8 ml (360 mmol) of dimethylformamide was added dropwise over 10 minutes. After returning the reaction solution to room temperature, a mixed solution of 20 ml of concentrated hydrochloric acid and 90 ml of water was added, and the mixture was stirred for 10 hours. After removing the aqueous layer, 100 ml of tetrahydrofuran and 1 ml of concentrated hydrochloric acid were added to the organic layer, and the mixture was further stirred at room temperature for 10 hours. The solvent was removed, and the residue was purified with a silica gel column to obtain 25.8 g (136 mmol, yield: 52%) of 3-trifluoromethylsalicylaldehyde represented by the following formula as white crystals.

  In a 100 ml reactor sufficiently purged with nitrogen, 10 ml of toluene, 2.52 g (11.0 mmol) of 3,5-bis (trifluoromethyl) aniline, 1.90 g of 3-trifluoromethylsalicylaldehyde (10.0 mmol), and a catalyst , A small amount of p-toluenesulfonic acid was charged, and stirring was continued for 20 hours while refluxing. The reaction solution was concentrated under reduced pressure, and recrystallized from hexane to obtain 3.61 g (yield 90%) of a compound of yellow powdery crystal represented by the following formula (d).

  In a 100 ml reactor sufficiently purged with nitrogen, 2.01 g (5.00 mmol) of the compound (d) obtained above and 20 ml of anhydrous diethyl ether were charged, cooled to -78 ° C, and stirred. To this, 3.16 ml of n-butyllithium (n-hexane solution, 1.58 M, 5.00 mmol) was added dropwise over 5 minutes, and then the temperature was slowly raised to room temperature. After stirring at room temperature for 3 hours, the mixture was gradually added to an ether slurry of 2.50 ml of titanium tetrachloride (toluene solution, 1M, 2.50 mmol) cooled to -78 ° C. After the addition, the temperature was slowly raised to room temperature. After replacing the solvent of the reaction solution with anhydrous dichloromethane and removing the precipitated salt, the solid precipitated from the obtained filtrate was collected, and washed with diethyl ether and then with n-hexane. The obtained solid was dried under reduced pressure to obtain 0.28 g (yield: 12%) of a red compound represented by the following formula (4). In addition, the result of FD-mass spectrometry of the transition metal compound (4) was 918 (M +).

[Synthesis Example 5]
In a 100 ml reactor which was sufficiently purged with nitrogen, 50 ml of toluene, 2.73 g (11.9 mmol) of 3,5-bis (trifluoromethyl) aniline, and 3-i-propylsalicylaldehyde (as described in JP-A-11-315109). Synthesis) 1.30 g (7.92 mmol) and a small amount of p-toluenesulfonic acid as a catalyst were added, and the mixture was refluxed and stirred for 12 hours. After cooling to room temperature, the catalyst was removed by filtration, and the mixture was concentrated under reduced pressure. The residue was washed with hexane to obtain 2.35 g (yield 79%) of a yellow solid represented by the following formula (e).

Into a 100 ml reactor sufficiently purged with nitrogen, 1.00 g (2.66 mmol) of the compound (e) obtained in the above Synthesis Example and anhydrous diethyl ether were charged and cooled to -78 ° C. To this, 1.67 ml of n-butyllithium (n-hexane solution, 1.59 M, 2.66 mmol) was added dropwise over 5 minutes, and then the temperature was slowly raised to room temperature. After stirring at room temperature for 2.5 hours, the mixture was gradually added to a slurry of 1.33 ml (1.00 M, 1.33 mmol) of a titanium tetrachloride toluene solution cooled to -78 ° C in anhydrous diethyl ether. After the addition, the mixture was stirred for 18 hours while slowly warming to room temperature. The slurry was concentrated under reduced pressure, 30 ml of methylene chloride was added, the slurry was filtered, and the filtrate was concentrated. A small amount of dichloromethane was added to the residue to dissolve it, n-hexane was added with stirring, and the precipitated solid was collected and washed with n-hexane. The obtained solid was dried under reduced pressure to obtain 0.768 g (yield 67%) of a yellow compound represented by the following formula (5). In addition, the result of FD-mass spectrometry of the transition metal compound (5) was 866 (M ⁺ ).

[Synthesis Example 6]
In a well dried 500 ml reactor, 15.0 g (95.0 mmol) of 3,5-difluorophenylboronic acid, 11.5 g (52.2 mmol) of 2-iodophenol, 1.43 g of tetrakis (triphenylphosphine) palladium. (1.24 mmol), 17.3 g (81.5 mmol) of potassium phosphate, and 300 ml of dimethylformamide were charged and heated at 120 ° C. for 6 hours under a nitrogen atmosphere. After allowing to cool, 800 ml of toluene and 400 ml of water were added, and the organic layer was separated, followed by washing with 200 ml of saturated saline. The organic layer was dried over magnesium sulfate, and the reddish brown oil obtained by concentration was purified by silica gel column chromatography to obtain 8.1 g (yield: 75%) of a yellow solid represented by the following formula (f1).

  In a 500 ml reactor sufficiently purged with nitrogen, 14.20 ml of ethyl magnesium bromide (3.0 M, 42.6 mmol in diethyl ether) and 5 ml of tetrahydrofuran were charged, and 10.2 g of the compound (f1) obtained above in 20 ml of tetrahydrofuran was charged. The solution was added dropwise under ice cooling. After completion of the dropwise addition, 100 ml of toluene, 8.40 ml of triethylamine and 3.91 g of paraformaldehyde were added, and the mixture was stirred at 80 ° C. for 20 minutes. After allowing to cool to room temperature, a mixed solution of 10 ml of hydrochloric acid and 10 ml of water was added, and the mixture was further stirred at room temperature for 10 minutes. The reaction solution was separated into an organic layer and an aqueous layer, and the organic layer was washed once with 50 ml of a saturated aqueous solution of sodium hydrogen carbonate and 50 ml of a saturated aqueous solution of sodium chloride, and dried by adding magnesium sulfate. After magnesium sulfate was filtered off and the solution was concentrated, the residue was purified using a silica gel column to obtain 7.6 g (yield: 65%) of a yellow solid represented by the following formula (f2).

  In a 100 ml reactor sufficiently purged with nitrogen, 20 ml of toluene, 1.205 g (4.29 mmol) of the compound (f2) obtained above, and 2.012 g (8.78 mmol) of 3,5-bis (trifluoromethyl) aniline And a small amount of p-toluenesulfonic acid was added as a catalyst, and the mixture was stirred at 110 ° C for 14 hours. After allowing to cool to room temperature, purification was performed by silica gel column chromatography to obtain 2.06 g (yield 98%) of a yellow solid represented by the following formula (f).

1.843 g (3.74 mmol) of the compound (f) obtained in the above Synthesis Example and 30 ml of anhydrous diethyl ether were charged into a 100 ml reactor sufficiently purged with nitrogen, and cooled to -78 ° C. To this, 2.50 ml of n-butyllithium (n-hexane solution, 1.58 M, 3.95 mmol) was added dropwise over 5 minutes, and then the temperature was slowly raised to room temperature. After stirring at room temperature for 2.5 hours, the mixture was gradually added to a slurry of 1.87 ml (1.00 M, 1.87 mmol) of a titanium tetrachloride toluene solution cooled to -78 ° C in 20 ml of anhydrous diethyl ether. After the addition, the mixture was stirred for 17 hours while slowly raising the temperature to room temperature. The slurry was concentrated under reduced pressure, 30 ml of methylene chloride was added, the slurry was filtered, and the filtrate was concentrated. 15 ml of ether was added to the residue, and the precipitated solid was collected and washed with n-hexane. The obtained solid was dried under reduced pressure to obtain 1.00 g (yield 49%) of a reddish brown compound represented by the following formula (6). In addition, the result of FD-mass spectrometry of the transition metal compound (6) was 1006 (M ⁺ ).

  The transition metal compounds (7) to (9) were synthesized according to the synthesis method described in JP-A-11-315109, which has already been published.

[ Example 1 ]
235 ml of cyclohexane was charged into a 500 ml-volume glass autoclave sufficiently purged with nitrogen, and the liquid phase and the gas phase were saturated with ethylene at a flow rate of 50 l / hr. Thereafter, tetracyclo 2ml of the autoclave [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene (hereinafter abbreviated as "TD".), 1.25 mmol of methylaluminoxane and (MAO) with an aluminum atom in terms Subsequently, 0.001 mmol of the transition metal compound (1) was added to initiate polymerization. After reacting at 25 ° C. and normal pressure for 10 minutes in an ethylene gas atmosphere, the polymerization was stopped by adding a small amount of isobutyl alcohol. After completion of the polymerization, the reaction product was poured into a mixed solvent of acetone / methanol (500 ml each) to which 5 ml of concentrated hydrochloric acid was added, and the entire amount of the polymer was precipitated. After stirring, the mixture was filtered with a glass filter. After the polymer was dried under reduced pressure at 130 ° C. for 10 hours, an ethylene / TD copolymer was obtained. The results are shown in Table 1 below.

(1) Molecular weight of the obtained polymer GPC measurement was performed under the following conditions.

Equipment: GPC Alliance 2000 (Waters)
Column: TSKgel GMH6-HT x 2 + TSKgel GMH6-HTL x 2
(Total 30cm x 4, Tosoh Corporation)
Detector: Differential refractometer Measurement solvent: o-dichlorobenzene Measurement flow rate: 1 mL / min
Measurement temperature: 140 ° C
Sample injection volume: 500 μL
Standard sample: monodisperse polystyrene x 16 (Tosoh Corporation)
The weight average molecular weight (Mw) was measured.

(2) Monomer composition ratio in the obtained polymer The correlation formula between the cyclic olefin content of the polymer by ¹³ C-NMR analysis and the Tg by DSC (differential scanning calorimeter) measurement was determined in advance. The cyclic olefin content was calculated from the Tg by DSC measurement using this correlation equation.
Measurement of cyclic olefin content by ¹³ C-NMR:
Equipment: JEOL EX400
Frequency: 100.4MHz
Quantitation of NB:
NB (mol%) = 1/3 × [2 × (C7) + (C1, C4) + (C2, C3)] / (C5, C6 & ethylene) × 100
Here, the value in parentheses indicates the peak intensity. Respectively,
C2,3 44-46.5ppm
C1,4 38.5-41ppm
C7 30.5-32ppm
C5,6 & ethylene 27-30ppm
It is.
The number of C (carbon atom) is as shown in the following figure.

Quantification of TD TD (mol%) = (TD) / ((TD) + (ethylene)) × 100
here,
(TD) = ((3) + (c)) / 2
(Ethylene) = [(29.5-32.5 ppm)-(5)-(e)-(f)] / 2
= [(29.5-32.5 ppm)-(TD)-(c) / 2]) / 2
Here, the value in parentheses indicates the peak intensity. Respectively
C (3) 51.0ppm
C (c) 54.5ppm
The number of C (carbon atom) is as shown in the following figure.

Measurement of Tg: The Tg of the obtained polymer was determined by performing a DSC measurement under the following conditions.
Equipment: Shimadzu Corporation DSC-60
Measurement conditions: The sample held at 300 ° C. for 5 minutes was rapidly cooled to 0 ° C., and then Tg was determined in the course of heating to 250 ° C. at a rate of 20 ° C./min.

[Examples 2 to 17]
Α-olefin / cyclic olefin copolymerization was carried out using the transition metal compounds (2) to (6) under the conditions shown in Table 1. The results are summarized in Table 1. In Table 1, NB represents bicyclo [2.2.1] hept-2-ene. In each case, an α-olefin / cyclic olefin copolymer having a high cyclic olefin content was obtained.

[Comparative Examples 1 to 5]
Α-olefin / cyclic olefin copolymerization was carried out using the transition metal compounds (7) to (9) under the conditions shown in Table 2. The results are summarized in Table 2. In Table 2, NB represents bicyclo [2.2.1] hept-2-ene. In each case, no polymer was obtained, or even a very small amount was obtained.

  Polyolefin is an environmentally friendly clean material composed of carbon and hydrogen, and has excellent workability and physical properties. Due to these characteristics, they are used in a wide range of fields, such as automobiles, electric equipment parts, food packaging, beverage / cosmetic / medical containers, civil engineering, and agricultural materials. The novel olefin polymerization catalyst and the polymerization using the transition metal compound in the present invention use a catalyst exhibiting excellent copolymerizability and high activity. Products that meet the requirements for polyolefins can be produced with high efficiency.

Claims (2)

(A) a linear or branched α-olefin having 2 to 30 carbon atoms,
(B) The following general formula (I)

(In the formula (I), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, R ^{61 to} R ⁷⁸ and R ^a1 and R ^b1 are the same or different. A hydrogen atom, a halogen atom or a hydrocarbon group; R ^{75 to} R ⁷⁸ may be combined with each other to form a monocyclic or polycyclic ring; it may have a double bond, or may form a R ⁷⁵ and between R ^76, or alkylidene group and R ⁷⁷ and R ^78.)
A cyclic olefin represented by the following general formula (II)

(In the formula (II), x and d are 0 or an integer of 1 or more; y and z are 0, 1 or 2; R ^{81 to} R ⁹⁹ may be the same or different from each other; , A halogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group or an alkoxy group, wherein the carbon atom to which R ⁸⁹ and R ⁹⁰ are bonded and the carbon atom to which R ⁹³ is bonded or R ⁹¹ are bonded. May be bonded directly or via an alkylene group having 1 to 3 carbon atoms, and when y = z = 0, R ⁹⁵ and R ⁹² or R ⁹⁵ and R ⁹⁹ They may combine with each other to form a monocyclic or polycyclic aromatic ring.)
And a cyclic olefin represented by the following general formula (III)

(In the formula (III), R ¹⁰⁰ and R ¹⁰¹ may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and f is 1 ≦ f ≦ 18.)
And at least one cyclic olefin selected from the group consisting of cyclic olefins represented by
(C) a transition metal compound represented by the following general formula (IV),

(Wherein, M represents a transition metal atom belonging to Groups 4 to 5 of the periodic table, m represents an integer of 1 to 4, and R ¹ represents a fluorine atom or a fluorine-containing hydrocarbon group having 1 to 30 carbon atoms. And R ^{2 to} R ⁵ may be the same or different from each other, and represent a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group. , A phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, two or more of which may be connected to each other to form a ring, and R ⁶ is hydrogen, primary, or C1-C4 hydrocarbon groups consisting of only secondary carbons, C5 or more aliphatic hydrocarbon groups, aryl-substituted alkyl groups, monocyclic or bicyclic alicyclic hydrocarbon groups and aromatics And n represents a number that satisfies the valency of M. X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, Represents a silicon-containing group, a germanium-containing group, or a tin-containing group, and when n is 2 or more, a plurality of groups represented by X may be the same or different from each other; It may combine to form a ring.)
(D) (D-1) an organometallic compound,
(D-2) an organic aluminum oxy compound, and
(D-3) copolymerization in the presence of an olefin polymerization catalyst comprising at least one compound selected from compounds which form an ion pair by reacting with the transition metal compound (C). A method for producing an olefin / cyclic olefin copolymer. The α- olefin is ethylene, claim 1, wherein said cyclic olefin is bicyclo [2.2.1] hept-2-ene and / or tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3-dodecene A method for producing the olefin / cyclic olefin copolymer described in the above.