JP2011122145A - Olefin polymerization catalyst and method for producing olefin polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an olefin polymerization catalyst having high polymerization activity and high copolymerizability for an olefin to produce a polymer with a high molecular weight. <P>SOLUTION: The olefin polymerization catalyst includes a transition metal compound (A) represented by formula (I) (wherein M represents a transition metal atom of group 4-6 in a periodic table, m represents an integer of 1-4, n is a number satisfying a valence of M, X represents a hydrogen atom, a halogen atom or the like, R<SP>1</SP>represents a 6-30C substituted or unsubstituted aryl group, R<SP>2</SP>, R<SP>3</SP>, R<SP>4</SP>and R<SP>5</SP>represent a hydrogen atom, a halogen atom, a hydrocarbon group or the like, and R<SP>6</SP>represents an iodine atom or a bromine atom). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a novel olefin polymerization catalyst and an olefin polymerization method using the olefin polymerization catalyst.

  Conventionally, as a catalyst for producing an olefin polymer such as an ethylene polymer and an ethylene / α-olefin copolymer, a titanium catalyst composed of a titanium compound and an organoaluminum compound, and a vanadium compound and an organoaluminum compound. Vanadium-based catalysts are known.

  Further, a catalyst comprising a metallocene compound such as zirconocene and an organoaluminum oxy compound (aluminoxane) is known as a catalyst capable of producing an olefin polymer with high polymerization activity.

  Further, as a new olefin polymerization catalyst, the present applicant has proposed a transition metal compound having a salicylaldoimine ligand in Japanese Patent Application Laid-Open Nos. 11-315109 and 2006-233063. The polymerization catalyst described in JP-A-11-315109 has been shown to exhibit high olefin polymerization activity, but polymerization activity and copolymerizability (comonomer uptake ability when two or more olefins are polymerized) ) Needed further improvement. The catalyst described in Japanese Patent Application Laid-Open No. 2006-233063 has improved polymerization activity and copolymerizability when polymerizing two or more types of olefins, but the resulting polymer has a low molecular weight and is not sufficient.

  On the other hand, as a catalyst having a high polymerization activity and copolymerizability when polymerizing two or more olefins, and a polymer having a high molecular weight to some extent, the present applicant has disclosed salicylaldoimine in Japanese Patent Application Laid-Open No. 2007-297453. A catalyst for polymerization in which a halogen atom is introduced at a specific site of a ligand and a polymerization method using these are proposed. Examples of introducing a halogen atom at a specific site of a salicylaldoimine ligand as in this example have been reported in Non-Patent Documents 1 to 11 and Patent Documents 4 to 8, but both complexes are (1) on imine (2) The substituent on the imine contains an oxygen atom, (3) The substituent on the imine is bonded to another ligand. (4) The polymerization activity is low because the introduction amount and type of halogen are inappropriate and the effect is not sufficiently exhibited.

  Under such circumstances, there has been a strong demand for an olefin polymerization catalyst and an olefin polymerization method that exhibit high activity and high copolymerizability and give a high molecular weight polymer.

Japanese Patent Laid-Open No. 11-315109 JP 2006-233063 A JP 2007-297453 A Chinese Patent No. 1995044 Specification International Publication No. 2009/076152 Pamphlet European Patent Application Publication No. 1834970 European Patent Application No. 874,005 Chinese Patent No. 10125265

J.Mol.Cat.A 2009, 297, 9 J. Am. Chem. Soc. 2008, 130, 4968 Russian.Chem.Bull.2006, 55, 179 Organometallics 2007, 26, 3690 J.Mol.Cat.A 2006, 258, 284 Macromolecules 2006, 39, 7812 Macromol. Rapid Commun. 2006, 27, 1009 Polymer 2006, 47, 4505 J. Organomet. Chem. 2006, 691, 2945 Macromol. Symp. 2006, 236, 111 Organometallics 2008, 27, 3840

  An object of the present invention has been made in view of the prior art as described above, and provides an olefin polymerization catalyst for producing a polymer having a high molecular weight and a high polymerization activity and high copolymerizability. Is to provide. Furthermore, it aims at providing the polymerization method of the olefin using this olefin polymerization catalyst.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have introduced a suitable number and type of substituents at specific sites of the salicylaldoimine ligand, thereby achieving high polymerization activity and high copolymerization for olefins. It has been found that the catalyst can be an olefin polymerization catalyst for producing a polymer having a high comonomer content and a high molecular weight.

  That is, the catalyst for olefin polymerization according to the present invention comprises a transition metal compound (A) represented by the following general formula (I).

（一般式（Ｉ）中、Ｍは周期表第４〜６族の遷移金属原子を示し、ｍは、１〜４の整数を示し、Ｒ¹は炭素原子数６〜３０の置換または無置換のアリール基を示し、Ｒ²，Ｒ³およびＲ⁵は、水素原子、ハロゲン原子、炭化水素基、ヘテロ環式化合物残基、酸素含有基、窒素含有基、ホウ素含有基、イオウ含有基、リン含有基、ケイ素含有基、ゲルマニウム含有基、およびスズ含有基から選ばれ、互いに同一でも異なっていてもよく、これらのうちの２個以上が互いに連結して環を形成していてもよく、Ｒ⁴は、水素原子、ハロゲン原子、炭化水素基、酸素含有基、および窒素含有基から選ばれ、Ｒ⁶はヨウ素原子または臭素原子であり、ｎはＭの価数を満たす数であり、Ｘは、水素原子、ハロゲン原子、炭化水素基、酸素含有基、イオウ含有基、窒素含有基、ホウ素含有基、アルミニウム含有基、リン含有基、ハロゲン含有基、ヘテロ環式化合物残基、ケイ素含有基、ゲルマニウム含有基、またはスズ含有基を示し、ｎが２以上の場合は、Ｘで示される複数の基は互いに同一でも異なっていてもよく、またＸで示される複数の基は互いに結合して環を形成してもよい。）

(In General Formula (I), M represents a transition metal atom of Groups 4 to 6 of the periodic table, m represents an integer of 1 to 4, and R ¹ is a substituted or unsubstituted group having 6 to 30 carbon atoms. Represents an aryl group, R ² , R ³ and R ⁵ are hydrogen atom, halogen atom, hydrocarbon group, heterocyclic compound residue, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing group, a silicon-containing group, a germanium-containing group, and is selected from tin-containing group, may be the same or different from each other, may form a ring more than is bonded to each other of these, R ⁴ Is selected from a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, and a nitrogen-containing group, R ⁶ is an iodine atom or a bromine atom, n is a number that satisfies the valence of M, and X is Hydrogen atom, halogen atom, hydrocarbon group, oxygen-containing group, 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, a silicon-containing group, a germanium-containing group, or a tin-containing group, and when n is 2 or more And a plurality of groups represented by X may be the same or different from each other, and a plurality of groups represented by X may be bonded to each other to form a ring.)

In the transition metal compound (A) represented by the general formula (I), R ⁴ is preferably a bromine atom or an iodine atom.

In the transition metal compound (A) represented by the general formula (I), R ¹ is preferably an alkyl-substituted aryl group having 7 to 30 carbon atoms.

The alkyl-substituted aryl group for R ¹ is tolyl, iso-propylphenyl, t-butylphenyl, dimethylphenyl, di-t-butylphenyl, benzylphenyl, cumylphenyl, tritylphenyl, n-octylphenyl, n-dodecylphenyl, More preferably, it is selected from trifluoromethylphenyl and di (trifluoromethyl) phenyl.

  Furthermore, in the olefin polymerization catalyst of the present invention, in the transition metal compound (A) represented by the general formula (I), M is preferably a transition metal atom of Group 4 of the periodic table, and M is a titanium atom. More preferably it is.

  The olefin polymerization catalyst of the present invention comprises a transition metal compound (A) represented by the general formula (I), (B) (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and ( B-3) It preferably comprises at least one compound selected from compounds that react with the transition metal compound (A) to form ion pairs.

The olefin polymerization method of the present invention is characterized in that at least one olefin is polymerized in the presence of the olefin polymerization catalyst as described above.
In the present specification, the term “polymerization” is sometimes used in the meaning including not only homopolymerization but also copolymerization, and the term “polymer” refers not only to homopolymer but also to copolymerization. It may be used in the meaning that also includes coalescence.

  The olefin polymerization catalyst containing a transition metal compound (A) having a bromine atom or iodine atom introduced into a specific site of a salicylaldoimine ligand according to the present invention exhibits high polymerization activity when polymerizing a single olefin. In addition, even when two or more olefins are polymerized, the polymer exhibits high polymerization activity and good copolymerizability, and the resulting polymer has a high molecular weight.

In the transition metal compound represented by the above general formula (I), the effect is (1) improvement in activity due to an electronic effect of a halogen atom (bromine atom or iodine atom), and (2) a position near the polymerization active point. Due to improvement of co-monomer coordination ability due to moderate bulk height of halogen atom (bromine atom or iodine atom), and (3) improvement of activity and molecular weight by having substituents of appropriate size and shape in R ¹ I think that.

  Hereinafter, the olefin polymerization catalyst and the olefin polymerization method in the present invention will be specifically described.

[Olefin polymerization catalyst]
The olefin polymerization catalyst according to the present invention comprises (A) a transition metal compound represented by the general formula (I), or (A) a transition metal compound represented by the general formula (I), and (B) ( From B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) at least one compound selected from compounds that react with a transition metal compound (A) to form an ion pair. Is formed. Hereinafter, each component will be described in detail.

<(A) Transition metal compound>
The (A) transition metal compound constituting the olefin polymerization catalyst used in the present invention is a compound represented by the following general formula (I).

一般式（Ｉ）において、Ｎ……Ｍは、一般的には配位していることを示すが、本発明においては配位していてもしていなくてもよい。

In the general formula (I), N... M generally indicates coordination, but may or may not be coordinated in the present invention.

  In the general formula (I), M represents a transition metal of Groups 4 to 6 in the periodic table, specifically, titanium atom, zirconium atom, hafnium atom, vanadium atom, niobium atom, tantalum atom, chromium atom, molybdenum atom. Or a tungsten atom, preferably a transition metal atom of Group 4 of the periodic table, specifically a titanium atom, a zirconium atom or a hafnium atom, more preferably a titanium atom.

m shows the integer of 1-4, Preferably it is 1-2, Especially preferably, it is 2.
R ² , R ³ , and R ⁵ are 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, and a silicon-containing group. , A germanium-containing group, and a tin-containing group, which may be the same as or different from each other.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine.
Examples of the hydrocarbon group include 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, n-hexyl, and n-heptyl. Preferably a linear or branched alkyl group having 1 to 20; a linear or branched alkenyl group having 2 to 30, preferably 2 to 20, carbon atoms such as vinyl, allyl, isopropenyl, etc .; ethynyl, A linear or branched alkynyl group having 2 to 30, preferably 2 to 20 carbon atoms such as propargyl; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, cycloheptyl, cyclooctyl, adamantyl, norbornyl, 3-30 carbon atoms, such as tetracyclododecyl, preferably 3 A cyclic unsaturated hydrocarbon group having 5 to 30 carbon atoms such as cyclopentadienyl, indenyl and fluorenyl; 6 to 30 carbon atoms such as phenyl, naphthyl, phenanthryl and anthracenyl, preferably 6-20 aryl groups; alkyl-substituted aryl groups such as tolyl, iso-propylphenyl, t-butylphenyl, dimethylphenyl, di-t-butylphenyl; aryl group-substituted aryl groups such as biphenyl and terphenyl .

  The hydrocarbon group may have a hydrogen atom substituted with halogen, for example, monotrifluoromethyl, ditrifluoromethyl, monofluorophenyl, difluorophenyl, trifluorophenyl, pentafluorophenyl, chlorophenyl, trifluoromethylphenyl A halogenated alkyl group or a halogenated aryl group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, such as ditrifluoromethylphenyl.

  The hydrocarbon group may be substituted with other hydrocarbon groups, and examples thereof include aryl-substituted alkyl groups such as benzyl, cumyl, trityl, and tri (4-methylphenyl) methyl.

  Further, the hydrocarbon group is a heterocyclic compound residue; oxygen such as alkoxy group, aryloxy group, ester group, ether group, acyl group, carboxyl group, carbonate group, hydroxy group, peroxy group, carboxylic acid anhydride group, etc. 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, amino group and ammonium salt Nitrogen-containing groups such as those; boron-containing groups such as alkyl-substituted boron, aryl-substituted boron, boron halide, alkyl-substituted boron halide; mercapto group, thioester group, dithioester group, alkylthio group, arylthio group, thioacyl group , Thioether group, thiocyanate group, isothia Sulfur-containing groups such as acid ester groups, sulfone ester groups, sulfonamido groups, thiocarboxyl groups, dithiocarboxyl groups, sulfo groups, sulfonyl groups, sulfinyl groups, sulfenyl groups, sulfonate groups, sulfinate groups; phosphorus-containing groups; silicon-containing groups A group; a germanium-containing group; or a tin-containing group.

  Examples of the hydrocarbon group include 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, neopentyl, n-hexyl, and n-heptyl. , Preferably a linear or branched alkyl group having 1 to 20 carbon atoms such as cyclopropyl, cyclobutyl, cyclohexyl, 2-methylcyclohexyl, cycloheptyl, cyclooctyl, adamantyl, norbornyl, tetracyclododecyl, etc. 30 or preferably a cycloalkyl group having 3 to 20 carbon atoms; aryl groups having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms such as phenyl, naphthyl, phenanthryl, anthracenyl, etc .; 30, preferably 1-20 alkyl or alkoxy groups A substituted aryl group substituted with 1 to 9 substituents such as an aryl group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, or an aryloxy group is preferable.

  Examples of the heterocyclic compound residue include cyclic groups containing 1 to 5 heteroatoms, and examples of the heteroatom include an oxygen atom, a nitrogen atom, an atom, a phosphorus atom, and a boron atom. Examples of the ring include 4 to 7-membered monocyclic and polycyclic rings, preferably 5 to 6-membered monocyclic and polycyclic rings. Specifically, residues of nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline and triazine, residues of oxygen-containing compounds such as furan and pyran, residues of sulfur-containing compounds such as thiophene, etc. Examples of the group include a group further substituted with a substituent such as an alkyl group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, and an alkoxy group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.

  Examples of the oxygen-containing group include groups containing 1 to 5 oxygen atoms, specifically, alkoxy groups such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy and the like. Aryloxy groups such as phenoxy, 2,6-dimethylphenoxy, 2,4,6-trimethylphenoxy and naphthoxy; ester groups such as acetyloxy, benzoyloxy, methoxycarbonyl, phenoxycarbonyl and p-chlorophenoxycarbonyl; ether groups; Examples include acyl groups such as formyl group, acetyl group, benzoyl group, p-chlorobenzoyl group and p-methoxybenzoyl group; carboxyl group; carbonate group; hydroxy group; peroxy group; carboxylic anhydride group. Among these, an alkoxy group, an aryloxy group, an acyl group, an ester group, and the like are preferable in terms of easy synthesis of the transition metal compound. When the oxygen-containing group contains a carbon atom, the number of carbon atoms is preferably in the range of 1 to 30, preferably 1 to 20.

  Examples of the nitrogen-containing group include groups containing 1 to 5 nitrogen atoms. Specifically, alkyl groups such as methylamino, dimethylamino, diethylamino, dipropylamino, ethylmethylamino, dibutylamino, and dicyclohexylamino are used. Amino group; arylamino group or alkylarylamino group such as phenylamino, diphenylamino, ditolylamino, dinaphthylamino, methylphenylamino; imino group such as methylimino, ethylimino, propylimino, butylimino, phenylimino; acetamide, N-methyl Amido groups such as acetamide and N-methylbenzamide; Imido groups such as acetimide and benzimide; Hydrazino group; Hydrazono group; Nitro group; Nitroso group; Cyano group; Isocyano group; Cyanate ester group; Jinomoto; diazo groups; amino groups and the like and was the ammonium salt. Of these, an amino group, an imino group, an amide group, an imide group, a nitro group, and a cyano group are preferable in terms of easy synthesis of the transition metal compound. In addition, when a nitrogen-containing group contains a carbon atom, it is desirable that the number of carbon atoms is in the range of 1 to 30, preferably 1 to 20.

  Examples of the nitrogen-containing group include alkylamino groups such as methylamino, dimethylamino, diethylamino, dipropylamino, ethylmethylamino, dibutylamino, and dicyclohexylamino; aryls such as diphenylamino, ditolylamino, dinaphthylamino, and methylphenylamino An amino group or an alkylarylamino group; a nitro group and the like are preferable.

Examples of the boron-containing group include groups containing 1 to 5 boron atoms. Specifically, (Et) ₂ B-, (iPr) ₂ B-, (iBu) ₂ B-, (nC Alkyl-substituted boron such as ₅ H ₁₁ ) ₂ B-, C ₈ H ₁₄ B- (9-borabicyclononyl group); aryl-substituted boron such as (C ₆ H ₅ ) ₂ B-; halogenation such as BCl ₂ — Boron; groups such as alkyl-substituted boron halides such as (Et) BCl- and (iBu) BCl-. Here, Et represents an ethyl group, iPr represents an isopropyl group, and iBu represents an isobutyl group.

  Examples of the sulfur-containing group include groups containing 1 to 5 sulfur atoms. Specifically, mercapto groups; thioester groups such as acetylthio, benzoylthio, methylthiocarbonyl, and phenylthiocarbonyl; dithioester groups; Alkylthio groups such as ethylthio; arylthio groups such as phenylthio, methylphenylthio and naphthylthio; thioacyl groups; thioether groups; thiocyanate groups; isothiocyanate groups; sulfones such as methyl sulfonate, ethyl sulfonate and phenyl sulfonate Group; sulfonamide group such as phenylsulfonamide, N-methylsulfonamide, N-methyl-p-toluenesulfonamide; thiocarboxyl group; dithiocarboxyl group; sulfo group; sulfonyl group; Group; a sulfenyl group; sulfonato group; and sulfinate groups. Among these, an alkylthio group, an arylthio group, a thioester group, a sulfone ester group, and a sulfonamide group are preferable in terms of easy synthesis of the transition metal compound. In addition, when a sulfur containing group contains a carbon atom, it is desirable that the number of carbon atoms is in the range of 1 to 30, preferably 1 to 20.

  Specific examples of the phosphorus-containing group include trialkylphosphine groups such as trimethylphosphine group, tributylphosphine group, and tricyclohexylphosphine group; triarylphosphine groups such as triphenylphosphine group and tolylphosphine group; methylphosphite group, Examples thereof include phosphite groups (phosphide groups) such as ethyl phosphite group and phenyl phosphite group; phosphonic acid groups; phosphinic acid groups.

  Specific examples of the silicon-containing group include a silyl group; a siloxy group; methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, diphenylmethylsilyl, triphenylsilyl, dimethylphenylsilyl, dimethyl-t-butylsilyl, dimethyl And hydrocarbon-substituted silyl groups such as (pentafluorophenyl) silyl; hydrocarbon-substituted siloxy groups such as trimethylsiloxy and the like. Of these, hydrocarbon-substituted silyl groups such as methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, dimethylphenylsilyl, and triphenylsilyl are preferred. Trimethylsilyl, triethylsilyl, triphenylsilyl, and dimethylphenylsilyl are particularly preferable in that a transition metal compound can be easily synthesized.

Examples of the germanium-containing group and the tin-containing group include those obtained by replacing silicon of the silicon-containing group with germanium and tin.
R ¹ is an aryl group having 6 to 30 carbon atoms, preferably 6 to 25 carbon atoms.

In R ¹ , examples of the aryl group include unsubstituted aryl groups such as phenyl, naphthyl, phenanthryl, and anthracenyl, and substituted aryl groups in which a substituent is bonded to the aryl group. Particularly preferred is a phenyl group or a substituted phenyl group.

Here, examples of the substituent for the aryl group include linear or branched alkyl groups having 1 to 24 carbon atoms, preferably 1 to 20 carbon atoms, and examples of the above R ² , R ³ and R ⁵ . The mentioned heterocyclic compound residues, nitrogen-containing groups, boron-containing groups, sulfur-containing groups, phosphorus-containing groups, silicon-containing groups, germanium-containing groups or tin-containing groups may be substituted.
Preferred examples of the alkyl group include a hydrocarbon group-substituted alkyl group in which the hydrogen atom of the alkyl group is substituted with another hydrocarbon group, and a halogen-substituted alkyl group in which the hydrogen atom of the alkyl group is substituted with a halogen atom. Included as

Specific examples of the alkyl group substituted for the aryl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, n-hexyl, n-octyl, n -Dodecyl and the like.
Specific examples of the hydrocarbon group-substituted alkyl group include benzyl, cumyl, trityl, tri (4-methylphenyl) methyl and the like.

Specific examples of the halogen-substituted alkyl group include monofluoromethyl, difluoromethyl, trifluoromethyl, pentafluorophenylmethyl and the like.
In addition, among the heterocyclic compound residues, nitrogen-containing groups, boron-containing groups, sulfur-containing groups, phosphorus-containing groups, silicon-containing groups, germanium-containing groups or tin-containing groups exemplified as substituents bonded to the aryl group More preferred are nitrogen-containing groups. Specific examples of the nitrogen-containing group include alkylamino group-substituted aryl groups such as methylamino group, dimethylamino group, diethylamino group, ethylmethylamino group, dipropylamino group, diphenylamino group, and dicyclohexylamino group, or aryl. Examples include amino group-substituted aryl groups.

Specific examples of preferred R ¹ include phenyl group, naphthyl group, phenanthryl group, anthracenyl group, tolyl group, iso-propylphenyl group, dimethylphenyl group, t-butylphenyl group, di-t-butylphenyl group, n-octylphenyl group, n-dodecylphenyl group, benzylphenyl group, cumylphenyl group, tritylphenyl group, tri (4-methylphenyl) methylphenyl group, trifluoromethylphenyl group, di (trifluoromethyl) phenyl group, dimethyl An aminophenyl group is mentioned. More preferably, a t-butylphenyl group, an n-octylphenyl group, an n-dodecylphenyl group, a tritylphenyl group, a trifluoromethylphenyl group, and a di (trifluoromethyl) phenyl group are exemplified. More preferred are t-butylphenyl group and tritylphenyl group.

R ⁴ is selected from a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group and a nitrogen-containing group, and may be the same as or different from each other.

Halogen atom R ^4, examples of the hydrocarbon group, an oxygen-containing group and nitrogen-containing groups can be the same as the examples listed above ^{R 2, R 3, R 5} .

R ⁴ is preferably a halogen atom.
The halogen atom for R ⁴ is preferably a bromine atom or an iodine atom. These halogen atoms are more preferably the same atom as the halogen atom of R ⁶ described later.

Two or more of these groups represented by R ^{1 to} R ⁵ may be bonded to each other to form a ring.
when m is 2 or greater, R ¹ to R ⁵ in which two or more groups may be linked of the groups indicated, but who R ¹ each other not linked is preferable.

R ⁶ represents a halogen atom. Preferred examples of the halogen atom include a bromine atom and an iodine atom.

When m is 2 or more, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ may be the same or different from each other.
n is a number satisfying the valence of M, specifically 0 to 5, preferably 1 to 4, more preferably an integer of 1 to 3, and particularly preferably 2.

  X is a hydrogen atom, halogen atom, hydrocarbon group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, heterocyclic compound residue, silicon-containing Group, germanium-containing group, or tin-containing group. When n is 2 or more, they may be the same or different.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine.
Examples of the hydrocarbon group include linear or branched alkyl having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, such as methyl, ethyl, propyl, butyl, hexyl, octyl, nonyl, dodecyl, and eicosyl. Groups; cycloalkyl groups having 3 to 30 carbon atoms such as cyclopentyl, cyclohexyl, norbornyl, adamantyl; alkenyl groups such as vinyl, propenyl, cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl, phenylpropyl; phenyl, tolyl , Aryl groups such as dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, naphthyl, methylnaphthyl, anthryl, phenanthryl and the like. These hydrocarbon groups also include halogenated hydrocarbons, specifically, groups in which at least one hydrogen of a hydrocarbon group having 1 to 30 carbon atoms is substituted with halogen.

  Among these, alkyl groups having 1 to 20 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, neopentyl, n-hexyl, etc .; cyclopentyl, cyclohexyl, norbornyl And cycloalkyl groups such as adamantyl; arylalkyl groups such as benzyl, phenylethyl and phenylpropyl are preferred.

  Examples of the oxygen-containing group include an oxy group; a peroxy group; a hydroxy group; a hydroperoxy group; an alkoxy group such as methoxy, ethoxy, propoxy, and butoxy; an aryloxy group such as phenoxy, methylphenoxy, dimethylphenoxy, and naphthoxy; Arylalkoxy groups such as ethoxy; acetoxy group; carbonyl group; acetylacetonato group (acac); oxo group and the like.

  Examples of the sulfur-containing group include methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, p-toluene sulfonate, trimethyl benzene sulfonate, triisobutyl benzene sulfonate, p- Sulfonate groups such as chlorobenzene sulfonate and pentafluorobenzene sulfonate; methyl sulfinate, phenyl sulfinate, benzyl sulfinate, p-toluene sulfinate, trimethylbenzene sulfinate, pentafluorobenzene sulfite Sulfinate groups such as nate; alkylthio group; arylthio group; sulfate group; sulfide group; polysulfide group; thiolate group and the like. However, the sulfur-containing group is not limited to these.

  Examples of the nitrogen-containing group include amino groups; alkylamino groups such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, and dicyclohexylamino; phenylamino, diphenylamino, ditolylamino, dinaphthylamino, methylphenylamino, and the like. Arylamino group or alkylarylamino group; trimethylamine, triethylamine, triphenylamine, N, N, N ′, N′-tetramethylethylenediamine (tmeda), N, N, N ′, N′-tetraphenylpropylenediamine (tppda And alkyl or arylamine groups such as However, the nitrogen-containing group is not limited to these.

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

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

  Specific examples of the phosphorus-containing group include trialkylphosphine groups such as trimethylphosphine group, tributylphosphine group, and tricyclohexylphosphine group; triarylphosphine groups such as triphenylphosphine group and tolylphosphine group; methylphosphite group, Examples include, but are not limited to, phosphite groups (phosphide groups) such as ethyl phosphite group and phenyl phosphite group; phosphonic acid groups; phosphinic acid groups.

Specific examples of the halogen-containing group include fluorine-containing groups such as PF ₆ and BF ₄ , chlorine-containing groups such as ClO ₄ and SbCl _6, and iodine-containing groups such as IO ₄ , but are not limited thereto. is not.

  Specific examples of the heterocyclic compound residues include residues such as nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline, and triazine, oxygen-containing compounds such as furan and pyran, sulfur-containing compounds such as thiophene, and the like. And a group obtained by further substituting a substituent such as an alkyl group or an alkoxy group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.

  Specific examples of the silicon-containing group include hydrocarbon-substituted silyls such as phenylsilyl, diphenylsilyl, trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, methyldiphenylsilyl, tolylsilyl, trinaphthylsilyl, and the like. A hydrocarbon-substituted silyl ether group such as trimethylsilyl ether; a silicon-substituted alkyl group such as trimethylsilylmethyl; a silicon-substituted aryl group such as trimethylsilylphenyl, and the like, but is not limited thereto.

Examples of the germanium-containing group and the tin-containing group include, but are not limited to, groups in which silicon of the silicon-containing group is replaced with germanium and tin.
In the general formula (I), when n is 2 or more, a plurality of groups represented by X may be the same or different from each other. A plurality of groups represented by X may be bonded to each other to form a ring.

  In the present invention, by using the transition metal compound represented by the general formula (I) as a catalyst component, it exhibits high polymerization activity when polymerizing a single olefin, and when polymerizing two or more olefins. The reason why the polymer exhibits high polymerization activity and good copolymerizability, and the polymer obtained has a high molecular weight is as follows.

By substituting a σ electron-withdrawing and π-electron donating atom near the metal that is the polymerization active site, that is, the position of R ⁶ , such as a bromine atom or an iodine atom, (1) Due to the mechanical effect, an appropriate coordination space necessary for copolymerization is generated around the central metal of the transition metal compound. (2) The balance between the cationic property of the central metal and the stability of the transition metal compound is good due to the electronic effect. It is considered that the effects of improving the copolymerization, improving the polymerization activity, and increasing the molecular weight are exhibited due to the reasons described above.

Moreover, it is considered that by using R ¹ as a substituent centered on an aryl group, the stability of the transition metal compound is improved, and the effects of improving the polymerization activity and increasing the molecular weight are exhibited.
Specific examples of the transition metal compound represented by (A) the above general formula (I) are shown below, but are not limited thereto.

本発明では、上記のような化合物において、チタン原子をジルコニウム原子、ハフニウム原子に置き換えた遷移金属化合物を用いることもできる。

In the present invention, a transition metal compound in which a titanium atom is replaced with a zirconium atom or a hafnium atom in the above compound can also be used.

The method for producing such a transition metal compound (A) is not particularly limited and can be produced, for example, as follows.
First, the ligand constituting the transition metal (A) is obtained by reacting a salicylaldehyde compound with a formula R ¹ —NH ₂ primary amine compound (R ¹ is as defined above). It is done. Specifically, both starting compounds are dissolved in a solvent. As the solvent, those generally used for such a reaction can be used, and among them, an alcohol solvent such as methanol and ethanol, or a hydrocarbon solvent such as toluene is preferable. Next, when the mixture is stirred at room temperature to reflux for about 1 to 48 hours, the corresponding ligand is obtained in good yield. When synthesizing the ligand compound, an acid catalyst such as formic acid, acetic acid, and paratoluenesulfonic acid may be used as a catalyst. Further, when molecular sieves, anhydrous magnesium sulfate or anhydrous sodium sulfate is used as a dehydrating agent, or while dehydrating with Dean Stark, the reaction proceeds effectively.

  Next, the corresponding transition metal compound can be synthesized by reacting the thus obtained ligand with the transition metal M-containing compound. 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 metal alkylate at a low temperature, Stir for about 1-48 hours at -78 ° C to room temperature or under reflux conditions. As the solvent, those commonly used for such a reaction can be used, and among them, polar solvents such as ether and tetrahydrofuran (THF), hydrocarbon solvents such as toluene and the like are preferably used. Examples of the base used in preparing the phenoxide salt include lithium salts such as n-butyllithium, metal salts such as sodium salts such as sodium hydride, triethylamine, and pyridine. This is not the case.

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 with another transition metal by a conventional method. For example, when one or more of R ^{1 to} R ⁵ are hydrogen, a substituent other than hydrogen can be introduced at any stage of the synthesis.
Moreover, the reaction solution of a ligand and a metal compound can also be used for polymerization as it is without isolating the transition metal compound.

<(B-1) Organometallic compound>
As (B-1) organometallic compound used in the present invention, specifically, an organoaluminum compound represented by the following general formula (B-1a), a periodic table represented by the general formula (B-1b) Examples include complex alkylated products of Group 1 metal and aluminum, and complex alkyl compounds of Group 1 metal and aluminum of the periodic table represented by Formula (B-1c).

R ^a _m Al (OR ^b ) _n H _p X _q (B-1a)
(In the general formula (B-1a), R ^a and R ^b may be the same or different from each other, and each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and X represents a halogen atom. Where m is 0 <m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is 0 ≦ q <3, and m + n + p + q = 3.
M ² AlR ^a ₄ (B-1b)
(In the general formula (B-1b), M ² represents Li, Na or K, and R ^a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms.)
R ^a R ^b M ³ (B-1c)
(In the general formula (B-1c), R ^a and R ^b may be the same or different from each other, and each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and M ³ represents Mg. , Zn or Cd.)

Examples of the organoaluminum compound represented by the general formula (B-1a) include the following compounds.
R ^a _m Al (OR ^b ) _3-m
(In the formula, R ^a and R ^b may be the same or different from each other, and each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and m is preferably 1.5 ≦ m ≦ An organoaluminum compound represented by the following formula:
R ^a _m AlX _3-m
(Wherein, R ^a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, and m is preferably 0 <m <3). Organoaluminum compounds,
R ^a _m AlH _3-m
(Wherein R ^a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and m is preferably 2 ≦ m <3),
R ^a _m Al (OR ^b ) _n Xq
(In the formula, R ^a and R ^b may be the same or different from each other, each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, and m represents 0. <M ≦ 3, n is a number 0 ≦ n <3, q is a number 0 ≦ q <3, and m + n + q = 3).

More specifically, as an organoaluminum compound belonging to the general formula (B-1a), trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, etc. Tri-n-alkylaluminum; triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylbutylaluminum, tri-2-methylpentylaluminum, tri-3 -Methylpentylaluminum, tri-4-methylpentylaluminum, tri-2-methylhexylaluminum, tri-3-methylhexyla Tri-branched alkylaluminums such as luminium and tri-2-ethylhexylaluminum; tricycloalkylaluminums such as tricyclohexylaluminum and tricyclooctylaluminum;
Triarylaluminums such as triphenylaluminum and tolylylaluminum
_{(I-C 4 H 9)} x Al y (C 5 H 10) z; dialkylaluminum hydrides such as diisobutylaluminum hydride (wherein, x, y, z are each a positive number, and z ≧ 2x.) Trialkenylaluminum such as triisoprenylaluminum represented by the above; alkylaluminum alkoxide such as isobutylaluminum methoxide, isobutylaluminum ethoxide, isobutylaluminum isopropoxide; dimethylaluminum methoxide, diethylaluminum ethoxide, dibutylaluminum butoxide, etc. Dialkylaluminum alkoxides; alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide;
Partially alkoxylated alkylaluminum having an average composition represented by R ^a _2.5 Al (OR ^b ) _0.5 or the like (wherein R ^a and R ^b may be the same or different from each other, and the number of carbon atoms Represents a hydrocarbon group of 1-15, preferably 1-4; diethylaluminum phenoxide, diethylaluminum (2,6-di-t-butyl-4-methylphenoxide), ethylaluminum bis (2,6-di) -T-butyl-4-methylphenoxide), diisobutylaluminum (2,6-di-t-butyl-4-methylphenoxide), isobutylaluminum bis (2,6-di-t-butyl-4-methylphenoxide), etc. Dialkylaluminum aryloxide; dimethylaluminum chloride, diethylaluminum chloride, dibutylal Dialkylaluminum halides such as nium chloride, diethylaluminum bromide, diisobutylaluminum chloride; alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide; ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide, etc. Partially halogenated alkylaluminums such as alkylaluminum dihalides; Dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride; Other partials such as alkylaluminum dihydrides such as ethylaluminum dihydride and propylaluminum dihydride Hydrogenated Al Le Aluminum; ethylaluminum ethoxy chloride, butyl aluminum butoxide cycloalkyl chloride, etc. partially alkoxylated and halogenated alkylaluminum such as ethylaluminum ethoxy bromide and the like.

A compound similar to (B-1a) can also be used in the present invention. Examples of such a compound include an organoaluminum compound in which two or more aluminum compounds are bonded via a nitrogen atom.
Specific examples of such a compound include (C ₂ H ₅ ) ₂ AlN (C ₂ H ₅ ) Al (C ₂ H ₅ ) ₂ .

Examples of the compound belonging to the general formula (B-1b) include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .
Examples of the compound belonging to the general formula (B-1c) include dimethyl magnesium, diethyl magnesium, dibutyl magnesium, butyl ethyl magnesium, dimethyl zinc, diethyl zinc, diphenyl zinc, di-n-propyl zinc, diisopropyl zinc, di-n- Examples thereof include butyl zinc, diisobutyl zinc, bis (pentafluorophenyl) zinc, dimethyl cadmium, diethyl cadmium and the like.

  In addition, examples of the organometallic compound (B-1) include methyl lithium, ethyl lithium, propyl lithium, butyl lithium, methyl magnesium bromide, methyl magnesium chloride, ethyl magnesium bromide, ethyl magnesium chloride, propyl magnesium bromide, propyl magnesium. Chloride, butyl magnesium bromide, butyl magnesium chloride, dimethyl magnesium, diethyl magnesium, dibutyl magnesium, butyl ethyl magnesium and the like can also be used.

In addition, a compound capable of forming the organoaluminum compound in the polymerization system, such as a combination of an aluminum halide and an alkyl lithium, or a combination of an aluminum halide and an alkyl magnesium, is used as the organometallic compound (B-1). It can also be used as
The above organometallic compound (B-1) is used individually by 1 type or in combination of 2 or more types.

<(B-2) Organoaluminum oxy compound>
The organoaluminum oxy compound (B-2) used in the present invention may be a conventionally known aluminoxane or a benzene-insoluble organoaluminum oxy compound as exemplified in JP-A-2-78687. May be. Specific examples of the organic aluminum oxy compound (B-2) include methylaluminoxane, ethylaluminoxane, and isobutylaluminoxane.

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

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

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

Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum is particularly preferable.
The organoaluminum compounds as described above are used singly or in combination of two or more.

  Solvents used for 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. , Cycloaliphatic hydrocarbons such as cyclohexane, cyclooctane and methylcyclopentane, petroleum fractions such as gasoline, kerosene and light oil or halides of the above aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons, especially chlorine And hydrocarbon solvents such as bromide and bromide. Furthermore, ethers such as ethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic hydrocarbons or aliphatic hydrocarbons are particularly preferable.

  The benzene-insoluble organoaluminum oxy compound used in the present invention has an Al component dissolved 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 that are insoluble or hardly soluble in benzene are preferred.

  Examples of the organoaluminum oxy compound (B-2) used in the present invention include an organoaluminum oxy compound containing boron represented by the following general formula.

一般式中、Ｒ³¹は炭素原子数が１〜１０の炭化水素基を示し、４つのＲ³²は互いに同一でも異なっていても良く、水素原子、ハロゲン原子、炭素原子数が１〜１０の炭化水素基を表す）。

In the general formula, R ³¹ represents a hydrocarbon group having 1 to 10 carbon atoms, and four R ³² may be the same or different from each other, and are a hydrogen atom, a halogen atom, or a carbon atom having 1 to 10 carbon atoms. Represents a hydrogen group).

The organoaluminum oxy compound containing boron represented by the general formula (VI) comprises an alkyl boronic acid represented by the following general formula (VII) and an organoaluminum compound) in an inert solvent under an inert gas atmosphere. In particular, it can be produced by reacting at a temperature of −80 ° C. to room temperature for 1 minute to 24 hours.
R ³¹ —B (OH) ₂ ... (VII) (wherein R ³¹ represents the same group as described above).

  Specific examples of the alkyl boronic acid represented by the general formula (VII) include methyl boronic acid, ethyl boronic acid, isopropyl boronic acid, n-propyl boronic acid, n-butyl boronic acid, isobutyl boronic acid, n-hexyl boron. Examples include acid, cyclohexyl boronic acid, phenyl boronic acid, 3,5-difluoroboronic acid, pentafluorophenyl boronic acid, 3,5-bis (trifluoromethyl) phenyl boronic acid, and the like. Among these, methyl boronic acid, n-butyl boronic acid, isobutyl boronic acid, 3,5-difluorophenyl boronic acid, and pentafluorophenyl boronic acid are preferable. These may be used alone or in combination of two or more.

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

As the organoaluminum compound, 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 organoaluminum oxy compounds (B-2) as described above are used singly or in combination of two or more.

<(B-3) Compound that reacts with transition metal compound (A) to form an ion pair>
As a compound (B-3) (hereinafter referred to as “ionized ionic compound”) which forms an ion pair by reacting with the transition metal compound (A) used in the present invention, JP-A-1-501950, Lewis acids described in Kaihei 1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, USP-5321106, etc. , Ionic compounds, borane compounds and carborane compounds. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned.

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

  Examples of the ionic compound include compounds represented by the following general formula (VIII).

（一般式（ＶＩＩＩ）中、Ｒ³³としては、Ｈ⁺、カルボニウムカチオン、オキソニウムカチオン、アンモニウムカチオン、ホスホニウムカチオン、シクロヘプチルトリエニルカチオン、または遷移金属を有するフェロセニウムカチオンであり、Ｒ³⁴〜Ｒ³⁷は、互いに同一でも異なっていてもよく、有機基、好ましくはアリール基または置換アリール基である。）

(In the formula (VIII), examples of R ^33, H ^+, a carbonium cation, ferrocenium cation having oxonium cation, ammonium cation, phosphonium cation, a cycloheptyltrienyl cation or a transition metal,, R ³⁴ to R ³⁷ may be the same or different from each other, 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 cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation, and tri (n-butyl) ammonium cation; N, N-dimethylanilinium cation; N, N-diethylanilinium cation, N, N-2,4,6-pentamethylanilinium cation, etc., N, N-dialkylanilinium cation; di (isopropyl) ammonium cation, dicyclohexylammonium cation, etc. dialkylammonium cation Etc.

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

R ³³ is preferably a carbonium cation, an ammonium cation or the like, and particularly preferably a triphenylcarbonium cation, an N, N-dimethylanilinium cation or an N, N-diethylanilinium cation.

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

  Specific examples of the trialkyl-substituted ammonium salt include triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron, and trimethylammonium tetra (p-tolyl). ) Boron, trimethylammonium tetra (o-tolyl) boron, tri (n-butyl) ammonium tetra (pentafluorophenyl) boron, tripropylammonium tetra (o, p-dimethylphenyl) boron, tri (n-butyl) ammonium tetra (M, m-dimethylphenyl) boron, tri (n-butyl) ammonium tetra (p-trifluoromethylphenyl) boron, tri (n-butyl) ammonium tetra (3,5-ditrifluoromethyl) Eniru) boron, tri (n- butyl) ammonium tetra (o-tolyl) and boron and the like.

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

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

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

（式中、Ｅｔはエチル基を示す。）

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

（式中、Ｅｔはエチル基を示す。）

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

  Specific examples of borane compounds that are examples of ionized ionic compounds (compound (B-3)) include decaborane; bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate. Bis [tri (n-butyl) ammonium] undecaborate, bis [tri (n-butyl) ammonium] dodecaborate, bis [tri (n-butyl) ammonium] decachlorodecaborate, bis [tri (n-butyl) ) Ammonium] salt of anion such as dodecachlorododecaborate; tri (n-butyl) ammonium bis (dodecahydridododecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (dodecahydride dodecaborate) ) Metals such as nickelate (III) Such as the salt of the run-anion, and the like.

Specific examples of the carborane compound that is an example of the ionized ionic compound (compound (B-3)) include 4-carbanonaborane, 1,3-dicarbanonarborane, 6,9-dicarbadecarborane, dodecahydride- 1-phenyl-1,3-dicarbanonaborane, dodecahydride-1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7, 8-dicarbaound decaborane, 2,7-dicarbound decaborane, undecahydride-7,8-dimethyl-7,8-dicarbound decaborane, dodecahydride-11-methyl-2,7-dicarbound decaborane , Tri (n-butyl) ammonium 1-carbadecaborate, tri (n-butyl) ammonium 1-carbadecacate , Tri (n-butyl) ammonium 1-carbadodecaborate, tri (n-butyl) ammonium 1-trimethylsilyl-1-carbadecaborate, tri (n-butyl) ammonium bromo-1-carbadodecaborate, tri (n -Butyl) ammonium 6-carbadecaborate, tri (n-butyl) ammonium 6-carbadecaborate, tri (n-butyl) ammonium 7-carbaundecaborate, tri (n-butyl) ammonium 7,8-dicarbaun Decaborate, tri (n-butyl) ammonium 2,9-dicarbaundecaborate, tri (n-butyl) ammonium dodecahydride-8-methyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium Decahydride-8-ethyl-7,9 Dicarbaound decaborate, tri (n-butyl) ammonium undecahydride-8-butyl-7,9-dicarbaound decaborate, tri (n-butyl) ammonium undecahydride-8-allyl-7,9-dicarbaun Decaborate, tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,8-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-4,6-dibromo-7-carbaundecaborate Anionic salts such as;
Tri (n-butyl) ammonium bis (nonahydride-1,3-dicarbanonaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) Ferrate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7) , 8-dicarbaundecaborate) nickelate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundeborate) cuprate (III), tri (n-butyl) Ammonium bis (undecahydride-7,8-dicarbaundecaborate) aurate (III , Tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate) ferrate (III), tri (n-butyl) ammonium bis (nonahydride-7,8 -Dimethyl-7,8-dicarbaundecaborate) chromate (III), tri (n-butyl) ammonium bis (tribromooctahydride-7,8-dicarbaundecaborate) cobaltate (III), tris [Tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) chromate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundeca Borate) manganate (IV), bis [tri (n-butyl) ammonium] bis (undeca) Metal carborane anions such as idride-7-carbaundecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) nickelate (IV) And the like.

  The heteropoly compound which is an example of the ionized ionic compound (compound (B-3)) is an atom selected from silicon, phosphorus, titanium, germanium, arsenic and tin, and one or more selected from vanadium, niobium, molybdenum and tungsten A compound containing two or more atoms. Specifically, phosphovanadic acid, germanovanadic acid, arsenic vanadic acid, phosphoniobic acid, germanoniobic acid, siliconomolybdic acid, phosphomolybdic acid, titanium molybdic acid, germanomolybdic acid, arsenic molybdic acid, tin molybdic acid, phosphorus Tungstic acid, germanotungstic acid, tin tungstic acid, phosphomolybdovanadic acid, phosphotungstovanadic acid, germanotungstovanadic acid, phosphomolybdotungstovanadic acid, germanomolybdo tungstovanadate, phosphomolybdo Examples include, but are not limited to, tungstic acid, phosphomolybdniobic acid, and salts of these acids. Examples of the salt include metals of Group 1 or 2 of the periodic table, specifically, lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, and the like, An organic salt such as phenylethyl salt can be used, but is not limited thereto.

The ionized ionic compound (B-3) as described above is used singly or in combination of two or more.
When the transition metal compound according to the present invention is used as a catalyst, when it is used in combination with an organoaluminum oxy compound (B-2) such as methylaluminoxane as a promoter component, it exhibits a very high polymerization activity with respect to the olefin compound.

  Moreover, the catalyst for olefin polymerization according to the present invention includes the transition metal compound (A), the organometallic compound (B-1), the organoaluminum oxy compound (B-2), and the ionized ionic compound (B-3). Together with at least one compound (B) selected from the group consisting of:

(D) Carrier The carrier (D) used in the present invention is an inorganic or organic compound and is a granular or particulate solid. By supporting the transition metal compound (A) and the compound (B) on the carrier (D), a polymer having a good morphology can be obtained.
The inorganic compound is preferably a porous oxide, inorganic halide, clay, clay mineral, or ion-exchangeable layered compound.

Specific examples of the porous oxide include SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, and ThO ₂ , or a composite or mixture containing these. Further, for example, natural or synthetic zeolite, SiO ₂ —MgO, SiO ₂ —Al ₂ O ₃ , SiO ₂ —TiO ₂ , SiO ₂ —V ₂ O ₅ , SiO ₂ —Cr ₂ O ₃ , SiO it can be used, such as ₂ -TiO ₂ -MgO.

Of these, the porous oxide is preferably composed mainly of SiO ₂ and / or Al ₂ O ₃ .
Note that the inorganic oxide includes 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 , Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, Li ₂ O and other carbonates, sulfates, nitrates, and oxide components may be contained.

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

As the inorganic halide, MgCl ₂ , MgBr ₂ , MnCl ₂ , MnBr ₂ or the like is used. The inorganic halide may be used as it is or after being pulverized by a ball mill or a vibration mill. In addition, an inorganic chloride dissolved in a solvent such as alcohol and then precipitated in a fine particle form by a precipitating agent may be used.

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

In addition, as clay, clay mineral, or ion-exchangeable layered compound, clay, clay mineral, ionic crystalline compound having a layered crystal structure such as hexagonal fine packing type, antimony type, CdCl ₂ type, CdI ₂ type, etc. It can be illustrated.

Examples of such clays and clay minerals include kaolin, bentonite, kibushi clay, gyrome clay, allophane, hysinger gel, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokdeite group, palygorskite, kaolinite, nacrite, dickite And halloysite, and the ion-exchangeable layered compounds include α-Zr (HAsO ₄ ) ₂ .H ₂ O, α-Zr (HPO ₄ ) ₂ , α-Zr (KPO ₄ ) ₂ .3H ₂ O, α-Ti (HPO ₄ ) ₂ , α-Ti (HAsO ₄ ) ₂ .H ₂ O, α-Sn (HPO ₄ ) ₂ .H ₂ O, γ-Zr (HPO ₄ ) ₂ , γ-Ti (HPO ₄ ) ₂ , crystalline acidic salts of polyvalent metals such as γ-Ti (NH ₄ PO ₄ ) ₂ .H ₂ O.

  Such a clay, clay mineral, or ion-exchange layered compound preferably has a pore volume of 0.1 cc / g or more and a diameter of 0.3 to 5 cc / g measured by mercury porosimetry. Particularly preferred. Here, the pore volume is measured in a range of pore radius of 20 to 30000 mm by mercury porosimetry using a mercury porosimeter.

When a carrier having a pore volume with a radius of 20 mm or more and smaller than 0.1 cc / g is used as a carrier, high polymerization activity tends to be difficult to obtain.
The clay and clay mineral used in the present invention are preferably subjected to chemical treatment. As the chemical treatment, any of a surface treatment that removes impurities adhering to the surface and a treatment that affects the crystal structure of clay can be used. Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, and organic matter treatment. In addition to removing impurities on the surface, the acid treatment increases the surface area by eluting cations such as Al, Fe, and Mg in the crystal structure. Alkali treatment destroys the crystal structure of the clay, resulting in a change in the structure of the clay. In the salt treatment and the organic matter treatment, an ion complex, a molecular complex, an organic derivative, or the like can be formed, and the surface area or interlayer distance can be changed.

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

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

Of these, preferred are clays or clay minerals, and particularly preferred are montmorillonite, vermiculite, pectolite, teniolite and synthetic mica.
As described above, the carrier (D) is an inorganic or organic compound, and examples of the organic compound include a granular or fine particle solid having a particle size in the range of 1 to 300 μm. Specifically, a (co) polymer produced mainly from an α-olefin having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, vinylcyclohexane, styrene (Co) polymers produced by the main component, and their modified products.

  The catalyst for olefin polymerization according to the present invention is selected from the above transition metal compounds (A), (B-1) organometallic compounds, (B-2) organoaluminum oxy compounds, and (B-3) ionized ionic compounds. The following specific organic compound component (E) can also be included as needed together with at least one compound (B) and, if necessary, the carrier (D).

(E) Organic compound component In the present invention, the (E) organic compound component improves the polymerization performance of the olefin polymerization catalyst of the present invention and the physical properties of the produced polymer (for example, the molecular weight of the produced polymer) as necessary ( If it has a molecular weight, it is used for the purpose of increasing the molecular weight. Such organic compounds include, but are not limited to, alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, sulfonates, and the like.

As the alcohols and the phenolic compounds, those represented by R ³⁷ —OH are usually used, wherein R ³⁷ is a hydrocarbon group having 1 to 50 carbon atoms (in the case of phenols, carbon atoms The number is 6 to 50) or a halogenated hydrocarbon group having 1 to 50 carbon atoms (in the case of phenols, the number of carbon atoms is 6 to 50).

As the alcohols, R ³⁷ is preferably a halogenated hydrocarbon. Moreover, as a phenolic compound, what substituted the (alpha) and (alpha) '-position of the hydroxyl group with the C1-C20 hydrocarbon is preferable.

As the carboxylic acid, one represented by R ³⁸ —COOH is usually used. R ³⁸ represents a hydrocarbon group having 1 to 50 carbon atoms or a halogenated hydrocarbon group having 1 to 50 carbon atoms, and a halogenated hydrocarbon group having 1 to 50 carbon atoms is particularly preferable.

As the phosphorus compound, phosphoric acids having a P—O—H bond, P—OR, phosphates having a P═O bond, and phosphine oxide compounds are preferably used.
As said sulfonate, what is represented by the following general formula (XI) is used.

（式中、Ｍは周期律表第１〜１４族の元素であり、Ｒ³⁹は水素、炭素原子数１〜２０の炭化水素基または炭素原子数１〜２０のハロゲン化炭化水素であり、Ｘは水素原子、ハロゲン原子、炭素原子数が１〜２０の炭化水素基または炭素原子数が１〜２０のハロゲン化炭化水素であり、ｍは１〜７の整数であり、ｎは１〜７の整数であり、また、ｍ−ｎ≧１である。）

(In the formula, M is an element of Groups 1 to 14 of the periodic table, R ³⁹ is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon 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 having 1 to 20 carbon atoms, m is an integer of 1 to 7, and n is 1 to 7 Integer, and mn ≧ 1.)

  In the method for producing a polyolefin according to the present invention, a polyolefin is obtained by polymerizing or copolymerizing an olefin in the presence of the olefin polymerization catalyst as described above. As described above, in the present specification, olefin refers to any compound having a polymerizable double bond.

The method for using each component constituting the catalyst of the present invention in polymerization and the order of addition to the polymerization vessel are arbitrarily selected, and the following methods are exemplified.
(1) A method of adding the transition metal compound (A) alone to the polymerization vessel.
(2) A method of adding the transition metal compound (A) and the compound (B) to the polymerization vessel in an arbitrary order.
(3) A method in which the catalyst component having the transition metal compound (A) supported on the carrier (D) and the compound (B) are added to the polymerization vessel in any order.
(4) A method in which the catalyst component having the compound (B) supported on the carrier (D) and the transition metal compound (A) are added to the polymerization vessel in any order.
(5) A method in which a catalyst component in which a transition metal compound (A) and a compound (B) are supported on a carrier (D) is added to a polymerization vessel.

(6) A method in which the catalyst component having the transition metal compound (A) and the compound (B) supported on the carrier (D) and the compound (B) are added to the polymerization vessel in an arbitrary order. In this case, the compound (B) supported on the carrier (D) and the compound (B) added alone may be the same or different. (7) The catalyst carrying the compound (B) on the carrier (D) A method of adding a component, a transition metal compound (A), and a compound (B) to a polymerization vessel in an arbitrary order. In this case, the compound (B) supported on the carrier (D) and the compound (B) added alone may be the same or different. (8) The transition metal compound (A) is used as the carrier (D). A method in which a supported catalyst component and a component in which the compound (B) is supported on the carrier (D) are added to the polymerization vessel in an arbitrary order.
(9) A catalyst component in which the transition metal compound (A) is supported on the carrier (D), a catalyst component in which the compound (B) is supported on the carrier (D), and the compound (B) are added to the polymerization vessel in any order. Method. In this case, the compound (B) supported on the carrier (D) and the compound (B) added alone may be the same or different.
(10) A method of adding the transition metal compound (A), the compound (B), and the organic compound component (E) to the polymerization vessel in an arbitrary order.

(11) A method in which the component in which the compound (B) and the organic compound component (E) are contacted in advance, and the transition metal compound (A) are added to the polymerization vessel in an arbitrary order.
(12) A method in which the component (B) and the organic compound component (E) supported on the carrier (D) and the transition metal compound (A) are added to the polymerization vessel in any order.
(13) A method in which the catalyst component obtained by previously contacting the transition metal compound (A) and the compound (B) and the organic compound component (E) are added to the polymerization vessel in an arbitrary order.
(14) A method in which the catalyst component obtained by previously contacting the transition metal compound (A) and the compound (B), the compound (B), and the organic compound component (E) are added to the polymerization vessel in an arbitrary order.
(15) A catalyst component in which the transition metal compound (A) and the compound (B) are contacted in advance, and a component in which the compound [B] and the organic compound component (E) are contacted in advance are added to the polymerization vessel in an arbitrary order. Method. In this case, the compound (B) brought into contact with the transition metal compound (A) and the compound (B) brought into contact with the organic compound component (E) may be the same or different.
(16) A method in which the component having the transition metal compound (A) supported on the carrier (D), the compound (B), and the organic compound component (E) are added to the polymerization vessel in any order.

(17) A method in which a component in which the transition metal compound (A) is supported on the carrier (D) and a component in which the compound (B) and the organic compound component (E) are contacted in advance are added to the polymerization vessel in any order.
(18) A method in which a catalyst component obtained by previously contacting a transition metal compound (A), a compound (B), and an organic compound component (E) in an arbitrary order is added to a polymerization vessel.
(19) A method in which the transition metal compound (A), the compound (B) and the organic compound component (E) are contacted in advance, and the compound (B) is added to the polymerization vessel in any order. In this case, the compound (B) brought into contact with the transition metal compound (A) and the organic compound component (E) and the compound [B] added alone may be the same or different.
(20) A method of adding a catalyst in which a transition metal compound (A), a compound (B), and an organic compound component (E) are supported on a carrier (D) to a polymerization vessel.
(21) A method in which a transition metal compound (A), a compound (B), a catalyst component in which an organic compound component (E) is supported on a carrier (D), and a compound (B) are added to the polymerization vessel in an arbitrary order. In this case, the compound (B) supported on the carrier (D) and the compound (B) added alone may be the same or different.

  The solid catalyst component in which the transition metal compound (A) is supported on the carrier (D) and the solid catalyst component in which the transition metal compound (A) and the compound (B) are supported on the carrier (D) are prepolymerized with olefin. The catalyst component may be further supported on the prepolymerized solid catalyst component.

  In the present invention, the polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization or a gas phase polymerization method. Specific examples of the inert hydrocarbon medium used in the liquid phase polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, and methylcyclopentane. Alicyclic hydrocarbons such as benzene, toluene, xylene and other aromatic hydrocarbons; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, or mixtures thereof, and the olefin itself is used as a solvent. You can also.

When olefin polymerization is performed using the olefin polymerization catalyst as described above, the transition metal compound (A) is usually 10 ⁻¹² to 10 ⁻² mol, preferably 10 ⁻¹⁰ to 10 ⁻¹⁰ liter per reaction volume. Used in such an amount as to be ^-3 mol.

  The organometallic compound (B-1) usually has a molar ratio [(B-1) / M] of the organometallic compound (B-1) and all transition metal atoms (M) in the transition metal compound (A). It is used in an amount of 0.01 to 100,000, preferably 0.05 to 50,000. The organoaluminum oxy compound (B-2) is a molar ratio of the aluminum atom in the organoaluminum oxy compound (B-2) to the total transition metal (M) in the transition metal compound (A) [(B-2). / M] is usually used in an amount of 10 to 500,000, preferably 20 to 100,000. The ionized ionic compound (B-3) has a molar ratio [(B-3) / M] of the ionized ionic compound (B-3) and the transition metal atom (M) in the transition metal compound (A). The amount is usually 1 to 10, preferably 1 to 5.

  The organic compound component (E) has a molar ratio [(E) / (B-1)] with the organometallic compound (B-1) of usually 0.01 to 10, preferably 0.1 to 5. Used in various amounts. The organic compound component (E) has a molar ratio [(E) / (B-2)] to the organoaluminum oxy compound (B-2) of usually 0.01 to 2, preferably 0.005 to 1. Used in such amounts. The organic compound component (E) has a molar ratio [(E) / (B-3)] to the ionized ionic compound (B-3) of usually 0.01 to 10, preferably 0.1 to 5. Used in such amounts.

Moreover, the polymerization temperature of the olefin using such an olefin polymerization catalyst is -50- + 200 degreeC normally, Preferably it is the range of 0-170 degreeC. The polymerization pressure is usually from normal pressure to 100 kg / cm ² , preferably from normal pressure to 50 kg / cm ² , and the polymerization reaction can be carried out in any of batch, semi-continuous and continuous methods. it can. Furthermore, the polymerization can be performed in two or more stages having different reaction conditions.

  The molecular weight of the resulting olefin polymer can also be adjusted by the presence of hydrogen in the polymerization system or by changing the polymerization temperature. Furthermore, it can also adjust with the quantity of the compound (B) to be used.

  The olefin that can be polymerized by such an olefin polymerization catalyst is not particularly limited as long as it has a polymerizable double bond. For example, a linear or branched α-olefin, a cyclic olefin, or a polar group-containing non-olefin. Examples thereof include saturated hydrocarbons and conjugated / nonconjugated polyenes.

Examples of the linear or branched α-olefin include (C-1) a linear or branched α-olefin having 2 to 30 carbon atoms, specifically 2 to 30 carbon atoms. Preferably 2 to 20 linear or branched α-olefins such as ethylene, propylene, 1-butene, 2-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl Examples include -1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicocene.

The cyclic olefin is (C-2) at least one cyclic selected from the group consisting of compounds represented by the following general formula (II), general formula (III), general formula (IV) or general formula (V). Examples include olefins.

（式（ＩＩ）中、ｕは０または１であり、ｖは０または正の整数であり、ｗは０または１であり、Ｒ⁶¹〜Ｒ⁷⁸ならびにＲ^a1およびＲ^b1は、水素原子、ハロゲン原子、炭化水素基から選ばれ、互いに同一でも異なっていてもよく、Ｒ⁷⁵〜Ｒ⁷⁸は、互いに結合して単環または、多環を形成していてもよく、かつ該単環または多環が二重結合を有していてもよく、またＲ⁷⁵とＲ⁷⁶とで、またはＲ⁷⁷とＲ⁷⁸とでアルキリデン基を形成していてもよい。）

(In the formula (II), 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 a hydrogen atom, a halogen atom, It is selected from atoms and hydrocarbon groups, and may be the same or different from each other, and R ^{75 to} R ⁷⁸ may be bonded to each other to form a monocycle or polycycle, and the monocycle or polycycle May have a double bond, and R ⁷⁵ and R ⁷⁶ , or R ⁷⁷ and R ⁷⁸ may form an alkylidene group.)

（式（ＩＩＩ）中、ｘおよびｄは０または１以上の整数であり、ｙおよびｚは０、１または２であり、Ｒ⁸¹〜Ｒ⁹⁹は、水素原子、ハロゲン原子、炭化水素基から選ばれ、互いに同一でも異なっていてもよく、Ｒ⁸⁹およびＲ⁹⁰が結合している炭素原子と、Ｒ⁹³が結合している炭素原子またはＲ⁹¹が結合している炭素原子とは、直接あるいは炭素原子数１〜３のアルキレン基を介して結合していてもよく、またｙ＝ｚ＝０のとき、Ｒ⁹⁵とＲ⁹²またはＲ⁹⁵とＲ⁹⁹とは互いに結合して単環または多環の芳香族環を形成していてもよい。）

(In the formula (III), x and d are 0 or an integer of 1 or more, y and z are 0, 1 or 2, and R ^{81 to} R ⁹⁹ are selected from a hydrogen atom, a halogen atom and a hydrocarbon group. are may be the same or different from each other, the carbon atom to which R ⁸⁹ and R ⁹⁰ is bonded, the carbon atom to which carbon atoms or R ⁹¹ R ⁹³ is attached is bound directly or carbon It may be bonded via an alkylene group having 1 to 3 atoms. When y = z = 0, R ⁹⁵ and R ⁹² or R ⁹⁵ and R ⁹⁹ are bonded to each other to form a monocyclic or polycyclic ring. An aromatic ring may be formed.)

（式（ＩＶ）中、Ｒ¹⁰⁰、Ｒ¹⁰¹は、互いに同一でも異なっていてもよく、水素原子または炭素原子数１〜５の炭化水素基を示し、ｆは１≦ｆ≦１８である。）

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

（一般式（Ｖ）中、ｘは０または１以上の整数であり、Ｒ¹¹¹〜Ｒ¹¹⁸は水素原子、ハロゲン原子、炭化水素基から選ばれ、互いに同一でも異なっていてもよく、Ｒ¹²¹〜Ｒ¹²⁴は水素原子、ハロゲン原子、炭化水素基から選ばれ、互いに同一でも異なっていてもよく、隣接する２つの基は互いに結合し単環または複環の芳香族環を形成していてもよい。）。

(In the general formula (V), x is 0 or an integer of 1 or more, R ¹¹¹ to R ¹¹⁸ is a hydrogen atom, a halogen atom, selected from hydrocarbon groups may be the same or different, R ¹²¹ ~ R ¹²⁴ is selected from a hydrogen atom, a halogen atom, and a hydrocarbon group, and may be the same or different from each other, and two adjacent groups may be bonded to each other to form a monocyclic or multicyclic aromatic ring. .)

Hereinafter, general formula (II), general formula (III), general formula (IV), and general formula (V) will be described in detail.
Specifically, the general formula (II) has the following structure.

式（ＩＩ）中、ｕは０または１であり、ｖは０または正の整数であり、ｗは０または１である。なおｗが１の場合には、ｗを用いて表される環は６員環となり、ｗが０の場合には、この環は５員環となる。

In formula (II), 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, this ring is a 5-membered ring.

R ^{61 to} R ⁷⁸ and R ^a1 and R ^b1 may be the same or different from each other, 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.

  The hydrocarbon group has 1 to 30 carbon atoms, preferably 1 to 30 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, and n-hexyl. 20 linear or branched alkyl groups; linear or branched alkenyl groups having 2 to 30, preferably 2 to 20 carbon atoms such as vinyl, allyl, isopropenyl, etc .; carbon atoms such as ethynyl, propargyl, etc. A linear or branched alkynyl group having 2 to 30, preferably 2 to 20 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, adamantyl, norbornyl, tetracyclododecyl, etc. 30, preferably 3 to 20 cycloalkyl groups; cyclopentadienyl, inde Cyclic unsaturated hydrocarbon groups having 5 to 30 carbon atoms such as ru and fluorenyl; aryls having 6 to 30 carbon atoms, such as phenyl, benzyl, naphthyl, biphenyl, terphenyl, phenanthryl and anthracenyl, preferably 6 to 20 aryl Groups; alkyl-substituted aryl groups such as tolyl, iso-propylphenyl, t-butylphenyl, dimethylphenyl, and di-t-butylphenyl;

  The hydrocarbon group may have a hydrogen atom substituted with a halogen, such as monotrifluoromethyl, ditrifluoromethyl, monofluorophenyl, difluorophenyl, trifluorophenyl, pentafluorophenyl, chlorophenyl, etc. Examples thereof include 1-30, preferably 1-20, halogenated alkyl groups or halogenated aryl groups.

The hydrocarbon group may be substituted with another hydrocarbon group, and examples thereof include aryl-substituted alkyl groups such as benzyl and cumyl.
Further, the hydrocarbon group is a heterocyclic compound residue; oxygen such as alkoxy group, aryloxy group, ester group, ether group, acyl group, carboxyl group, carbonate group, hydroxy group, peroxy group, carboxylic acid anhydride group, etc. 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, amino group and ammonium salt Nitrogen-containing groups such as those; boron-containing groups such as boranediyl group, boranetriyl group, diboranyl group; mercapto group, thioester group, dithioester group, alkylthio group, arylthio group, thioacyl group, thioether group, thiocyanate group, Isothiocyanate group, sulfone ester group, sulfo group Sulfur-containing groups such as amide groups, thiocarboxyl groups, dithiocarboxyl groups, sulfo groups, sulfonyl groups, sulfinyl groups, sulfenyl groups; phosphorus-containing groups such as phosphide groups, phosphoryl groups, thiophosphoryl groups, phosphato groups, silicon-containing groups A germanium-containing group; or a tin-containing group.

  Examples of the hydrocarbon group include 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, neopentyl, and n-hexyl, preferably 1 -20 linear or branched alkyl groups; cyclopropyl, cyclobutyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantyl, norbornyl, tetracyclododecyl, etc., having 3 to 30, preferably 3 to 20 carbon atoms Alkyl groups; aryl groups having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms such as phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, anthracenyl; halogen atoms, 1 to 30 carbon atoms, preferably these aryl groups 1-20 alkyl or alkoxy groups, carbon atoms 30, preferably including a substituted aryl group substituents, such as 6 to 20 aryl group or aryloxy group is 1-5 substituents is preferred.

In addition the general formula (II), and R ⁷⁵ and R ⁷⁶ are, the R ⁷⁷ and R ⁷⁸ are, the R ⁷⁵ and R ⁷⁷ are, the R ⁷⁶ and R ⁷⁸ are, and the 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 You may have. Specific examples of the monocyclic or polycyclic ring formed here include the following.

なお、上記例示において、１または２の番号を付した炭素原子は、上記一般式（Ｉ）においてそれぞれＲ⁷⁵（Ｒ⁷⁶）またはＲ⁷⁷（Ｒ⁷⁸）が結合している炭素原子を表す。

In the above examples, the carbon atom numbered 1 or 2 represents a carbon atom to which R ⁷⁵ (R ⁷⁶ ) or R ⁷⁷ (R ⁷⁸ ) is bonded in the general formula (I).

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

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

式（ＩＩＩ）中、ｘおよびｄは０または正の整数であり、ｙおよびｚは０、１または２である。

In formula (III), 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, or a hydrocarbon group.
Examples of the halogen atom and hydrocarbon group are the same as the halogen atom and hydrocarbon group in the above formula (II).

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. It may be connected 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 are combined with each other to form a methylene group (—CH ₂ -), An alkylene group (—CH ₂ CH ₂ —) or a propylene group (—CH ₂ CH ₂ CH ₂ —) is formed.

Further, when y = z = 0, R ⁹⁵ and R ⁹² or R ⁹⁵ and R ⁹⁹ may be bonded to 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 are exemplified.

ここで、ｌは上記一般式（ＩＩＩ）におけるｄと同じである。

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

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

式（ＩＶ）中、Ｒ¹⁰⁰とＲ¹⁰¹は、互いに同一でも異なっていてもよく、水素原子または炭素原子数１〜５の炭化水素基であり、またｆは１≦ｆ≦１８である。

Wherein (IV), R ¹⁰⁰ and R ¹⁰¹ may be the same or different from each other, a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, also f is 1 ≦ f ≦ 18.

Preferred examples of the hydrocarbon group having 1 to 5 carbon atoms include an alkyl group, a halogenated alkyl group, and a cycloalkyl group. Specific examples thereof are the same as the specific examples of R ^{61 to} R ^{78 in} the above formula (II).

一般式（Ｖ）において、ｘは０または１以上の整数である。

In general formula (V), x is 0 or an integer of 1 or more.

R ^{111 to} R ¹¹⁸ and R ^{121 to} R ¹²⁴ are selected from a hydrogen atom, a halogen atom, and a hydrocarbon group, and may be the same as or different from each other.
Examples of the halogen atom and hydrocarbon group are the same as the halogen atom and hydrocarbon group in the above formula (II).

Further, two adjacent groups of R ^{121 to} R ¹²⁴ may be bonded to each other to form a monocyclic or multicyclic aromatic ring. Among these, specific examples of the cyclic olefin in which R ¹²¹ and R ¹²² are bonded to form an aromatic ring include the following structures.

また、Ｒ¹²²とＲ¹²³が結合して芳香族環が形成される環状オレフィンとして具体的には、以下のような構造が挙げられる。

Specific examples of the cyclic olefin in which R ¹²² and R ¹²³ are bonded to form an aromatic ring include the following structures.

また、Ｒ¹²¹とＲ¹²²、Ｒ¹²³とＲ¹²⁴が結合して芳香族環が形成される環状オレフィンとして具体的には、以下のような構造が挙げられる。

Specific examples of the cyclic olefin in which R ¹²¹ and R ¹²² , R ¹²³ and R ¹²⁴ are combined to form an aromatic ring include the following structures.

これらの芳香族環上にハロゲン原子、アルキル基、およびアリール基から選ばれる置換基が置換された環状オレフィンも例として挙げられる。

Examples of the cyclic olefin in which a substituent selected from a halogen atom, an alkyl group, and an aryl group are substituted on these aromatic rings are also exemplified.

As the cyclic olefin represented by the general formula (II), (III), (IV) or (V) as described above, specifically,
Bicyclo-2-heptene derivative (bicyclohept-2-ene derivative), tricyclo-3-decene derivative, tricyclo-3-undecene derivative, tetracyclo-3-dodecene derivative, pentacyclo-4-pentadecene derivative, pentacyclopentadecadien derivative, Pentacyclo-3-pentadecene derivative, pentacyclo-4-hexadecene derivative, pentacyclo-3-hexadecene derivative, hexacyclo-4-heptadecene derivative, heptacyclo-5-eicosene derivative, heptacyclo-4-eicosene derivative, heptacyclo-5-heneicosene derivative, octacyclo -5-docosene derivative, nonacyclo-5-pentacocene derivative, nonacyclo-6-hexacocene derivative, cyclopentadiene-acenaphthylene adduct, 1,4-methano-1 4,4a, 9a-tetrahydrofluorene derivative, 1,4-methano-1,4,4a, 5,10,10a-hexahydroanthracene derivative, cycloalkylene derivative having 3 to 20 carbon atoms, benzonorbornadiene derivative, 1, Examples include 4-dihydro-1,4-methanoanthracene derivatives.

  Specific examples of the cyclic olefin represented by the above formula (II), (III), (IV) or (V) are shown below.

シクロブテン、シクロペンテン、シクロヘキセン、３−メチルシクロヘキセン、シクロヘプテン、シクロオクテン、シクロデセン、シクロドデセン、シクロエイコセンなど。
ベンゾノルボルナジエンおよびその誘導体

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

１，４−ジヒドロ−１，４−メタノアントラセンおよびその誘導体

1,4-dihydro-1,4-methanoanthracene and its derivatives

これらの中では、ビシクロ［２.２.１］−２−ヘプテン誘導体、テトラシクロ［４.４.０.^12,5.１^7,10］−３−ドデセン誘導体、ベンゾノルボルナジエン誘導体および１，４−ジヒドロ−１，４−メタノアントラセン誘導体が好ましく、特にビシクロ［２.２.１］−２−ヘプテン、テトラシクロ［４.４.０.１^2,5.１^7,10］−３−ドデセン、ベンゾノルボルナジエン、１，４−ジヒドロ−１，４−メタノアントラセンが好ましい。

Among these, bicyclo [2.2.1] -2-heptene derivatives, tetracyclo [ ^{4.4.0.12.5.1 7,10} ] -3-dodecene derivatives, benzonorbornadiene derivatives and 1,4- dihydro-1,4-methanolate anthracene derivatives are preferable, especially bicyclo [2.2.1] -2-heptene, tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene, benzo Norbornadiene and 1,4-dihydro-1,4-methanoanthracene are preferred.

You may superpose | polymerize including 2 or more types of these cyclic olefins represented by general formula (II), (III), (IV) or (V).
The unsaturated hydrocarbon having a polar group is, for example, a chain-like unsaturated hydrocarbon having a carbonyl group, a hydroxyl group, an ether bond group or the like as a polar group, and specifically includes acrylic acid, 3-butene Acid, 4-pentenoic acid, 5-hexenoic acid, 6-heptenoic acid, 7-octenoic acid, 8-nonenoic acid, 9-decenoic acid, 10-undecenoic acid, 11-dodecenoic acid, 12-tridecenoic acid, 13-tetradecene Acid, 14-pentadecenoic acid, 15-hexadecenoic acid, 16-heptadecenoic acid, 17-octadecenoic acid, 18-nonadecenoic acid, 19-eicosenoic acid, 20-henicosenoic acid, 21-docosenoic acid, 22-tricosenoic acid, methacrylic acid, 2-methylpentenoic acid, 2,2-dimethyl-3-butenoic acid, 2,2-dimethyl-4-pentenoic acid, 3-vinylbenzoic acid, 4-vinyl Benzoic acid, 2,6-heptadienoic acid, 2- (4-isopropylbenzylidene) -4-pentenoic acid, allylmalonic acid, 2- (10-undecenyl) malonic acid, fumaric acid, itaconic acid, bicyclo [2.2.1 ] -5-heptene-2-carboxylic acid, unsaturated carboxylic acids such as bicyclo [2.2.1] -5-heptene-2,3-dicarboxylic acid, and sodium, potassium, lithium and zinc salts thereof Metal salts such as salts, magnesium salts, calcium salts, and methyl esters, ethyl esters, n-propyl esters, isopropyl esters, n-butyl esters, isobutyl esters, (5-norbornen-2-yl) of these unsaturated carboxylic acids Unsaturated carboxylic acid esters such as esters (when the unsaturated carboxylic acid is a dicarboxylic acid May be a monoester or a diester), and amides of these unsaturated carboxylic acids, and unsaturated carboxylic acid amides such as N, N-dimethylamide (the unsaturated carboxylic acid is a dicarboxylic acid) In some cases it may be a monoamide or a diamide);
Maleic anhydride, itaconic anhydride, allyl succinic anhydride, isobutenyl succinic anhydride, (2,7-octadien-1-yl) succinic anhydride, tetrahydrophthalic anhydride, bicyclo [2.2.1 ] -5-heptene-2,3-dicarboxylic acid anhydrides and other unsaturated carboxylic acid anhydrides;
Vinyl esters such as vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate;
Allyl esters such as allyl acetate, allyl propionate, allyl caproate, allyl caprate, allyl laurate, allyl stearate;
Halogenated olefins such as vinyl chloride, vinyl fluoride, vinyl bromide, vinyl iodide, allyl bromide, allyl chloride, allyl fluoride, allyl bromide;
halogenated styrenes such as o-chlorostyrene and p-chlorostyrene;
Silylated olefins such as allyltrimethylsilane, diallyldimethylsilane, 3-butenyltrimethylsilane, allyltriisopropylsilane, allyltriphenylsilane;
Unsaturated nitriles such as acrylonitrile, 2-cyanobicyclo [2.2.1] -5-heptene, 2,3-dicyanobicyclo [2.2.1] -5-heptene;
Unsaturated alcohol compounds such as allyl alcohol, 3-butenol, 4-pentenol, 5-hexenol, 6-hebutenol, 7-octenol, 8-nonenol, 9-decenol, 10-undecenol, 11-dodecenol, 12-tridecenol And unsaturated esters thereof such as acetates, benzoates, propionates, caproates, caprates, laurates, stearates;

Substituted phenols such as vinylphenol and allylphenol, and unsaturated esters such as acetate, benzoate, propionate, caproate, caprate, laurate, and stearate;
Substituted benzyl alcohols such as vinyl benzyl alcohol and allyl benzyl alcohol, and unsaturated esters thereof such as acetate, benzoate, propionate, caproate, caprate, laurate and stearate;
Unsaturated ethers such as methyl vinyl ether, ethyl vinyl ether, allyl methyl ether, allyl propyl ether, allyl butyl ether, allyl methallyl ether, methoxy styrene, ethoxy styrene, allyl anisole;
Unsaturated epoxides such as butadiene monoxide, 1,2-epoxy-7-octene, 3-vinyl 7-oxabicyclo [4.1.0] heptane;
Unsaturated aldehydes such as acrolein and undecenal, and unsaturated acetals such as dimethyl acetal and diethyl acetal;
Unsaturated ketones such as methyl vinyl ketone, ethyl vinyl ketone, allyl methyl ketone, allyl ethyl ketone, allyl propyl ketone, allyl butyl ketone, and allyl benzyl ketone, and unsaturated acetals such as dimethyl acetal and diethyl acetal;
Unsaturated thioethers such as allyl methyl sulfide, allyl phenyl sulfide, allyl isopropyl sulfide, allyl n-propyl sulfide, 4-pentenyl phenyl sulfide;
Unsaturated sulfoxides such as allyl phenyl sulfoxide;
Unsaturated sulfones such as allyl phenyl sulfone;
Unsaturated phosphines such as allyldiphenylphosphine;
And unsaturated phosphine oxides such as allyldiphenylphosphine oxide.

  Furthermore, unsaturated hydrocarbons having two or more polar groups listed above, such as vinyl trifluoroacetate, allyl trifluoroacetate, methyl 4- (3-butenyloxy) benzoate, glycidyl acrylate, allyl glycidyl ether, (2H-perfluoropropyl) -2-propenyl ether, linalool oxide, 3-allyloxy-1,2-propanediol, 2- (allyloxy) ethanol, N-allylmorpholine, allylglycine, N-vinylpyrrolidone, allyltrichlorosilane, Acrylic trimethylsilane, allyldimethyl (diisopropylamino) silane, 7-octenyltrimethoxysilane, allyloxytrimethylsilane, allyloxytriphenylsilane, etc. can also be (co) polymerized by the olefin polymerization catalyst of the present invention. Kill.

The olefin polymerization catalyst of the present invention can also (co) polymerize vinylcyclohexane, diene, polyene, or the like.
As the conjugated / nonconjugated 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 , 3-octadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, ethylidenenorbornene, 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-methylstyrene , O, p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene Mono- or polyalkyl styrene such as methoxy styrene, ethoxy styrene, vinyl benzoic acid, methyl vinyl benzoate, vinyl benzyl acetate, hydroxy styrene, o-chlorostyrene, p-chlorostyrene, divinylbenzene, and other functional group-containing styrene derivatives; And 3-phenylpropylene, 4-phenylpropylene, α-methylstyrene and the like.

  As described above, the transition metal compound (A) of the present invention has a novel structure in which a halogen atom is introduced into a specific site of a salicylaldoimine ligand, and includes the compound (A) of the present invention. The olefin polymerization catalyst has a higher polymerization activity than a conventional transition metal compound having a salicylaldoimine ligand, and can produce a polymer having a high comonomer content and molecular weight.

EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these.
In addition, the structure of the compound obtained by the synthesis example was determined using FD-mass spectrometry (JEOL SX-102A), 270MHz < ¹ > H-NMR (JEOL GSH-270), etc.

In this example, the intrinsic viscosity ([η]) was measured at 135 ° C. in decalin.
Moreover, the comonomer content of the copolymer obtained in the Example was measured by 400 MHz < ¹³ > C-NMR (JEOL ECX400P) or IR (JASCO, FT / IR-4200 or FT / IR-410). IR used the film obtained by melt-extending the copolymer obtained in the Example with the hot press heated at 135 degreeC, and carrying out pressure cooling at room temperature as a measurement sample.

As for the monomer composition ratio of the cyclic olefin copolymer, a correlation equation between the cyclic olefin content of the polymer by ¹³ C-NMR analysis and Tg (glass transition temperature) by DSC (differential scanning calorimeter) was obtained in advance. The cyclic olefin content was calculated from the Tg by DSC measurement using this correlation formula.

[Measurement of cyclic olefin content by ¹³ C-NMR]
Device: EX400 manufactured by JEOL Ltd.
Frequency: 100.4MHz
[Quantification of TD (tetracyclododecene)]
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 () represents the peak intensity. C (3) 51.0ppm each
C (c) 54.5ppm
The number of C (carbon atom) is as shown in the following figure.

[Quantitative determination of NB (norbornene)]
NB (mol%) = 1/3 × [2 × (C7) + (C1, C4) + (C2, C3)] / (C5, C6 & ethylene) × 100
Here, the value in () represents the peak intensity. Respectively,
C2, C3 44-46.5ppm
C1, C4 38.5-41 ppm
C7 30.5-32ppm
C5, C6 & ethylene 27-30ppm
It is.
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 DSC measurement under the following conditions.
Apparatus: SII Nano Technology Co., Ltd. DSC6220
Measurement conditions: A sample held at 300 ° C. for 5 minutes was rapidly cooled to 0 ° C., and then Tg was determined in the process of raising the temperature to 250 ° C. at a rate of temperature increase of 20 ° C./min.

(1) Synthesis of ligand [Ligand synthesis example-1]
A 100 ml reactor thoroughly dried and purged with nitrogen was charged with 2.66 g (7.1 mmol) of 3,5-diiodosalicylaldehyde and 20 ml of toluene. Thereto were added 10 ml of a toluene solution containing 0.73 g (7.8 mmol) of aniline and 0.1 g of p-toluenesulfonic acid, and the mixture was stirred for 3 hours with heating under reflux. The residue obtained by distilling off the solvent was purified by silica gel column chromatography to obtain 2.4 g (yield 75%) of the desired product represented by the following formula (1).
¹ H NMR (CDCl ₃ , 270 MHz): δ 7.24-7.49 (m, 5H), 7.67 (d, 1H, J = 2.0 Hz), 8.10 (d, 1H, J = 2) .0Hz), 8.45 (s, 1H), 14.71 (s, 1H)

[Ligand synthesis example-2]
A 100 ml reactor thoroughly dried and purged with nitrogen was charged with 2.46 g (6.6 mmol) of 3,5-diiodosalicylaldehyde and 20 ml of toluene. Thereto were added 10 ml of a toluene solution containing 1.08 g (7.2 mmol) of 4-t-butylaniline and 0.1 g of p-toluenesulfonic acid, and the mixture was stirred for 4 hours with heating under reflux. The residue obtained by distilling off the solvent was purified by silica gel column chromatography to obtain 1.7 g (yield 51%) of the desired product represented by the following formula (2).
¹ H NMR (CDCl ₃ , 270 MHz): δ 1.35 (s, 9H), 7.25 (d, 2H, J = 8.9 Hz), 7.46 (d, 2H, J = 8.9 Hz), 7.66 (d, 1H, J = 2.0 Hz), 8.09 (d, 1H, J = 2.0 Hz), 8.46 (s, 1H), (14.90 (s, 1H)

[Ligand synthesis example-3]
In a 100 ml reactor thoroughly dried and purged with nitrogen, 5.6 g (20.0 mmol) of 3,5-dibromosalicylaldehyde and 50 ml of toluene were charged. Thereto were added 20 ml of a toluene solution containing 3.28 g (22.0 mmol) of 4-t-butylaniline and 0.1 g of p-toluenesulfonic acid, and the mixture was stirred for 4 hours while heating under reflux. The residue obtained by distilling off the solvent was purified by silica gel column chromatography to obtain 6.0 g (yield 73%) of the desired product represented by the following formula (3).
¹ H NMR (CDCl ₃ , 270 MHz): δ 1.35 (s, 9H), 2.56 (m, 2H), 7.47 (m, 2H), 7.48 (d, 1H, J = 2. 3 Hz), 7.74 (d, 1 H, J = 2.3 Hz), 8.55 (d, 1 H, 2.3 Hz), 14.68 (s, 1 H)

[Ligand synthesis example-4]
A 100 ml reactor thoroughly dried and purged with nitrogen was charged with 1.87 g (5.0 mmol) of 3,5-diiodosalicylaldehyde and 20 ml of toluene. Thereto were added 10 ml of a toluene solution containing 1.68 g (5.0 mmol) of 4-tritylaniline and 0.1 g of p-toluenesulfonic acid, and the mixture was stirred for 4 hours while heating under reflux. The residue obtained by distilling off the solvent was purified by silica gel column chromatography to obtain 3.1 g (yield 89%) of the desired product represented by the following formula (4).
¹ H NMR (CDCl ₃ , 270 MHz): δ 7.24 (m, 19 H), 7.61 (d, 1 H, J = 2.0 Hz), 8.06 (d, 1 H, J = 2.0 Hz), 8.42 (d, 1H, J = 2.0 Hz), 14.8 (s, 1H)

[Ligand synthesis example-5]
In a 100 ml reactor thoroughly dried and purged with nitrogen, 2.88 g (10.3 mmol) of 3,5-dibromosalicylaldehyde and 20 ml of toluene were charged. 10 ml of a toluene solution containing 3.69 g (11.0 mmol) of 4-tritylaniline and 0.1 g of p-toluenesulfonic acid were added, and the mixture was stirred for 4 hours with heating under reflux. The residue obtained by distilling off the solvent was purified by silica gel column chromatography to obtain 5.7 g (yield 93%) of the desired product represented by the following formula (5).
¹ H NMR (CDCl ₃ , 270 MHz): δ 7.25 (m, 19 H), 7.46 (d, 1 H, J = 2.3 Hz), 7.77 (d, 1 H, J = 2.3 Hz), 8.54 (s, 1H), 14.5 (s, 1H)

[Ligand synthesis example-6]
A 100 ml reactor thoroughly dried and purged with nitrogen was charged with 0.261 g (1.00 mmol) of 3,5-diiodosalicylaldehyde and 10 ml of toluene. 10 ml of a toluene solution containing 0.374 g (1.00 mmol) of p-dodecylaniline and 0.1 g of p-toluenesulfonic acid were added and stirred for 4 hours while heating under reflux. The residue obtained by distilling off the solvent was purified by silica gel column chromatography to obtain 0.57 g (yield 93%) of the target compound represented by the following formula (6).
¹ H NMR (CDCl ₃ , 270 MHz): δ 0.88 (t, 3H, J = 7.0 Hz), 1.26-1.32 (m, 18H), 1.60-1.65 (m, 2H) ), 2.61-2.66 (t, br, 2H, J = 8.1 Hz), 7.23 (s, br, 4H), 7.65 (d, 1H, J = 2.2 Hz), 8 .09 (d, 1H, J = 2.2 Hz), 8.45 (s, 1H), 14.92 (s, 1H)

[Ligand synthesis example-7]
A 100 ml reactor thoroughly dried and purged with nitrogen was charged with 1.04 g (5.00 mmol) of 3,5-dibromosalicylaldehyde and 20 ml of toluene. 10 ml of a toluene solution containing 1.03 g (5.00 mmol) of 4-octylaniline and 0.1 g of p-toluenesulfonic acid were added and stirred for 4 hours while heating under reflux. The residue obtained by distilling off the solvent was purified by silica gel column chromatography to obtain 2.6 g (yield 92%) of the desired product represented by the following formula (7).
¹ H NMR (CDCl ₃ , 270 MHz): δ 0.88 (t, 3H, J = 6.8 Hz), 1.29 (m, 10H), 1.61 (m, 2H), 2.63 (t, 2H, J = 7.7 Hz), 7.22 (m, 4H), 7.63 (d, 1H, J = 2.0 Hz), 8.07 (d, 1H, J = 2.0 Hz), 8. 43 (s, 1H), 14.9 (s, 1H)

[Ligand synthesis example-8]
A 100 ml reactor thoroughly dried and purged with nitrogen was charged with 3.74 g (10.0 mmol) of 3,5-diiodosalicylaldehyde and 20 ml of toluene. 10 ml of a toluene solution containing 1.77 g (11.0 mmol) of p-trifluoromethylaniline and 0.1 g of p-toluenesulfonic acid were added, and the mixture was stirred for 4 hours with heating under reflux. The residue obtained by distilling off the solvent was purified by silica gel column chromatography to obtain 4.1 g (yield 80%) of the desired product represented by the following formula (8).
¹ H NMR (CDCl ₃ , 270 MHz): δ 7.36 (d, 2H, J = 7.9 Hz), 7.71 (d, 1H, J = 2.0 Hz), 7.71 (d, 2H, J = 7.9 Hz), 8.15 (d, 1 H, J = 2.0 Hz), 8.46 (s, 1 H)

[Ligand synthesis example-9]
In a 100 ml reactor thoroughly dried and purged with nitrogen, 5.60 g (20.0 mmol) of 3,5-dibromosalicylaldehyde and 20 ml of toluene were charged. 10 ml of a toluene solution containing 3.54 g (22.0 mmol) of p-trifluoromethylaniline and 0.1 g of p-toluenesulfonic acid were added and stirred for 4 hours while heating under reflux. The residue obtained by distilling off the solvent was purified by silica gel column chromatography to obtain 2.7 g (yield 32%) of the target compound represented by the following formula (9).
¹ H NMR (CDCl ₃ , 270 MHz): δ 7.37 (d, 2H, J = 8.2 Hz), 7.53 (d, 1H, J = 2.3 Hz), 7.72 (d, 2H, J = 8.2 Hz), 7.80 (d, 1 H, J = 2.3 Hz), 8.55 (s, 1 H), 13.9 (s, 1 H)

[Ligand Synthesis Example-10]
Into a 100 ml reactor thoroughly dried and purged with nitrogen, 0.748 g (2.00 mmol) of 3,5-diiodosalicylaldehyde and 20 ml of toluene were charged. 10 ml of a toluene solution containing 0.458 g (2.00 mmol) of 3,5-bistrifluoromethylaniline and 0.1 g of p-toluenesulfonic acid were added and stirred for 4 hours while heating under reflux. The residue obtained by distilling off the solvent was purified by silica gel column chromatography to obtain 0.76 g (yield 65%) of the target compound represented by the following formula (10).
¹ H NMR (CDCl ₃ , 270 MHz): δ 7.70 (s, br, 2H), 7.76 (d, 1H, J = 1.9 Hz), 7.84 (s, br, 1H), 8. 18 (d, 1H, J = 1.9 Hz), 8.52 (s, 1H), 13.61 (s, 1H)

[Ligand synthesis example-11]
A 100 ml reactor thoroughly dried and purged with nitrogen was charged with 2.07 g (5.53 mmol) of 3,5-diiodosalicylaldehyde and 20 ml of toluene. 10 ml of a toluene solution containing 1.14 g (5.53 mmol) of 3,5-bis-t-butylaniline and 0.1 g of p-toluenesulfonic acid were added and stirred for 4 hours while heating under reflux. The residue obtained by distilling off the solvent was purified by silica gel column chromatography to obtain 2.7 g (yield 88%) of the desired product represented by the following formula (11).
¹ H NMR (CDCl ₃ , 270 MHz): δ 1.35 (s, 18H), 7.14? d, 2H, J = 1.8 Hz), 7.40 (t, 1H, J = 1.8 Hz), 7.70 (d, 1H, J = 2.3 Hz), 8.09 (d, 1H, J = 2.3 Hz), 8.48 (s, 1H), 15.2 (s, 1H).

[Ligand synthesis example-12]
A 100 ml reactor thoroughly dried and purged with nitrogen was charged with 1.87 g (5.00 mmol) of 3,5-diiodosalicylaldehyde and 20 ml of toluene. 10 ml of a toluene solution containing 0.68 g (5.00 mmol) of 4-dimethylaminoaniline and 0.1 g of p-toluenesulfonic acid were added and stirred for 4 hours while heating under reflux. The residue obtained by distilling off the solvent was purified by silica gel column chromatography to obtain 2.7 g (yield 55%) of the desired product represented by the following formula (12).
¹ H NMR (CDCl ₃ , 270 MHz): δ 3.02 (s, 6H, CH ₃ ), 6.75 (d, br, 2H, J = 8.6 Hz), 7.29 (d, 2H, J = 8.6 Hz), 7.61 (d, 1 H, J = 2.0 Hz), 8.03 (d, 1 H, J = 2.0 Hz), 8.40 (s, 1 H), 15.4 (s, 1H).

[Ligand synthesis example-13]
-Synthesis of 5-heptylsalicylaldehyde 4-heptylphenol (4.83 g, 25.0 mmol) and 50 ml of diethyl ether were charged into a well-dried and nitrogen-substituted 500 ml reactor, and the reactor was cooled to 0 ° C. 9.17 ml of ethyl magnesium bromide (diethyl ether solution, 3.00 M, 27.5 mmol) was added dropwise over 15 minutes, and the resulting light green solution was stirred at room temperature for 2 hours. Diethyl ether was distilled off, and 50 ml of toluene was added, followed by heating in a 100 ° C. oil bath for 5 minutes. Thereto were added 14.5 ml (10.6 g, 104.3 mmol) of triethylamine and 2.85 g of paraformaldehyde (toluene slurry, 15 ml), and the mixture was stirred at the same temperature for 1 hour. After cooling to room temperature, 240 ml of 1N hydrochloric acid was added and stirred at room temperature for 1 hour. Extraction was performed using hexane, and the organic layer was washed with a saturated aqueous sodium hydrogen carbonate solution and saturated brine, and dried over anhydrous magnesium sulfate. The crude product obtained by concentration was purified by silica gel column chromatography to obtain 5-heptylsalicylaldehyde (4.11 g, 75%) represented by the following formula (13-1) as a colorless oil.
¹ H NMR (CDCl ₃ , 270 MHz): δ 0.88 (t, 3H, J = 9.2 Hz), 1.30 (m, 8H), 1.59 (m, 2H), 2.59 (t, 2H, J = 7.6 Hz), 6.91 (d, 1H, J = 4.5 Hz), 7.33 (s, 1H), 7.35 (m, 2H), 9.87 (d, 1H, J = 0.7Hz), 10.85 (s, 1H)

Synthesis of 5-heptyl-3-iodosalicylaldehyde 5-heptylsalicylaldehyde (1.00 g, 4.54 mmol) and acetic acid shown in the above formula (13-1) in a 30 ml reactor thoroughly dried and purged with nitrogen 4.50 ml was charged and the reactor was heated in an 80 ° C. oil bath. 6.81 ml of iodine monochloride (dichloromethane solution, 1.00 M, 6.81 mmol) was added and stirred at that temperature for 8 hours. After cooling to room temperature, the reaction was stopped by adding a 10% aqueous sodium thiosulfate solution. The mixture was extracted with ethyl acetate, and the organic layer was washed with saturated aqueous sodium hydrogen carbonate solution and saturated brine, and dried over anhydrous magnesium sulfate. The obtained crude product was purified by silica gel column chromatography to obtain 0.70 g (yield 45%) of 5-heptyl-3-iodosalicylaldehyde represented by the following formula (13-2).
¹ H NMR (CDCl ₃ , 270 MHz): δ 0.89 (t, 3H, J = 6.8 Hz), 1.28-1.31 (m, 8H), 1.55-1.65 (m, 2H) ), 2.57 (t, 2H, J = 7.6 Hz), 7.35 (d, 1H, J = 2.0 Hz), 7.83 (d, 1H, J = 2.0 Hz), 9.73. (S, 1H), 11.62 (s, 1H)

-Synthesis | combination of ligand 13 1.48 g (4.26 mmol) 3-iodo-5-heptyl salicylaldehyde shown by said Formula (13-2) in 20 ml of toluene to 100 ml reactor fully dried and nitrogen-substituted. Was charged. 10 ml of a toluene solution containing 1.43 g (4.26 mmol) of 4-tritylaniline and 0.1 g of p-toluenesulfonic acid were added and stirred for 4 hours while heating under reflux. The residue obtained by distilling off the solvent was purified by silica gel column chromatography to obtain 2.41 g (yield 85%) of the desired product represented by the following formula (13).
¹ H NMR (CDCl ₃ , 270 MHz): δ 0.88 (t, 3H, J = 6.8 Hz), 1.28 (m, 8H), 1.59 (m, 2H), 2.54 (t, 2H, J = 7.7 Hz), 7.22 (m, 20H), 7.67 (d, 1H, J = 2.0 Hz), 8.50 (s, 1H), 14.36 (s, 1H)

[Ligand synthesis example-14]
To a 100 ml reactor thoroughly dried and purged with nitrogen, 1.00 g (5.00 mmol) of 3-bromosalicylaldehyde and 20 ml of toluene were charged. 10 ml of a toluene solution containing 0.746 g (5.00 mmol) of 4-t-butylaniline and 0.1 g of p-toluenesulfonic acid were added and stirred for 4 hours while heating under reflux. The residue obtained by distilling off the solvent was purified by silica gel column chromatography to obtain 1.2 g (yield 73%) of the desired product represented by the following formula (14).
¹ H NMR (CDCl ₃ , 270 MHz): δ 1.35 (s, 9H), 6.83 (t, 1H, J = 7.7 Hz), 7.26 (dt, 2H, J = 9.1, 2) .5Hz), 7.36? dd, 1H, J = 7.7, 1.5 Hz), 7.46 (dt, 2H, J = 9.1, 2.5 Hz), 7.63 (dd, 1H, J = 7.7, 1. 5Hz), 8.61 (s, 1H), 14.6 (s, 1H)

(2) Complex synthesis [Complex synthesis example-1]
To a 100 ml reactor thoroughly dried and purged with nitrogen, 20 ml of diethyl ether was added and cooled to -78 ° C. Thereto was added 1.46 ml of titanium tetrachloride (toluene solution, 1.00 M, 1.46 mmol). An ether solution (25 ml) containing 1.3 g (2.9 mmol) of compound (1) was added dropwise to the solution over 15 minutes. After completion of dropping, stirring was continued for 14 hours while slowly returning to room temperature. After the solvent of the reaction solution was distilled off, the obtained solid was dissolved in 50 ml of methylene chloride, and the insoluble matter was removed with a glass filter. The filtrate was concentrated under reduced pressure, and the precipitated solid was reprecipitated with diethyl ether and dried under reduced pressure to obtain 0.7 g of a red brown powder compound represented by the following formula (A) (yield 78%).
FD-mass spectrometry (M +): 1014

[Complex Synthesis Example-2]
To a 100 ml reactor thoroughly dried and purged with nitrogen, 20 ml of diethyl ether was added and cooled to -78 ° C. Thereto was added 1.00 ml of titanium tetrachloride (toluene solution, 1.00 M, 1.00 mmol). An ether solution (25 ml) containing 1.01 g (2.00 mmol) of compound (2) was added dropwise to the solution over 15 minutes. After completion of dropping, stirring was continued for 14 hours while slowly returning to room temperature. After the solvent of the reaction solution was distilled off, the obtained solid was dissolved in 30 ml of methylene chloride, and insoluble matters were removed with a glass filter. The filtrate was concentrated under reduced pressure, and the precipitated solid was reprecipitated with diethyl ether and dried under reduced pressure to obtain 0.78 g of a compound of reddish brown powder represented by the following formula (B) (yield 69%). FD-mass spectrometry (M +): 1126

[Complex Synthesis Example-3]
To a 100 ml reactor thoroughly dried and purged with nitrogen, 20 ml of diethyl ether was added and cooled to -78 ° C. 2.00 ml of titanium tetrachloride (toluene solution, 1.00 M, 2.00 mmol) was added thereto. An ether solution (25 ml) containing 1.64 g (4.00 mmol) of compound (3) was added dropwise to the solution over 15 minutes. After completion of dropping, stirring was continued for 14 hours while slowly returning to room temperature. After the solvent of the reaction solution was distilled off, the obtained solid was dissolved in 50 ml of methylene chloride, and the insoluble matter was removed with a glass filter. The filtrate was concentrated under reduced pressure, and the precipitated solid was reprecipitated with diethyl ether and dried under reduced pressure to obtain 0.9 g of a red brown powder compound represented by the following formula (C) (yield 50%). FD-mass spectrometry (M +): 938

[Complex Synthesis Example-4]
To a 100 ml reactor thoroughly dried and purged with nitrogen, 10 ml of diethyl ether was added and cooled to -78 ° C. Thereto, 0.50 ml of titanium tetrachloride (toluene solution, 1.00 M, 0.50 mmol) was added. An ether solution (20 ml) containing 0.71 g (1.0 mmol) of the compound (4) was added dropwise to the solution over 15 minutes. After completion of dropping, stirring was continued for 14 hours while slowly returning to room temperature. After the solvent of the reaction solution was distilled off, the obtained solid was dissolved in 30 ml of methylene chloride, concentrated under reduced pressure until the amount of the solvent was reduced to half, and reprecipitated with hexane. The solid was collected by filtration and dried under reduced pressure to obtain 0.68 g of a red brown powder compound represented by the following formula (D) (yield 91%).
¹ H NMR (CDCl ₃ , 270 MHz): δ 7.0-7.31 (m, 19H), 7.35 (d, 1H, J = 2.3 Hz), 7.89 (s, 1H), 8. 14 (d, 1H, J = 2.3Hz)

[Complex Synthesis Example-5]
To a 100 ml reactor thoroughly dried and purged with nitrogen, 10 ml of diethyl ether was added and cooled to -78 ° C. Thereto, 0.50 ml of titanium tetrachloride (toluene solution, 1.00 M, 0.50 mmol) was added. To the solution, an ether solution (20 ml) containing 0.60 g (1.0 mmol) of the compound (5) was added dropwise over 15 minutes. After completion of dropping, stirring was continued for 14 hours while slowly returning to room temperature. After the solvent of the reaction solution was distilled off, the obtained solid was dissolved in 30 ml of methylene chloride, and then concentrated under reduced pressure, and the precipitated solid was reprecipitated with hexane. The solid was collected by filtration and dried under reduced pressure to obtain 0.45 g of a red-brown powder compound represented by the following formula (E) (yield 80%).
¹ H NMR (CDCl ₃ , 270 MHz): δ 7.30? 7.07 (m, 19H), 7.35 (d, 1H, J = 2.3 Hz), 7.73 (d, 1H, J = 2) .3Hz), 7.95 (s, 1H)

[Complex Synthesis Example-6]
To a 100 ml reactor thoroughly dried and purged with nitrogen, 10 ml of diethyl ether was added and cooled to -78 ° C. Thereto was added 0.25 ml of titanium tetrachloride (toluene solution, 1.00 M, 0.25 mmol). An ether solution (20 ml) containing 0.309 g (0.500 mmol) of compound (6) was added dropwise to the solution over 15 minutes. After completion of dropping, stirring was continued for 14 hours while slowly returning to room temperature. After the solvent of the reaction solution was distilled off, the obtained solid was dissolved in 15 ml of tetrahydrofuran and stirred at room temperature for 3 hours. After the solvent of the reaction solution was distilled off, the obtained solid was dissolved in 15 ml of methylene chloride, and then concentrated under reduced pressure, and the precipitated solid was reprecipitated with hexane. The solid was collected by filtration and dried under reduced pressure to obtain 0.19 g of a compound of reddish brown powder represented by the following formula (F) (yield 58%).
¹ H NMR (CDCl ₃ , 270 MHz): δ 0.89 (t, br, J = 7.0 Hz, 6H), 1.29-1.44 (m, 40H), 2.41-2.46 (t , Br, 4H, J = 7.6 Hz), 6.94-7.04 (m, 8H), 7.41 (s, br, 2H), 7.84 (s, 2H), 7.97 (s) , Br, 2H)

[Complex Synthesis Example-7]
A 100 ml reactor thoroughly dried and purged with nitrogen was charged with 24 mg (1.0 mmol) of sodium hydride and 10 ml of ether and cooled to 0 ° C. An ether solution (20 ml) containing 0.56 g (1.0 mmol) of the compound (7) was added dropwise over 5 minutes. The reaction temperature was raised to room temperature and stirred for 1 hour to prepare a sodium salt. This solution was added dropwise to 10 ml of a diethyl ether solution containing 0.50 ml of titanium tetrachloride (toluene solution, 1.00 M, 0.50 mmol) cooled to −78 ° C. After completion of dropping, stirring was continued for 14 hours while slowly returning to room temperature. After the solvent of the reaction solution was distilled off, the obtained solid was dissolved in 30 ml of methylene chloride, and insoluble matters were removed with a glass filter. The filtrate was concentrated under reduced pressure, and the precipitated solid was reprecipitated with diethyl ether and dried under reduced pressure to obtain 0.15 g of an ocherous powder compound represented by the following formula (G) (yield 28%).
¹ H NMR (CDCl ₃ , 270 MHz): δ 0.90 (d, 3H, J = 6.6 Hz), 1.39 (m, 12H), 2.44 (t, 2H, J = 7.6 Hz), 7.00 (dd, 4H, J = 19.6, 8.1 Hz), 7.41 (d, 1H, J = 2.0 Hz), 7.84 (s, 1H), 7.98 (d, 1H) , J = 2.0Hz)

[Complex Synthesis Example-8]
To a 100 ml reactor thoroughly dried and purged with nitrogen, 10 ml of diethyl ether was added and cooled to -78 ° C. Thereto, 0.50 ml of titanium tetrachloride (toluene solution, 1.00 M, 0.50 mmol) was added. To the solution, an ether solution (20 ml) containing 0.517 g (1.0 mmol) of the compound (8) was added dropwise over 15 minutes. After completion of dropping, stirring was continued for 14 hours while slowly returning to room temperature. After the solvent of the reaction solution was distilled off, the obtained solid was dissolved in 30 ml of methylene chloride, and then concentrated under reduced pressure, and the precipitated solid was reprecipitated with hexane. The solid was collected by filtration and dried under reduced pressure to obtain 0.31 g of a red brown powder compound represented by the following formula (H) (yield: 54%).
¹ H NMR (CD ₂ Cl ₂ , 270 MHz): δ 7.13 (d, 4H, J = 8.1 Hz), 7.33 (d, 4H, J = 8.1 Hz), 7.44 (d, 2H) , J = 1.9 Hz), 7.90 (s, 2H), 8.02 (d, 2H, J = 1.9 Hz)

[Complex Synthesis Example-9]
To a 100 ml reactor thoroughly dried and purged with nitrogen, 10 ml of diethyl ether was added and cooled to -78 ° C. Thereto was added 1.00 ml of titanium tetrachloride (toluene solution, 1.00 M, 1.00 mmol). An ether solution (20 ml) containing 0.846 g (2.00 mmol) of compound (9) was added dropwise to the solution over 15 minutes. After completion of dropping, stirring was continued for 14 hours while slowly returning to room temperature. After the solvent of the reaction solution was distilled off, the obtained solid was dissolved in 40 ml of tetrahydrofuran. The solid obtained by removing the insoluble matter and concentrating under reduced pressure was dissolved in ether, and then reprecipitated with hexane. The solid was collected by filtration and dried under reduced pressure to obtain 0.78 g of a red brown powder compound represented by the following formula (I) (yield 81%). FD-mass spectrometry (M +): 958

[Complex Synthesis Example-10]
To a 100 ml reactor thoroughly dried and purged with nitrogen, 10 ml of diethyl ether was added and cooled to -78 ° C. Thereto was added 0.25 ml of titanium tetrachloride (toluene solution, 1.00 M, 0.25 mmol). An ether solution (20 ml) containing 0.293 g (0.500 mmol) of the compound (10) was added dropwise to the solution over 15 minutes. After completion of dropping, stirring was continued for 14 hours while slowly returning to room temperature. After the solvent of the reaction solution was distilled off, the obtained solid was dissolved in 20 ml of methylene chloride, and then concentrated under reduced pressure, and the precipitated solid was reprecipitated with hexane. The solid was collected by filtration and dried under reduced pressure to obtain 0.29 g of a compound of reddish brown powder represented by the following formula (J) (yield 55%).
¹ H NMR (CDCl ₃ , 270 MHz): δ 7.37 (s, br, 4H), 7.67 (d, 2H, J = 2.2 Hz), 7.74 (s, br, 2H), 8. 10 (s, 2H), 8.16 (d, 2H, J = 2.2 Hz)

[Complex Synthesis Example-11]
To a 100 ml reactor thoroughly dried and purged with nitrogen, 10 ml of diethyl ether was added and cooled to -78 ° C. Thereto, 0.50 ml of titanium tetrachloride (toluene solution, 1.00 M, 0.50 mmol) was added. To the solution, an ether solution (20 ml) containing 0.56 g (1.0 mmol) of the compound (11) was added dropwise over 15 minutes. After completion of dropping, stirring was continued for 14 hours while slowly returning to room temperature. After the solvent of the reaction solution was distilled off, the obtained solid was dissolved in 30 ml of methylene chloride, concentrated under reduced pressure until the amount of the solvent was reduced to half, and reprecipitated with hexane. The solid was collected by filtration and dried under reduced pressure to obtain 0.49 g of a compound of a reddish brown powder represented by the following formula (K) (yield 93%).
¹ H NMR (CD ₂ Cl ₂ , 270 MHz): δ 1.21 (s, 18H), 6.81? s, br, 2H? , 7, 21 (t, 1H, J = 1.6 Hz), 7.52 (d, 1H, J = 2.0 Hz), 8.01 (s, 1H), 8.04 (d, 1H, J = 2.0Hz)

[Complex Synthesis Example-12]
To a 100 ml reactor thoroughly dried and purged with nitrogen, 10 ml of diethyl ether was added and cooled to -78 ° C. Thereto, 0.50 ml of titanium tetrachloride (toluene solution, 1.00 M, 0.50 mmol) was added. An ether solution (20 ml) containing 0.49 g (1.0 mmol) of the compound (12) was added dropwise to the solution over 15 minutes. After completion of dropping, stirring was continued for 14 hours while slowly returning to room temperature. After the solvent of the reaction solution was distilled off, 30 ml of dichloromethane and 0.14 ml (1.0 mmol) of triethylamine were added, and the resulting suspension was stirred for 1 hour. The solid was collected by filtration, washed with hexane, and dried under reduced pressure to obtain 0.26 g of a red brown powder compound represented by the following formula (L) (yield 47%).
¹ H NMR (CDCl ₃ , 270 MHz): δ 2.90? s, 6H), 6.46 (2H, m), 7.00 (d, 2H, J = 10 Hz), 7.39 (d, 1H, J = 2.0 Hz), 7.77 (s, 1H) 7.49 (d, 1H, J = 2.0 Hz)

[Complex Synthesis Example-13]
To a 100 ml reactor thoroughly dried and purged with nitrogen, 10 ml of diethyl ether was added and cooled to -78 ° C. Thereto, 0.500 ml of titanium tetrachloride (toluene solution, 1.00 M, 0.500 mmol) was added. To the solution, an ether solution (20 ml) containing 0.663 g (1.00 mmol) of the compound (13) was added dropwise over 15 minutes. After completion of dropping, stirring was continued for 14 hours while slowly returning to room temperature. After the solvent of the reaction solution was distilled off, the obtained solid was dissolved in 30 ml of methylene chloride, and then concentrated under reduced pressure, and the precipitated solid was reprecipitated with hexane. The solid was collected by filtration and dried under reduced pressure to obtain 0.49 g of a red brown powder compound represented by the following formula (M) (yield 68%).
¹ H NMR (CDCl ₃ , 270 MHz): δ 0.85 (t, 3H, J = 6.8 Hz), 1.22 (m, 8H), 1.46 (m, 2H), 2.46 (t, 2H, J = 7.7 Hz), 7.26-7.01 (m, 20H), 7.76 (d, 1H, J = 2.0 Hz), 7.93 (s, 1H)

[Complex Synthesis Example-14]
To a 100 ml reactor thoroughly dried and purged with nitrogen, 10 ml of diethyl ether was added and cooled to -78 ° C. Thereto was added 0.905 ml of titanium tetrachloride (toluene solution, 1.00 M, 0.905 mmol). An ether solution (20 ml) containing 0.601 g (1.81 mmol) of the compound (14) was added dropwise to the solution over 15 minutes. After completion of dropping, stirring was continued for 14 hours while slowly returning to room temperature. After the solvent of the reaction solution was distilled off, the obtained solid was dissolved in 30 ml of methylene chloride, and then concentrated under reduced pressure, and the precipitated solid was reprecipitated with hexane. The solid was collected by filtration and dried under reduced pressure to obtain 0.58 g of a red brown powder compound represented by the following formula (N) (yield 41%).
¹ H NMR (CDCl ₃ , 270 MHz): δ 1.26 (s, 9 H), 6.67 (t, 1 H, J = 7.7 Hz), 7.06 to 7.16 (m, 5 H), 7. 46 (dd, 1H, J = 7.7, 1.6 Hz), 8.00 (s, 1H)

[Example 1]
A glass reactor having an internal volume of 500 ml sufficiently purged with nitrogen was charged with 250 ml of toluene, and the liquid phase and gas phase were saturated with 100 l / hr of ethylene. Thereafter, methylaluminoxane was added in an amount of 1.25 mmol in terms of aluminum atom, and then 0.0001 mmol of the titanium compound (A) obtained in the complex synthesis example-1 was added to initiate polymerization. Ethylene was continuously supplied at 100 liters / hr, polymerization was performed at 25 ° C. for 5 minutes under normal pressure, and then the polymerization was stopped by adding a small amount of isobutanol. After completion of the polymerization, the reaction product was added to 1 liter of methanol containing a small amount of hydrochloric acid to precipitate a polymer. After washing with methanol, it was dried under reduced pressure at 80 ° C. for 10 hours to obtain 1.53 g of polyethylene. The polymerization activity was 183.6 kg / mmol-Ti · hr, and the obtained polyethylene had an intrinsic viscosity [η] of 3.22 dl / g.

[Example 2]
To a glass reactor having an internal volume of 500 ml sufficiently purged with nitrogen, 250 ml of toluene was charged, and the liquid phase and the gas phase were saturated with a mixed gas of ethylene 100 liter / hr and propylene 100 liter / hr. Thereafter, methylaluminoxane was added in an amount of 1.25 mmol in terms of aluminum atom, and subsequently 0.005 mmol of the titanium compound (A) obtained in the complex synthesis example-1 was added, and copolymerization was started under normal pressure. After copolymerization at 50 ° C. for 10 minutes, the polymerization was stopped by adding a small amount of isobutanol. To the obtained polymer suspension, 100 ml of water containing a small amount of hydrochloric acid was added, shaken vigorously, allowed to stand, and then the aqueous layer was removed. After repeating this operation three times in total, the solvent was distilled off under reduced pressure and further dried under reduced pressure at 130 ° C. for 10 hours. The obtained ethylene / propylene copolymer (EPR) was 12.18 g. The polymerization activity was 14.6 kg / mmol-Ti · hr. The intrinsic viscosity [η] of the obtained ethylene / propylene copolymer was 0.75 dl / g. The propylene content measured by IR was 64.0 mol%.

Example 3
A glass reactor having an internal volume of 500 ml sufficiently purged with nitrogen was charged with 250 ml of toluene and 5 ml of tetracyclododecene, and the liquid phase and gas phase were saturated with 50 liters / hr of ethylene. Thereafter, methylaluminoxane was added in an amount of 1.25 mmol in terms of aluminum atom, and then 0.0002 mmol of the titanium compound (A) obtained in the complex synthesis example-1 was added to initiate polymerization. Ethylene was continuously supplied at 50 liters / hr, polymerization was performed at 25 ° C. for 10 minutes under normal pressure, and then the polymerization was stopped by adding a small amount of isobutanol. After completion of the polymerization, the reaction product was added to 1.25 liters of methanol / acetone (1: 1) containing a small amount of hydrochloric acid to precipitate a polymer. After washing with methanol and acetone, it was dried under reduced pressure at 130 ° C. for 10 hours to obtain 0.52 g of an ethylene / tetracyclododecene copolymer. The polymerization activity was 15.6 kg / mmol-Ti · hr, and the intrinsic viscosity [η] of the obtained ethylene / tetracyclododecene copolymer was 1.22 dl / g. The glass transition temperature measured by DSC was 162 ° C., and the content of tetracyclododecene in the polymer estimated from this value was 40.5 mol%.

Example 4
In Example 1, the same procedure as in Example 1 was performed except that 0.00005 mmol of the titanium compound (B) obtained in Complex Synthesis Example-2 was used instead of the titanium compound (A). 92 g was obtained. The polymerization activity was 220.8 kg / mmol-Ti · hr, and the obtained polyethylene had an intrinsic viscosity [η] of 7.50 dl / g.

Example 5
In Example 1, except that 0.00002 mmol of the titanium compound (B) obtained in the complex synthesis example-2 was used in place of the titanium compound (A), the same operation as in Example 1 was performed, and polyethylene 0. 43 g was obtained. The polymerization activity was 258.0 kg / mmol-Ti · hr, and the intrinsic viscosity [η] of the obtained polyethylene was 6.27 dl / g.

Example 6
An ethylene / propylene copolymer was prepared in the same manner as in Example 2, except that the titanium compound (B) obtained in Complex Synthesis Example-2 was used in place of the titanium compound (A). 10.67 g of (EPR) was obtained. The polymerization activity was 12.8 kg / mmol-Ti · hr. The intrinsic viscosity [η] of the obtained ethylene / propylene copolymer was 1.24 dl / g. The propylene content measured by IR was 53.7 mol%.

Example 7
In Example 3, an operation similar to that in Example 3 was performed except that 0.0002 mmol of the titanium compound (B) obtained in Complex Synthesis Example-2 was used instead of the titanium compound (A). 0.547 g of cyclododecene copolymer was obtained. The polymerization activity was 16.4 kg / mmol-Ti · hr, and the intrinsic viscosity [η] of the obtained ethylene · tetracyclododecene copolymer was 2.10 dl / g. The glass transition temperature determined by DSC measurement was 149 ° C., and the content of tetracyclododecene in the polymer estimated from this value was 37.5 mol%.

Example 8
A glass reactor having an internal volume of 500 ml sufficiently purged with nitrogen was charged with 250 ml of toluene and 5 g of norbornene, and the liquid phase and gas phase were saturated with 50 liters / hr of ethylene. Thereafter, methylaluminoxane was added in an amount of 1.25 mmol in terms of aluminum atom, and subsequently 0.0001 mmol of the titanium compound (B) obtained in Complex Synthesis Example-2 was added to initiate polymerization. Ethylene was continuously supplied at 50 liters / hr, polymerization was performed at 25 ° C. for 10 minutes under normal pressure, and then the polymerization was stopped by adding a small amount of isobutanol. After completion of the polymerization, the reaction product was added to 1.25 liters of methanol / acetone (1: 1) containing a small amount of hydrochloric acid to precipitate a polymer. After washing with methanol and acetone, it was dried under reduced pressure at 80 ° C. for 10 hours to obtain 0.23 g of an ethylene / norbornene copolymer. The polymerization activity was 13.8 kg / mmol-Ti · hr, and the intrinsic viscosity [η] of the obtained ethylene · tetracyclododecene copolymer was 3.20 dl / g. The glass transition temperature determined by DSC measurement was 100 ° C., and the norbornene content in the polymer estimated from this value was 40.1 mol%.

Example 9
In Example 8, except that 10 g was used instead of 5 g of norbornene, the same operation as in Example 8 was performed to obtain 0.0772 g of an ethylene / norbornene copolymer. The polymerization activity was 4.63 kg / mmol-Ti · hr, and the intrinsic viscosity [η] of the obtained ethylene / norbornene copolymer was 2.66 dl / g. The glass transition temperature determined by DSC measurement was 115 ° C., and the norbornene content in the polymer estimated from this value was 43.7 mol%.

Example 10
A glass reactor having an internal volume of 500 ml sufficiently purged with nitrogen was charged with 250 ml of toluene and 6.09 g of 1-hexene, and the liquid phase and the gas phase were saturated with 100 liter / hr of ethylene. Thereafter, methylaluminoxane was added in an amount of 1.25 mmol in terms of aluminum atom, and subsequently 0.0001 mmol of the titanium compound (B) obtained in Complex Synthesis Example-2 was added to initiate polymerization. Ethylene was continuously supplied at 100 liter / hr, polymerization was performed at 50 ° C. under normal pressure for 5 minutes, and then the polymerization was stopped by adding a small amount of isobutanol. After completion of the polymerization, the reaction product was added to 1.25 liters of methanol / acetone (1: 1) containing a small amount of hydrochloric acid to precipitate a polymer. After washing with methanol and acetone, it was dried under reduced pressure at 130 ° C. for 10 hours to obtain 0.685 g of an ethylene / 1-hexene copolymer. The polymerization activity was 82.2 kg / mmol-Ti · hr, and the intrinsic viscosity [η] of the obtained ethylene / 1-hexene copolymer was 3.32 dl / g. The melting point by DSC measurement was 95 ° C. The 1-hexene content measured by IR was 5.2 mol%.

Example 11
In Example 1, except that 0.0002 mmol of the titanium compound (C) obtained in the complex synthesis example-3 was used instead of the titanium compound (A), the same operation as in Example 1 was performed, and polyethylene 1. 43 g was obtained. The polymerization activity was 85.8 kg / mmol-Ti · hr, and the intrinsic viscosity [η] of the obtained polyethylene was 7.26 dl / g.

Example 12
In Example 1, the same procedure as in Example 1 was performed except that 0.00002 mmol of the titanium compound (C) obtained in Complex Synthesis Example-3 was used instead of the titanium compound (A). 161 g was obtained. The polymerization activity was 96.6 kg / mmol-Ti · hr, and the intrinsic viscosity [η] of the obtained polyethylene was 6.24 dl / g.

Example 13
An ethylene / propylene copolymer was prepared in the same manner as in Example 2 except that the titanium compound (C) obtained in Complex Synthesis Example-3 was used in place of the titanium compound (A). 5.26 g of (EPR) was obtained. The polymerization activity was 6.31 kg / mmol-Ti · hr. The intrinsic viscosity [η] of the obtained ethylene / propylene copolymer was 0.74 dl / g. The propylene content measured by IR was 42.1 mol%.

Example 14
In Example 3, except that 0.0005 mmol of the titanium compound (C) obtained in the complex synthesis example-3 was used instead of the titanium compound (A), the same operation as in Example 3 was performed, and ethylene tetra 2.19 g of a cyclododecene copolymer was obtained. The polymerization activity was 26.3 kg / mmol-Ti · hr, and the intrinsic viscosity [η] of the obtained ethylene · tetracyclododecene copolymer was 1.80 dl / g. The glass transition temperature determined by DSC measurement was 135 ° C., and the content of tetracyclododecene in the polymer estimated from this value was 34.2 mol%.

Example 15
In Example 8, the same operation as in Example 8 was performed except that 0.0001 mmol of the titanium compound (C) obtained in Complex Synthesis Example-3 was used instead of the titanium compound (B), and ethylene norbornene was obtained. 0.38 g of copolymer was obtained. The polymerization activity was 22.8 kg / mmol-Ti · hr, and the intrinsic viscosity [η] of the obtained ethylene / norbornene copolymer was 2.74 dl / g. The glass transition temperature measured by DSC was 99 ° C., and the norbornene content in the polymer estimated from this value was 39.8 mol%.

Example 16
In Example 8, 0.0001 mmol of the titanium compound (C) obtained in the complex synthesis example-3 in place of the titanium compound (B) and 10 g in place of 5 g of norbornene were used, and the same as in Example 8. Operation was performed to obtain 0.135 g of an ethylene / norbornene copolymer. The polymerization activity was 8.1 kg / mmol-Ti · hr, and the intrinsic viscosity [η] of the obtained ethylene / norbornene copolymer was 3.06 dl / g. The glass transition temperature determined by DSC measurement was 117 ° C., and the norbornene content in the polymer estimated from this value was 44.2 mol%.

Example 17
In Example 10, the same operation as in Example 10 was performed except that 0.0001 mmol of the titanium compound (C) obtained in the complex synthesis example-3 was used instead of the titanium compound (B). -0.17g of hexene copolymer was obtained. The polymerization activity was 20.4 kg / mmol-Ti · hr, and the intrinsic viscosity [η] of the obtained ethylene / 1-hexene copolymer was 2.88 dl / g. The melting point by DSC measurement was 101 ° C. The 1-hexene content measured by IR was 4.1 mol%.

Example 18
In Example 1, except that 0.00002 mmol of the titanium compound (D) obtained in Complex Synthesis Example-4 was used instead of the titanium compound (A), the same operation as in Example 1 was carried out, and polyethylene 0. 75 g was obtained. The polymerization activity was 450.0 kg / mmol-Ti · hr, and the intrinsic viscosity [η] of the obtained polyethylene was 5.50 dl / g.

Example 19
An ethylene / propylene copolymer was prepared in the same manner as in Example 2, except that the titanium compound (D) obtained in Complex Synthesis Example-4 was used instead of the titanium compound (A). 15.7 g of (EPR) was obtained. The polymerization activity was 18.8 kg / mmol-Ti · hr. The intrinsic viscosity [η] of the obtained ethylene / propylene copolymer was 0.73 dl / g. The propylene content measured by IR was 33.9 mol%.

Example 20
In Example 3, the same procedure as in Example 3 was performed, except that 0.00005 mmol of the titanium compound (D) obtained in Complex Synthesis Example-4 was used instead of the titanium compound (A). 0.84 g of cyclododecene copolymer was obtained. The polymerization activity was 100.8 kg / mmol-Ti · hr, and the intrinsic viscosity [η] of the obtained ethylene / tetracyclododecene copolymer was 1.55 dl / g. The glass transition temperature measured by DSC was 151 ° C., and the content of tetracyclododecene in the polymer estimated from this value was 37.1 mol%.

Example 21
In Example 3, 0.0001 mmol of the titanium compound (D) obtained in the complex synthesis example-4 instead of the titanium compound (A), cyclohexane instead of toluene, and 2 ml instead of 5 ml of tetracyclododecene were used. Otherwise by performing the same operations as in Example 3, 0.255 g of an ethylene / tetracyclododecene copolymer was obtained. The polymerization activity was 15.3 kg / mmol-Ti · hr. The glass transition temperature determined by DSC measurement was 158 ° C., and the content of tetracyclododecene in the polymer estimated from this value was 38.4 mol%.

[Example 22]
In Example 8, ethylene norbornene was prepared in the same manner as in Example 8 except that 0.00002 mmol of the titanium compound (D) obtained in Complex Synthesis Example-4 was used instead of the titanium compound (B). 0.187 g of copolymer was obtained. The polymerization activity was 56.1 kg / mmol-Ti · hr, and the intrinsic viscosity [η] of the obtained ethylene / norbornene copolymer was 4.02 dl / g. The glass transition temperature determined by DSC measurement was 97 ° C., and the norbornene content in the polymer estimated from this value was 39.3 mol%.

Example 23
Example 8 is the same as Example 8 except that 0.00002 mmol of the titanium compound (D) obtained in Complex Synthesis Example-4 is used instead of the titanium compound (B), and 10 g is used instead of 5 g of norbornene. Operation was performed to obtain 0.064 g of an ethylene / norbornene copolymer. The polymerization activity was 19.2 kg / mmol-Ti · hr. The glass transition temperature determined by DSC measurement was 108 ° C., and the norbornene content in the polymer estimated from this value was 42.0 mol%.

Example 24
In Example 8, 0.00004 mmol of the titanium compound (D) obtained in the complex synthesis example-4 instead of the titanium compound (B) and 10 g instead of 5 g of norbornene were used, and the same as in Example 8. Operation was performed to obtain 0.122 g of an ethylene / norbornene copolymer. The polymerization activity was 18.3 kg / mmol-Ti · hr. The glass transition temperature determined by DSC measurement was 108 ° C., and the norbornene content in the polymer estimated from this value was 42.0 mol%.

Example 25
In Example 1, the same procedure as in Example 1 was performed except that 0.00002 mmol of the titanium compound (E) obtained in Complex Synthesis Example-5 was used instead of the titanium compound (A). 38 g was obtained. The polymerization activity was 226.9 kg / mmol-Ti · hr, and the obtained polyethylene had an intrinsic viscosity [η] of 6.14 dl / g.

Example 26
In Example 3, in place of the titanium compound (A), 0.0001 mmol of the titanium compound (E) obtained in the complex synthesis example-5, and 0.5 mmol of methylaluminoxane was used instead of 1.25 mmol in terms of aluminum atom. Otherwise, the same operation as in Example 3 was performed to obtain 1.20 g of an ethylene / tetracyclododecene copolymer. The polymerization activity was 72.0 kg / mmol-Ti · hr, and the intrinsic viscosity [η] of the obtained ethylene · tetracyclododecene copolymer was 1.34 dl / g. The glass transition temperature measured by DSC was 147 ° C., and the content of tetracyclododecene in the polymer estimated from this value was 36.2 mol%.

Example 27
In Example 3, instead of the titanium compound (A), 0.0001 mmol of the titanium compound (E) obtained in the complex synthesis example-5, 0.5 mmol of toluene instead of 1.25 mmol in terms of aluminum aluminoxane in terms of aluminum atom, toluene Instead of using cyclohexane, the same operation as in Example 3 was performed to obtain 0.138 g of an ethylene / tetracyclododecene copolymer. The polymerization activity was 8.3 kg / mmol-Ti · hr. The glass transition temperature as measured by DSC was 189 ° C., and the content of tetracyclododecene in the polymer estimated from this value was 44.7 mol%.

Example 28
In Example 8, except that 0.00002 mmol of the titanium compound (E) obtained in the complex synthesis example-5 was used in place of the titanium compound (B), the same operation as in Example 8 was performed, and ethylene norbornene 0.20 g of copolymer was obtained. The polymerization activity was 60.0 kg / mmol-Ti · hr, and the intrinsic viscosity [η] of the obtained ethylene / norbornene copolymer was 3.58 dl / g. The glass transition temperature determined by DSC measurement was 97 ° C., and the norbornene content in the polymer estimated from this value was 39.3 mol%.

Example 29
In Example 8, 0.00002 mmol of the titanium compound (E) obtained in Complex Synthesis Example-5 in place of the titanium compound (B) and 10 g in place of 5 g of norbornene were used, and the same as in Example 8. Operation was performed to obtain 0.072 g of an ethylene / norbornene copolymer. The polymerization activity was 21.5 kg / mmol-Ti · hr, and the intrinsic viscosity [η] of the obtained ethylene / norbornene copolymer was 4.00 dl / g. The glass transition temperature determined by DSC measurement was 112 ° C., and the norbornene content in the polymer estimated from this value was 43.0 mol%.

Example 30
In Example 1, the same procedure as in Example 1 was performed except that 0.00005 mmol of the titanium compound (F) obtained in Complex Synthesis Example-6 was used instead of the titanium compound (A). 80 g was obtained. The polymerization activity was 192.0 kg / mmol-Ti · hr, and the intrinsic viscosity [η] of the obtained polyethylene was 3.49 dl / g.

Example 31
In Example 2, ethylene / propylene was prepared in the same manner as in Example 2 except that 0.005 mmol of the titanium compound (F) obtained in Complex Synthesis Example-6 was used instead of the titanium compound (A). 15.5 g of copolymer (EPR) was obtained. The polymerization activity was 18.6 kg / mmol-Ti · hr. The intrinsic viscosity [η] of the obtained ethylene / propylene copolymer was 0.86 dl / g. The propylene content measured by IR was 46.9 mol%.

[Example 32]
In Example 3, 0.0002 mmol of the titanium compound (F) obtained in Complex Synthesis Example-6 in place of the titanium compound (A) and 2 ml in place of 5 ml of tetracyclododecene were used. The same operation was performed to obtain 1.21 g of an ethylene / tetracyclododecene copolymer. The polymerization activity was 36.3 kg / mmol-Ti · hr, and the intrinsic viscosity [η] of the obtained ethylene / tetracyclododecene copolymer was 1.18 dl / g. The glass transition temperature determined by DSC measurement was 154 ° C., and the content of tetracyclododecene in the polymer estimated from this value was 37.6 mol%.

Example 33
In Example 3, 0.0002 mmol of the titanium compound (F) obtained in the complex synthesis example-6 in place of the titanium compound (A), 2 ml of cyclohexane instead of toluene, and 2 ml of tetracyclododecene were used. Otherwise by performing the same operations as in Example 3, 0.17 g of an ethylene / tetracyclododecene copolymer was obtained. The polymerization activity was 5.1 kg / mmol-Ti · hr, and the intrinsic viscosity [η] of the obtained ethylene / tetracyclododecene copolymer was 1.35 dl / g. The glass transition temperature determined by DSC measurement was 153 ° C., and the content of tetracyclododecene in the polymer estimated from this value was 37.4 mol%.

Example 34
In Example 1, the same procedure as in Example 1 was performed except that 0.00005 mmol of the titanium compound (G) obtained in Complex Synthesis Example-7 was used instead of the titanium compound (A). 76 g was obtained. The polymerization activity was 182.4 kg / mmol-Ti · hr, and the obtained polyethylene had an intrinsic viscosity [η] of 3.20 dl / g.

Example 35
In Example 3, 0.0002 mmol of the titanium compound (G) obtained in the complex synthesis example-7 in place of the titanium compound (A) and 2 ml in place of 5 ml of tetracyclododecene were used. The same operation was performed to obtain 1.01 g of an ethylene / tetracyclododecene copolymer. The polymerization activity was 30.3 kg / mmol-Ti · hr, and the intrinsic viscosity [η] of the obtained ethylene / tetracyclododecene copolymer was 1.15 dl / g. The glass transition temperature determined by DSC measurement was 105 ° C., and the content of tetracyclododecene in the polymer estimated from this value was 27.7 mol%.

Example 36
In Example 3, in place of the titanium compound (A), 0.0002 mmol of the titanium compound (G) obtained in the complex synthesis example-7, cyclohexane instead of toluene, and 2 ml of tetracyclododecene were used instead of 5 ml. Otherwise by performing the same operations as in Example 3, 0.16 g of an ethylene / tetracyclododecene copolymer was obtained. The polymerization activity was 4.8 kg / mmol-Ti · hr, and the intrinsic viscosity [η] of the obtained ethylene / tetracyclododecene copolymer was 1.28 dl / g. The glass transition temperature measured by DSC was 158 ° C., and the content of tetracyclododecene in the polymer estimated from this value was 38.5 mol%.

Example 37
In Example 1, the same procedure as in Example 1 was performed except that 0.00002 mmol of the titanium compound (H) obtained in Complex Synthesis Example-8 was used instead of the titanium compound (A). 40 g was obtained. The polymerization activity was 240.0 kg / mmol-Ti · hr, and the intrinsic viscosity [η] of the obtained polyethylene was 5.58 dl / g.

Example 38
In Example 2, ethylene / propylene was prepared in the same manner as in Example 2 except that 0.005 mmol of the titanium compound (H) obtained in Complex Synthesis Example-8 was used instead of the titanium compound (A). 8.69 g of copolymer (EPR) was obtained. The polymerization activity was 10.4 kg / mmol-Ti · hr. The intrinsic viscosity [η] of the obtained ethylene / propylene copolymer was 1.11 dl / g. The propylene content measured by IR was 41.7 mol%.

Example 39
In Example 3, the same procedure as in Example 3 was performed, except that 0.00005 mmol of the titanium compound (H) obtained in Complex Synthesis Example-8 was used instead of the titanium compound (A). 0.419 g of dodecene copolymer was obtained. The polymerization activity was 50.2 kg / mmol-Ti · hr. The glass transition temperature as measured by DSC was 153 ° C., and the content of tetracyclododecene in the polymer estimated from the value was 37.4 mol%.

Example 40
In Example 3, 0.0002 mmol of the titanium compound (H) obtained in the complex synthesis example-8 in place of the titanium compound (A), 2 ml of cyclohexane instead of toluene, and 5 ml of tetracyclododecene were used. Otherwise by performing the same operations as in Example 3, 0.23 g of an ethylene / tetracyclododecene copolymer was obtained. The polymerization activity was 6.9 kg / mmol-Ti · hr, and the intrinsic viscosity [η] of the obtained ethylene · tetracyclododecene copolymer was 1.00 dl / g. The glass transition temperature determined by DSC measurement was 149 ° C., and the content of tetracyclododecene in the polymer estimated from this value was 36.6 mol%.

Example 41
In Example 8, ethylene norbornene was prepared in the same manner as in Example 8 except that 0.00002 mmol of the titanium compound (H) obtained in Complex Synthesis Example-8 was used instead of the titanium compound (B). 0.051 g of copolymer was obtained. The polymerization activity was 15.3 kg / mmol-Ti · hr, and the intrinsic viscosity [η] of the obtained ethylene / norbornene copolymer was 3.12 dl / g. The glass transition temperature measured by DSC was 99 ° C., and the norbornene content in the polymer estimated from this value was 39.8 mol%.

Example 42
In Example 8, the same operation as in Example 8 was performed except that 0.0001 mmol of the titanium compound (H) obtained in Complex Synthesis Example-8 was used instead of the titanium compound (B), and ethylene norbornene was obtained. 0.290 g of copolymer was obtained. The polymerization activity was 17.4 kg / mmol-Ti · hr, and the intrinsic viscosity [η] of the obtained ethylene / norbornene copolymer was 3.12 dl / g. The glass transition temperature measured by DSC was 99 ° C., and the norbornene content in the polymer estimated from this value was 39.8 mol%.

Example 43
In Example 8, 0.0001 mmol of the titanium compound (H) obtained in Complex Synthesis Example-8 was used instead of the titanium compound (B), and 10 g was used instead of 5 g of norbornene, and the same as in Example 8. Operation was performed to obtain 0.067 g of an ethylene / norbornene copolymer. The polymerization activity was 4.0 kg / mmol-Ti · hr, and the intrinsic viscosity [η] of the obtained ethylene / norbornene copolymer was 1.95 dl / g. The glass transition temperature determined by DSC measurement was 115 ° C., and the norbornene content in the polymer estimated from this value was 43.7 mol%.

Example 44
In Example 1, in place of the titanium compound (A), 0.0001 mmol of the titanium compound (I) obtained in the complex synthesis example-9 was used. 54 g was obtained. The polymerization activity was 64.8 kg / mmol-Ti · hr, and the obtained polyethylene had an intrinsic viscosity [η] of 6.38 dl / g.

Example 45
In Example 3, except that 0.0002 mmol of the titanium compound (I) obtained in Complex Synthesis Example-9 was used instead of the titanium compound (A), the same operation as in Example 3 was performed, and ethylene tetracyclo 1.13 g of dodecene copolymer was obtained. The polymerization activity was 33.9 kg / mmol-Ti · hr, and the intrinsic viscosity [η] of the obtained ethylene · tetracyclododecene copolymer was 1.27 dl / g. The glass transition temperature determined by DSC measurement was 143 ° C., and the content of tetracyclododecene in the polymer estimated from this value was 35.4 mol%.

Example 46
In Example 3, 0.0008 mmol of the titanium compound (I) obtained in Complex Synthesis Example-9 in place of the titanium compound (A), cyclohexane in place of toluene, and 2 ml in place of 5 ml of tetracyclododecene were used. Otherwise by performing the same operations as in Example 3, 0.98 g of an ethylene / tetracyclododecene copolymer was obtained. The polymerization activity was 7.4 kg / mmol-Ti · hr, and the intrinsic viscosity [η] of the obtained ethylene · tetracyclododecene copolymer was 1.23 dl / g. The glass transition temperature determined by DSC measurement was 136 ° C., and the content of tetracyclododecene in the polymer estimated from this value was 34.1 mol%.

Example 47
In Example 1, the same procedure as in Example 1 was performed except that 0.00002 mmol of the titanium compound (J) obtained in Complex Synthesis Example-10 was used instead of the titanium compound (A). 31 g was obtained. The polymerization activity was 186.0 kg / mmol-Ti · hr, and the obtained polyethylene had an intrinsic viscosity [η] of 1.87 dl / g.

Example 48
In Example 3, 0.0001 mmol of the titanium compound (J) obtained in the complex synthesis example-10 in place of the titanium compound (A) and 2 ml in place of 5 ml of tetracyclododecene were used. The same operation was performed to obtain 1.95 g of an ethylene / tetracyclododecene copolymer. The polymerization activity was 117.0 kg / mmol-Ti · hr, and the intrinsic viscosity [η] of the obtained ethylene / tetracyclododecene copolymer was 0.80 dl / g. The glass transition temperature measured by DSC was 74 ° C., and the content of tetracyclododecene in the polymer estimated from this value was 21.8 mol%.

Example 49
In Example 3, 0.0001 mmol of the titanium compound (J) obtained in the complex synthesis example-10 in place of the titanium compound (A), cyclohexane in place of toluene, and 2 ml in place of 5 ml of tetracyclododecene were used. Otherwise by performing the same operations as in Example 3, 0.26 g of an ethylene / tetracyclododecene copolymer was obtained. The polymerization activity was 15.6 kg / mmol-Ti · hr, and the intrinsic viscosity [η] of the obtained ethylene · tetracyclododecene copolymer was 0.40 dl / g. The glass transition temperature measured by DSC was 160 ° C., and the content of tetracyclododecene in the polymer estimated from this value was 38.8 mol%.

Example 50
In Example 8, except that 0.0001 mmol of the titanium compound (J) obtained in Complex Synthesis Example-10 was used instead of the titanium compound (B), the same operation as in Example 8 was performed, and ethylene norbornene 0.14 g of copolymer was obtained. The polymerization activity was 8.4 kg / mmol-Ti · hr, and the intrinsic viscosity [η] of the obtained ethylene / norbornene copolymer was 1.57 dl / g. The glass transition temperature determined by DSC measurement was 91 ° C., and the norbornene content in the polymer estimated from this value was 37.9 mol%.

Example 51
In Example 8, 0.0001 mmol of the titanium compound (J) obtained in Complex Synthesis Example-10 in place of the titanium compound (B) and 10 g in place of 5 g of norbornene were used, and the same as in Example 8. Operation was performed to obtain 0.049 g of an ethylene / norbornene copolymer. The polymerization activity was 2.9 kg / mmol-Ti · hr, and the intrinsic viscosity [η] of the obtained ethylene / norbornene copolymer was 1.59 dl / g. The glass transition temperature as measured by DSC was 107 ° C., and the norbornene content in the polymer estimated from this value was 41.8 mol%.

Example 52
In Example 1, the same procedure as in Example 1 was performed except that 0.00002 mmol of the titanium compound (K) obtained in Complex Synthesis Example-11 was used instead of the titanium compound (A). 143 g was obtained. The polymerization activity was 85.8 kg / mmol-Ti · hr, and the intrinsic viscosity [η] of the obtained polyethylene was 5.26 dl / g.

Example 53
In Example 3, 0.0002 mmol of the titanium compound (K) obtained in the complex synthesis example-11 in place of the titanium compound (A) and 2 ml in place of 5 ml of tetracyclododecene were used. The same operation was performed to obtain 0.14 g of an ethylene / tetracyclododecene copolymer. The polymerization activity was 4.2 kg / mmol-Ti · hr, and the intrinsic viscosity [η] of the obtained ethylene · tetracyclododecene copolymer was 1.56 dl / g. The glass transition temperature determined by DSC measurement was 122 ° C., and the content of tetracyclododecene in the polymer estimated from this value was 31.1 mol%.

Example 54
In Example 8, except that 0.0001 mmol of the titanium compound (K) obtained in the complex synthesis example-11 was used instead of the titanium compound (B), the same operation as in Example 8 was performed, and ethylene norbornene 0.14 g of copolymer was obtained. The polymerization activity was 8.4 kg / mmol-Ti · hr, and the intrinsic viscosity [η] of the obtained ethylene / norbornene copolymer was 2.89 dl / g. The glass transition temperature determined by DSC measurement was 103 ° C., and the norbornene content in the polymer estimated from this value was 40.8 mol%.

Example 55
In Example 8, 0.0002 mmol of the titanium compound (K) obtained in the complex synthesis example-11 in place of the titanium compound (B) and 10 g in place of 5 g of norbornene were used, and the same as in Example 8. Operation was performed to obtain 0.10 g of an ethylene / norbornene copolymer. The polymerization activity was 3.0 kg / mmol-Ti · hr. The glass transition temperature determined by DSC measurement was 115 ° C., and the norbornene content in the polymer estimated from this value was 43.7 mol%.

Example 56
In Example 1, except that 0.0001 mmol of the titanium compound (L) obtained in Complex Synthesis Example-12 was used in place of the titanium compound (A), the same operation as in Example 1 was performed, and polyethylene 0. 20 g was obtained. The polymerization activity was 24.0 kg / mmol-Ti · hr, and the intrinsic viscosity [η] of the obtained polyethylene was 4.12 dl / g.

Example 57
In Example 8, except that 0.0001 mmol of the titanium compound (L) obtained in Complex Synthesis Example-12 was used in place of the titanium compound (B), the same operation as in Example 8 was performed, and ethylene norbornene 0.23 g of copolymer was obtained. The polymerization activity was 13.8 kg / mmol-Ti · hr, and the intrinsic viscosity [η] of the obtained ethylene / norbornene copolymer was 3.55 dl / g. The glass transition temperature determined by DSC measurement was 87 ° C., and the norbornene content in the polymer estimated from this value was 36.9 mol%.

Example 58
In Example 8, 0.0001 mmol of the titanium compound (L) obtained in Complex Synthesis Example-12 in place of the titanium compound (B) and 10 g in place of 5 g of norbornene were used, and the same as in Example 8. Operation was performed to obtain 0.12 g of an ethylene / norbornene copolymer. The polymerization activity was 7.2 kg / mmol-Ti · hr. The glass transition temperature determined by DSC measurement was 104 ° C., and the norbornene content in the polymer estimated from this value was 41.0 mol%.

Example 59
In Example 1, instead of the titanium compound (A), 0.00005 mmol of the titanium compound (M) obtained in the complex synthesis example-13, and 0.5 mmol of methylaluminoxane was used instead of 1.25 mmol in terms of aluminum atom. Otherwise, the same operation as in Example 1 was performed to obtain 0.97 g of polyethylene. The polymerization activity was 232.8 kg / mmol-Ti · hr, and the intrinsic viscosity [η] of the obtained polyethylene was 7.25 dl / g.

Example 60
In Example 3, the same procedure as in Example 3 was performed, except that 0.0001 mmol of the titanium compound (M) obtained in Complex Synthesis Example-13 was used instead of the titanium compound (A). 0.73 g of dodecene copolymer was obtained. The polymerization activity was 43.8 kg / mmol-Ti · hr. The glass transition temperature determined by DSC measurement was 159 ° C., and the content of tetracyclododecene in the polymer estimated from this value was 38.7 mol%.

Example 61
In Example 3, in place of the titanium compound (A), 0.0002 mmol of the titanium compound (M) obtained in the complex synthesis example-13, cyclohexane instead of toluene, and 2 ml of tetracyclododecene were used instead of 5 ml. Otherwise by performing the same operations as in Example 3, 0.37 g of an ethylene / tetracyclododecene copolymer was obtained. The polymerization activity was 11.1 kg / mmol-Ti · hr, and the intrinsic viscosity [η] of the obtained ethylene / tetracyclododecene copolymer was 1.77 dl / g. The glass transition temperature determined by DSC measurement was 143 ° C., and the content of tetracyclododecene in the polymer estimated from this value was 35.5 mol%.

Example 62
In Example 1, except that 0.0002 mmol of the titanium compound (N) obtained in Complex Synthesis Example-14 was used in place of the titanium compound (A), the same operation as in Example 1 was performed, and polyethylene 0. 74 g was obtained. The polymerization activity was 44.4 kg / mmol-Ti · hr, and the obtained polyethylene had an intrinsic viscosity [η] of 9.66 dl / g.

Example 63
In Example 3, the same procedure as in Example 3 was performed, except that 0.00025 mmol of the titanium compound (I) obtained in Complex Synthesis Example 9 was used instead of the titanium compound (A). 0.46 g of cyclododecene copolymer was obtained. The polymerization activity was 11.0 kg / mmol-Ti · hr, and the intrinsic viscosity [η] of the obtained ethylene / tetracyclododecene copolymer was 2.45 dl / g. The glass transition temperature determined by DSC measurement was 157 ° C., and the content of tetracyclododecene in the polymer estimated from this value was 38.2 mol%.

[Comparative Example 1]
In Example 1, 0.98 g of polyethylene was obtained in the same manner as in Example 1 except that 0.0001 mmol of the following titanium compound (O) was used instead of the titanium compound (A). The polymerization activity was 117.6 kg / mmol-Ti · hr, and the intrinsic viscosity [η] of the obtained polyethylene was 0.40 dl / g. The following titanium compound (O) was obtained by the method described in JP-A-2006-233063.

[Comparative Example 2]
In Example 2, except that the titanium compound (O) was used instead of the titanium compound (A), the same operation as in Example 2 was performed to obtain 10.2 g of an ethylene / propylene copolymer (EPR). It was. The polymerization activity was 12.2 kg / mmol-Ti · hr. The intrinsic viscosity [η] of the obtained ethylene / propylene copolymer was 0.08 dl / g. The propylene content measured by IR was 29.9 mol%.

[Comparative Example 3]
In Example 3, except that 0.0005 mmol of the titanium compound (O) was used in place of the titanium compound (A), the same operation as in Example 3 was performed, and the ethylene / tetracyclododecene copolymer was reduced to 0.00. 455 g was obtained. The polymerization activity was 5.45 kg / mmol-Ti · hr, and the intrinsic viscosity [η] of the obtained ethylene / tetracyclododecene copolymer was 0.30 dl / g. The glass transition temperature determined by DSC measurement was 190 ° C., and the content of tetracyclododecene in the polymer estimated from this value was 47.2 mol%.

[Comparative Example 4]
In Example 1, 0.005 mmol of the following titanium compound (P) was used instead of the titanium compound (A), and the polymerization time was changed to 30 minutes. Got. The polymerization activity was 0.28 kg / mmol-Ti · hr, and the intrinsic viscosity [η] of the obtained polyethylene was 3.47 dl / g. The following titanium compound (P) was obtained by the method described in JP-A-11-315109.

[Comparative Example 5]
In Example 2, except that the titanium compound (P) was used in place of the titanium compound (A), the same operation as in Example 2 was performed to obtain 0.19 g of an ethylene / propylene copolymer (EPR). It was. The polymerization activity was 0.23 kg / mmol-Ti · hr. The intrinsic viscosity [η] of the obtained ethylene / propylene copolymer was 0.98 dl / g. The propylene content measured by IR was 13.1 mol%.

[Comparative Example 6]
In Example 3, except that 0.005 mmol of the titanium compound (P) was used in place of the titanium compound (A), the same operation as in Example 3 was performed, and the ethylene / tetracyclododecene copolymer was reduced to 0.00. 018 g was obtained. The polymerization activity was 0.022 kg / mmol-Ti · hr, and the intrinsic viscosity [η] of the obtained ethylene / tetracyclododecene copolymer was 1.01 dl / g. The glass transition temperature determined by DSC measurement was 130 ° C., and the content of tetracyclododecene in the polymer estimated from this value was 33.0 mol%.

[Comparative Example 7]
In Example 1, 0.96 g of polyethylene was obtained in the same manner as in Example 1 except that 0.005 mmol of the following titanium compound (Q) was used instead of the titanium compound (A). The polymerization activity was 2.30 kg / mmol-Ti · hr, and the intrinsic viscosity [η] of the obtained polyethylene was 5.79 dl / g. The following titanium compound (Q) was obtained by the method described in JP-A-2007-297453.

[Comparative Example 8]
In Example 2, except that the titanium compound (Q) was used in place of the titanium compound (A), the same operation as in Example 2 was performed to obtain 0.20 g of an ethylene / propylene copolymer (EPR). It was. The polymerization activity was 0.24 kg / mmol-Ti · hr. The intrinsic viscosity [η] of the obtained ethylene / propylene copolymer was 0.60 dl / g. The propylene content measured by IR was 18.5 mol%.

[Comparative Example 9]
In Example 3, except that 0.005 mmol of the titanium compound (Q) was used in place of the titanium compound (A), the same operation as in Example 3 was performed, and the ethylene / tetracyclododecene copolymer was reduced to 0.00. 32 g was obtained. The polymerization activity was 0.384 kg / mmol-Ti · hr, and the intrinsic viscosity [η] of the obtained ethylene / tetracyclododecene copolymer was 0.30 dl / g. The glass transition temperature determined by DSC measurement was 178 ° C., and the content of tetracyclododecene in the polymer estimated from this value was 44.3 mol%.

[Comparative Example 10]
In Example 1, it replaced with the titanium compound (A), and except having used the following titanium compound (R) 0.003mmol, operation similar to Example 1 was performed and 1.49g of polyethylene was obtained. The polymerization activity was 5.96 kg / mmol-Ti · hr, and the intrinsic viscosity [η] of the obtained polyethylene was 8.61 dl / g. The following titanium compound (R) was obtained by the method described in JP-A-2007-297453.

[Comparative Example 11]
In Example 2, except that the titanium compound (R) was used in place of the titanium compound (A), the same operation as in Example 2 was performed to obtain 1.33 g of an ethylene / propylene copolymer (EPR). It was. The polymerization activity was 1.60 kg / mmol-Ti · hr. The intrinsic viscosity [η] of the obtained ethylene / propylene copolymer was 0.98 dl / g. The propylene content measured by IR was 20.4 mol%.

[Comparative Example 12]
In Example 3, except that 0.005 mmol of the titanium compound (R) was used in place of the titanium compound (A), the same operation as in Example 3 was carried out, and the ethylene / tetracyclododecene copolymer was changed to 0.00. 402 g was obtained. The polymerization activity was 0.482 kg / mmol-Ti · hr, and the intrinsic viscosity [η] of the obtained ethylene / tetracyclododecene copolymer was 1.30 dl / g. The glass transition temperature determined by DSC measurement was 183 ° C., and the content of tetracyclododecene in the polymer estimated from this value was 45.5 mol%.

  Polyolefin is an environmentally friendly clean material consisting of carbon and hydrogen, and has excellent processability and physical properties. Because of this characteristic, it is used in a wide range of fields such as automobiles, electrical equipment parts, food packaging, beverage / cosmetics / medical containers, civil engineering, and agricultural materials. The novel olefin polymerization catalyst in the present invention has high polymerization activity and high copolymerizability for olefins, and can produce a polymer having a high comonomer content and molecular weight. Therefore, it is possible to manufacture a product that satisfies the recent demand for diversified polyolefin with high efficiency.

Claims (10)

An olefin polymerization catalyst comprising a transition metal compound (A) represented by the following general formula (I):

(In General Formula (I), M represents a transition metal atom of Groups 4 to 6 of the periodic table, m represents an integer of 1 to 4, and R ¹ is a substituted or unsubstituted group having 6 to 30 carbon atoms. Represents an aryl group, R ² , R ³ and R ⁵ are hydrogen atom, halogen atom, hydrocarbon group, heterocyclic compound residue, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing group, a silicon-containing group, a germanium-containing group, and is selected from tin-containing group, may be the same or different from each other, may form a ring more than is bonded to each other of these, R ⁴ Is selected from a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, and a nitrogen-containing group, R ⁶ is an iodine atom or a bromine atom, n is a number that satisfies the valence of M, and X is Hydrogen atom, halogen atom, hydrocarbon group, oxygen-containing group, 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, a silicon-containing group, a germanium-containing group, or a tin-containing group, and when n is 2 or more And a plurality of groups represented by X may be the same or different from each other, and a plurality of groups represented by X may be bonded to each other to form a ring.) The catalyst for olefin polymerization according to claim 1, wherein in the transition metal compound (A) represented by the general formula (I), R ⁴ is a bromine atom or an iodine atom. 3. The olefin polymerization catalyst according to claim 1, wherein in the transition metal compound (A) represented by the general formula (I), R ¹ is an alkyl-substituted aryl group having 7 to 30 carbon atoms.   The alkyl-substituted aryl group is tolyl, iso-propylphenyl, t-butylphenyl, dimethylphenyl, di-t-butylphenyl, benzylphenyl, cumylphenyl, tritylphenyl, n-octylphenyl, n-dodecylphenyl, trifluoromethylphenyl. The catalyst for olefin polymerization according to claim 3, which is selected from di (trifluoromethyl) phenyl.   5. The olefin according to claim 1, wherein in the transition metal compound (A) represented by the general formula (I), M is a transition metal atom of Group 4 of the periodic table. Polymerization catalyst.   5. The olefin polymerization catalyst according to claim 1, wherein M is a titanium atom in the transition metal compound (A) represented by the general formula (I). A transition metal compound (A) represented by the general formula (I);
(B) (B-1) an organometallic compound,
It consists of at least one compound selected from (B-2) an organoaluminum oxy compound and (B-3) a compound that reacts with a transition metal compound (A) to form an ion pair. The catalyst for olefin polymerization according to any one of -6.   An olefin polymerization method comprising polymerizing or copolymerizing an olefin in the presence of the olefin polymerization catalyst according to any one of claims 1 to 7. The said olefin is the following (C-1) and (C-2), The polymerization method of the olefin of Claim 8 characterized by the above-mentioned.
(C-1) a linear or branched α-olefin having 2 to 30 carbon atoms,
(C-2) At least one cyclic olefin selected from the group consisting of compounds represented by the following general formula (II), general formula (III), general formula (IV), and general formula (V)

(In the formula (II), 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 a hydrogen atom, a halogen atom, It is selected from atoms and hydrocarbon groups, and may be the same or different from each other, and R ^{75 to} R ⁷⁸ may be bonded to each other to form a monocycle or polycycle, and the monocycle or polycycle May have a double bond, and R ⁷⁵ and R ⁷⁶ , or R ⁷⁷ and R ⁷⁸ may form an alkylidene group.)

(In the formula (III), x and d are 0 or an integer of 1 or more, y and z are 0, 1 or 2, and R ^{81 to} R ⁹⁹ are selected from a hydrogen atom, a halogen atom and a hydrocarbon group. are may be the same or different from each other, the carbon atom to which R ⁸⁹ and R ⁹⁰ is bonded, the carbon atom to which carbon atoms or R ⁹¹ R ⁹³ is attached is bound directly or carbon It may be bonded via an alkylene group having 1 to 3 atoms. When y = z = 0, R ⁹⁵ and R ⁹² or R ⁹⁵ and R ⁹⁹ are bonded to each other to form a monocyclic or polycyclic ring. An aromatic ring may be formed.)

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

(In the general formula (V), x is 0 or an integer of 1 or more, R ¹¹¹ to R ¹¹⁸ is a hydrogen atom, a halogen atom, selected from hydrocarbon groups may be the same or different, R ¹²¹ ~ R ¹²⁴ is selected from a hydrogen atom, a halogen atom, and a hydrocarbon group, and may be the same or different from each other, and two adjacent groups may be bonded to each other to form a monocyclic or multicyclic aromatic ring. .) The (C-1) is ethylene, and the (C-2) is bicyclo [2.2.1] hept-2-enetetracyclo [4.4.0.1 ^2,5 . The process for polymerizing olefins according to claim 9, which is ^1,7,10 ] -3-dodecene, benzonorbornadiene and / or 1,4-dihydro-1,4-methanoanthracene.