JP2023033422A - Transition metal compound, catalyst for olefin polymerization and method for producing olefin polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel transition metal compound useful for a catalyst for olefin polymerization that shows superior performance in production of olefin polymers; for example, it has high polymerization activity and, in olefin copolymerization, has high polymerization activity and excellent copolymerization reactivity.

SOLUTION: The present invention provides a transition metal compound (A) represented by general formula (1) (In general formula (1), M is a transition metal atom of groups 3-10 in the periodic table, R¹-R¹³ each denote a hydrogen atom, a hydrocarbon group or the like, Y is an oxygen atom or the like, n is a valence of M, X is a halogen atom or the like).

SELECTED DRAWING: None

COPYRIGHT: (C)2023,JPO&INPIT

Description

The present invention relates to a transition metal compound, an olefin polymerization catalyst containing the transition metal compound, and a method for producing an olefin polymer using the catalyst.

Conventionally, as catalysts for producing olefin polymers such as ethylene polymers and ethylene/α-olefin copolymers, titanium-based catalysts comprising a titanium compound and an organoaluminum compound and vanadium compounds and an organoaluminum compound are used. Vanadium-based catalysts are known. Metallocene-based catalysts comprising a metallocene compound such as zirconocene and an organoaluminumoxy compound (aluminoxane) are known as catalysts capable of producing olefin polymers with high polymerization activity.

In recent years, various post-metallocene catalysts have been reported as next-generation olefin polymerization catalysts (for example, Non-Patent Document 1). In the technical field of olefin polymerization catalysts, it is very important to research and provide highly active and highly functional post-metallocene catalysts. Among them, post-metallocene catalysts having multidentate ligands are attractive in terms of their stability and functionality, but there are few examples of their industrial use.

On the other hand, the present applicant has found that a transition metal compound having a phenoxyimine ligand can enhance the activation of an olefin polymerization catalyst and provide various functions to the olefin polymer obtained by converting the ligand skeleton and substituents. It has already been discovered that it is possible to impart the characteristics and features (for example, Non-Patent Document 2).

Chemical Reviews 2003, 103, 283-315. Chemical Reviews 2011, 111, 2363-2449.

As described above, there are few examples of industrial use of multidentate postmetallocene catalysts. In order to be adopted at the industrial level, it is also important to have performance that exhibits effects specific to multidentate post-metallocene catalysts, in addition to conventional index effects such as polymerization activity.

When multiple olefins are copolymerized, there is often a difference in copolymerization reactivity for each type of olefin. In particular, ethylene often has extremely high polymerization reactivity compared to other olefins. Specifically, it is known that olefins with a small number of carbon atoms and olefins with a low bulk tend to exhibit higher copolymerization reactivity. For this reason, there is a risk that the composition distribution will widen, especially when the olefin copolymer is produced by a batch polymerization process. In the continuous polymerization process, the risk of widening the composition distribution can be suppressed by process control technology, etc., but in many cases, advanced management is required to control the gas composition when recovering and using the unreacted olefin. Therefore, a catalyst that can improve the copolymerization reactivity of olefins during copolymerization is considered to have great industrial merit. For example, when producing a copolymer by copolymerizing ethylene and propylene, if ethylene and propylene have the same reactivity, the composition of the unreacted olefin gas will be the same as the composition of the olefin gas supplied to the reaction. It is considered to be a great advantage in controlling copolymerization and stabilizing the manufacturing process.

Of course, even if the copolymerization reactivity is not the same, even if the difference can be reduced, it will have an advantage over the prior art in controlling the copolymerization reaction and stabilizing the production process.
Accordingly, an object of the present invention is to achieve high polymerization activity and, in the copolymerization of olefins, high polymerization activity and excellent copolymerization reactivity (in the present invention, the difference in copolymerization reactivity between different olefins is small). is expressed as "excellent copolymerization reactivity".), a novel transition metal compound used in such an olefin polymerization catalyst, a transition An object of the present invention is to provide an olefin polymerization catalyst containing a metal compound and a method for producing an olefin polymer using this catalyst.

As a result of intensive studies by the present inventors to achieve the above object, a polydentate ligand comprising an oxygen atom derived from a phenoxy group, a nitrogen atom derived from an amino group, and further donor atoms (such as an oxygen atom) It was found that an olefin polymerization catalyst containing a specific transition metal compound having a ligand having a completed the invention. That is, the present invention relates to the following [1] to [6].

[1] A transition metal compound (A) represented by the following general formula (1).

（一般式（１）において、Ｍは周期律表第３～１０族の遷移金属原子を示す。
Ｒ¹～Ｒ¹³は、互いに同一でも異なっていてもよく、水素原子、ハロゲン原子、炭化水素基、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、またはスズ含有基を示し、またＲ¹～Ｒ¹³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、その環はさらに前記置換基を有していてもよい。

(In general formula (1), M represents a transition metal atom of groups 3 to 10 of the periodic table.
R ¹ to R ¹³ may be the same or different, and may be 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, silicon-containing group, germanium-containing group, or tin-containing group, and two or more of R ¹ to R ¹³ may be linked together to form a ring, and the ring may be further substituted with You may have a group.

Y is an oxygen atom, a sulfur atom, or a structure represented by -N(-R ¹⁴ )- (R ¹⁴ is a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen A containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group are indicated.The leftmost and rightmost straight lines indicate the bond between the nitrogen atom and the adjacent carbon atom.
).
n represents the valence of M;
X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, germanium-containing group, or tin-containing group, and when there are a plurality of X's, they may be the same or different, and two or more of them may be linked together to form a ring. )

[2] The transition metal compound (A) of the above [1], wherein M is a transition metal atom of Group 4 of the periodic table and n is 4 in the general formula (1).
[3] The transition metal compound (A) of [1] or [2], wherein Y in the general formula (1) is an oxygen atom.
[4] An olefin polymerization catalyst containing the transition metal compound (A) according to any one of [1] to [3].
[5] (B) (B-1) an organometallic compound (B-2) an organoaluminumoxy compound, and
(B-3) The olefin polymerization catalyst of [4] above, further comprising at least one compound selected from the group consisting of compounds that form an ion pair by reacting with the transition metal compound (A).
[6] A method for producing an olefin polymer, comprising homopolymerizing or copolymerizing an olefin in the presence of the olefin polymerization catalyst of [4] or [5].
In the present invention, the term "polymerization" is used in the sense of including "homopolymerization" and "copolymerization". Moreover, the term "polymer" is used in the sense of including "homopolymer" and "copolymer".

The transition metal compound of the present invention has a ligand having an excellent electron transfer ability, a chemically stable phenoxy structure and an amine structure, and a structure having an excellent electron transfer ability (Y in general formula (1) Since it has a three-dimensional structure having a structure represented by the structure represented), an olefin polymerization catalyst containing this transition metal compound exhibits high olefin polymerization activity, and in olefin copolymerization, exhibits high olefin polymerization activity and excellent copolymerization reactivity. show.

<Transition metal compound (A)>
The transition metal compound of the present invention (hereinafter referred to as "transition metal compound (A)") is represented by the following general formula (1).

In general formula (1), M is a transition metal atom of groups 3 to 10 of the periodic table (group 3 also includes lanthanoids), preferably groups 3 to 9 (group 3 also includes lanthanoids). is a transition metal atom of, more preferably a transition metal atom of Groups 3 to 6 (lanthanides are also included in Group 3), particularly preferably a transition metal atom of Groups 4 to 6, most preferably 4 group of transition metal atoms. Specifically, scandium atoms, yttrium atoms, titanium atoms, zirconium atoms, hafnium atoms, vanadium atoms, niobium atoms, tantalum atoms, chromium atoms, molybdenum atoms, tungsten atoms, manganese atoms, rhenium atoms, iron atoms, ruthenium atoms, cobalt atom, rhodium atom, iridium atom, nickel atom, palladium atom, platinum atom and the like, preferably scandium atom, titanium atom, zirconium atom, hafnium atom, vanadium atom, niobium atom, tantalum atom, chromium atom, molybdenum atom, tungsten atom, cobalt atom, rhodium atom and iridium atom, more preferably titanium atom, zirconium atom, hafnium atom, vanadium atom, niobium atom, tantalum atom, chromium atom, molybdenum atom and tungsten atom, particularly preferably A titanium atom, a zirconium atom, a hafnium atom, a chromium atom and a tantalum atom, most preferably a titanium atom, a zirconium atom and a hafnium atom.

In general formula (1), R ¹ to R ¹³ may be the same or different, and are hydrogen atoms, halogen atoms, hydrocarbon groups, heterocyclic compound residues, oxygen-containing groups, nitrogen-containing groups, boron-containing group, sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium-containing group, or tin-containing group, and two or more of R ¹ to R ¹³ may be linked together to form a ring. , the ring may further have the substituents described above. It should be noted that the ranges of these substituents may overlap with each other, eg a pyridinyl group is included in both the heterocyclic compound residue and the nitrogen-containing group.

Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Specific examples of the hydrocarbon group include
A methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, neopentyl group, n-hexyl group, etc. having 1 to 30 carbon atoms, preferably is a linear or branched alkyl group of 1 to 20;
linear or branched alkenyl groups having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, such as vinyl groups, allyl groups, and isopropenyl groups;
linear or branched alkynyl groups having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms such as ethynyl group and propargyl group;
cyclic saturated hydrocarbon groups having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and adamantyl group;
Cyclic unsaturated hydrocarbon groups having 5 to 30 carbon atoms such as cyclopentadienyl group, indenyl group and fluorenyl group; are 6 to 30, preferably 6 to 20 aryl groups.

In the hydrocarbon group, a hydrogen atom may be substituted with a halogen, and examples of the hydrocarbon group having a hydrogen atom substituted with a halogen include a trifluoromethyl group, a pentafluorophenyl group, a chlorophenyl group, and the like. and a halogenated hydrocarbon group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.

In addition, in the alkyl group, alkenyl group, alkynyl group, cyclic saturated hydrocarbon group, cyclic unsaturated hydrocarbon group, and aryl group, hydrogen atoms may be substituted with other hydrocarbon groups. Hydrocarbon groups in which a hydrogen atom is substituted with a hydrocarbon group include, for example, aryl group-substituted alkyl groups such as benzyl group, cumyl group, and trityl group; tolyl group, iso-propylphenyl group, tert-butylphenyl group, dimethylphenyl di-tert-butylphenyl group, tri-iso-propylphenyl group, and other alkyl-substituted aryl groups.

Furthermore, the hydrocarbon group is
heterocyclic compound residue;
Oxygen-containing groups such as alkoxy groups, aryloxy groups, ester groups, ether groups, acyl groups, carboxyl groups, carbonate groups, hydroxy groups, peroxy groups, carboxylic anhydride groups;
Ammonium salts of amino group, imino group, amido group, imido group, hydrazino group, hydrazono group, nitro group, nitroso group, cyano group, isocyano group, cyanate ester group, amidino group, diazo group and amino group Nitrogen-containing groups such as
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, isocyanate group, sulfone ester group, sulfonamide group, thiocarboxyl group, dithiocarboxyl group, sulfo group , a sulfonyl group, a sulfinyl group, a sulfur-containing group such as a sulfenyl group;
phosphorus-containing groups such as phosphide groups, phosphoryl groups, thiophosphoryl groups, phosphato groups;
silicon-containing groups;
germanium-containing groups; or tin-containing groups.

Specific examples of the heterocyclic compound residue include nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline, triazine, carbazole, and phenanthroline, oxygen-containing compounds such as furan, pyran, benzofuran, and benzopyran, thiophene, benzothiophene, and the like. and the hydrogen atoms of these heterocyclic compound residues are alkyl groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, alkoxy groups, groups further substituted with substituents such as aryl groups, and the like.

Examples of the silicon-containing group include a silyl group, a siloxy group, a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxy group, etc. More specifically, a methylsilyl group, a dimethylsilyl group, a trimethylsilyl group, an ethylsilyl group, and a diethylsilyl group. group, triethylsilyl group, diphenylmethylsilyl group, triphenylsilyl group, dimethylphenylsilyl group, dimethyl-tert-butylsilyl group, dimethyl(pentafluorophenyl)silyl group, tribenzylsilyl group and the like. Among these, a methylsilyl group, a dimethylsilyl group, a trimethylsilyl group, an ethylsilyl group, a diethylsilyl group, a triethylsilyl group, a dimethylphenylsilyl group, a triphenylsilyl group, a tribenzylsilyl group, etc. are preferred, and a trimethylsilyl group and a triethylsilyl group are particularly preferred. group, triphenylsilyl group, dimethylphenylsilyl group and tribenzylsilyl group are preferred. Specific examples of the hydrocarbon-substituted siloxy group include a trimethylsiloxy group, a triethylsiloxy group, a triphenylsiloxy group, and a tribenzylsiloxy group.

Examples of the germanium-containing group and the tin-containing group include groups in which the silicon of the silicon-containing group is substituted with germanium or tin.
As described above, R ¹ to R ¹³ also include oxygen-containing groups, nitrogen-containing groups, boron-containing groups, sulfur-containing groups, phosphorus-containing groups, silicon-containing groups, germanium-containing groups and tin-containing groups, examples of which are Examples thereof include the same groups as those exemplified as the groups that the hydrocarbon group may have.

Among the oxygen-containing groups, specific examples of the alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, etc. Specific examples of the aryloxy group include Specific examples thereof include a phenoxy group, 2,6-dimethylphenoxy group, 2,4,6-trimethylphenoxy group, 3,5-di-tert-butylphenoxy group, etc. Specific examples of the ester group include acetyl An oxy group, a benzoyloxy group, a methoxycarbonyl group, a phenoxycarbonyl group, a p-chlorophenoxycarbonyl group, and the like, and specific examples of the acyl group include a formyl group, an acetyl group, a benzoyl group, a p-chlorobenzoyl group, a p -Methoxybenzoyl group and the like.

Among the nitrogen-containing groups, specific examples of the amino group include a dimethylamino group, an ethylmethylamino group, and a diphenylamino group. Specific examples of the imino group include a methylimino group, an ethylimino group, a propylimino group, and a butylimino group. group, phenylimino group, etc. Specific examples of the amide group include an acetamide group, N-methylacetamide group, N-methylbenzamide group, etc. Specific examples of the imide group include an acetimido group and a benzimide group. etc.

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

R ¹ to R ¹³ are preferably hydrogen atoms, hydrocarbon groups or heterocyclic compound residues, more preferably hydrogen atoms or hydrocarbon groups. As a hydrocarbon group, in particular,
1 to 30 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, neopentyl group, n-hexyl group, preferably 1 to 20 linear or branched alkyl groups;
an aryl group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms such as a phenyl group, naphthyl group, biphenyl group, terphenyl group, phenanthryl group, anthracenyl group;
1 to 5 hydrogen atoms of these aryl groups are respectively halogen atoms, alkyl groups or alkoxy groups having 1 to 30, preferably 1 to 20 carbon atoms, and 6 to 30, preferably 6 to 20 carbon atoms. A substituted aryl group substituted with a substituent such as an aryloxy group is preferred.

Heterocyclic compound residues include nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline, triazine, carbazole and phenanthroline; oxygen-containing compounds such as furan, pyran, benzofuran and benzopyran; A residue obtained by removing one hydrogen atom from a compound or the like, and a hydrogen atom of these heterocyclic compound residues are alkyl groups or alkoxy groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, carbon A group substituted with a substituent such as an aryl group having 6 to 30 atoms, preferably 6 to 20 atoms is preferred.

Two or more groups among R ¹ to R ¹³ in formula (1) may be linked together to form a ring. More specifically, two or more groups, preferably adjacent groups, of R ¹ to R ¹³ are linked together to form an aliphatic ring, an aromatic ring, or a hetero ring containing a heteroatom such as a nitrogen atom. may form a ring, and these rings may further have a substituent.

In general formula (1), Y is an oxygen atom, a sulfur atom, or a structure represented by —N(—R ¹⁴ )— (the leftmost and rightmost straight lines indicate the bond between the nitrogen atom and the adjacent carbon atom. ). The definition of R ¹⁴ is the same as for R ¹ to R ¹³ , and R ¹⁴ can be selected from the same substituents as exemplified for R ¹ to R ¹³ , preferably a hydrocarbon group. As Y, an oxygen atom is particularly preferable.

In general formula (1), X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic ring represents a formula compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group.

Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Specific examples of the hydrocarbon group are the same as those exemplified for R ¹ to R ¹³ . Specifically, alkyl groups such as methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, nonyl group, dodecyl group and eicosyl group; carbon groups such as cyclopentyl group, cyclohexyl group, norbornyl group and adamantyl group cycloalkyl groups having 3 to 30 atoms; alkenyl groups such as vinyl group, propenyl group and cyclohexenyl group; arylalkyl groups such as benzyl group, phenylethyl group and phenylpropyl group; phenyl group, tolyl group and dimethylphenyl group , trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, naphthyl, methylnaphthyl, anthryl and phenanthryl groups. These hydrocarbon groups also include halogenated hydrocarbon groups, specifically groups in which at least one hydrogen of a hydrocarbon group having 1 to 20 carbon atoms is substituted with halogen. Among these, halogenated hydrocarbon groups having 1 to 10 carbon atoms are preferable as the halogenated hydrocarbon group.

Specific examples of the oxygen-containing group include a hydroxy group; an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group; an aryloxy group such as a phenoxy group, a methylphenoxy group, a dimethylphenoxy group, and a naphthoxy group; and a phenylmethoxy group. , an arylalkoxy group such as a phenylethoxy group; an acetoxy group; and a carbonyl group.

Specific examples of the sulfur-containing group are the same as those exemplified for R ¹ to R ¹³ . Specifically, methylsulfonate group, trifluoromethanesulfonate group, phenylsulfonate group, benzylsulfonate group, p-toluenesulfonate group, trimethylbenzenesulfonate group, triisobutylbenzenesulfonate sulfonate group, p-chlorobenzenesulfonate group, pentafluorobenzenesulfonate group; methylsulfinate group, phenylsulfinate group, benzylsulfinate group, p-toluenesulfinate group, sulfinate groups such as trimethylbenzenesulfinate group and pentafluorobenzenesulfinate group; alkylthio groups; and arylthio groups.

Specific examples of the nitrogen-containing groups are the same as those exemplified for R ¹ to R ¹³ . Specifically, amino group; alkylamino group such as methylamino group, dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, dicyclohexylamino group; phenylamino group, diphenylamino group, ditolylamino group, dinaphthyl Examples include an amino group, an arylamino group such as a methylphenylamino group, or an alkylarylamino group.

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

Specific examples of the phosphorus-containing group include trialkylphosphine groups such as trimethylphosphine group, tributylphosphine group and tricyclohexylphosphine group; triarylphosphine groups such as triphenylphosphine group and tritolylphosphine group; methylphosphite group; phosphite groups (phosphide groups) such as ethylphosphite group and phenylphosphite group; phosphonic acid groups; and phosphinic acid groups.

Specific examples of the halogen-containing groups 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 .
Specific examples of the heterocyclic compound residue are the same as those exemplified for R ¹ to R ¹³ .

Specific examples of the silicon-containing groups are the same as those exemplified for R ¹ to R ¹³ . Specifically, phenylsilyl group, diphenylsilyl group, trimethylsilyl group, triethylsilyl group, tripropylsilyl group, tricyclohexylsilyl group, triphenylsilyl group, methyldiphenylsilyl group, tritolylsilyl group, trinaphthylsilyl group and the like. a hydrocarbon-substituted silyl group such as a trimethylsilyl ether group; a silicon-substituted alkyl group such as a trimethylsilylmethyl group; and a silicon-substituted aryl group such as a trimethylsilylphenyl group.

Specific examples of the germanium-containing groups are the same as those exemplified for R ¹ to R ¹³ . Specifically, a group obtained by substituting germanium for silicon in the above silicon-containing group is exemplified.

Specific examples of the tin-containing group are the same as those exemplified for R ¹ to R ¹³ . Specifically, a group obtained by substituting tin for silicon in the above silicon-containing group is exemplified.
Among these, X is preferably a halogen atom or a hydrocarbon group.

In the general formula (1), n represents the valence of M, specifically the same number as the valence of M. n is usually an integer of 3 to 7, preferably an integer of 3 to 6, more preferably 3 or 4, particularly preferably 4. When n is 4 or more, multiple X's may be the same or different, and two or more of them may be linked together to form a ring.

In the present invention, a compound in which the presence or absence of a bond between Y and M in general formula (1) is unclear is also regarded as the transition metal compound (A) represented by general formula (1).
Preferred specific examples of the transition metal compound (A) represented by formula (1) are shown below.

なお、上記例示中、Ａｄはアダマンチル基、Ｐｈはフェニル基を示す。また上記例示において、チタン原子をジルコニウム原子またはハフニウム原子に置き換えた遷移金属化合物も、遷移金属化合物（Ａ）の好ましい例として挙げることができる。

In the above examples, Ad represents an adamantyl group and Ph represents a phenyl group. In the above examples, transition metal compounds in which titanium atoms are replaced with zirconium atoms or hafnium atoms are also preferred examples of the transition metal compound (A).

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

First, the ligand that constitutes the transition metal compound (A) can be produced, for example, using the following synthesis method, more specifically, a reaction that couples two or more materials. . Suzuki-Miyaura coupling reaction using boronic acid derived from hydroxyl-protected phenols as a raw material for oxygen-containing sites and halogenated ethers having a nitro group as raw materials for nitrogen-containing sites, An example is the method of then obtaining the resulting compound by reductive amination of the nitro group and deprotection of the hydroxyl group.

Specifically, the Suzuki-Miyaura coupling reaction between boronic acids derived from phenols with protected hydroxyl groups and halogenated ethers having a nitro group involves these compounds and a basic compound, and a palladium catalyst as a catalyst. Solvent 1, which will be described later, is added to a mixture of compounds that serve as ligands of the catalyst. The mixture may or may not be dissolved in the solvent 1, and a ligand compound may or may not be added.

Basic compounds include, for example, sodium hydroxide, potassium hydroxide, barium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, lithium tert-butoxide, potassium tert-butoxide, tripotassium phosphate and the like.

Specific examples of palladium catalysts include bis(dibenzylideneacetone)palladium, tris(dibenzylideneacetone)dipalladium, tris(dibenzylideneacetone)(chloroform)dipalladium, palladium chloride, palladium acetate, and dichlorobis(acetonitrile)palladium. , dichlorobis(benzonitrile) palladium, allyl palladium chloride dimer, and the like.

Specific examples of compounds that serve as ligands for palladium catalysts include tricyclohexylphosphine, tri-tert-butylphosphine, di-tert-butyl(methyl)phosphine, 2-(dicyclohexylphosphino)biphenyl, and 2-dicyclohexylphosphine. Phosphine compounds such as phino-2′-(dimethylamino)biphenyl, 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl, 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl, and Salts of phosphine compounds such as di-tert-butyl(methyl)phosphonium tetrafluoroborate are included.

Also, a complex compound of the phosphine compound and palladium, such as dichlorobis(tricyclohexylphosphine)palladium, {1,3-bis(2,6-diisopropylphenyl)imidazolidene}(3-chloropyridyl)palladium dichloride A complex compound of a carbene type compound and palladium, such as , may be used as a catalyst.

As the solvent 1, those commonly used in such reactions can be used. Polar solvents such as propanol, or hydrocarbon solvents such as toluene and xylene are preferred. A mixture obtained by adding water to any of these solvents may be used as solvent 1, and the mixing ratio (mass ratio) is preferably from 0/100 to 25/75 for water/solvent.

A boronic acid derived from a hydroxyl-protected phenol can be synthesized by lithiating with an alkyllithium reagent in solvent 2 described later and then adding a boronic acid ester.
Specific examples of alkyllithium reagents include methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, lithium diisopropylamide and the like. Also, N,N,N',N'-tetramethylethylenediamine (TMEDA), hexamethylphosphoric acid triamide (HMPA), etc. may be added as an activator, and these may be used in a solvent amount.

Specific examples of boronic acid esters include trimethoxyboronic acid, triethoxyboronic acid, and triisopropoxyboronic acid.
Specific examples of the solvent 2 include diethyl ether, tetrahydrofuran (THF), tert-butyl methyl ether (TBME), cyclopentyl methyl ether (CPME) and the like.

Protection of hydroxyl groups of phenols is carried out according to a conventional method. Examples of protective groups include tert-butyl, trityl, benzyl, p-methoxybenzyl, methoxymethyl, trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl, tert-butyldiphenylsilyl, and triisopropyl. silyl group, methanesulfonyl group, acetyl group, pivaloyl group, 2,2,2-trichloroethoxycarbonyl group and allyloxycarbonyl group.

Commercially available phenols can be used as they are, but in the case of synthesis, they can be easily obtained by alkylating phenols with alcohols or by Suzuki-Miyaura coupling reactions between halogenated phenols and arylboronic acids. .

Commercially available halogenated ethers having a nitro group can be used as they are, but in the case of synthesis, they are obtained by an electrophilic substitution reaction between 2-halogenated phenols and 2-halogenated nitrobenzenes. Specifically, 2-halogenated phenols, 2-halogenated nitrobenzenes, and a basic compound as a catalyst are added to the solvent 3 and reacted.

Examples of basic compounds include sodium hydroxide, potassium hydroxide, barium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, lithium tert-butoxide, potassium tert-butoxide and tripotassium phosphate.

Specific examples of the solvent 3 include N,N-dimethylformamide and dimethylsulfoxide.
Commercially available 2-halogenated phenols can be used as they are, but in the case of synthesis, halogenation of phenols is carried out according to a conventional method.
Commercially available 2-halogenated nitrobenzenes can be used as they are, but when synthesizing them, halogenation of nitrobenzenes or nitration of halogenated benzenes is carried out according to a conventional method.

The protecting group is then removed with a deprotecting agent such as hydrochloric acid, p-toluenesulfonic acid and the like to yield the ligand.
Next, the ligand thus obtained is combined with a transition metal M-containing compound represented by MX _n (M, X and n are respectively synonymous with M, X and n in the general formula (1)) The corresponding transition metal compound (A) can be synthesized by reacting them. Specifically, after dissolving the synthesized ligand in a solvent and, if necessary, contacting it with a base to prepare anion bodies, transition metal M-containing compounds such as metal halides, metal alkylates, and metal amidides are prepared. and at a low temperature, and stirred at -78°C to room temperature or under reflux conditions for about 1 to 48 hours. Solvents commonly used for such reactions can be used, and among them, polar solvents such as diethyl ether and tetrahydrofuran (THF), hydrocarbon solvents such as toluene, and dichloromethane are preferably used. Examples of the base used for preparing the anion include lithium salts such as n-butyllithium, metal salts such as sodium salts such as sodium hydride, triethylamine and pyridine.

Further, depending on the properties of the compound, the corresponding transition metal compound (A) can be synthesized by directly reacting the ligand with the metal compound without going through the preparation of the anion body. Furthermore, it is also possible to replace the metal M in the synthesized transition metal compound (A) with another transition metal by a conventional method. Further, for example, when one or more of R ¹ to R ¹³ are hydrogen, substituents other than hydrogen can be introduced at any stage of the synthesis.

Alternatively, the reaction solution of the ligand and the metal compound may be directly used for the production of the olefin polymerization catalyst described below without isolating the transition metal compound.

<Catalyst for Olefin Polymerization>
The olefin polymerization catalyst of the present invention is a catalyst containing the transition metal compound (A) represented by the above-described general formula (1). The catalyst further comprises (B) an organometallic compound (B-1), an organoaluminumoxy compound (B-2) and a compound (B-3) that reacts with the transition metal compound (A) to form an ion pair. It preferably contains at least one compound selected from the group. In the present invention, the olefin means a hydrocarbon having one carbon-carbon double bond in the molecule.
The compound (B) will be described in detail below.

[Compound (B)]
The olefin polymerization catalyst of the present invention reacts with (B) an organometallic compound (B-1), an organoaluminumoxy compound (B-2), and a transition metal compound (A) in addition to the transition metal compound (A). From the viewpoint of polymerization activity, it is preferable to further contain at least one compound selected from compounds (B-3) that form an ion pair with each other. Compounds (B-1), (B-2) and (B-3) are described below.

((B-1) organometallic compound)
Specific examples of the organometallic compound (B-1) include organometallic compounds represented by the following general formulas (B-1a), (B-1b) and (B-1c).
R ^a _p Al (OR ^b ) _q H _r Y _s (B-1a)
(In the general formula (B-1a), R ^a and R ^b may be the same or different and represent a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms, and Y is a halogen atom. , p is 0 < p ≤ 3, q is 0 ≤ q < 3, r is 0 ≤ r < 3, s is a number of 0 ≤ s < 3, and p + q + r + s = 3.)
M ³ AlR ^c ₄ (B-1b)
(In general formula (B-1b), M ³ represents Li, Na or K, and R ^c represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms.)
R ^d R ^e M ⁴ (B-1c)
(In general formula (B-1c), R ^d and R ^e may be the same or different and each represents a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms, and M ⁴ is Mg , Zn or Cd.)

Examples of the organoaluminum compound represented by formula (B-1a) include the following compounds.
R ^a _p Al (OR ^b ) _3-p
(Wherein, R ^a and R ^b may be the same or different and represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and p is preferably 1.5 ≤ p ≤ is the number of 3.)
an organoaluminum compound represented by
R ^a _p AlY _3-p
(In the formula, R ^a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, Y represents a halogen atom, and p is preferably a number of 0<p<3.)
an organoaluminum compound represented by
^Rap _{AlH3 -p}
(In the formula, R ^a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and p is preferably a number satisfying 2≦p<3.)
an organoaluminum compound represented by
R ^a _p Al (OR ^b ) _q Y _s
(Wherein, R ^a and R ^b may be the same or different and represent a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms, Y represents a halogen atom, p is 0 <p≤3, q is 0≤q<3, s is a number satisfying 0≤s<3, and p+q+s=3.)
Organoaluminum compound represented by.

More specifically, the organoaluminum compound represented by the general formula (B-1a) is
tri-n-alkylaluminum such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum;
triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylbutylaluminum, tri-2-methylpentylaluminum, tri-3-methylpentylaluminum, tri-4 - tri-branched alkyl aluminum such as methylpentylaluminum, tri-2-methylhexylaluminum, tri-3-methylhexylaluminum, tri-2-ethylhexylaluminum;
tricycloalkylaluminum such as tricyclohexylaluminum, tricyclooctylaluminum;
triarylaluminum such as triphenylaluminum, tritolylaluminum;
dialkylaluminum hydride such as diisobutylaluminum hydride;
triisoprenyl aluminum represented by (iC ₄ H ₉ ) _{x Aly} (C ₅ H ₁₀ ) _z (wherein x, y and z are positive numbers and z≧2x), etc. of trialkenyl aluminum;
alkylaluminum alkoxides such as isobutylaluminum methoxide, isobutylaluminum ethoxide, isobutylaluminum isopropoxide;
dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide, dibutylaluminum butoxide;
alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide, butylaluminum sesquibutoxide;
R ^a _2.5 Al(OR ^b ) _0.5 (wherein R ^a and R ^b may be the same or different and represent a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms); Partially alkoxylated aluminum alkyls having the indicated average composition;
diethylaluminum phenoxide, diethylaluminum (2,6-di-t-butyl-4-methylphenoxide), ethylaluminum bis(2,6-di-t-butyl-4-methylphenoxide), diisobutylaluminum (2,6- dialkylaluminum aryloxides such as di-t-butyl-4-methylphenoxide), isobutylaluminum bis(2,6-di-t-butyl-4-methylphenoxide);
dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride;
alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide;
partially halogenated aluminum alkyls such as alkylaluminum dihalides such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide;
dialkylaluminum hydride such as diethylaluminum hydride, dibutylaluminum hydride;
Other partially hydrogenated aluminum alkyls such as alkylaluminum dihydrides such as ethylaluminum dihydride, propylaluminum dihydride;
Partially alkoxylated and halogenated aluminum alkyls such as ethylaluminum ethoxychloride, butylaluminum butoxychloride, ethylaluminum ethoxybromide and the like can be mentioned.

A compound similar to the compound represented by (B-1a) can also be used as the organometallic compound (B-1). and organoaluminum compounds. Specific examples of such compounds include (C ₂ H ₅ ) ₂ AlN(C ₂ H ₅ )Al(C ₂ H ₅ ) ₂ and the like.

Examples of the compound represented by the general formula (B-1b) include LiAl(C ₂ H ₅ ) ₄ and LiAl(C ₇ H ₁₅ ) ₄ .
Examples of compounds represented by the general formula (B-1c) include dimethylmagnesium, diethylmagnesium, dibutylmagnesium, butylethylmagnesium, dimethylzinc, diethylzinc, diphenylzinc, di-n-propylzinc, diisopropylzinc, di-n -Butyl zinc, diisobutyl zinc, bis(pentafluorophenyl) zinc, dimethyl cadmium, diethyl cadmium and the like.

In addition, the organometallic compound (B-1) includes methyllithium, ethyllithium, propyllithium, butyllithium, methylmagnesium bromide, methylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium chloride, propylmagnesium bromide, and propylmagnesium. Chloride, butylmagnesium bromide, butylmagnesium chloride, and the like can also be used.

Further, a compound capable of forming the organoaluminum compound in the polymerization system, such as a combination of an aluminum halide and an alkyllithium, or a combination of an aluminum halide and an alkylmagnesium, may be used as the organometallic compound (B-1). can also be used as
The organometallic compound (B-1) as described above may be used singly or in combination of two or more.

((B-2) Organic aluminum oxy compound)
The organoaluminumoxy compound (B-2) may be a conventionally known aluminoxane, or a benzene-insoluble organoaluminumoxy compound as exemplified in JP-A-2-78687. Specific examples of the organoaluminumoxy compound (B-2) include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane and the like.

Conventionally known aluminoxanes can be produced, for example, by the following method, and are usually obtained as a solution in 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, cerous chloride hydrate, etc. A method of adding an organoaluminum compound such as trialkylaluminum to the hydrocarbon medium suspension of (1) and reacting the adsorbed water or water of crystallization with the organoaluminum compound.
(2) A method in which water, ice or steam is directly acted on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran.
(3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

The aluminoxane may contain a small amount of organometallic components. After removing the solvent or unreacted organoaluminum compound by distillation from the recovered aluminoxane solution, the obtained aluminoxane may be redissolved in the solvent or suspended in a poor solvent for the aluminoxane.

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

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

Solvents used for the preparation of aluminoxanes include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane; , cyclohexane, cyclooctane, alicyclic hydrocarbons such as methylcyclopentane, petroleum fractions such as gasoline, kerosene, light oil, or the above aromatic hydrocarbons, aliphatic hydrocarbons, halides of alicyclic hydrocarbons, especially chlorine and hydrocarbon solvents such as sulfides and bromides. Ethers such as ethyl ether and tetrahydrofuran can also be used. Among these solvents, aromatic hydrocarbons or aliphatic hydrocarbons are particularly preferred.

In the benzene-insoluble organoaluminumoxy compound used in the present invention, the Al component dissolved in benzene at 60° C. is usually 10% or less, preferably 5% or less, and particularly preferably 2% or less in terms of Al atoms. That is, it is preferably insoluble or sparingly soluble in benzene.

Examples of the organoaluminumoxy compound (B-2) include an organoaluminumoxy compound containing boron represented by the following general formula (3).

（一般式（３）中、Ｒ¹⁵は炭素原子数が１～１０の炭化水素基を示し、４つのＲ¹⁶は、互いに同一でも異なっていてもよく、水素原子、ハロゲン原子、炭素原子数が１～１０の炭化水素基を示す。）

(In the general formula (3), R ¹⁵ represents a hydrocarbon group having 1 to 10 carbon atoms, and the four R ¹⁶ may be the same or different, and may contain a hydrogen atom, a halogen atom, or a 1 to 10 hydrocarbon groups are shown.)

The organoaluminumoxy compound containing boron represented by the general formula (3) is obtained by adding an alkylboronic acid represented by the following general formula (4) and an organoaluminum compound in an inert solvent under an inert gas atmosphere. at -80°C to room temperature for 1 minute to 24 hours.
R ¹⁷ -B(OH) ₂ (4)
(In general formula (4), R ¹⁷ represents the same group as R ¹⁵ in general formula (3) above.)

Specific examples of the alkylboronic acid represented by the general formula (4) include methylboronic acid, ethylboronic acid, isopropylboronic acid, n-propylboronic acid, n-butylboronic acid, isobutylboronic acid, and n-hexylboronic acid. acids, cyclohexylboronic acid, phenylboronic acid, 3,5-difluoroboronic acid, pentafluorophenylboronic acid, 3,5-bis(trifluoromethyl)phenylboronic acid and the like. Among these, methylboronic acid, n-butylboronic acid, isobutylboronic acid, 3,5-difluorophenylboronic acid and pentafluorophenylboronic acid are preferred. These are used individually by 1 type or in combination of 2 or more types.

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

As the organoaluminum compound, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum, triethylaluminum and triisobutylaluminum are particularly preferable. These are used individually by 1 type or in combination of 2 or more types.
The organoaluminumoxy compound (B-2) as described above may be used alone or in combination of two or more.

((B-3) a compound that forms an ion pair by reacting with the transition metal compound (A))
The compound (B-3) (hereinafter referred to as "ionized ionic compound") that reacts with the transition metal compound (A) to form an ion pair includes JP-A-1-501950 and JP-A-1-502036. Publications, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, US Pat. No. 5,321,106 Lewis acids, ionic compounds, Examples include borane compounds and carborane compounds. In addition, heteropolycompounds and isopolycompounds may also be mentioned.

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

（一般式（５）中、Ｒ¹⁸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、Ｒ¹⁹～Ｒ²²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 general formula (5), R ¹⁸ is H ⁺ , carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation or ferrocenium cation having a transition metal, and R ¹⁹ to R ²² are the same or different and are organic groups, preferably aryl or substituted aryl groups.)

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

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

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

As R ¹⁸ , carbonium cations and ammonium cations are preferred, and triphenylcarbonium cations, N,N-dimethylanilinium cations and N,N-diethylanilinium cations are particularly preferred.

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

Specific examples of the trialkyl-substituted ammonium salts include triethylammoniumtetra(phenyl)boron, tripropylammoniumtetra(phenyl)boron, tri(n-butyl)ammoniumtetra(phenyl)boron, trimethylammoniumtetra(p-tolyl ) boron, trimethylammonium tetra(o-tolyl) boron, tri(n-butyl) ammonium tetra(pentafluorophenyl) boron, tripropylammonium tetra(o,p-dimethylphenyl) boron, tri(n-butyl) ammonium tetra (m,m-dimethylphenyl) boron, tri(n-butyl) ammonium tetra(p-trifluoromethylphenyl) boron, tri(n-butyl) ammonium tetra(3,5-ditrifluoromethylphenyl) boron, tri( and n-butyl)ammonium tetra(o-tolyl)boron.

Specific examples of the N,N-dialkylanilinium salts include N,N-dimethylanilinium tetra(phenyl)boron, N,N-diethylaniliniumtetra(phenyl)boron, N,N,2,4, 6-pentamethylaniliniumtetra(phenyl)boron and the like.

Specific examples of the dialkylammonium salts include di(1-propyl)ammoniumtetra(pentafluorophenyl)boron, dicyclohexylammoniumtetra(phenyl)boron and the like.

Furthermore, as ionic compounds, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, ferroceniumtetra(pentafluorophenyl)borate, triphenylcarbeniumpentaphenyl Cyclopentadienyl complexes, N,N-diethylanilinium pentaphenylcyclopentadienyl complexes, boron compounds represented by the following formula (6) or (7), and the like can also be mentioned.

（式（６）中、Ｅｔはエチル基を示す。）

(In formula (6), Et represents an ethyl group.)

（式（７）中、Ｅｔはエチル基を示す。）

(In formula (7), Et represents an ethyl group.)

Specific examples of borane compounds that are examples of the ionized ionic compound (B-3) include decaborane (14);
Bis[tri(n-butyl)ammonium]nonaborate, bis[tri(n-butyl)ammonium]decaborate, bis[tri(n-butyl)ammonium]undecaborate, bis[tri(n-butyl)ammonium]dodecaborate , salts of anions such as bis[tri(n-butyl)ammonium]decachlorodecaborate, bis[tri(n-butyl)ammonium]dodecachlorododecaborate;
metal borane anions such as tri(n-butyl)ammonium bis(dodecahydride dodecaborate) cobaltate (III) and bis[tri(n-butyl)ammonium]bis(dodecahydride dodecaborate) nickelate (III); Examples include salt.

Specific carborane compounds that are examples of the ionizable ionic compound (B-3) include, for example, 4-carbanonaborane (14), 1,3-dicarbanonaborane (13), 6,9-dicarbadecaborane ( 14), dodecahydride-1-phenyl-1,3-dicarbanonaborane, dodecahydrite-1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-di carbanonaborane, 7,8-dicarboundecaborane (13), 2,7-dicarboundecaborane (13), undecahydride-7,8-dimethyl-7,8-dicarboundecaborane, dodecahydride- 11-methyl-2,7-dicarbaundecaborate, tri(n-butyl)ammonium 1-carbadecaborate, tri(n-butyl)ammonium 1-carbaundecaborate, tri(n-butyl)ammonium 1-carbado Decaborate, Tri(n-butyl)ammonium 1-trimethylsilyl-1-carbadecaborate, Tri(n-butyl)ammonium bromo-1-carbadodecaborate, Tri(n-butyl)ammonium 6-carbadecaborate (14) , tri(n-butyl)ammonium 6-carbadecaborate (12), tri(n-butyl)ammonium 7-carbadecaborate (13), tri(n-butyl)ammonium 7,8-dicarbadecaborate ( 12), tri(n-butyl)ammonium 2,9-dicarbaundecaborate (12), tri(n-butyl)ammonium dodecahydride-8-methyl-7,9-dicarbaundecaborate, tri(n-butyl) ) ammonium undecahydride-8-ethyl-7,9-dicarbaundecaborate, tri(n-butyl)ammonium undecahydride-8-butyl-7,9-dicarbaundecaborate, tri(n-butyl)ammonium Undecahydride-8-allyl-7,9-dicarbaundecaborate, tri(n-butyl)ammonium undecahydride-9-trimethylsilyl-7,8-dicarbaundecaborate, tri(n-butyl)ammonium undeca salts of anions such as hydride-4,6-dibromo-7-carbaundecaborate;
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-dicarboundecaborate) cobaltate (III), tri(n-butyl)ammonium bis(undecahydride-7 ,8-dicarbaundecaborate)nickelate (III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbaundecaborate)cuprate(III), tri(n-butyl) Ammonium bis(undecahydride-7,8-dicarbaundecaborate)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-carboundecaborate) manganate (IV), bis[tri(n-butyl)ammonium]bis(undecahydride-7-carbohydrate) boundecaborate) cobaltate (III), bis[tri(n-butyl)ammonium]bis(undecahydride-7-carboundecaborate)nickelate (IV), and the like salts of metal carborane anions; be done.

A heteropoly compound, which is an example of the ionizable ionic compound (B-3), includes atoms selected from silicon, phosphorus, titanium, germanium, arsenic and tin, and one or more selected from vanadium, niobium, molybdenum and tungsten. is a compound containing an atom of 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, stannotungstic acid, phosphomolybdovanadate, phosphotungstovanadate, germanotungstovanadate, phosphomolybdotungstovanadate, germanomolybdotungstovanadate, phosphomolybdotungstic acid , phosphomolybdoniobic acid, and salts of these acids. Further, as the salt, for example, a metal of Group 1 or Group 2 of the periodic table, specifically lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, etc., of the acid. and organic salts such as triphenylethyl salts.

The isopoly compound, which is an example of the ionized ionic compound (B-3), is a compound composed of metal ions of one atom selected from vanadium, niobium, molybdenum and tungsten, and is a molecular ionic species of metal oxide. can be assumed to be Specific examples include, but are not limited to, vanadic acid, niobic acid, molybdic acid, tungstic acid, and salts of these acids. Further, the salt may be a salt of the acid with, for example, a metal of Group 1 or Group 2 of the periodic table, specifically lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, or the like. organic salts such as salts and triphenylethyl salts;

The ionized ionic compound (compound (B-3) that forms an ion pair by reacting with the transition metal compound (A)) as described above may be used singly or in combination of two or more.
When an organoaluminumoxy compound (B-2) such as methylaluminoxane is used as a co-catalyst component in addition to the transition metal compound (A), extremely high polymerization activity is exhibited for olefin compounds.

Further, the olefin polymerization catalyst according to the present invention comprises the transition metal compound (A), the organometallic compound (B-1), the organoaluminumoxy compound (B-2), and the ionized ionic compound (B-3). At least one compound (B) selected from the group consisting of and, if necessary, the following carrier (C) may be included.

[Carrier (C)]
The carrier (C) 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 (C), a polymer with good morphology can be obtained.

As the inorganic compound, porous oxides, inorganic halides, clays, clay minerals, or ion-exchange layered compounds are preferable.
Specific examples of the porous oxide include SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ and the like, or composites or mixtures containing these. can also be used, for example natural or synthetic zeolites, SiO ₂ --MgO, SiO ₂ --Al ₂ O ₃ , SiO ₂ --TiO ₂ , SiO ₂ --V ₂ O ₅ , SiO ₂ --Cr ₂ O ₃ , SiO ₂ --TiO ₂ --MgO and the like can be used. Among these, the porous oxide is preferably composed mainly of SiO ₂ and/or Al ₂ O ₃ .

Incidentally, the porous oxide contains _a small amount of _{Na2CO3 , K2CO3} , _CaCO3 , _MgCO3 , _Na2SO4 , _Al2 ( _SO4 ) ₃ , _BaSO4 , _{KNO3 ,} Mg( _NO3). ) ₂ , Al(NO ₃ ) ₃ , Na ₂ O, K ₂ O, Li ₂ O and other carbonates, sulfates, nitrates, and oxide components.

Such porous oxides have different properties depending on the type and manufacturing method. Desirably, the pore volume is in the range of 50 to 1000 m ² /g, preferably 100 to 700 m ² /g, and the pore volume is in the range of 0.3 to 3.0 cm ³ /g. Such porous oxides are 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 and the like are used. The inorganic halide may be used as it is, or may be used after pulverizing with a ball mill or vibration mill. Moreover, after dissolving an inorganic halide in a solvent such as alcohol, it is possible to use a product obtained by depositing fine particles using a precipitating agent.

The clay is usually composed mainly of clay minerals. The ion-exchangeable layered compound is a compound having a crystal structure in which planes formed by ionic bonds and the like are stacked in parallel with a weak bonding force, and the ions contained therein are exchangeable. Most clay minerals are ion exchange layered compounds. Moreover, as these clays, clay minerals, and ion-exchangeable layered compounds, not only naturally occurring ones but also artificially synthesized ones can be used.

Examples of clays, clay minerals, or ion-exchangeable layered compounds include ionic crystalline compounds having layered crystal structures such as hexagonal close-packing type, antimony type, _CdCl2 type, and _CdI2 type.

Furthermore, clays and clay minerals include kaolin, bentonite, kibushi clay, gyrome clay, allophane, hisingerite, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokudite group, palygorskite, kaolinite, nacrite, dickite, halloy sites, etc.
Examples of the ion-exchange layered compound include α-Zr(HAsO ₄ ) ₂ ·H ₂ O, α-Zr(HPO ₄ ) ₂ , α-Zr(KPO ₄ ) ₂ ·3H ₂ O, α-Ti(HPO ₄ ). ₂ , α-Ti(HAsO ₄ ) ₂ ·H ₂ O, α-Sn(HPO ₄ ) ₂ ·H ₂ O, γ-Zr(HPO ₄ ) ₂ , γ-Ti(HPO ₄ ) ₂ , γ-Ti( _NH4PO4 ) _2.H2O and other polyvalent metal crystalline _acid salts _.

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

When a carrier having a pore volume of less than 0.1 cc/g with a radius of 20 Å or more is used, it tends to be difficult to obtain high polymerization activity.
It is also preferable to chemically treat the clay and clay mineral. Any chemical treatment can be used, such as a surface treatment for removing impurities adhering to the surface, a treatment for affecting the crystal structure of clay, and the like. Specific examples of chemical treatment include acid treatment, alkali treatment, salt treatment, and organic treatment. The acid treatment removes surface impurities and also elutes cations such as Al, Fe and Mg in the crystal structure to increase the surface area. Alkaline treatment destroys the crystalline structure of the clay, resulting in changes in the clay structure. Also, in salt treatment and organic matter treatment, ionic complexes, molecular complexes, organic derivatives, etc. are formed, and the surface area and interlayer distance can be changed.

The ion-exchangeable layered compound may be a layered compound in which the interlayer spacing is expanded by exchanging the exchangeable ions between the layers with other large bulky ions by utilizing the ion-exchangeability. Such bulky ions play a pillar-like role supporting the layered structure and are usually called pillars. Also, the introduction of another substance between the layers of a layered compound is called intercalation. Guest compounds for intercalation include cationic inorganic compounds such as TiCl ₄ and ZrCl ₄ , metal alkoxides such as Ti(OR) ₄ , Zr(OR) ₄ , PO(OR) ₃ and B(OR) ₃ ( R is a hydrocarbon group, etc.), metal hydroxide ions such as [ _Al13O4 (OH) ₂₄ ] ⁷⁺ , [ _Zr4 (OH _{) 14} ] ²⁺ , [ _Fe3O ( _OCOCH3 ) ₆ ] ⁺ etc. These compounds are used singly or in combination of two or more. In addition, when intercalating these compounds, metal alkoxides such as Si(OR) ₄ , Al(OR) ₃ and Ge(OR) ₄ (R represents a hydrocarbon group) are hydrolyzed. The resulting polymer, a colloidal inorganic compound such as SiO _{2 ,} etc., can also coexist. The pillars also include oxides produced by intercalating the metal hydroxide ions between layers and then dehydrating them by heating.

The clay, clay mineral, and ion-exchangeable layered compound may be used as they are, or may be used after being subjected to treatments such as ball milling and sieving. Alternatively, water may be newly added and adsorbed, or may be used after heat dehydration treatment. Furthermore, these may be used individually by 1 type, or may be used in combination of 2 or more type.

Among these, preferred are clays or clay minerals, and particularly preferred are montmorillonite, vermiculite, pectolite, taeniolite and synthetic mica.
As described above, the carrier (C) is an inorganic or organic compound, and examples of organic compounds include granular or particulate solids having a particle size in the range of 10 to 300 μm. Specifically, (co)polymers produced mainly from α-olefins having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, vinylcyclohexane, and styrene can be exemplified as a (co)polymer produced as a main component, and a modified product thereof.

The olefin polymerization catalyst according to the present invention contains the transition metal compound (A), preferably the compound (B), and optionally a carrier (C). It may also contain an organic compound component (D).

[Organic compound component (D)]
In the present invention, the organic compound component (D) optionally improves the polymerization performance (e.g., catalytic activity) of the olefin polymerization catalyst of the present invention and the physical properties of the produced polymer (e.g., increase in molecular weight of the produced polymer). used for the purpose. Examples of such organic compounds include, but are not limited to, alcohols, phenolic compounds, carboxylic acids, organophosphorus compounds and sulfonic acids.

As the alcohols and phenolic compounds, those represented by R ²³ —OH are usually used, where R ²³ is a hydrocarbon group having 1 to 50 carbon atoms (in the case of phenols, carbon atoms 6 to 50) or a halogenated hydrocarbon group having 1 to 50 carbon atoms (6 to 50 carbon atoms in the case of phenols).

As alcohols, those in which R ²³ is a halogenated hydrocarbon group are preferred. Preferable phenolic compounds are those in which α,α'-positions of hydroxyl groups are substituted with hydrocarbons having 1 to 20 carbon atoms.

As the carboxylic acid, those represented by R ²⁴ —COOH are usually used. R ²⁴ represents a hydrocarbon group of 1 to 50 carbon atoms or a halogenated hydrocarbon group of 1 to 50 carbon atoms, preferably a halogenated hydrocarbon group of 1 to 50 carbon atoms.

As the organic phosphorus compound, phosphoric acids having a P—O—H bond, phosphates having a P—OR and P=O bond, and phosphine oxide compounds are preferably used.
Examples of the sulfonic acids include those represented by the following general formula (8).

（一般式（８）中、Ｍ²は周期律表第１～１４族の元素であり、
Ｒ²⁵は水素原子、炭素原子数１～２０の１価の炭化水素基または炭素原子数１～２０の１価のハロゲン化炭化水素基であり、
Ｚは水素原子、炭素原子数１～２０の１価の炭化水素基または炭素原子数１～２０の１価のハロゲン化炭化水素基であり、
ｔはＭ²の価数であり、
ｔ－ｕは０以上の整数である。）

(In the general formula (8), M ² is an element of Groups 1 to 14 of the periodic table,
R ²⁵ is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms or a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms,
Z is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms or a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms,
t is the valence of ^M2 ,
tu is an integer of 0 or more. )

In the above formula (8), M ² is preferably an element of Groups 2 to 14 of the periodic table. Also, M ² is preferably a metal element.
As the sulfonic acids, sulfonates are preferable.
Moreover, said organic compound component may be used individually by 1 type, and may be used in combination of 2 or more type.

<Method for Producing Olefin Polymer>
The method for producing an olefin polymer of the present invention is a method of homopolymerizing or copolymerizing an olefin in the presence of the olefin polymerization catalyst described above. As described above, the olefin in the present invention indicates a hydrocarbon having one carbon-carbon double bond in the molecule. In the present invention, olefin copolymerization may be carried out as long as at least one of the monomers is an olefin. Two or more olefins may be copolymerized, or a monomer other than an olefin may be copolymerized with an olefin.

In polymerization, the method of using each component constituting the catalyst of the present invention and the order of addition to the polymerization vessel are arbitrarily selected, but the following methods are exemplified.
(1) A method of adding the transition metal compound (A) alone to a polymerization vessel.
(2) A method of adding the transition metal compound (A) and the compound (B) in any order to the polymerization vessel.
(3) A method of adding a catalyst component in which a transition metal compound (A) is supported on a carrier (C) and a compound (B) in an arbitrary order to a polymerization vessel.
(4) A method in which the catalyst component in which the compound (B) is supported on the carrier (C) and the transition metal compound (A) are added in any order to the polymerization vessel.
(5) A method of adding a catalyst component in which a transition metal compound (A) and a compound (B) are supported on a carrier (C) to a polymerization reactor.
(6) A method of adding a catalyst component in which a transition metal compound (A) and a compound (B) are supported on a carrier (C), and the compound (B) in an arbitrary order to a polymerization vessel. In this case, the compounds (B) may be the same or different.
(7) A method of adding the catalyst component in which the compound (B) is supported on the carrier (C) and the transition metal compound (A) in any order to the polymerization vessel.
(8) A method in which the catalyst component in which the compound (B) is supported on the carrier (C), the transition metal compound (A), and the compound (B) are added in any order to the polymerization vessel. In this case, the compounds (B) may be the same or different.
(9) A method of adding a component in which a transition metal compound (A) is supported on a carrier (C) and a component in which a compound (B) is supported on a carrier (C) in an arbitrary order to a polymerization vessel.
(10) A method of adding a component in which a transition metal compound (A) is supported on a carrier (C), a component in which a compound (B) is supported on a carrier (C), and a compound (B) to an arbitrary sequential polymerization vessel. In this case, the compounds (B) may be the same or different.
(11) A method of adding the transition metal compound (A), the compound (B), and the organic compound component (D) to the polymerization vessel in any order.
(12) A method of adding the components obtained by contacting the compound (B) and the organic compound component (D) in advance, and the transition metal compound (A) in an arbitrary order to a polymerization vessel.
(13) A method of adding the component in which the compound (B) and the organic compound component (D) are supported on the carrier (C), and the transition metal compound (A) in any order to the polymerization vessel.
(14) A method of adding the catalyst component in which the transition metal compound (A) and the compound (B) are brought into contact in advance and the organic compound component (D) in an arbitrary order to the polymerization vessel.
(15) A method of adding the catalyst component obtained by contacting the transition metal compound (A) and the compound (B) in advance, the compound (B), and the organic compound component (D) in an arbitrary order to a polymerization vessel. In this case, the compounds (B) may be the same or different.
(16) A catalyst component in which the transition metal compound (A) and the compound (B) are brought into contact in advance and a component in which the compound (B) and the organic compound component (D) are brought into contact in advance are added in an arbitrary order to the polymerization vessel. Method. In this case, the compounds (B) may be the same or different.
(17) A method in which the component in which the transition metal compound (A) is supported on the carrier (C), the compound (B), and the organic compound component (D) are added in any order to a polymerization vessel.
(18) A method in which the component in which the transition metal compound (A) is supported on the carrier (C) and the component in which the compound (B) and the organic compound component (D) are brought into contact in advance are added to the polymerization vessel in any order.
(19) A method in which the transition metal compound (A), the compound (B) and the organic compound component (D) are brought into contact in advance in an arbitrary order and added to the polymerization reactor.
(20) A method in which the transition metal compound (A), the compound (B), and the organic compound component (D) are brought into contact in advance in an arbitrary order, and the compound (B) is added in an arbitrary order to a polymerization vessel. In this case, the compounds (B) may be the same or different.
(21) A method of adding a catalyst in which a transition metal compound (A), a compound (B) and an organic compound component (D) are supported on a carrier (C) to a polymerization vessel.
(22) A method of adding a catalyst component in which a transition metal compound (A), a compound (B) and an organic compound component (D) are supported on a carrier (C), and the compound (B) in an arbitrary order to a polymerization vessel. In this case, the compounds (B) may be the same or different.

The solid catalyst component in which the transition metal compound (A) is supported on the carrier (C), and the solid catalyst component in which the transition metal compound (A) and the compound (B) are supported on the carrier (C) are prepared with an olefin. It may be polymerized, and a further catalyst component may be supported on the prepolymerized solid catalyst component.

In the present invention, 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 inert hydrocarbon media 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; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane; and mixtures thereof. The supplied olefin (monomer) itself can also be used as a solvent.

When olefin polymerization is carried out using the olefin polymerization catalyst as described above, the transition metal compound (A) is generally 1×10 ⁻¹² to 1×10 ⁻² mol, preferably 1 mol per liter of reaction volume. It is used in an amount such that it becomes ×10 ^-10 to 1×10 ^-3 mol.

The organometallic compound (B-1) has a molar ratio [(B-1)/M] between the organometallic compound (B-1) and all the 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 organoaluminumoxy compound (B-2) has a molar ratio of the aluminum atoms in the organoaluminumoxy compound (B-2) to the total transition metal (M) in the transition metal compound (A) [(B-2) /M] is generally 10 to 500,000, preferably 20 to 100,000. The compound (ionized ionic compound) (B-3) that reacts with the transition metal compound (A) to form an ion pair is the ionized ionic compound (B-3) and the transition metal in the transition metal compound (A) It is used in such an amount that the molar ratio [(B-3)/M] to the atom (M) is generally 1-10, preferably 1-5.

When the carrier (C) is used, the weight ratio [(A)/(C)] of the transition metal compound (A) and the carrier (C) is preferably 0.0001 to 1, more preferably 0.0005 to 0. .5, more preferably 0.001 to 0.1.

In the organic compound component (D), when the compound (B) is an organometallic compound (B-1), the molar ratio [(D)/(B-1)] is usually 0.01 to 10, preferably 0. .1 to 5 are used. When the compound (B) is an organoaluminumoxy compound (B-2), the molar ratio [(D)/(B-2)] is usually 0.001 to 2, preferably 0.005 to 1. used in large amounts. When the compound (B) is an ionized ionic compound (B-3), the molar ratio [(D)/(B-3)] is usually 0.01 to 10, preferably 0.1 to 5. Used in quantity.

The temperature for olefin polymerization using such an olefin polymerization catalyst is usually -50 to +200°C, preferably 0 to 170°C. The polymerization pressure is usually normal pressure to 100 kg/cm ² -G, preferably normal pressure to 50 kg/cm ² -G, and the polymerization reaction can be carried out in any of batch, semi-continuous and continuous processes. can also be done. Furthermore, it is also possible to carry out the polymerization in two or more stages with different reaction conditions.

The molecular weight of the resulting olefinic polymer can be adjusted by allowing hydrogen to exist in the polymerization system or by changing the polymerization temperature. Furthermore, it can also be adjusted by the amount of the compound (B) used.

When olefins are copolymerized in the presence of the olefin polymerization catalyst of the present invention, the difference in copolymerization reactivity between olefins tends to be smaller than in the past, depending on the types of olefins to be combined. For this reason, in the industrial production of a copolymer, if the olefin copolymerization is carried out in the presence of the olefin polymerization catalyst of the present invention, the process control becomes simple, and a copolymer with a narrow composition distribution can be produced. It can be expected that it is easy to manufacture stably.

Although the reason for having such characteristics is not clear at present, the present inventors make several assumptions as follows.
The transition metal compound (A) has a structure in which one ligand coordinates to the metal atom via at least three heteroatoms. Therefore, the transition metal compound (A) is expected to have a structurally stable structure with little fluctuation. One idea is that the less bulky olefin is easier to coordinate with the heteroatom, the polymerization rate is suppressed, and the difference in polymerization rate from the bulky olefin is smaller.

Further, the transition metal compound (A) of the present invention is expected from computational science to have a wide coordination space in addition to being structurally stable and less fluctuating as described above. In other words, even bulky olefins tend to approach the central metal (considered as an active site).

In addition, although the accuracy of analysis is not high at present, the polymer obtained using the olefin polymerization catalyst of the present invention seems to have many heterogeneous bond structures. Conventionally, in a reaction process that forms a heterogeneous bond, the polymerization rate may be extremely lowered. (The reaction rate of α-olefins with 3 or more carbon atoms (structures that can form heterogeneous bonds) is low relative to ethylene (structures that do not form heterogeneous bonds). ) The olefin polymerization catalyst containing the transition metal compound (A) of the present invention has the property that the polymerization rate does not decrease even if a heterogeneous bond reaction occurs, so the difference in copolymerization reactivity is There is also the idea that there is less

Owing to such characteristics, the use of the olefin polymerization catalyst of the present invention enables easy production of copolymers of any composition. For example, when producing a polymer using two kinds of olefins, the compositional ratio can be freely adjusted from 1/99 to 99/1 in molar ratio.

The olefin that can be polymerized using the olefin polymerization catalyst of the present invention is not particularly limited, but a linear or branched α having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms. - olefins such as ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1- Decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene; cyclic olefins having 3 to 30, preferably 3 to 20 carbon atoms, such as cyclopentene, cycloheptene, norbornene, 5-methyl- 2-norbornene, tetracyclododecene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene and the like. These olefins can be used singly or in combination of two or more. Among the above olefins, olefins having 2 to 20 carbon atoms are preferred, and olefins having 2 to 10 carbon atoms are more preferred.

In the method for producing an olefin polymer of the present invention, it is preferable to use an olefin having 2 to 10 carbon atoms as an essential component, and an olefin selected from ethylene, propylene and 1-butene is used as an essential component. is more preferable, it is more preferable to use ethylene and propylene as essential components, and particularly preferably an embodiment in which ethylene is used as an essential component.

In the method for producing an olefin polymer of the present invention, an olefin may be copolymerized with another monomer. Other monomers are not particularly limited as long as they are monomers other than olefins. (hereinafter also referred to as a polar group-containing monomer).

Specific examples of polar group-containing monomers include acrylic acid, 3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid, 6-heptenoic acid, 7-octenoic acid, 8-nonenoic acid, and 9-decenoic acid. , 10-undecenoic acid, 11-dodecenoic acid, 12-tridecenoic acid, 13-tetradecenoic 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-vinyl Benzoic acid, 4-vinylbenzoic acid, 2,6-heptadienoic acid, 2-(4-isopropylbenzylidene)-4-pentenoic acid, allylmalonic acid, 2-(10-undecenyl)malonic acid, fumaric acid, itaconic acid, bicyclo Unsaturated carboxylic acids such as [2.2.1]-5-heptene-2-carboxylic acid and bicyclo[2.2.1]-5-heptene-2,3-dicarboxylic acid, sodium of these unsaturated carboxylic acids Salts, potassium salts, lithium salts, zinc salts, magnesium salts, metal salts such as calcium salts, methyl esters, ethyl esters, n-propyl esters, isopropyl esters, n-butyl esters, isobutyl esters of these unsaturated carboxylic acids, ( 5-Norbornen-2-yl) esters and other unsaturated carboxylic acid esters (when the unsaturated carboxylic acid is a dicarboxylic acid, it may be a monoester or a diester), and these unsaturated carboxylic acid esters amides of acids, unsaturated carboxylic acid amides such as N,N-dimethylamide (when the unsaturated carboxylic acid is a dicarboxylic acid, it may be a monoamide or a diamide);
maleic anhydride, itaconic anhydride, allylsuccinic anhydride, isobutenylsuccinic anhydride, (2,7-octadien-1-yl)succinic anhydride, tetrahydrophthalic anhydride, bicyclo[2.2.1 ]-Unsaturated carboxylic anhydrides such as 5-heptene-2,3-dicarboxylic anhydride;
vinyl esters such as vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl trifluoroacetate;
halogenated olefins such as vinyl chloride, vinyl fluoride, vinyl bromide, vinyl iodide, allyl bromide, allyl chloride, allyl fluoride, allyl bromide;
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, and 12-tridecenol , and unsaturated esters such as these acetates, benzoates, propionates, caproates, caprates, laurates, and stearates;
substituted phenols such as vinylphenol and allylphenol;
Unsaturated ethers such as methyl vinyl ether, ethyl vinyl ether, allyl methyl ether, allyl propyl ether, allyl butyl ether, allylmethallyl ether, methoxystyrene, ethoxystyrene, allylanisole;
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 thereof such as dimethylacetal and diethylacetal;
Unsaturated ketones such as methyl vinyl ketone, ethyl vinyl ketone, allyl methyl ketone, allyl ethyl ketone, allyl propyl ketone, allyl butyl ketone, allyl benzyl ketone, and unsaturated acetals thereof such as dimethyl acetal and diethyl acetal;
Unsaturated thioethers such as allylmethylsulfide, allylphenylsulfide, allylisopropylsulfide, allyl n-propylsulfide, 4-pentenylphenylsulfide;
Unsaturated sulfoxides such as allylphenyl sulfoxide;
Unsaturated sulfones such as allylphenyl sulfone;
Unsaturated phosphines such as allyldiphenylphosphine;
and unsaturated phosphine oxides such as allyldiphenylphosphine oxide.

Furthermore, examples of the polar group-containing monomer include vinylbenzyl acetate, hydroxystyrene, methyl 4-(3-butenyloxy)benzoate, methoxystyrene, ethoxystyrene, allyl trifluoroacetate, o-chlorostyrene, p-chlorostyrene. , glycidyl acrylate, allyl glycidyl ether, (2H-perfluoropropyl)-2-propenyl ether, linalool oxide, 3-allyloxy-1,2-propanediol, 2-(allyloxy)ethanol, N-allylmorpholine, allylglycine, Also included are N-vinylpyrrolidone, allyltrichlorosilane, acryltrimethylsilane, allyldimethyl(diisopropylamino)silane, 7-octenyltrimethoxysilane, allyloxytrimethylsilane, allyloxytriphenylsilane, etc., which are used for the olefin polymerization of the present invention. It can be copolymerized with olefins in the presence of a catalyst.

In addition to the polar group-containing monomers, vinylcyclohexane, dienes, polyenes, and the like can be used. These monomers can also be copolymerized with olefins in the presence of the olefin polymerization catalysts of the present invention.

Examples of the diene or polyene include cyclic or chain compounds having 4 to 30 carbon atoms, preferably 4 to 20 carbon atoms and two or more carbon-carbon double bonds. 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, divinylbenzene; 7-methyl-1,6- octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, 5,9-dimethyl-1,4,8-decatriene and the like.

Furthermore, aromatic vinyl compounds can be used as other monomers. Specifically mono- or polyalkylstyrenes such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o,p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene and p-ethylstyrene; Functional group-containing styrene derivatives such as methoxystyrene, ethoxystyrene, vinyl benzoic acid, methyl vinyl benzoate, vinyl benzyl acetate, hydroxystyrene, o-chlorostyrene, p-chlorostyrene; and 3-phenylpropylene, 4-phenylpropylene. , and α-methylstyrene.

Depending on the types of monomers used, there is a possibility that the copolymerization reactivity will be greatly different in combination. In such a case, the difference in copolymerization reactivity can be reduced by appropriately selecting the structure of the olefin polymerization catalyst depending on the type of monomer used.

According to the method for producing an olefin polymer of the present invention, it is possible to obtain an olefin polymer having a wide molecular weight range from low molecular weight to ultra-high molecular weight. As a specific example, it is possible to produce an olefin polymer with a weight average molecular weight of 10-5 million. The lower limit of the weight average molecular weight is preferably 5,000, more preferably 10,000, still more preferably 30,000. On the other hand, the upper limit is preferably 3 million, more preferably 2 million, even more preferably 1 million.

As described above, the polymer produced by the method for producing an olefin polymer of the present invention may contain many heterogeneous bonds. Formation of heterologous bonds is conventionally considered to be disadvantageous in terms of increasing the molecular weight. However, if the method for producing an olefinic polymer of the present invention is used, it may be possible to obtain a polymer having a high molecular weight even with many heterogeneous bonds.

The molecular weight of the olefin polymer produced by the production method of the system polymer of the present invention is determined by GPC measurement performed under the conditions described in the Examples section below.
According to the method for producing an olefin polymer of the present invention, a polymer can be produced with high polymerization activity as described above. In addition, there is little difference in copolymerization reactivity during copolymerization, and it may exhibit advantageous characteristics for industrially obtaining a copolymer. Therefore, the present invention has great industrial value. Specifically, while the present invention can be suitably used in continuous polymerization processes, it can be said to have a great advantage particularly in production in batch polymerization processes.

EXAMPLES The present invention will be described in more detail based on examples below, but the present invention is not limited to these.
The structures of the compounds obtained in Synthesis Examples are 270 MHz ¹ H NMR (manufactured by JEOL Ltd., device name GSH-270), GC-MS (manufactured by Shimadzu Corporation, device name QP2010 Ultra), FD-mass spectrometry (manufactured by JEOL Ltd., It was determined using the device name SX-102A) or the like.

The molecular weights of the polymers obtained in the examples were measured by a gel permeation chromatograph (manufactured by Waters, device name: Alliance GPC2000). The operating conditions were as follows.

Measuring device; gel permeation chromatograph alliance GPC2000 type (Waters)
Analysis software; chromatography data system Empower3 (trademark, Waters)
Column; TSKgel GMH6-HT × 2 + TSKgel GMH6-HTL × 2 (both inner diameter 7.5 mm × length 30 cm, Tosoh Corporation)
Mobile phase; o-dichlorobenzene [= ODCB] (Wako Pure Chemical special grade reagent)
Detector: Differential refractometer (built-in)
Column temperature; 140°C
Flow rate; 1.0 mL/min Injection volume; 400 μL
Sampling time interval; 0.5 seconds Sample concentration; 0.15% (w/v)
Molecular weight calibration; monodisperse polystyrene (Tosoh Corporation) / molecular weight from 495 to 20,600,000

The weight average molecular weight is according to J. Am. Polym. Sci. 1967, B5, 753. was calculated as a polyethylene molecular weight conversion according to the universal calibration procedure described in .
The propylene content of the ethylene/propylene copolymer was measured by 125 MHz ¹³ C NMR (manufactured by Bruker Biospin, device name AVANCEIIIcryo-500).

[Synthesis Example 1]
3.13 g (14.2 mmol) of 2-iodophenol, 1.0 mL (9.47 mmol) of 2-fluoronitrobenzene, and 2.16 g (14.2 mmol) of cesium fluoride were placed in a 100 mL reactor that had been sufficiently dried and purged with nitrogen. , 3.96 g (28.6 mmol) of potassium carbonate, and 14 mL of dimethyl sulfoxide were added, and the mixture was stirred at 50° C. for 6 hours. After cooling to room temperature, 20 mL of water was added to the reaction solution, and the soluble matter was extracted with dichloromethane. The resulting fraction was washed with 1M aqueous sodium hydroxide solution and saturated brine, and dried over anhydrous magnesium sulfate. After filtering off the magnesium sulfate, the filtrate was distilled under reduced pressure to remove the solvent. Then, it was diluted with ethyl acetate, washed with water and saturated brine, and dried over anhydrous magnesium sulfate. After the magnesium sulfate was filtered, the filtrate was evaporated under reduced pressure to obtain 3.14 g (yield 97%) of the desired product represented by the following formula (1) (hereinafter referred to as compound (1)).

GC-mass (M+): 341
¹ H-NMR (270 MHz, CDCl ₃ ): 8.00 (1H, dd, J = 8.4, 1.6 Hz), 7.91 (1H, dd, J = 7.8, 1.4 Hz), 7 .50 (1H, ddd, J = 8.1, 7.6, 1.6Hz), 7.35 (1H, ddd, J = 8.1, 7.6, 1.6Hz), 7.22 (1H , ddd, J = 8.4, 7.0, 0.8 Hz), 6.98 (1H, d, J = 7.0 Hz), 6.95 (1H, dd, J = 8.4, 1.6 Hz ), 6.86 (1H, dd, J = 8.4, 0.8 Hz) ppm

[Synthesis Example 2]
10.3 g (50.0 mmol) of 2,4-di-t-butylphenol and 75 mL of tetrahydrofuran were charged into a 300 mL reactor that had been sufficiently dried and purged with nitrogen, and cooled to 0°C. After adding 2.83 g (60 wt %, 70.7 mmol) of sodium hydride (oil-based) and stirring at 0°C for 1 hour, 5.2 mL (68.5 mmol) of chloromethyl methyl ether was added at 0°C. After stirring at room temperature for 16 hours, water was added little by little under ice-cooling to quench the reaction. The soluble matter was extracted with ethyl acetate, and the resulting fraction was washed with saturated brine and dried over anhydrous magnesium sulfate. After filtering the magnesium sulfate, the filtrate was evaporated under reduced pressure to obtain a light brown solid. The solid obtained here was charged into a 200 mL reactor that was sufficiently dried and purged with nitrogen, and dissolved by adding 55 mL of diethyl ether. 18 mL (29.5 mmol) of n-butyl lithium hexane solution was added to this solution. After stirring at room temperature for 3 hours, the mixture was cooled to −78° C., 3.2 mL (28.7 mmol) of trimethoxyborane was added, and the mixture was stirred while the temperature was gradually raised to room temperature. After 16 hours, the solvent was distilled off from the reaction solution under reduced pressure, and the residue was thoroughly dried under reduced pressure to obtain a white solid. To this, 6.83 g (20.0 mmol) of compound (1), 0.23 g (1.01 mmol) of palladium acetate, 0.82 g (2.01 mmol) of 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl, 12.8 g (60.2 mmol) of potassium phosphate, 34 mL of tetrahydrofuran, and 8.5 mL of water were charged and heated in an oil bath at 60° C. for 6 hours. After the reaction solution was cooled to room temperature, ethyl acetate was added and filtered through celite. The filtrate was diluted with ethyl acetate, washed with water and saturated brine, and dried over anhydrous magnesium sulfate. After filtering magnesium sulfate, the residue obtained by evaporating the solvent under reduced pressure from the filtrate was purified by silica gel column chromatography to obtain the desired product represented by the following formula (2) (hereinafter referred to as compound (2)). 8.00 g (86% yield) was obtained.

GC-mass (M+): 463
¹ H-NMR (270 MHz, CDCl ₃ ): 7.87 (1H, dd, J = 8.4, 1.6 Hz), 7.50 (1H, dd, J = 7.6, 1.9 Hz), 7 .46-7.22 (4H, m), 7.12-6.97 (4H, m), 4.58 (2H, s), 3.25 (3H, s), 1.41 (9H, s ), 1.21 (9H, s) ppm

[Synthesis Example 3]
7.99 g (17.2 mmol) of compound (2), 1.29 g (10 wt%, 1.22 mmol) of palladium carbon, 3 mL of acetic acid, and 57 mL of ethanol were placed in a 300 mL reactor that had been sufficiently dried and replaced with nitrogen, and a hydrogen atmosphere was established. The mixture was stirred at room temperature. After 8 hours, the reactor was purged with nitrogen, and the reaction solution was filtered through celite. The resulting filtrate was diluted with ethyl acetate, washed with aqueous sodium hydrogencarbonate solution and saturated brine, and dried over anhydrous magnesium sulfate. After the magnesium sulfate was filtered, the filtrate was evaporated under reduced pressure to obtain 7.41 g of a light brown amorphous substance. 6.58 g (15.2 mmol) of the amorphous material obtained here was placed in a 500 mL reactor, and 6.90 g (38.0 mmol) of copper (II) acetate, 4.3 mL (53.4 mmol) of pyridine, 1,4 - 187 mL of dioxane was added and stirred at room temperature. After 15 minutes, 2.28 g (38.0 mmol) of methylboronic acid were added and stirred at 100°C. After 6 hours, cool to room temperature, filter the reaction mixture through celite, and evaporate the solvent from the filtrate under reduced pressure. (hereinafter referred to as compound (3)) was obtained in an amount of 4.75 g (yield 69%).

GC-mass spec (M+): 447
¹ H-NMR (270 MHz, CDCl ₃ ): 7.39 (1H, dd, J = 7.3, 1.6 Hz), 7.37 (1H, d, J = 2.4 Hz), 7.26-7 .21 (1H, m), 7.19 (1H, d, J = 2.7 Hz), 7.09 (1H, dd, J = 7.3, 1.4 Hz), 7.07-7.01 ( 1H, m), 6.85 (2H, dt, J = 8.3, 1.4 Hz), 6.66 (1H, dd, J = 8.1, 1.6 Hz), 6.59 (1H, dt , J = 7.6, 1.6 Hz), 5.07 (1H, d, J = 5.1 Hz), 4.69 (1H, s), 4.49 (1H, s), 3.15 (3H , s), 2.80 (3H, d, J = 5.1 Hz), 1.47 (9H, s), 1.31 (9H, s) ppm

[Synthesis Example 4]
4.75 g (10.6 mmol) of compound (3), 6.06 g (31.9 mmol) of paratoluenesulfonic acid monohydrate, 75 mL of ethanol, and 15 mL of dichloromethane were charged in a sufficiently dried 200 mL reactor, and the temperature was kept at 50°C. and stirred for 4 hours. After cooling the reaction solution to room temperature, the solvent was distilled off under reduced pressure. After diluting with dichloromethane, the extract was washed with an aqueous sodium hydrogencarbonate solution and saturated brine, and dried over anhydrous magnesium sulfate. After the magnesium sulfate was filtered, the filtrate was evaporated under reduced pressure to obtain 4.24 g (yield 99%) of the desired product represented by the following formula (4) (hereinafter referred to as compound (4)).

GC-mass spec: 403
¹ H-NMR (270 MHz, CDCl ₃ ): 7.40 (1H, dd, J=7.6, 1.6 Hz), 7.35-7.27 (1H, m), 7.32 (1H, d , J = 2.4 Hz), 7.18 (1H, dt, J = 7.6, 1.4 Hz), 7.09 (1H, d, J = 1.4 Hz), 7.07-7.00 ( 1H, m), 6.96 (1H, dd, J = 8.1, 1.1 Hz), 6.85 (1H, dd, J = 8.1, 1.1 Hz), 6.63 (1H, dd , J = 7.6, 1.6 Hz), 6.64-6.58 (1H, m), 5.33 (1H, s), 4.24 (1H, s), 2.74 (3H, s ), 1.44 (9H, s), 1.30 (9H, s) ppm

[Example A1]
0.13 g (60 wt %, 3.30 mmol) of sodium hydride (oil-based) was placed in a 100 mL reaction vessel which was sufficiently dried and purged with nitrogen, and 0.40 g (0.40 g) of compound (4) obtained in Synthesis Example 4 was added. 99 mmol) in tetrahydrofuran solution was added dropwise over 10 minutes, and the mixture was stirred at room temperature for 4 hours. This reaction solution was cooled to −78° C. with dry ice-acetone, and 0.99 mL of titanium tetrachloride (0.99 mmol of 1 M toluene solution) was added. Then, it was stirred for 16 hours while slowly returning to room temperature. The solvent of the reaction solution was distilled off, 20 mL of methylene chloride was added to the residue, and the mixture was stirred for a while. After adding 30 mL of n-hexane there and concentrating about 1/3, the insoluble matter was filtered off with a glass filter, and the obtained solid was washed with 15 mL of n-hexane and dried under reduced pressure to give the following formula ( 0.23 g (yield 45%) of the desired product shown in A) (hereinafter referred to as titanium compound (A)) was obtained.
FD-mass spectroscopy (M ⁺ ): 519

[Example B1]
250 ml of toluene was charged into a glass reactor having an inner volume of 500 ml which was sufficiently purged with nitrogen, and the liquid phase and gas phase were saturated with ethylene (supplied at 100 liter/hr). After that, 0.125 mmol of triisobutylaluminum (TIBA) was added, followed by 0.001 mmol of the titanium compound (A) obtained in Example A1, and 0.003 mmol of triphenylcarbenium tetrakis(pentafluorophenyl)borate (TrB). addition to initiate polymerization. Ethylene was continuously supplied at 100 liters/hr and polymerization was carried out at 25° C. under normal pressure for 5 minutes, and then the polymerization was stopped by adding a small amount of isobutanol.

After the polymerization was completed, the reactant 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 0.51 g of polyethylene. The polymerization activity was 6,120 kg/mol-Ti·hr, and the weight average molecular weight (M _w ) of the obtained polyethylene was 660,000.

[Example B2]
250 ml of toluene was charged into a glass reactor with an internal volume of 500 ml which was sufficiently purged with nitrogen, and the liquid phase and gas phase were saturated with ethylene (supplied at 50 liters/hr) and propylene (supplied at 150 liters/hr). rice field. After that, 0.125 mmol of triisobutylaluminum (TIBA) was added, followed by 0.005 mmol of the titanium compound (A) obtained in Example A1, and 0.015 mmol of triphenylcarbenium tetrakis(pentafluorophenyl)borate (TrB). addition to initiate polymerization. Ethylene was continuously supplied at 50 liters/hr and propylene at 150 liters/hr. Polymerization was carried out at 50° C. for 10 minutes under normal pressure, and then the polymerization was stopped by adding a small amount of isobutanol.

After the polymerization was completed, the reactant 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 130° C. for 10 hours to obtain 3.83 g of an ethylene/propylene copolymer. The polymerization activity was 4,596 kg/mol-Ti·hr, the propylene content of the resulting copolymer was 69.5 mol %, and the weight average molecular weight (M _w ) was 260,000.

[Example B3]
250 ml of toluene was charged into a glass reactor having an internal volume of 500 ml which was sufficiently purged with nitrogen, and the liquid phase and gas phase were saturated with ethylene (supplied at 100 liters/hr) and propylene (supplied at 100 liters/hr). rice field. After that, 0.125 mmol of triisobutylaluminum (TIBA) was added, followed by 0.005 mmol of the titanium compound (A) obtained in Example A1, and 0.015 mmol of triphenylcarbenium tetrakis(pentafluorophenyl)borate (TrB). addition to initiate polymerization. 100 liters/hr of ethylene and 100 liters/hr of propylene were continuously supplied, and polymerization was carried out at 50° C. for 10 minutes under normal pressure, and then the polymerization was stopped by adding a small amount of isobutanol.

After the polymerization was completed, the reactant 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 130° C. for 10 hours to obtain 3.68 g of an ethylene/propylene copolymer. The polymerization activity was 4416 kg/mol-Ti·hr, the propylene content of the resulting copolymer was 50.3 mol %, and the weight average molecular weight (M _w ) was 510,000.

Since the olefin polymerization catalyst containing the novel transition metal compound according to the present invention exhibits high olefin polymerization activity and excellent copolymerization reactivity, the present invention is industrially extremely valuable.

Claims (6)

A transition metal compound (A) represented by the following general formula (1).

(In general formula (1), M represents a transition metal atom of groups 3 to 10 of the periodic table.
R ¹ to R ¹³ may be the same or different, and may be 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, silicon-containing group, germanium-containing group, or tin-containing group, and two or more of R ¹ to R ¹³ may be linked together to form a ring, and the ring may be further substituted with You may have a group.
Y is an oxygen atom, a sulfur atom, or a structure represented by -N(-R ¹⁴ )- (R ¹⁴ is a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen A containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group are indicated.The leftmost and rightmost straight lines indicate the bond between the nitrogen atom and the adjacent carbon atom. ).
n represents the valence of M;
X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, germanium-containing group, or tin-containing group, and when there are a plurality of X's, they may be the same or different, and two or more of them may be linked together to form a ring. ) 2. The transition metal compound (A) according to claim 1, wherein M is a transition metal atom of Group 4 of the periodic table and n is 4 in the general formula (1). 3. The transition metal compound (A) according to claim 1 or 2, wherein Y in the general formula (1) is an oxygen atom. An olefin polymerization catalyst comprising the transition metal compound (A) according to any one of claims 1 to 3. (B) (B-1) an organometallic compound (B-2) an organoaluminumoxy compound, and
5. The olefin polymerization catalyst according to claim 4, further comprising (B-3) at least one compound selected from the group consisting of compounds that react with the transition metal compound (A) to form an ion pair. A method for producing an olefin polymer, comprising homopolymerizing or copolymerizing an olefin in the presence of the olefin polymerization catalyst according to claim 4 or 5.