JP2005263906A - Olefin polymerization catalyst and method for polymerizing olefin by using the olefin polymerization catalyst - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a novel olefin polymerization catalyst which is excellent in olefin polymerization activity. <P>SOLUTION: The olefin polymerization catalyst comprises a transition metal compound of formula (I) (wherein at least one of R1 and R7-R10 is a 1-30C hydrocarbon group having at least one fluorine atom) and at least one compound chosen from an organic metal compound, an organic aluminum oxy compound and a compound which reacts with the transition metal compound to form an ion pair. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an olefin polymerization catalyst and an olefin polymerization method using the catalyst, and more particularly to a novel olefin polymerization catalyst having high copolymerizability and an olefin polymerization method using the catalyst. More specifically, the present invention relates to an olefin polymerization method in which an olefin is polymerized or copolymerized using a specific transition metal compound, an organometallic compound, and a compound that reacts with the transition metal compound to form an ion pair.

  Conventionally, as a catalyst for producing an olefin polymer such as an ethylene polymer and an ethylene / α-olefin copolymer, a titanium-based catalyst composed of a titanium compound and an organoaluminum compound, and a vanadium compound and an organoaluminum compound. Vanadium-based catalysts are known. In recent years, a metallocene catalyst comprising a metallocene compound having a cyclopentadienyl group and an organoaluminum oxy compound (aluminoxane) has been known as a catalyst capable of producing an olefin polymer with high polymerization activity. Recently, a novel catalyst system composed of a transition metal compound having a ligand of diimine structure has been proposed (see International Patent No. 9623010).

In recent years, transition metal compounds having a salicylaldoimine ligand have been described as new olefin polymerization catalysts in JP-A-11-315109 and JP-A-12-119313. This complex has a good polymerization activity and a very high molecular weight. It is described that a polymer having a high molecular weight distribution and a narrow composition distribution is formed. More recently, JP-A 2004-002640 discloses that an α-olefin content can be obtained by using a transition metal compound having a salicylaldoimine ligand containing a fluorine atom in an olefin polymerization catalyst or ethylene / α-olefin copolymerization. The present invention provides an olefin polymerization catalyst that produces a high copolymer. However, the catalyst in these polymerization methods has insufficient polymerization activity, and further improvement in polymerization activity has been desired.
Japanese Patent Laid-Open No. 11-315109 JP-A-12-119313 Japanese Patent Laid-Open No. 2004-002640 International Patent Publication No. 9623010

  The problem to be solved is that the polymerization activity is not sufficient in the transition metal compound having a salicylaldoimine ligand containing a fluorine atom.

  The catalyst for olefin polymerization according to the present invention includes (A) a transition metal compound represented by the following general formula (I).

(In the formula, m represents an integer of 1 to 2, and at least one of R ¹ and R ^{7 to} R ¹⁰ is a hydrocarbon group having 1 to 30 carbon atoms having one or more fluorine atoms; A hydrogen atom, a fluorine atom, or a hydrocarbon group (however, when R ¹ is a C 1-30 hydrocarbon group having one or more fluorine atoms, at least one of R ^{7 to} R ¹⁰ is a hydrogen atom or 1 When the hydrocarbon group or hydrocarbon group having 1 to 30 carbon atoms having one or more fluorine atoms and R ⁷ and R ¹⁰ are both hydrocarbon groups having 1 to 30 carbon atoms having one or more fluorine atoms Represents at least one of R ¹ , R ⁸ and R ⁹ is a fluorine atom or a hydrocarbon group or hydrocarbon group having 1 to 30 carbon atoms having one or more fluorine atoms, and R ^{2 to} R ⁵ may be the same as or different from each other, Hydrocarbon group, a hydrogen atom, a hydrocarbon-substituted silyl group, an oxygen-containing group, a nitrogen-containing group or a sulfur-containing group,, R ⁶ is hydrogen, primary or secondary hydrocarbon having 1 to 4 carbon atoms consisting of only carbon A group selected from six groups: a hydrogen group, an aliphatic hydrocarbon group having 5 or more carbon atoms, an aryl group-substituted alkyl group, a monocyclic or bicyclic alicyclic hydrocarbon group and an aromatic hydrocarbon group; And when m is 2, ^two groups represented by R ^{2 to} R ⁶ may be linked, n is a number satisfying the valence of Ti, X is a hydrogen atom, Halogen atom, hydrocarbon group, oxygen-containing group, nitrogen-containing group, sulfur-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, heterocyclic compound residue, silicon-containing group, germanium-containing group, Or a soot-containing group, and when n is 2 or more, In the plurality of groups may be the same or different from each other, and a plurality of groups represented by X may be bonded to each other to form a ring represented.)

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

(In the formula, m represents an integer of 1 to 2, and at least one of R ¹ and R ^{7 to} R ¹⁰ is a hydrocarbon group having 1 to 30 carbon atoms having one or more fluorine atoms; A hydrogen atom, a fluorine atom, or a hydrocarbon group (however, when R ¹ is a C 1-30 hydrocarbon group having one or more fluorine atoms, at least one of R ^{7 to} R ¹⁰ is a hydrogen atom or 1 When the hydrocarbon group or hydrocarbon group having 1 to 30 carbon atoms having one or more fluorine atoms and R ⁷ and R ¹⁰ are both hydrocarbon groups having 1 to 30 carbon atoms having one or more fluorine atoms Represents at least one of R ¹ , R ⁸ and R ⁹ is a fluorine atom or a hydrocarbon group or hydrocarbon group having 1 to 30 carbon atoms having one or more fluorine atoms, and R ^{2 to} R ⁵ may be the same as or different from each other, Hydrocarbon group, a hydrogen atom, a hydrocarbon-substituted silyl group, an oxygen-containing group, a nitrogen-containing group or a sulfur-containing group,, R ⁶ is hydrogen, primary or secondary hydrocarbon having 1 to 4 carbon atoms consisting of only carbon A group selected from six groups: a hydrogen group, an aliphatic hydrocarbon group having 5 or more carbon atoms, an aryl group-substituted alkyl group, a monocyclic or bicyclic alicyclic hydrocarbon group and an aromatic hydrocarbon group; And when m is 2, ^two groups represented by R ^{2 to} R ⁶ may be linked, n is a number satisfying the valence of Ti, X is a hydrogen atom, Halogen atom, hydrocarbon group, oxygen-containing group, nitrogen-containing group, sulfur-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, heterocyclic compound residue, silicon-containing group, germanium-containing group, Or a soot-containing group, and when n is 2 or more, In the plurality of groups may be the same or different from each other, and a plurality of groups represented by X may be bonded to each other to form a ring represented.)

In the transition metal compound (A) represented by the above general formula (I), the olefin polymerization catalyst of the present invention has 1 to 30 carbon atoms, m is 2, and R ¹ has one or more fluorine atoms. It is an aromatic hydrocarbon group, and n is preferably 2.

The olefin polymerization catalyst of the present invention is a transition metal compound (A) represented by the general formula (I), wherein R ⁶ is carbon atom having 1 to 4 carbon atoms consisting of hydrogen, primary or secondary carbon only. A group selected from six groups: a hydrogen group, an aliphatic hydrocarbon group having 5 or more carbon atoms, an aryl group-substituted alkyl group, a monocyclic or bicyclic alicyclic hydrocarbon group and an aromatic hydrocarbon group; Preferably there is.

The olefin polymerization catalyst of the present invention is the transition metal compound (A) represented by the general formula (I), wherein R ¹ is a trifluoromethyl group, R ^{7 to} R ¹⁰ are hydrogen atoms, and R ⁶ is a phenyl group. It is particularly preferred that

  The olefin polymerization method of the present invention is characterized in that the olefin is polymerized in the presence of the olefin polymerization catalyst as described above.

  The novel catalyst for olefin polymerization of the present invention provides a polymerization method having high copolymerization properties and high polymerization activity.

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

  In the present specification, the term “polymerization” is sometimes used in the meaning including not only homopolymerization but also copolymerization, and the term “polymer” refers not only to homopolymer but also to copolymerization. It may be used in the meaning that also includes coalescence.

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

[(A) Transition metal compound]
The transition metal compound (A) used in the present invention is a compound represented by the following general formula (I).

(Note that N ... Ti generally indicates coordination, but may or may not be coordinated in the present invention.)
m represents an integer of 1 to 2, and is preferably 2. At least one of R ¹ and R ^{7 to} R ¹⁰ is a hydrocarbon group having 1 to 30 carbon atoms having one or more fluorine atoms, and other than that, a hydrogen atom, a fluorine atom, or a hydrocarbon group (however, R ¹ Is a hydrocarbon group having 1 to 30 carbon atoms and having 1 or more fluorine atoms, at least one of R ^{7 to} R ¹⁰ is a hydrogen atom or carbon atoms having 1 to 30 carbon atoms having one or more fluorine atoms. When R ⁷ and R ¹⁰ are both a hydrogen group or a hydrocarbon group and a C 1-30 hydrocarbon group having one or more fluorine atoms, at least one of R ¹ , R ⁸ , and R ⁹ Is a C 1-30 hydrocarbon group or hydrocarbon group having one or more fluorine atoms, and R ^{2 to} R ⁵ may be the same or different from each other, Groups, hydrogen atoms, hydrocarbons Silyl group, an oxygen-containing group, a nitrogen-containing group or a sulfur-containing group,, R ⁶ is hydrogen, primary or secondary only of carbon hydrocarbon group having 1 to 4 carbon atoms, 5 or more aliphatic carbon A group selected from six groups of a hydrocarbon group, an aryl group-substituted alkyl group, a monocyclic or bicyclic alicyclic hydrocarbon group, and an aromatic hydrocarbon group. ^Two groups out of the groups represented by ^{2 to} R ⁶ may be linked, n is a number satisfying the valence of Ti, and X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group. , A nitrogen-containing group, a sulfur-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a soot-containing group, and n Is 2 or more, the plurality of groups represented by X are the same as each other It may be the or different, and a plurality of groups may be bonded to each other to form a ring represented by X.

Specific examples of the hydrocarbon group having 1 to 30 carbon atoms having one or more fluorine atoms of at least one of R ¹ and R ^{7 to} R ¹⁰ include trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluoro Fluorobutyl, perfluoropentyl, perfluorohexyl, monofluorophenyl, difluorophenyl, trifluorophenyl, tetrafluorophenyl, pentafluorophenyl, (trifluoromethyl) fluorophenyl, bis (trifluoromethyl) phenyl, tris (trifluoro Methyl) phenyl, tetrakis (trifluoromethyl) phenyl, pentakis (trifluoromethyl) phenyl, perfluoroethylphenyl, bis (perfluoroethyl) phenyl, perfluoropropylphenyl, perfluorobutyl Examples include phenyl, perfluoropentylphenyl, perfluorohexylphenyl, bis (perfluorohexyl) phenyl, perfluoronaphthyl, perfluorophenanthrenyl, perfluoroanthracenyl, and the like.

As the hydrocarbon group having 1 to 30 carbon atoms and having at least one fluorine atom of at least one of R ¹ and R ^{7 to} R ¹⁰ , a trifluoromethyl group is particularly preferable.

Examples of the hydrocarbon group of R ¹ and R ^{7 to} R ¹⁰ include those having 1 to 30 carbon atoms. Specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, n-hexyl and the like have 1 to 30 carbon atoms, preferably linear or A branched alkyl group; a linear or branched alkenyl group having 2 to 30, preferably 2 to 20 carbon atoms such as vinyl, allyl, and isopropenyl; and 2 to 30 carbon atoms such as ethynyl and propargyl; Preferably a linear or branched alkynyl group having 2 to 20; a cyclic saturated hydrocarbon group having 3 to 30, preferably 3 to 20 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl; C5-C30 cyclic unsaturated hydrocarbon group such as dienyl, indenyl, fluorenyl; phenyl, naphthyl, Aryl groups having 6 to 30, preferably 6 to 20 carbon atoms such as phenyl, terphenyl, phenanthryl, anthracenyl; alkyl substitution such as tolyl, isopropylphenyl, tert-butylphenyl, dimethylphenyl, di-tert-butylphenyl An aryl group etc. are mentioned.

The hydrocarbon group of R ² to R ^5, for example include those having 1 to 30 carbon atoms. Specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, n-hexyl and the like have 1 to 30 carbon atoms, preferably linear or A branched alkyl group; a linear or branched alkenyl group having 2 to 30, preferably 2 to 20 carbon atoms such as vinyl, allyl, and isopropenyl; and 2 to 30 carbon atoms such as ethynyl and propargyl; Preferably a linear or branched alkynyl group having 2 to 20; a cyclic saturated hydrocarbon group having 3 to 30, preferably 3 to 20 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl; C5-C30 cyclic unsaturated hydrocarbon group such as dienyl, indenyl, fluorenyl; phenyl, naphthyl, Aryl groups having 6 to 30, preferably 6 to 20 carbon atoms such as phenyl, terphenyl, phenanthryl, anthracenyl; alkyl substitution such as tolyl, isopropylphenyl, tert-butylphenyl, dimethylphenyl, di-tert-butylphenyl An aryl group etc. are mentioned.

  Moreover, the said hydrocarbon group may be substituted by other hydrocarbon groups, for example, aryl group substituted alkyl groups, such as benzyl and cumyl, etc. are mentioned.

Examples of the hydrocarbon-substituted silyl group of R ^{2 to} R ⁵ include groups having 1 to 30 carbon atoms in total. Specific examples include methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, diphenylmethylsilyl, triphenylsilyl, dimethylphenylsilyl, dimethyl-t-butylsilyl, dimethyl (pentafluorophenyl) silyl and the like. Among these, methylsilyl, triethylsilyl, dimethylphenylsilyl, triphenylsilyl and the like are preferable. Particularly preferred are trimethylsilyl, triethylsilyl, triphenylsilyl, dimethylphenylsilyl and the like.

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

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

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

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

Examples of the aromatic hydrocarbon group for R ⁶ include those having 6 to 30 carbon atoms. Specific examples include phenyl, naphthyl, biphenylyl, triphenylyl, fluorenyl, anthranyl, phenanthryl and the like.

In the present invention, R ⁶ is particularly preferably an aryl group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms such as phenyl, benzyl, naphthyl, and anthranyl, and methyl, ethyl, isopropyl, isobutyl, sec -Linear or branched (secondary) alkyl groups having 1 to 30, preferably 1 to 20 carbon atoms such as -butyl, neopentyl, etc., cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 2,6-dimethyl A group selected from cyclic saturated hydrocarbon groups having 3 to 30, preferably 3 to 20 carbon atoms, such as cyclohexyl, 3,5-dimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, cyclododecyl and the like It is also preferable.

  n is a number satisfying the valence of Ti, specifically an integer of 0 to 3, more preferably 2.

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

Examples of the halogen atom include fluorine, chlorine, bromine and iodine. Examples of the hydrocarbon group include the same groups as those exemplified by the R ² to R ^5. Specifically, alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, octyl, nonyl, dodecyl, and eicosyl; cycloalkyl groups having 3 to 30 carbon atoms such as cyclopentyl, cyclohexyl, norbornyl, adamantyl; vinyl, Alkenyl groups such as propenyl and cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl and phenylpropyl; aryl groups such as phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, naphthyl, methylnaphthyl and phenanthryl However, it is not limited to these. These hydrocarbon groups also include halogenated hydrocarbons, specifically, groups in which at least one hydrogen of a hydrocarbon group having 1 to 20 carbon atoms is substituted with halogen.

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

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

  Specific examples of the sulfur-containing group include methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, p-toluene sulfonate, trimethyl benzene sulfonate, triisobutyl benzene sulfonate. Sulfonate groups such as sulfonate, p-chlorobenzene sulfonate, pentafluorobenzene sulfonate; methyl sulfinate, phenyl sulfinate, benzyl sulfinate, p-toluene sulfinate, trimethylbenzene sulfinate, penta Examples thereof include, but are not limited to, sulfinate groups such as fluorobenzenesulfinate; alkylthio groups; arylthio groups.

  Specific examples of nitrogen-containing groups include amino groups; alkylamino groups such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, dicyclohexylamino; phenylamino, diphenylamino, ditolylamino, dinaphthylamino, methylphenylamino Arylamino groups or alkylarylamino groups such as, but not limited to.

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

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

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

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

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

Specific examples of the halogen-containing group include fluorine-containing groups such as PF ₆ and BF ₄ , chlorine-containing groups such as ClO ₄ and SbCl _6, and iodine-containing groups such as IO ₄ , but are not limited thereto. Absent. Specific examples of the aluminum-containing group include, but are not limited to, AlR ₄ (R represents hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, or the like).

As a structure of the transition metal compound (A) used in the present invention, m in the general formula (I) is 2, and R ¹ is a hydrocarbon group having 1 to 30 carbon atoms having one or more fluorine atoms. Yes, n is preferably 2.

Further, it is particularly preferable that R ¹ is a trifluoromethyl group, R ⁶ is a phenyl group, and R ^{7 to} R ¹⁰ are hydrogen atoms.

  Specific examples of the transition metal compound represented by the general formula (I) are shown below, but are not limited thereto. In the following examples, Ph represents a phenyl group.

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

First, the ligand constituting the transition metal compound (A) is a salicylaldehyde compound, a primary amine compound represented by the following general formula (II) (R ¹ and R ^{7 to} R ¹⁰ are as defined above). For example, by reaction with an aniline compound or an alkylamine compound. Specifically, both starting compounds are dissolved in a solvent. As the solvent, those commonly used in such a reaction can be used, and among them, alcohol solvents such as methanol and ethanol, and hydrocarbon solvents such as toluene solvent are preferable. The resulting solution is then stirred from room temperature under reflux conditions for about 1 to 48 hours to give the corresponding ligand in good yield. When synthesizing the ligand compound, an acid catalyst such as formic acid, acetic acid or toluenesulfonic acid may be used as a catalyst. Further, when molecular sieves, magnesium sulfate or sodium sulfate is used as a dehydrating agent, or dehydration is performed by Dean Stark, it is effective for the progress of the reaction.

  Next, the corresponding transition metal compound can be synthesized by reacting the ligand thus obtained with a transition metal (Ti) -containing compound. Specifically, the synthesized ligand is dissolved in a solvent, and a base is reacted as necessary to prepare a phenoxide salt, which is then mixed with a metal compound such as a transition metal halogen compound and a transition metal alkyl compound at a low temperature. The mixture is stirred for about 1 to 48 hours at -78 ° C to room temperature or under reflux conditions. As the solvent, those generally used for such a reaction can be used, and among them, polar solvents such as ether and tetrahydrofuran, and hydrocarbon solvents such as toluene are preferably used. In addition, the base used in preparing the phenoxide salt is preferably a metal salt such as a lithium salt such as n-butyllithium, a sodium salt such as sodium hydride, or an organic base such as triethylamine or pyridine. is not.

Depending on the properties of the compound, the transition metal compound (A) represented by the general formula (I) may be synthesized by directly reacting the ligand and the transition metal compound without going through phenoxide salt adjustment. it can. Furthermore, for example, when any of R ^{2 to} R ⁶ is H, a substituent other than H can be introduced at any stage of the synthesis.

  Moreover, the reaction solution of a ligand and a transition metal compound can also be used for polymerization as it is without isolating the transition metal compound represented by the general formula (I).

  The above transition metal compounds (A) are used singly or in combination of two or more.

[(B-1) Organometallic compound]
As the (B-1) organometallic compound used in the present invention, specifically, the following organometallic compounds of Groups 1, 2 and 12, 13 of the periodic table are used.

(B-1a) General formula R ^a _m Al (OR ^b ) _n H _p X _q
(In the formula, R ^a and R ^b may be the same or different from each other, and each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, and m represents 0. <M ≦ 3, n is 0 ≦ n <3, p is a number of 0 ≦ p <3, q is a number of 0 ≦ q <3, and m + n + p + q = 3).

(B-1b) General formula M ² AlR ^a ₄
(Wherein M ² represents Li, Na, or K, and R ^a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms). Complex alkyl compound of aluminum and aluminum.

(B-1c) General formula R ^a R ^b M ³
(In the formula, R ^a and R ^b may be the same or different from each other, and each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and M ³ is Mg, Zn or Cd. A dialkyl compound of a metal of Group 2 or Group 12 of the periodic table represented by:

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

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

More specifically, as an organoaluminum compound belonging to (B-1a),
Tri-n-alkyl aluminums such as trimethylaluminum, trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum; triisopropylaluminum, triisobutylaluminum, trisec- Butylaluminum, tri-tert-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylbutylaluminum, tri-2-methylpentylaluminum, tri-3-methylpentylaluminum, tri-4-methylpentylaluminum, tri-2-methylhexylaluminum , Tri-3-methylhexylaluminum, tri-2-ethylhexylaluminum; tricyclohexylaluminum, tri Black tricycloalkyl aluminum such as octyl aluminum; dialkyl aluminum hydride such as diisobutyl aluminum hydride; triphenyl aluminum, triaryl aluminum such as tri tolyl aluminum _{(iC 4 H 9) x Al} y (C 5 H 10) z ( wherein Wherein x, y and z are positive numbers and z ≧ 2x.) Trialkenylaluminum such as triisoprenylaluminum, etc .; isobutylaluminum methoxide, isobutylaluminum ethoxide, isobutylaluminum isopropoxy Alkyl aluminum alkoxides such as dimethylaluminum; Dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide and dibutylaluminum ethoxide; R ^a _2.5 Al (OR ^b) partially alkylaluminum is alkoxylated with an average composition represented by like _0.5; Kietokishido, alkylaluminum sesqui alkoxides such as butyl sesquichloride butoxide diethylaluminum phenoxide, diethylaluminum (2, 6-di-tert-butyl-4-methylphenoxide), ethylaluminum bis (2,6-di-tert-butyl-4-methylphenoxide), diisobutylaluminum (2,6-di-tert-butyl-4-methyl) Phenoxide), dialkylaluminum aryloxides such as isobutylaluminum bis (2,6-di-tert-butyl-4-methylphenoxide); dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride Dialkylaluminum halides such as ethylaluminum sesquichloride, alkylaluminum sesquichlorides such as ethylaluminum sesquichloride, ethylaluminum sesquibromide; partial alkylaluminum dihalides such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide Halogenated alkylaluminum; Dialkylaluminum hydride such as diethylaluminum hydride and dibutylaluminum hydride; Other partially hydrogenated alkylaluminum such as alkylaluminum dihydride such as ethylaluminum dihydride and propylaluminum dihydride; Aluminum ethoxy chloride, butyl aluminum butoxy Examples thereof include partially alkoxylated and halogenated alkylaluminum such as cyclolide and ethylaluminum ethoxybromide.

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

Examples of the compound belonging to (B-1b) include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

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

  A compound that can form the organoaluminum compound in the polymerization system, for example, a combination of an aluminum halide and an alkyl lithium, or a combination of an aluminum halide and an alkyl magnesium can also be used.

  (B-1) Among organometallic compounds, organoaluminum compounds are preferred.

  The (B-1) organometallic compounds as described above are used singly or in combination of two or more.

[(B-2) Organoaluminum oxy compound]
The (B-2) aluminum oxy compound used in the present invention may be a conventionally known aluminoxane or a benzene-insoluble organoaluminum oxy compound exemplified in JP-A-2-78687. Good.

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

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

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

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

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

  Solvents used for the preparation of aluminoxane include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane, and cyclopentane. , Cycloaliphatic hydrocarbons such as cyclohexane, cyclooctane and methylcyclopentane, petroleum fractions such as gasoline, kerosene and light oil, or halides of the above aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons, especially chlorine And hydrocarbon solvents such as bromide and bromide. Furthermore, ethers such as ethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic hydrocarbons or aliphatic hydrocarbons are particularly preferable. The benzene-insoluble organoaluminum oxy compound used in the present invention has an Al component dissolved in benzene at 60 ° C. of usually 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atom, That is, those that are insoluble or hardly soluble in benzene are preferred.

  Examples of the organoaluminum oxy compound used in the present invention include organoaluminum oxy compounds containing boron represented by the following general formula (III).

In the formula, R ¹¹ represents a hydrocarbon group having 1 to 10 carbon atoms. R ¹² may be the same as or different from each other, and represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 10 carbon atoms.

  The organoaluminum oxy compound containing boron represented by the general formula (III) includes an alkyl boronic acid represented by the following general formula (IV):

(Wherein R ¹¹ represents the same group as described above.)
It can be produced by reacting an organoaluminum compound in an inert solvent under an inert gas atmosphere at a temperature of −80 ° C. to room temperature for 1 minute to 24 hours.

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

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

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

[(B-3) Compound that reacts with transition metal compound (A) to form an ion pair]
As a compound (B-3) that reacts with the transition metal compound (A) used in the present invention to form an ion pair (hereinafter referred to as “ionized ionic compound”), Japanese Patent Application Laid-Open No. 1-1501950, Lewis acids described in Kaihei 1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, USP-5321106, etc. , Ionic compounds, borane compounds and carborane compounds. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned.

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

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

In the formula, R ¹³⁺ includes H ⁺ , carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptatrienyl cation, ferrocenium cation having a transition metal, and the like.

R ^{14 to} R ¹⁷ may be the same as or different from each other, and are an organic group, preferably an aryl group or a substituted aryl group.

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

  Specific examples of the ammonium cation include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, and tri (n-butyl) ammonium cation; N, N-dimethylanilium cation, N, N -N, N-dialkylanilinium cations such as diethylanilium cation and N, N-2,4,6-pentamethylanilium cation; dialkylammonium cations such as di (isopropyl) ammonium cation and dicyclohexylammonium cation It is done.

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

R ¹³⁺ is preferably a carbonium cation, an ammonium cation or the like, and particularly preferably a triphenylcarbonium cation, an N, N-dimethylanilinium cation or an N, N-diethylanilinium cation.

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

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

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

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

  Further, as ionic compounds, triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) borate, triphenylcarbenium pentaphenyl Mention may also be made of cyclopentadienyl complexes, boron compounds represented by the following formula (VI) or (VII), and the like.

（式中、Ｅｔはエチル基を表す。）

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

Specific examples of the borane compound include decaborane (14); bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium] undeca Salts of anions such as borate, bis [tri (n-butyl) ammonium] dodecaborate, bis [tri (n-butyl) ammonium] decachlorodecaborate, bis [tri (n-butyl) ammonium] dodecachlorododecaborate; Of metal borane anions such as tri (n-butyl) ammonium bis (dodecahydridododecaborate) cobaltate (III) and bis [tri (n-butyl) ammonium] bis (dodecahydridododecaborate) nickate (III) Examples include salt.

  Specific examples of the carborane compound include, for example, 4-carbanonaborane (14), 1,3-dicarbanonaborane (13), 6,9-dicarbadecarborane (14), dodecahydride-1-phenyl-1, 3-dicarbanonaborane, dodecahydride-1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarbaundecaborane (13), 2,7-dicarbaound decaborane (13), undecahydride-7,8-dimethyl-7,8-dicarbaound decaborane, dodecahydride-11-methyl-2,7-dicarbaound decaborane , Tri (n-butyl) ammonium 1-carbadecaborate, tri (n-butyl) ammonium 1-carbadodecaborate, tri (n-butyl) ammonium 1-trimethylsilyl-1-carbadecaborate, tri (n-butyl) Ammonium 1-carbadodecaborate, tri (n-butyl) ammonium 6-carbadecaborate (14), tri (n-butyl) ammonium 6-carbadecaborate (12), tri (n-butyl) ammonium 7-carbaun Decaborate (13), tri (n-butyl) ammonium 7-carbaundecaborate (13), tri (n-butyl) ammonium 7,8-dicarbaundecaborate (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 Salts of anions such as undecahydride-8-allyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-4,6-dibromo-7-carbaundecaborate; Butyl) ammonium bis (nonahydride-1,3-dicarbanonaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) ferrate ( III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicar Bounce decaborate) nickelate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundeborate) cuprate (III), tri (n-butyrate) ) Ammonium bis (undecahydride-7,8-dicarbaundecaborate) aurate (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarbaoundecaborate ) Ferrate (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarboundecarboxylate) chromate (III), tri (n-butyl) ammonium bis (Tribromooctahydride-7,8-dicarboundecaborate) cobaltate (III), tris [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) chromate (III ), Bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) manganate (III), bis [tri (n-butyl) ammonium] bis (c Metal carboranes such as decahydride-7-carbaundecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) nickelate (IV) Anion salts and the like can be mentioned.

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

  The (B-3) ionizable compounds as described above are used singly or in combination of two or more.

  When the transition metal compound according to the present invention is used as a catalyst, when it is used in combination with an organoaluminum oxy compound (B-2) such as methylaluminoxane as a cocatalyst, it exhibits a very high polymerization activity for olefinic compounds.

  In the olefin polymerization catalyst according to the present invention, (A) the transition metal compound represented by (1) may be used alone, or (A) the transition metal compound represented by the general formula (1); B) (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) at least one compound selected from compounds that react with the transition metal compound (A) to form an ion pair. In this case, these compounds are represented by the following general formula (VIII) in the polymerization system.

(Wherein R ^{1 to} R ¹⁰ , M, m, n, and X are the same as those in the general formula (I), and Y represents a so-called weakly coordinating anion.)
In this formula, the bond between the metals M and Y may be covalently bonded or ionicly bonded. Specific examples of R ^{1 to} R ¹⁰ , M, m, n, and X in the formula are the same as those in (I), and examples of Y include
Chemical Review Journal Volume 88, 1405 (1988)
Chemical Review, Volume 93, 927 pages (1993)
WO 98/30162 The weakly coordinating anion described on page 6 can be mentioned, specifically, AlR ₄ ⁻
(R may be one kind or two or more kinds, oxygen atom, nitrogen atom, phosphorus atom, hydrogen atom, halogen atom or a substituent containing them, and aliphatic hydrocarbon group, aromatic hydrocarbon group, alicyclic group. A hydrocarbon group which may have a substituent containing an oxygen atom, a nitrogen atom, a phosphorus atom, a hydrogen atom or a halogen atom)
BR ₄ ⁻
(R may be one kind or two or more kinds, oxygen atom, nitrogen atom, phosphorus atom, hydrogen atom, halogen atom or a substituent containing them, and aliphatic hydrocarbon group, aromatic hydrocarbon group, alicyclic group. The hydrocarbon group may have a substituent containing an oxygen atom, a nitrogen atom, a phosphorus atom, a hydrogen atom, or a halogen atom.)
The olefin polymerization catalyst according to the present invention includes the transition metal compound (A), (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) an ionized ionic compound. In addition to at least one compound (B) selected from the above, a carrier (C) as described later can be used as necessary.

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

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

Used as the porous oxide, SiO _{2 specifically, Al 2 O 3, MgO,} ZrO, TiO2, B 2 O 3, CaO, ZnO, BaO, etc. ThO _2, or a composite or a mixture containing them, for example, natural or synthetic _{zeolites, SiO 2 -MgO, SiO 2 -Al} 2 O 3, SiO 2 -TiO2, SiO 2 -V 2 O 5, SiO 2 -MgO, be used, such as SiO ₂ -TiO ₂ -MgO it can. Of these, those containing SiO ₂ and / or Al ₂ O ₃ as main components are preferred.

Note that the inorganic oxide includes a small amount of Na ₂ CO ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ ). ₂ , Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, Li ₂ O and other carbonates, sulfates, nitrates, and oxide components may be contained.

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

As the inorganic chloride, MgCl ₂ , MgBr ₂ , MnCl ₂ , MnBr _{2 and the} like are used. The inorganic chloride may be used as it is, or may be used after being pulverized by a ball mill or a vibration mill. In addition, after dissolving the inorganic chloride in a solvent such as alcohol, these are precipitated into fine particles by a precipitant. It is also possible to use those.

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

Examples of clays, clay minerals or ionic layered compounds include clays, clay minerals, and ionic crystalline compounds having a layered crystal structure such as hexagonal close packing type, antimony type, CdCl ₂ type, CdI ₂ type, etc. can do.

Examples of such clays and clay minerals include kaolin, bentonite, kibushi clay, gyrome clay, allophane, hysinger gel, pyroferrite, unmo group, montmorillonite group, vermiculite, ryokdeite group, palygorskite, kaolinite, nacrite, siccatite, Examples of the ion-exchange layered compound include α-Zr (HAsO ₄ ) ₂ .H2O, α-Zr (HPO ₄ ) ₂ , α-Zr (KPO ₄ ) ₂ .3H ₂ O, α-Ti. (HPO ₄ ) ₂ . H ₂ O, 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- Examples thereof include crystalline acidic salts of polyvalent metals such as Ti (NH ₄ PO ₄ ) ₂ .H ₂ O.

Such a clay, clay mineral, or ion-exchange layered compound preferably has a pore volume of 0.1 cc / g or more and a diameter of 0.3 to 5 cc / g measured by mercury porosimetry. Particularly preferred. Here, the pore volume is measured in the range of a pore radius of 20 to 3 × 10 ⁴ by a mercury intrusion method using a mercury porosimeter.

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

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

The ion-exchangeable layered compound used in the present invention may be a layered compound in a state where the layers are expanded by exchanging the exchangeable ions between the layers with other large and bulky ions using the ion-exchange property. . Such bulky ions play a role of supporting pillars to support the layered structure and are usually called pillars. Moreover, introducing another substance between the layers of the layered compound in this way is called intercalation. Guest compounds that intercalate include cationic inorganic compounds such as TiCl ₄ and ZrCl ₄ , metal alkoxides such as Ti (OR) ₄ , Zr (OR) ₄ , PO (OR) ₃ , and B (OR) ₃ ( R is a hydrocarbon group), metal hydroxide ions such as [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH) ₁₄ ] ²⁺ , [Fe ₃ O (OCOCH ₃ ) ₆ ] + Etc. These compounds are used alone or in combination of two or more. Also, when intercalating these compounds, obtained by hydrolyzing metal alkoxides such as Si (OR) ₄ , Al (OR) _3, Ge (OR) ₄ (R is a hydrocarbon group, etc.) Polymers and colloidal inorganic compounds such as SiO ₂ can coexist. Examples of the pillar include oxides generated by heat dehydration after intercalation of the metal hydroxide ions between layers.

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

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

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

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

[(D) Organic compound component]
In the present invention, the organic compound component (D) is used for the purpose of improving the polymerization performance and the physical properties of the produced polymer, if necessary. Examples of such organic compounds include, but are not limited to, alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, and sulfonates. As alcohols and phenolic compounds, those represented by R ¹⁸ —OH are usually used, wherein R ¹⁸ is a hydrocarbon group having 1 to 50 carbon atoms or a halogenated group having 1 to 50 carbon atoms. A hydrocarbon group is shown.

As the alcohols, those in which R ¹⁸ is a halogenated hydrocarbon are preferable. Moreover, as a phenolic compound, what substituted the o, o'-position of the hydroxyl group with the C1-C20 hydrocarbon is preferable.

As the carboxylic acid, one represented by R ¹⁹ —COOH is usually used. R ¹⁹ represents a hydrocarbon group having 1 to 50 carbon atoms or a halogenated hydrocarbon group having 1 to 50 carbon atoms, and a halogenated hydrocarbon group having 1 to 50 carbon atoms is particularly preferable.

  As the phosphorus compound, phosphoric acid having P—O—H bond, P—OR, phosphate having P═O bond, and phosphine oxide compound are preferably used.

  As the sulfonate, those represented by the following general formula (IX) are used.

  In the formula, M is an element of Groups 1 to 14 of the periodic table.

R ¹⁸ is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms.

  X is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms.

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

  In the polymerization, the method of using each component and the order of addition are arbitrarily selected, and the following methods are exemplified.

(1) A method of adding the component (A) alone to the polymerization vessel.
(2) A method of adding the component (A) and the component (B) to the polymerization vessel in an arbitrary order.
(3) A method in which the catalyst component having component (A) supported on carrier (C) and component (B) are added to the polymerization vessel in any order.
(4) A method in which the catalyst component having component (B) supported on carrier (C) and component (A) are added to the polymerization vessel in any order.
(5) A method in which a catalyst component in which the component (A) and the component (B) are supported on the carrier (C) is added to the polymerization vessel.
In each of the above methods (2) to (5), at least two or more of the catalyst components may be contacted in advance.

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

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

  In the olefin polymerization method according to the present invention, an olefin polymer is obtained by polymerizing or copolymerizing an olefin in the presence of the olefin polymerization catalyst as described above.

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

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

Using the above-mentioned olefin polymerization catalyst, in the polymerization of olefins, Component (A), reaction volume per liter, usually ¹⁰ -12 ^{to 10 -3} mol, preferably ¹⁰ -10 ^{to 10 -3} It is used in such an amount that it becomes a mole.

  Component (B-1) has a molar ratio [(B-1) / M] of component (B-1) and transition metal atom (M) in component (A) of usually 0.01 to 100,000, Preferably it is used in an amount of 0.05 to 50000. Component (B-2) has a molar ratio [(B-2) / M] of the aluminum atom in component (B-2) and the transition metal atom (M) in component (A) of usually 10 to 10. The amount used is 500,000, preferably 20 to 100,000. Component (B-3) has a molar ratio [(B-3) / M] of component (B-3) and transition metal atom (M) in component (A) of usually 1 to 10, preferably It is used in such an amount as to be 1-5.

  When component (B) is component (B-1), component (D) has a molar ratio [(D) / (B-1)] of usually 0.01 to 10, preferably 0.1 to 0.1. 5 and the component (B) is the component (B-2), the molar ratio [(D) / (B-2)] is usually 0.001 to 2, preferably 0.8. When the component (B) is the component (B-3) in such an amount as 005 to 1, the molar ratio [(D) / (B-3)] is usually 0.01 to 10, preferably The amount used is 0.1-5.

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

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

  Examples of the olefin that can be polymerized by such an olefin polymerization catalyst include linear or branched α-olefins having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, such as ethylene, propylene, and 1-butene. 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 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; polar monomers such as acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride , Α, β-unsaturated carboxylic acids such as bicyclo (2,2,1) -5-heptene-2,3-dicarboxylic acid anhydride, and sodium, potassium, lithium, zinc, and magnesium salts thereof , Metal salts such as calcium salts; methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid Α, β-unsaturated carboxylic acid esters such as methyl, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate; vinyl acetate, vinyl propionate, vinyl caproate, capric acid Vinyl, vinyl laurate, vinyl stearate, vinyl trifluoroacetate, etc. Tells; Unsaturated glycidyl esters such as glycidyl acrylate, glycidyl methacrylate, monoglycidyl itaconate; halogenated olefins such as vinyl fluoride, vinyl chloride, vinyl bromide, and vinyl iodide .

  Moreover, vinylcyclohexane, diene, polyene, etc. can also be used as an olefin. As the diene or polyene, a cyclic or chain compound having 4 to 30, preferably 4 to 20 carbon atoms and having two or more double bonds is used. Specifically, butadiene, isoprene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,3-hexadiene, 1 , 3-octadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, ethylidene norbornene, vinyl norbornene, dicyclopentadiene; 7-methyl-1,6-octadiene, 4 -Ethylidene-8-methyl-1,7-nonadiene, 5,9-dimethyl-1,4,8-decatriene; and as olefins, aromatic vinyl compounds such as styrene, o-methylstyrene, m-methylstyrene, p -Mono- or polyalkyl styrene such as methyl styrene, o, p-dimethyl styrene, o-ethyl styrene, m-ethyl styrene, p-ethyl styrene; methoxy styrene, ethoxy styrene, vinyl benzoic acid, vinyl Functional group-containing styrene derivatives such as methyl benzoate, vinyl benzyl acetate, hydroxystyrene, o-chlorostyrene, p-chlorostyrene, divinylbenzene; and 3-phenylpropylene, 4-phenylpropylene, α-methylstyrene, etc. It is done. These olefins can be used alone or in combination of two or more.

  EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.

  The structure of the compound obtained in the synthesis example was determined using FD-mass spectrometry (JEOL SX-102A) or the like.

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

[Synthesis Example 2]
A 100 ml reactor sufficiently purged with nitrogen was charged with 1.365 g (purity 4.00 mmol) of the compound (a) obtained in the above synthesis example and anhydrous diethyl ether, and cooled to -78 ° C. To this, 2.56 ml of n-butyllithium (n-hexane solution, 1.59M, 4.00 mmol) was added dropwise over 5 minutes, and then the temperature was slowly raised to room temperature. After stirring at room temperature for 2.5 hours, it was gradually added to an anhydrous diethyl ether slurry of 2.00 ml (1.00 M, 2.00 mmol) of titanium tetrachloride toluene solution cooled to −78 ° C. After the addition, the mixture was stirred for 17 hours while slowly warming to room temperature. The slurry was concentrated under reduced pressure, 30 ml of methylene chloride was added, the slurry was filtered, and the filtrate was concentrated. The residue was dissolved in 10 ml of ether and the precipitated solid was collected and washed with n-hexane. The obtained solid was dried under reduced pressure to obtain 0.981 g (yield 61%) of a brown compound represented by the following formula (1). In addition, the result of FD-mass spectrometry of the compound (1) was 798 (M ⁺ ).

[Example 1]
A glass autoclave with an internal volume of 500 ml that was sufficiently purged with nitrogen was charged with 250 ml of toluene, and the liquid phase and gas phase were saturated with ethylene. Thereafter, methylaluminoxane was added in an amount of 1.25 mmol in terms of aluminum atom, and subsequently, 0.0005 mmol of titanium compound (1) was added to initiate polymerization. After reacting at 25 ° C. for 5 minutes under an atmospheric pressure ethylene gas atmosphere, the polymerization was stopped by adding a small amount of isobutanol. After completion of the polymerization, hydrochloric acid was added to precipitate the whole amount of the polymer, methanol was added, and the mixture was filtered through a glass filter. After the polymer was dried under reduced pressure at 80 ° C. for 10 hours, 1.24 g of polyethylene (PE) was obtained. The polymerization activity per 1 mmol of titanium was 29.6 kg.

[Examples 2-3]
Polymerization was conducted in the same manner as in Example 1 except that the titanium compound, the amount of the titanium compound, and the polymerization temperature were changed as shown in Table 1. The polymerization results are shown in Table 1.

[Example 4]
To a glass autoclave having an internal volume of 500 ml sufficiently purged with nitrogen, 250 ml of toluene was charged, and a mixed gas of ethylene (50 l / h) and propylene (150 l / h) was circulated for 10 minutes with stirring. Thereafter, methylaluminoxane was added in an amount of 1.25 mmol in terms of aluminum atom, and then 0.005 mmol of titanium compound (1) was added to initiate polymerization. After reacting at 50 ° C. for 10 minutes at normal pressure, the polymerization was stopped by adding a small amount of isobutanol. After completion of the polymerization, the reaction solution was poured into methanol containing a small amount of hydrochloric acid to precipitate the whole amount of the polymer, and hydrochloric acid was added and filtered through a glass filter. After the polymer was dried under reduced pressure at 130 ° C. for 10 hours, 4.59 g of ethylene / propylene copolymer (EPR) was obtained. The polymerization activity per 1 mmol of titanium was 5.51 kg. The propylene content by IR measurement was 41.5 mol%.

[Comparative Example 1]
A glass autoclave with an internal volume of 500 ml that was sufficiently purged with nitrogen was charged with 250 ml of toluene, and the liquid phase and gas phase were saturated with ethylene. Thereafter, 1.25 mmol of methylaluminoxane in terms of aluminum atom and 0.0001 mmol of titanium compound (2) were subsequently added to initiate polymerization. After reacting at 25 ° C. for 5 minutes under an atmospheric pressure ethylene gas atmosphere, the polymerization was stopped by adding a small amount of isobutanol. After completion of the polymerization, hydrochloric acid was added to precipitate the whole amount of the polymer, methanol was added, and the mixture was filtered through a glass filter. After the polymer was dried under reduced pressure at 80 ° C. for 10 hours, 0.15 g of polyethylene (PE) was obtained. The polymerization activity per 1 mmol of titanium was 18.1 kg. The chemical formula of the titanium compound (2) is shown below.

[Comparative Examples 2-3]
Polymerization was conducted in the same manner as in Comparative Example 1 except that the titanium compound, the amount of the titanium compound, and the polymerization temperature were changed as shown in Table 2. The polymerization results are shown in Table 2.

[Comparative Example 4]
To a glass autoclave having an internal volume of 500 ml sufficiently purged with nitrogen, 250 ml of toluene was charged, and a mixed gas of ethylene (50 l / h) and propylene (150 l / h) was circulated for 10 minutes with stirring. Thereafter, methylaluminoxane was added in an amount of 1.25 mmol in terms of aluminum atom, and then 0.005 mmol of titanium compound (2) shown below was added to initiate polymerization. After reacting at 50 ° C. for 10 minutes at normal pressure, the polymerization was stopped by adding a small amount of isobutanol. After completion of the polymerization, the reaction solution was poured into methanol containing a small amount of hydrochloric acid to precipitate the whole amount of the polymer, and hydrochloric acid was added and filtered through a glass filter. After drying the polymer under reduced pressure at 130 ° C. for 10 hours, 5.20 g of an ethylene / propylene copolymer (EPR) was obtained. The polymerization activity per 1 mmol of titanium was 6.20 kg. The propylene content by IR measurement was 32.9 mol%.

  Polyolefin is an environmentally friendly clean material consisting of carbon and hydrogen, and has excellent processability and physical properties. Because of this characteristic, it is used in a wide range of fields such as automobiles, electrical equipment parts, food packaging, beverage / cosmetics / medical containers, civil engineering, and agricultural materials. The novel olefin polymerization catalyst in the present invention and the polymerization using the transition metal compound exhibit excellent copolymerizability and high activity. Therefore, by selecting the type and amount of comonomer, diversified polyolefin in recent years It is possible to manufacture a product that satisfies the requirements for high efficiency.

Claims (3)

(A) a transition metal compound represented by the following general formula (I);
(B) (B-1) an organometallic compound (B-2) an organoaluminum oxy compound, and (B-3) at least one compound selected from compounds that react with the transition metal compound (A) to form an ion pair. An olefin polymerization catalyst comprising a compound.

(In the formula, m represents an integer of 1 to 2, and at least one of R ¹ and R ^{7 to} R ¹⁰ is a hydrocarbon group having 1 to 30 carbon atoms having one or more fluorine atoms; A hydrogen atom, a fluorine atom, or a hydrocarbon group (however, when R ¹ is a C 1-30 hydrocarbon group having one or more fluorine atoms, at least one of R ^{7 to} R ¹⁰ is a hydrogen atom or 1 When the hydrocarbon group or hydrocarbon group having 1 to 30 carbon atoms having one or more fluorine atoms and R ⁷ and R ¹⁰ are both hydrocarbon groups having 1 to 30 carbon atoms having one or more fluorine atoms Represents at least one of R ¹ , R ⁸ and R ⁹ is a fluorine atom or a hydrocarbon group or hydrocarbon group having 1 to 30 carbon atoms having one or more fluorine atoms, and R ^{2 to} R ⁵ may be the same as or different from each other, Hydrocarbon group, a hydrogen atom, a hydrocarbon-substituted silyl group, an oxygen-containing group, a nitrogen-containing group or a sulfur-containing group,, R ⁶ is hydrogen, primary or secondary hydrocarbon having 1 to 4 carbon atoms consisting of only carbon A group selected from six groups: a hydrogen group, an aliphatic hydrocarbon group having 5 or more carbon atoms, an aryl group-substituted alkyl group, a monocyclic or bicyclic alicyclic hydrocarbon group and an aromatic hydrocarbon group; And when m is 2, ^two groups represented by R ^{2 to} R ⁶ may be linked, n is a number satisfying the valence of Ti, X is a hydrogen atom, Halogen atom, hydrocarbon group, oxygen-containing group, nitrogen-containing group, sulfur-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, heterocyclic compound residue, silicon-containing group, germanium-containing group, Or a soot-containing group, and when n is 2 or more, In the plurality of groups may be the same or different from each other, and a plurality of groups represented by X may be bonded to each other to form a ring represented.) 2. The olefin polymerization catalyst according to claim 1, wherein in the transition metal compound (A) represented by the general formula (I), R ¹ is a trifluoromethyl group, and R ^{7 to} R ¹⁰ are hydrogen atoms.   An olefin polymerization method comprising polymerizing an olefin in the presence of the olefin polymerization catalyst according to claim 1 or 2.