JP2006233063A - Olefin polymerization catalyst and method for polymerizing olefin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a catalyst for olefin polymerization having excellent polymerization activity of olefins and copolymerizability thereof, producing a polymer having high comonomer content. <P>SOLUTION: This olefin polymerization catalyst contains a transition metal compound expressed by general formula (I), wherein, M represents a group 4 to 5 transition metal atom; m denotes an integer of 1-4; R<SP>1</SP>represents a heterocyclic compound residue which may have one or more substituents; R<SP>2</SP>to R<SP>5</SP>are the same or different and each represents a hydrogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, etc. ; R<SP>6</SP>represents a group selected from among a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group and a phenanthryl group which may have one or more substituents, respectively; n is a number satisfying the valence of M; and X represents a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, etc. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

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

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

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

Further, as a new olefin polymerization catalyst, the present applicant has proposed a transition metal compound having a salicylaldoimine ligand in Japanese Patent Application Laid-Open No. 11-315109. Although it has been clarified that this complex exhibits high olefin polymerization activity, further improvement has been demanded with respect to the polymerization activity. Further, when polymerizing two or more types of olefins, the polymerization activity and copolymerizability were not sufficiently satisfactory.
Japanese Patent Laid-Open No. 11-315109

An object of the present invention is to provide an olefin polymerization catalyst for producing a polymer having an excellent olefin polymerization activity and copolymerizability and a high comonomer content. Furthermore, it aims at providing the polymerization method of the olefin using this olefin polymerization catalyst.

The olefin polymerization catalyst according to the present invention is:
(A) A transition metal compound represented by the following general formula (I) is included.

[Wherein, M represents a transition metal atom of Groups 4 to 5 in the periodic table, m represents an integer of 1 to 4, and R ¹ may have one or more locating groups. Represents a heterocyclic compound residue, R ^{2 to} R ⁵ may be the same or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group or a tin-containing group, may form a ring more than is bonded to each other of these, R ⁶ Has a phenyl group that may have one or more locating groups, a naphthyl group that may have one or more locating groups, and one or more locating groups An optionally biphenyl group, one or more terphenyl groups, Beauty represents one or more groups selected from optionally phenanthryl group which may have a置喚group, and when m is 2 or more two groups among the groups represented by R ¹ to R ⁶ May be linked (however, R ¹ is not bonded to each other), n is a number satisfying the valence of M, and X is a hydrogen atom, a halogen atom, a hydrocarbon group, or 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, a germanium-containing group, or a tin-containing group, and n is 2 In the above case, a plurality of groups represented by X may be the same as or different from each other, and a plurality of groups represented by X may be bonded to each other to form a ring. ]

  The olefin polymerization catalyst of the present invention comprises (A) a transition metal compound represented by the 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.

  The olefin polymerization method of the present invention is characterized in that at least one olefin is polymerized in the presence of the olefin polymerization catalyst as described above. As the olefin, it is preferable to use one or more olefins selected from ethylene, α-olefins and cyclic olefins.

  By using the olefin polymerization catalyst of the present invention, it becomes possible to produce a polymer having high polymerization activity, good copolymerizability, and high comonomer content.

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

The olefin polymerization catalyst according to the present invention is:
(A) the transition metal compound represented by the general formula (I), or (A) the transition metal compound represented by the 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.

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

(Here, N ... M generally indicates coordination, but may or may not be coordinated in the present invention.)

In the general formula (I), M represents a transition metal of groups 4 to 5 of the periodic table, specifically titanium, zirconium, hafnium, vanadium, niobium, and tantalum, preferably a group 4 metal atom. Specifically, titanium, zirconium, and hafnium are preferable, and titanium is more preferable.
m shows the integer of 1-4, Preferably it is 1-2, Especially preferably, it is 2.

R ¹ represents a heterocyclic compound residue that may have one or more locating groups. Specific examples of the heterocyclic compound residue of R ¹ include pyrrole, pyridine, imidazole, pyrazole, triazole, oxazole, pyrazine, pyridazine, pyrimidine, azepine, indolizine, indole, isoindole, indazole, quinoline, isoquinoline, naphthyridine , Quinazoline, phthalazine, quinoxaline, sinoline, carbazole, phenanthridine, acridine, phenazine, phenanthroline, aziridine, acetylidine, pyrrolidine, piperidine, pyrroline, imidazolidine, imidazoline, pyrazolidine, pyrazoline, piperazine, indoline, isoindoline, quinuclidine, purine , Furan, pyran, benzofuran, isobenzofuran, dioxolane, chromene, chroman, isochroman, xane Ten, oxirane, oxetane, oxolane, oxadiazole, thiophene, benzothiophene, thietane, thiazole, isothiazole, thianaphthene, thianthrene, thiadiazole, trithiane, phenoxatin, isoxazole, phenothiazine, phenoxazine, furazane, morpholine and the like.

Examples of the substituent for R ¹ include a hydrocarbon group, an oxygen-containing group, a nitrogen-containing group, and a halogen atom.

  Specific examples of the hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, neopentyl group, and n-hexyl group. Can be mentioned.

  Specific examples of the oxygen-containing group include an alkoxy group, an aryloxy group, an ester group, an ether group, an acyl group, a carboxyl group, a carbonate group, a hydroxy group, and a peroxy group.

  Specific examples of nitrogen-containing groups include amino groups, imino groups, amide groups, imide groups, hydrazino groups, hydrazono groups, nitro groups, nitroso groups, cyano groups, isocyano groups, cyanate ester groups, amidino groups, diazo groups, etc. Can be given.

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

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

  Specific examples of the hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a neopentyl group, and an n-hexyl group. Straight chain or branched alkyl group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms; straight chain having 2 to 30, preferably 2 to 20 carbon atoms such as vinyl group, allyl group, isopropenyl group, etc. A linear or branched alkynyl group having 2 to 30, preferably 2 to 20 carbon atoms, such as an ethynyl group or a propargyl group; a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group; A cyclic saturated hydrocarbon group having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms such as an adamantyl group; a cyclopentadienyl group, an indenyl group, a fluorenyl group A cyclic unsaturated hydrocarbon group having 5 to 30 carbon atoms such as a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a phenanthryl group, an anthracenyl group, etc., and an aryl having 6 to 30, preferably 6 to 20 carbon atoms Group; alkyl-substituted aryl groups such as tolyl group, iso-propylphenyl group, t-butylphenyl group, dimethylphenyl group, and di-t-butylphenyl group;

  In the hydrocarbon group, a hydrogen atom may be substituted with a halogen atom. For example, a halogenated carbon atom having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms such as a trifluoromethyl group, a pentafluorophenyl group, and a chlorophenyl group. A hydrogen group is mentioned.

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

  Furthermore, the hydrocarbon group is a heterocyclic compound residue; an alkoxy group, an aryloxy group, an ester group, an ether group, an acyl group, a carboxyl group, a carbonate group, a hydroxy group, a peroxy group, a carboxylic anhydride group, etc. Oxygen-containing group: amino group, imino group, amide group, imide group, hydrazino group, hydrazono group, nitro group, nitroso group, cyano group, isocyano group, cyanate ester group, amidino group, diazo group, amino group is ammonium salt Nitrogen-containing groups such as those; boron-containing groups such as boranediyl group, boranetriyl group, diboranyl group; mercapto group, thioester group, dithioester group, alkylthio group, arylthio group, thioacyl group, thioether group, thiocyanate group , Isothiocyanate ester group, sulfone ester group, Sulfur-containing groups such as sulfonamide groups, thiocarboxyl groups, dithiocarboxyl groups, sulfo groups, sulfonyl groups, sulfinyl groups, sulfenyl groups; phosphorus-containing groups such as phosphide groups, phosphoryl groups, thiophosphoryl groups, phosphato groups, silicon-containing groups , A germanium-containing group, or a tin-containing group.

  Of these, the number of carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, neopentyl group, n-hexyl group, etc. 1-30, preferably 1-20 linear or branched alkyl groups; 6-30 carbon atoms such as phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, anthracenyl, etc., preferably 6 An aryl group having ˜20; a halogen atom, an alkyl group or alkoxy group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, an aryl group or aryloxy having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms A substituted aryl group substituted with 1 to 5 substituents such as a group is preferred.

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

  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 thereof include a group further substituted with a substituent such as an alkyl group or alkoxy group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, in the compound residue.

  Silicon-containing groups include silyl groups, siloxy groups, hydrocarbon-substituted silyl groups, hydrocarbon-substituted siloxy groups, and more specifically, methylsilyl groups, dimethylsilyl groups, trimethylsilyl groups, ethylsilyl groups, diethylsilyl groups, triethylsilyl groups , Diphenylmethylsilyl group, triphenylsilyl group, dimethylphenylsilyl group, dimethyl-t-butylsilyl group, dimethyl (pentafluorophenyl) silyl group and the like. Among these, methylsilyl group, dimethylsilyl group, trimethylsilyl group, ethylsilyl group, diethylsilyl group, triethylsilyl group, dimethylphenylsilyl group, triphenylsilyl group and the like are preferable. In particular, a trimethylsilyl group, a triethylsilyl group, a triphenylsilyl group, and a dimethylphenylsilyl group are preferable. Specific examples of the hydrocarbon-substituted siloxy group include a trimethylsiloxy group.

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

Next, the examples of R ^{2 to} R ⁵ described above will be described more specifically.
Specific examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and a t-butoxy group.

  Specific examples of the alkylthio group include a methylthio group and an ethylthio group.

  Specific examples of the aryloxy group include a phenoxy group, a 2,6-dimethylphenoxy group, and a 2,4,6-trimethylphenoxy group.

  Specific examples of the arylthio group include a phenylthio group, a methylphenylthio group, and a naphthylthio group.

  Specific examples of the acyl group include formyl group, acetyl group, benzoyl group, p-chlorobenzoyl group, and p-methoxybenzoyl group.

  Specific examples of the ester group include an acetyloxy group, a benzoyloxy group, a methoxycarbonyl group, a phenoxycarbonyl group, and a p-chlorophenoxycarbonyl group.

  Specific examples of the thioester group include an acetylthio group, a benzoylthio group, a methylthiocarbonyl group, and a phenylthiocarbonyl group.

  Specific examples of the amide group include an acetamide group, an N-methylacetamide group, and an N-methylbenzamide group.

  Specific examples of the imide group include an acetimide group and a benzimide group. 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, a butylimino group, and a phenylimino group.

  Specific examples of the sulfone ester group include a methyl sulfonate group, an ethyl sulfonate group, and a phenyl sulfonate group.

  Specific examples of the sulfonamide group include a phenylsulfonamide group, an N-methylsulfonamide group, and an N-methyl-p-toluenesulfonamide group.

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

R ⁶ has a phenyl group optionally having one or more locating groups, a naphthyl group optionally having one or more priming groups, and one or more locating groups. A group selected from a biphenyl group which may have, a terphenyl group which may have one or more locating groups, and a phenanthryl group which may have one or more locating groups , Preferably a phenyl group optionally having one or more locating groups. Examples of the substituent include a hydrocarbon group, an oxygen-containing group, a nitrogen-containing group, and a halogen atom.

When m is 2 or more, two groups out of the groups represented by R ^{1 to} R ⁶ may be linked (however, R ¹ are not bonded to each other). Further, when m is 2 or more, R ^{1 s} , R ^{2 s} , R ^{3 s} , R ^{4 s} , R ^{5 s} , and R ^{6 s} may be the same as or different from each other.

  n is a number satisfying the valence of M, specifically 0 to 5, preferably 1 to 4, more preferably an integer of 1 to 3.

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

Examples of the hydrocarbon group include the same groups as those exemplified by the R ² to R ^5. 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 such as cyclopentyl group, cyclohexyl group, norbornyl group, and adamantyl group A cycloalkyl group having 3 to 30 atoms; an alkenyl group such as a vinyl group, a propenyl group and a cyclohexenyl group; an arylalkyl group such as a benzyl group, a phenylethyl group and a phenylpropyl group; a phenyl group, a tolyl group and a dimethylphenyl group , Aryl groups such as trimethylphenyl group, ethylphenyl group, propylphenyl group, biphenyl group, naphthyl group, methylnaphthyl group, anthryl group, phenanthryl group, and the like, but are not limited thereto. These hydrocarbon groups also include halogenated hydrocarbons, specifically, groups in which at least one hydrogen of a hydrocarbon group having 1 to 20 carbon atoms is substituted with halogen.
Of these, those having 1 to 20 carbon atoms are preferred.

Examples of the heterocyclic compound residues include the same ones as exemplified for the R ² to R ^5.

Examples of the oxygen-containing group include the same groups as those exemplified above for R ^{2 to} R ⁵ , and specifically include hydroxy groups; alkoxy groups such as methoxy groups, ethoxy groups, propoxy groups, and butoxy groups; phenoxy groups Aryloxy groups such as methylphenoxy group, dimethylphenoxy group and naphthoxy group; arylalkoxy groups such as phenylmethoxy group and phenylethoxy group; acetoxy group; carbonyl group and the like, but not limited thereto.

Examples of the sulfur-containing group include the same groups as those exemplified for R ^{2 to} R ⁵ , and specifically, methyl sulfonate group, trifluoromethane sulfonate group, phenyl sulfonate group, benzyl sulfonate group, and the like. Sulfonate groups such as phonate group, p-toluenesulfonate group, trimethylbenzenesulfonate group, triisobutylbenzenesulfonate group, p-chlorobenzenesulfonate group, pentafluorobenzenesulfonate group; Sulfinate groups such as ruffinate groups, phenylsulfinate groups, benzylsulfinate groups, p-toluenesulfinate groups, trimethylbenzenesulfinate groups, pentafluorobenzenesulfinate groups; alkylthio groups; arylthio groups, etc. But are limited to these Not.

Specific examples of the nitrogen-containing group include the same groups as those exemplified above for R ^{2 to} R ⁵ , and specific examples include an amino group; a methylamino group, a dimethylamino group, a diethylamino group, and a dipropylamino group. Alkylamino groups such as dibutylamino group and dicyclohexylamino group; arylamino groups such as phenylamino group, diphenylamino group, ditolylamino group, dinaphthylamino group, and methylphenylamino group; It is not limited to these.

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

Specific examples of the silicon-containing group include the same groups as those exemplified above for R ^{2 to} R ⁵ , and specifically, phenylsilyl group, diphenylsilyl group, trimethylsilyl group, triethylsilyl group, tripropylsilyl group. Group, tricyclohexylsilyl group, triphenylsilyl group, methyldiphenylsilyl group, tolylsilylsilyl group, trinaphthylsilyl group and other hydrocarbon-substituted silyl groups; trimethylsilyl ether group and other hydrocarbon-substituted silyl ether groups; trimethylsilylmethyl group and the like And silicon-substituted aryl groups such as trimethylsilylphenyl group.

Specific examples of the germanium-containing group include the same groups as those exemplified above for R ^{2 to} R ⁵ , and specific examples include a group in which silicon in the silicon-containing group is substituted with germanium.

Specific examples of the tin-containing group include the same groups as those exemplified for R ^{2 to} R ⁵ , and more specifically, a group in which silicon of 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, etc.).

  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.

  Specific examples of the transition metal compound represented by (A) the above general formula (I) are shown below, but are not limited thereto.

  In the above examples, Me represents a methyl group, and Ph represents a phenyl group.

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

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

First, a ligand constituting the transition metal (A) is obtained by reacting a salicylaldehyde compound with a formula R ¹ —NH ₂ primary amine compound (R ¹ is as defined above). It is done. Specifically, both starting compounds are dissolved in a solvent. As the solvent, those generally used for such a reaction can be used, and among them, an alcohol solvent such as methanol and ethanol, or a hydrocarbon solvent such as toluene is preferable. Next, when the mixture is stirred at room temperature to reflux conditions for about 1 to 48 hours, the corresponding ligand is obtained in good yield. When synthesizing the ligand compound, an acid catalyst such as formic acid, acetic acid, and paratoluenesulfonic acid may be used as a catalyst. Further, when molecular sieves, anhydrous magnesium sulfate or anhydrous sodium sulfate is used as a dehydrating agent, or while dehydrating with Dean Stark, the reaction proceeds effectively.

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

Depending on the properties of the compound, the corresponding transition metal compound can be synthesized by directly reacting the ligand with the metal compound without going through the preparation of the phenoxide salt. Further, the metal M in the synthesized transition metal compound can be exchanged with another transition metal by a conventional method. For example, when one or more of R ^{2 to} R ⁵ are hydrogen, a substituent other than hydrogen can be introduced at any stage of the synthesis.

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

(B-1) Organometallic compound As the (B-1) organometallic compound used in the present invention, specifically, organometallic compounds of Groups 1, 2 and 12, 13 of the periodic table as shown below are used. 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, 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 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). Alkylate complex 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 Group 2 or Group 12 metal represented by the following periodic table.

  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 each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and m is preferably 1.5 ≦ m ≦ An organoaluminum compound represented by the following formula:

General formula R ^a _m AlX _3-m
(Wherein, R ^a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, and m is preferably 0 <m <3). Organoaluminum compounds,

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 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, each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, and m represents 0. <M ≦ 3, n is a number 0 ≦ n <3, q is a number 0 ≦ q <3, and m + n + q = 3).

More specific examples of organoaluminum compounds belonging to (B-1a) include trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum and the like. n-alkylaluminum; triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylbutylaluminum, tri-2-methylpentylaluminum, tri-3-methyl Such as pentyl aluminum, tri 4-methylpentyl aluminum, tri 2-methyl hexyl aluminum, tri 3-methyl hexyl aluminum, tri 2-ethyl hexyl aluminum Li branched alkyl aluminum; tricyclohexyl aluminum, tri-cycloalkyl aluminum such as tri-cyclooctyl aluminum; dialkyl aluminum hydride such as diisobutyl aluminum hydride; triphenyl aluminum, triaryl aluminum such as tri-tolyl aluminum;
_{(i-C 4 H 9)} x Al y (C 5 H 10) z ( in the formula, x, y, z are each a positive number, and z ≧ 2x.) tri isoprenylaluminum represented by like Trialkenyl aluminum such as isobutylaluminum methoxide, isobutylaluminum ethoxide, isobutylaluminum isopropoxide, etc .; alkylaluminum alkoxide such as dimethylaluminum methoxide, diethylaluminum ethoxide, dibutylaluminum butoxide; ethylaluminum sesquiethoxy And alkylaluminum sesquialkoxides such as butylaluminum sesquibutoxide;
Partially alkoxylated alkylaluminum having an average composition represented by R ^a _2.5 Al (OR ^b ) _0.5, etc .; diethylaluminum phenoxide, diethylaluminum (2,6-di-t-butyl-4-methylphenoxide) , Ethylaluminum bis (2,6-di-t-butyl-4-methylphenoxide), diisobutylaluminum (2,6-di-t-butyl-4-methylphenoxide), isobutylaluminum bis (2,6-di-) dialkylaluminum aryloxides such as t-butyl-4-methylphenoxide); dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride; ethylaluminum sesquichloride, butylaluminum Alkyl aluminum sesquihalides such as squichloride, ethylaluminum sesquibromide; Partially halogenated alkylaluminums such as alkylaluminum dihalide such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide; Diethylaluminum hydride, dibutylaluminum hydride Dialkylaluminum hydrides such as: ethylaluminum dihydride, alkyl aluminum dihydrides such as propylaluminum dihydride and other partially hydrogenated alkylaluminums; ethylaluminum ethoxy chloride, butylaluminum butoxycyclolide, ethylaluminum ethoxybromide, etc. Partially alkoxylated and halogenated And alkyl aluminum can be exemplified.

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 .

As the compound belonging to (B-1b),
Examples thereof 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 aluminum halide and alkyllithium, or a combination of aluminum halide and alkylmagnesium 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 (B-2) The organoaluminum oxy compound used in the present invention may be a conventionally known aluminoxane, or as exemplified in JP-A-2-78687. It may be a benzene-insoluble organoaluminum oxy compound.

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

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

  Specific examples of the organoaluminum compound used when preparing the aluminoxane 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 is particularly preferable.

  The above organoaluminum compounds 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 an organoaluminum oxy compound containing boron represented by the following general formula (IV).

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 (IV), an alkyl boronic acid represented by the following general formula (V),
R ¹¹ -B (OH) ₂ (V)
(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 (V) include methyl boronic acid, ethyl boronic acid, isopropyl boronic acid, n-propyl boronic acid, n-butyl boronic acid, isobutyl boronic acid, n-hexyl boron. Examples include acid, cyclohexyl boronic acid, phenyl boronic acid, 3,5-difluoro 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.

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

(B-3) A compound that reacts with a transition metal compound to form an ion pair A compound that reacts with the transition metal compound (A) used in the present invention to form an ion pair (B-3) (hereinafter referred to as “ionized ions”) Examples of such compounds are as follows: JP-A-1-501950, JP-A-1-502016, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, Examples include Lewis acids, ionic compounds, borane compounds, and carborane compounds described in Kaihei 3-207704, USP-5321106, and the like. 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 ionized ionic compound include compounds represented by the following general formula (VI).

In the formula, examples of R ¹³ include H ⁺ , carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, and ferrocenium cation having a transition metal.

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 cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation, and tri (n-butyl) ammonium cation; N, N-dimethylanilinium cation, N, N-diethylanilinium cation, N, N-dialkylanilinium cation such as N, N-2,4,6-pentamethylanilinium cation; dialkylammonium cation such as di (isopropyl) ammonium cation and dicyclohexylammonium cation Etc.

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

R 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 ionized 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, and trimethylammonium tetra (p-tolyl). Boron, trimethylammonium tetra (o-tolyl) boron, tri (n-butyl) ammonium tetra (pentafluorophenyl) boron, tripropylammonium tetra (o, p-dimethylphenyl) boron, tri (n-butyl) ammonium tetra ( m, m-dimethylphenyl) boron, tri (n-butyl) ammonium tetra (p-trifluoromethylphenyl) boron, tri (n-butyl) ammonium tetra (3,5-ditrifluoromethylphenyl) boron, tri (n -Butyl) Ammoni Mutetora (o- tolyl) such as 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-dimethylaniliniumtetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) borate, triphenylcarbenium pentaphenyl Mention may also be made of cyclopentadienyl complexes, N, N-diethylanilinium pentaphenylcyclopentadienyl complexes, boron compounds represented by the following formula (VII) or (VIII).

（式中、Ｅｔはエチル基を示す。）

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

Specific examples of the borane compound include decaborane; bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium] undecaborate, bis Salts of anions such as [tri (n-butyl) ammonium] dodecaborate, bis [tri (n-butyl) ammonium] decachlorodecaborate, bis [tri (n-butyl) ammonium] dodecachlorododecaborate; -Butyl) ammonium bis (dodecahydridododecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (dodecahydridododecaborate) nickelate (III) and other metal borane anion salts Can be mentioned.

Specific examples of carborane compounds include:
4-carbanonaborane, 1,3-dicarbanonaborane, 6,9-dicarbadecarborane, dodecahydride-1-phenyl-1,3-dicarbanonaborane, dodecahydride-1-methyl-1,3-di Carbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarbaundecaborane, 2,7-dicarbaundecaborane, undecahydride-7,8-dimethyl -7,8-dicarbaound decaborane, dodecahydride-11-methyl-2,7-dicarbound decaborane, tri (n-butyl) ammonium 1-carbadecaborate, tri (n-butyl) ammonium 1-carbaun Decaborate, tri (n-butyl) ammonium 1-carbadodecaborate, tri (n-butyl) ammonium 1-trimethylsilyl-1-carbadecaborate, tri (n-butyl) ammonium bromo-1-carbadodecaborate, tri n-butyl) ammonium 6-carbadecaborate, tri (n-butyl) ammonium 6-carbadecaborate, tri (n-butyl) ammonium 7-carbaundecaborate, tri (n-butyl) ammonium 7,8-dicar Bound deborate, tri (n-butyl) ammonium 2,9-dicarbaundecaborate, tri (n-butyl) ammonium dodecahydride-8-methyl-7,9-dicarbundecaborate, tri (n-butyl) ammonium Undecahydride-8-ethyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-butyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undeca Hydride-8-allyl-7,9-dicarboundecaborate, tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,8-dica Salts of anions such as rubaundecaborate, tri (n-butyl) ammonium undecahydride-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) ironate (III), tri (n-butyl) ammonium bis ( Undecahydride-7,8-dicarbundecaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbundecaborate) nickelate (III), tri (N-Butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) cuprate (III), tri (n-butyl) ammonium bis (undecahydride-7 , 8-Dicarbaundecaborate) metallate (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarboundeboborate) 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-carbaundecaborate) manganate (IV), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) cobalt Salt (III), such as bis [tri (n- butyl) ammonium] bis (carborane borate) salt of a metal carborane anions such as nickel salt (IV).

  The heteropoly compound is composed of atoms selected from silicon, phosphorus, titanium, germanium, arsenic and tin, and one or more atoms selected from vanadium, niobium, molybdenum and tungsten. Specifically, phosphovanadic acid, germanovanadic acid, arsenic vanadic acid, phosphoniobic acid, germanoniobic acid, siliconomolybdic acid, phosphomolybdic acid, titanium molybdic acid, germanomolybdic acid, arsenic molybdic acid, tin molybdic acid, phosphorus Tungstic acid, germanotungstic acid, tin tungstic acid, phosphomolybdovanadic acid, phosphotungstovanadic acid, germanotungstovanadic acid, phosphomolybdotungstovanadic acid, germanomolybdo tungstovanadate, phosphomolybdo Tungstic acid, phosphomolybdoniobic acid, and salts of these acids, such as metals of Groups 1 or 2 of the periodic table, such as lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, Strontium, barium Salts with an equal, but organic salt with triphenylethyl salts, and the like can be used, not limited thereto.

  The above (B-3) ionized ionic compounds may be used alone or in combination of two or more.

  When the transition metal compound according to the present invention is used as a catalyst, when an organoaluminum oxy compound (B-2) such as methylaluminoxane as a co-catalyst component is used in combination, the olefin compound exhibits a very high polymerization activity.

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

As the porous oxide, specifically, SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ or the like, or a composite or mixture containing these is used. For example, natural or synthetic zeolite, SiO ₂ —MgO, SiO ₂ —Al ₂ O ₃ , SiO ₂ —TiO ₂ , SiO ₂ —V ₂ O ₅ , SiO ₂ —Cr ₂ O ₃ , SiO ₂ —TiO ₂ —MgO, etc. Can be used. Of these, those containing SiO ₂ and / or Al ₂ O ₃ as main components are preferred.

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 or the like is used. The inorganic chloride may be used as it is or after being pulverized by a ball mill or a vibration mill. In addition, an inorganic chloride dissolved in a solvent such as alcohol and then precipitated in a fine particle form by a precipitant can be used.

  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.

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

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

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

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

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

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

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

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

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

(D) Organic Compound Component In the present invention, the (D) organic compound component is used for the purpose of improving the polymerization performance and the physical properties of the produced polymer, if necessary. Such organic compounds include, but are not limited to, alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, sulfonates, and the like.

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 alcohols, those in which R ¹⁸ is a halogenated hydrocarbon are preferred. Further, as the phenolic compound, those in which the α, α′-position of the hydroxyl group is substituted with a hydrocarbon having 1 to 20 carbon atoms are 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 1-14 of the periodic table.

R ²⁰ 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.

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 in which component (A) and component (B) are added to the polymerization vessel in any 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 component (A) and component (B) are supported on a carrier (C) is added to a 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 each of 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 component (C) and the solid catalyst component in which the component (A) and the component (B) are supported on the component (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.

When the olefin polymerization is carried out using the olefin polymerization catalyst as described above, the component (A) is usually 10 ⁻¹² to 10 ⁻² mol, preferably 10 ⁻¹⁰ to 10 ⁻³ , per liter of the reaction volume. 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 all transition metal atoms (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 atoms in component (B-2) to all transition metals (M) in component (A) 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) to transition metal atom (M) in component (A) usually from 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 5. When component (B) is component (B-2), the molar ratio [(D) / (B-2)]
Is usually in an amount of 0.01-2, preferably 0.005-1, and when component (B) is component (B-3), the molar ratio (D) / (B-3)] is The amount is usually 0.01 to 10, preferably 0.1 to 5.

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

  The molecular weight of the resulting olefin polymer can also be adjusted by the presence of hydrogen in the polymerization system or by changing the polymerization temperature. Furthermore, it can also adjust with the quantity of the 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, 1-butene, 2-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;
Also, vinylcyclohexane, diene, polyene, or the like can be used.

As the diene or polyene, a cyclic or chain compound having 4 to 30, preferably 4 to 20 carbon atoms and having two or more double bonds is used. Specifically, butadiene, isoprene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,3-hexadiene, 1 , 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;
In addition, aromatic or vinyl compounds such as styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, o, p-dimethyl styrene, o-ethyl styrene, m-ethyl styrene, p-ethyl styrene etc. Alkylstyrene; functional group-containing styrene derivatives such as methoxystyrene, ethoxystyrene, vinyl benzoic acid, methyl vinyl benzoate, vinyl benzyl acetate, hydroxystyrene, o-chlorostyrene, p-chlorostyrene, divinylbenzene;
And 3-phenylpropylene, 4-phenylpropylene, α-methylstyrene and the like.

By the olefin polymerization method according to the present invention, it is possible to obtain an olefin copolymer having a high comonomer content with a good polymerization activity when two or more types of olefins are copolymerized. The present invention will be described more specifically based on examples, but the present invention is not limited thereto.

The structure of the compound obtained in the synthesis example was determined using 270 MHz ¹ H NMR (JEOL GSH-270), FD-mass spectrometry (JEOL SX-102A), or the like.

  In this example, the intrinsic viscosity ([η]) was measured at 135 ° C. in decalin.

(1) Ligand synthesis
[Synthesis Example 1]
A 300 ml reactor thoroughly dried and purged with nitrogen was charged with 20.0 ml of ethylmagnesium bromide (diethyl ether solution, 3M, 60.0 mmol) and 50 ml of tetrahydrofuran solution containing 9.50 g (55.8 mmol) of 2-phenylphenol under ice cooling. Was added dropwise over 30 minutes. After stirring at room temperature for 1 hour, paraformaldehyde 5.00 g (167 mmol), triethylamine 8.40 g (83.0 mmol) and toluene 150 ml were added, and the mixture was stirred at 60 ° C. for 1 hour. After cooling to room temperature, 40 ml of 18% hydrochloric acid was added. The organic layer was separated, washed with 50 ml of saturated aqueous sodium hydrogen carbonate solution and 50 ml of saturated brine, and dried over anhydrous magnesium sulfate. After filtration, the residue obtained by distilling off the filtrate was purified by silica gel column chromatography to obtain 9.70 g (yield 88%) of the desired product represented by the following formula (a).

[Synthesis Example-2]
A 100 ml reactor thoroughly dried and purged with nitrogen was charged with 1.07 g (5.40 mmol) of compound (a) and 10 ml of toluene. Thereto was added 10 ml of a toluene solution containing 0.59 g (7.19 mmol) of 1-aminopyrrole, and the mixture was stirred for 20 hours with heating under reflux. The residue obtained by distilling off the solvent was purified by silica gel column chromatography to obtain 1.33 g (yield 94%) of the target compound represented by the following formula (b).

[Synthesis Example-3]
In a 750 ml reactor thoroughly dried and purged with nitrogen, 2.58 g (2.23 mmol) tetrakis (triphenylphosphine) palladium (0), 34.5 g (163 mmol) tripotassium phosphate, 20.0 g 2-bromo-4-fluorophenol (105 mmol), phenylboronic acid 20.0 g (164 mmol), and DMF 300 ml were charged and stirred at 100 ° C. for 15 hours. After completion of the reaction, 200 ml of toluene and 100 ml of water were added. The aqueous layer was extracted 3 times with 100 ml of toluene and combined with the organic layer, then washed 3 times with 100 ml of water and once with 100 ml of saturated brine, and dried over anhydrous magnesium sulfate. After filtration, the residue obtained by evaporating the filtrate was purified by silica gel column chromatography to obtain 13.0 g (yield 66%) of the desired product represented by the following formula (c).

[Synthesis Example 4]
In a 750 ml reactor thoroughly dried and purged with nitrogen, 24.5 ml of ethylmagnesium bromide (diethyl ether solution, 3M, 73.5 mmol) was charged, and 300 ml of tetrahydrofuran solution containing 13.2 g (70.1 mmol) of compound (c) under ice cooling. Was added dropwise over 1 hour. After stirring at room temperature for 1 hour, 6.50 g (216 mmol) of paraformaldehyde and 10.7 g (106 mmol) of triethylamine were added and stirred at 60 ° C. for 1 hour. After cooling to room temperature, 50 ml of 18% hydrochloric acid was added. The organic layer was separated, washed with 100 ml of saturated aqueous sodium hydrogen carbonate solution and 100 ml of saturated brine, and dried over anhydrous magnesium sulfate. After filtration, the residue obtained by distilling off the filtrate was purified by silica gel column chromatography to obtain 8.97 g (yield 59%) of the target compound represented by the following formula (d).

[Synthesis Example-5]
A 100 ml reactor thoroughly dried and purged with nitrogen was charged with 1.15 g (5.31 mmol) of compound (d) and 10 ml of toluene. Thereto was added 10 ml of a toluene solution containing 0.74 g (8.97 mmol) of 1-aminopyrrole, and the mixture was stirred for 2 days with heating under reflux. The residue obtained by distilling off the solvent was purified by silica gel column chromatography to obtain 1.37 g (yield 92%) of the target compound represented by the following formula (e).

(2) Synthesis of transition metal compounds
[Synthesis Example-1 ']
In a 100 ml reactor thoroughly dried and purged with argon, 0.81 g (3.08 mmol) of compound (b) and 15 ml of diethyl ether were charged, cooled to −78 ° C. and stirred. To this, 2.05 ml of n-butyllithium (n-hexane solution, 1.60 M, 3.28 mmol) was added dropwise over 5 minutes, and the mixture was stirred at the same temperature for 2 hours. The lithium salt was adjusted by stirring for a period of time. This solution was added dropwise to 15 ml of diethyl ether solution containing 1.54 ml of toluene solution of titanium tetrachloride, 1.00 M, 1.54 mmol) cooled to −78 ° C. After completion of dropping, stirring was continued for 14 hours while slowly returning to room temperature. After the solvent of the reaction solution was distilled off, the obtained solid was dissolved in 40 ml of methylene chloride, and insoluble matters were removed with a glass filter. The filtrate was concentrated under reduced pressure, and the precipitated solid was reprecipitated with diethyl ether and dried under reduced pressure to obtain 0.35 g (yield 35%) of a red brown powder compound represented by the following formula (A). FD-mass spectrometry (M ⁺ ): 640

[Synthesis Example-2 ']
A 100 ml reactor thoroughly dried and purged with argon was charged with 1.06 g (3.77 mmol) of compound (e) and 20 ml of diethyl ether, cooled to −78 ° C. and stirred. To this, 2.47 ml of n-butyllithium (n-hexane solution, 1.60 M, 3.95 mmol) was added dropwise over 5 minutes, and the mixture was stirred at the same temperature for 2 hours. The lithium salt was adjusted by stirring for a period of time. This solution was added dropwise to 20 ml of a diethyl ether solution containing 1.89 ml of a titanium tetrachloride solution cooled to −78 ° C., 1.00 M, 1.89 mmol). After completion of dropping, stirring was continued for 15 hours while slowly returning to room temperature. After the solvent of the reaction solution was distilled off, the obtained solid was dissolved in 100 ml of methylene chloride, and insoluble matters were removed with a glass filter. The filtrate was concentrated under reduced pressure, and the precipitated solid was reprecipitated with diethyl ether and dried under reduced pressure to obtain 0.41 g (yield 32%) of a red brown powder compound represented by the following formula (B). FD-mass spectrometry (M ⁺ ): 676

  A glass reactor having an internal volume of 500 ml sufficiently purged with nitrogen was charged with 250 ml of toluene, and the liquid phase and gas phase were saturated with 100 liter / hr of ethylene. Thereafter, methylaluminoxane was added in an amount of 1.25 mmol in terms of aluminum atom, and subsequently 0.0003 mmol of the following titanium compound (A) synthesized in Synthesis Example-1 ′ was added to initiate polymerization. Ethylene was continuously supplied at 100 liter / hr, and polymerization was carried out at 25 ° C. for 5 minutes under normal pressure. Then, the polymerization was stopped by adding a small amount of isobutanol. After completion of the polymerization, the reaction product was added to 1 liter of methanol containing a small amount of hydrochloric acid to precipitate a polymer. After washing with methanol, it was dried under reduced pressure at 80 ° C. for 10 hours to obtain 1.62 g of polyethylene. The polymerization activity was 64, 800 g / mmol-Ti · hr, and the intrinsic viscosity [η] of the obtained polyethylene was 0.67 dl / g.

  A glass reactor having an internal volume of 500 ml sufficiently purged with nitrogen was charged with 250 ml of toluene, and the liquid phase and gas phase were saturated with a mixed gas of ethylene 100 liter / hr and propylene 100 liter / hr. Thereafter, methylaluminoxane was added in an amount of 1.25 mmol in terms of aluminum atom, and then 0.005 mmol of the titanium compound (A) was added to initiate copolymerization. After copolymerization at 50 ° C. for 10 minutes, the polymerization was stopped by adding a small amount of isobutanol. To the obtained polymer suspension, 100 ml of water containing a small amount of hydrochloric acid was added, shaken vigorously, allowed to stand, and then the aqueous layer was removed. After repeating this operation three times in total, the solvent was distilled off under reduced pressure and further dried under reduced pressure at 130 ° C. for 10 hours. The obtained ethylene / propylene copolymer (EPR) was 10.2 g. The polymerization activity was 12, 240 g / mmol-Ti · hr, and the intrinsic viscosity [η] of the obtained polyethylene was 0.16 dl / g. The propylene content measured by IR was 29.9 mol%.

235 ml of cyclohexane was charged into a glass reactor having an internal volume of 500 ml sufficiently purged with nitrogen, and the liquid phase and the gas phase were saturated with ethylene at a flow rate of 50 liters / hr. Thereafter, tetracyclo of 2g to the reactor [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene (hereinafter abbreviated as "TD".), 1 methylaluminoxane (MAO) in an aluminum atom basis. Polymerization was started by adding 0.0002 mmol of titanium compound (A), followed by 25 mmol. After reacting in an ethylene gas atmosphere at 25 ° C. and normal pressure for the time shown in Table 1, the polymerization was stopped by adding a small amount of isobutyl alcohol. After completion of the polymerization, the reaction product was poured into a mixed solvent of acetone / methanol (500 ml each) to which 5 ml of concentrated hydrochloric acid had been added to precipitate the whole amount of the polymer, and after stirring, filtered through a glass filter. After drying the polymer under reduced pressure at 130 ° C. for 10 hours, 0.20 g of an ethylene / TD copolymer was obtained. The polymerization activity was 5,940 g / mmol-Ti · hr, and the molecular weight measured by GPC (polyethylene equivalent) was Mw = 26,000. The TD content measured by ¹³ C-NMR analysis was 43 mol%.

  A glass reactor having an internal volume of 500 ml sufficiently purged with nitrogen was charged with 250 ml of toluene, and the liquid phase and gas phase were saturated with 100 liter / hr of ethylene. Thereafter, methylaluminoxane was added in an amount of 1.25 mmol in terms of aluminum atom, and then 0.0001 mmol of the following titanium compound (B) synthesized in Synthesis Example 2 'was added to initiate polymerization. Ethylene was continuously supplied at 100 liter / hr, and polymerization was carried out at 25 ° C. for 5 minutes under normal pressure. Then, the polymerization was stopped by adding a small amount of isobutanol. After completion of the polymerization, the reaction product was added to 1 liter of methanol containing a small amount of hydrochloric acid to precipitate a polymer. After washing with methanol, it was dried under reduced pressure at 80 ° C. for 10 hours to obtain 0.98 g of polyethylene. The polymerization activity was 117,600 g / mmol-Ti · hr, and the intrinsic viscosity [η] of the obtained polyethylene was 0.40 dl / g.

  A glass reactor having an internal volume of 500 ml sufficiently purged with nitrogen was charged with 250 ml of toluene, and the liquid phase and gas phase were saturated with a mixed gas of ethylene 100 liter / hr and propylene 100 liter / hr. Thereafter, methylaluminoxane was added in an amount of 1.25 mmol in terms of aluminum atom, and then 0.005 mmol of the titanium compound (B) was added to initiate copolymerization. After copolymerization at 50 ° C. for 10 minutes, the polymerization was stopped by adding a small amount of isobutanol. To the obtained polymer suspension, 100 ml of water containing a small amount of hydrochloric acid was added, shaken vigorously, allowed to stand, and then the aqueous layer was removed. After repeating this operation three times in total, the solvent was distilled off under reduced pressure and further dried under reduced pressure at 130 ° C. for 10 hours. The obtained ethylene / propylene copolymer (EPR) was 12.2 g. The polymerization activity was 14,640 g / mmol-Ti · hr, and the intrinsic viscosity [η] of the obtained polyethylene was 0.08 dl / g. The propylene content measured by IR was 39.6 mol%.

235 ml of cyclohexane was charged into a glass reactor having an internal volume of 500 ml sufficiently purged with nitrogen, and the liquid phase and the gas phase were saturated with ethylene at a flow rate of 50 liters / hr. Thereafter, tetracyclo of 2g to the reactor [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene (hereinafter abbreviated as "TD".), 1 methylaluminoxane (MAO) in an aluminum atom basis. Polymerization was started by adding 0.0001 mmol of titanium compound (B), followed by 25 mmol. After reacting in an ethylene gas atmosphere at 25 ° C. and normal pressure for the time shown in Table 1, the polymerization was stopped by adding a small amount of isobutyl alcohol. After completion of the polymerization, the reaction product was poured into a mixed solvent of acetone / methanol (500 ml each) to which 5 ml of concentrated hydrochloric acid had been added to precipitate the whole amount of the polymer, and after stirring, filtered through a glass filter. After drying the polymer under reduced pressure at 130 ° C. for 10 hours, 0.25 g of an ethylene / TD copolymer was obtained. The polymerization activity was 15,180 g / mmol-Ti · hr, and the TD content measured by ¹³ C-NMR analysis was 42 mol%.

[Comparative Example 1]
A glass reactor having an internal volume of 500 ml sufficiently purged with nitrogen was charged with 250 ml of toluene, and the liquid phase and gas phase were saturated with 100 liter / hr of ethylene. Thereafter, methylaluminoxane was added in an amount of 1.25 mmol in terms of aluminum atom, and then 0.005 mmol of the following titanium compound (C) was added to initiate polymerization. Ethylene was continuously supplied at 100 liter / hr, and polymerization was carried out at 25 ° C. for 5 minutes under normal pressure. Then, the polymerization was stopped by adding a small amount of isobutanol. After completion of the polymerization, the reaction product was added to 1 liter of methanol containing a small amount of hydrochloric acid to precipitate a polymer. After washing with methanol, it was dried under reduced pressure at 80 ° C. for 10 hours to obtain 1.16 g of polyethylene. The polymerization activity was 2,780 g / mmol-Ti · hr, and the intrinsic viscosity [η] of the obtained polyethylene was 1.27 dl / g.

[Comparative Example 2]
A glass reactor having an internal volume of 500 ml sufficiently purged with nitrogen was charged with 250 ml of toluene, and the liquid phase and gas phase were saturated with 100 liter / hr of ethylene. Thereafter, methylaluminoxane was added in an amount of 1.25 mmol in terms of aluminum atom, and then 0.002 mmol of the following titanium compound (D) was added to initiate polymerization. Ethylene was continuously supplied at 100 liter / hr, and polymerization was carried out at 25 ° C. for 5 minutes under normal pressure. Then, the polymerization was stopped by adding a small amount of isobutanol. After completion of the polymerization, the reaction product was added to 1 liter of methanol containing a small amount of hydrochloric acid to precipitate a polymer. After washing with methanol, it was dried under reduced pressure at 80 ° C. for 10 hours to obtain 1.79 g of polyethylene. The polymerization activity was 10,740 g / mmol-Ti · hr, and the intrinsic viscosity [η] of the obtained polyethylene was 6.80 dl / g.

[Comparative Example 3]
A glass reactor having an internal volume of 500 ml sufficiently purged with nitrogen was charged with 250 ml of toluene, and the liquid phase and gas phase were saturated with a mixed gas of ethylene 100 liter / hr and propylene 100 liter / hr. Thereafter, methylaluminoxane was added in an amount of 1.25 mmol in terms of aluminum atom, and then 0.005 mmol of the titanium compound (D) was added to start copolymerization. After copolymerization at 50 ° C. for 10 minutes, the polymerization was stopped by adding a small amount of isobutanol. To the obtained polymer suspension, 100 ml of water containing a small amount of hydrochloric acid was added, shaken vigorously, allowed to stand, and then the aqueous layer was removed. After repeating this operation three times in total, the solvent was distilled off under reduced pressure and further dried under reduced pressure at 130 ° C. for 10 hours. The obtained ethylene / propylene copolymer (EPR) was 4,85 g. The polymerization activity was 5,820 g / mmol-Ti · hr, and the intrinsic viscosity [η] of the obtained polyethylene was 1.37 dl / g. The propylene content measured by IR was 17.6 mol%.

[Comparative Example 4]
235 ml of cyclohexane was charged into a glass reactor having an internal volume of 500 ml sufficiently purged with nitrogen, and the liquid phase and the gas phase were saturated with ethylene at a flow rate of 50 liters / hr. Thereafter, tetracyclo of 2g to the reactor [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene (hereinafter abbreviated as "TD".), 1 methylaluminoxane (MAO) in an aluminum atom basis. Polymerization was started by adding 0.005 mmol of titanium compound (D), followed by 25 mmol. After reacting in an ethylene gas atmosphere at 25 ° C. and normal pressure for the time shown in Table 1, the polymerization was stopped by adding a small amount of isobutyl alcohol. After completion of the polymerization, the reaction product was poured into a mixed solvent of acetone / methanol (500 ml each) to which 5 ml of concentrated hydrochloric acid had been added to precipitate the whole amount of the polymer, and after stirring, filtered through a glass filter. After drying the polymer under reduced pressure at 130 ° C. for 10 hours, 0.53 g of an ethylene / TD copolymer was obtained. The polymerization activity was 630 g / mmol-Ti · hr, and the molecular weight measured by GPC (polyethylene equivalent) was Mw = 1240,000. The TD content measured by ¹³ C-NMR analysis was 35 mol%.

Claims (6)

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

[Wherein, M represents a transition metal atom of Groups 4 to 5 in the periodic table, m represents an integer of 1 to 4, and R ¹ may have one or more locating groups. Represents a heterocyclic compound residue, R ^{2 to} R ⁵ may be the same or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group or a tin-containing group, may form a ring more than is bonded to each other of these, R ⁶ Has a phenyl group that may have one or more locating groups, a naphthyl group that may have one or more locating groups, and one or more locating groups An optionally biphenyl group, one or more terphenyl groups, Beauty represents one or more groups selected from optionally phenanthryl group which may have a置喚group, and when m is 2 or more two groups among the groups represented by R ¹ to R ⁶ May be connected (however, R ¹ are not bonded to each other),
n is a number that satisfies the valence of M;
X is a hydrogen atom, halogen atom, hydrocarbon group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, heterocyclic compound residue, silicon-containing A group, a germanium-containing group, or a tin-containing group, and when n is 2 or more, a plurality of groups represented by X may be the same or different from each other, and a plurality of groups represented by X are bonded to each other. To form a ring. ]   Reaction with transition metal compound (A) according to claim 1, (B) (B-1) organometallic compound, (B-2) organoaluminum oxy compound, and (B-3) transition metal compound (A) And at least one compound selected from compounds that form ion pairs. The catalyst for olefin polymerization according to claim 1 or 2, wherein in the transition metal compound (A) represented by the general formula (I), R ¹ is an aromatic heterocyclic compound residue. The olefin polymerization according to claim 3, wherein in the transition metal compound (A) represented by the general formula (I), the heterocyclic compound residue of R ¹ is an pyrrole which may have a locating group. Catalyst.   An olefin polymerization method comprising polymerizing or copolymerizing an olefin in the presence of the olefin polymerization catalyst according to any one of claims 1 to 4.   6. The olefin polymerization method according to claim 5, wherein at least one olefin selected from ethylene, α-olefin and cyclic olefin is polymerized or copolymerized.