JP2005132731A - Catalyst for polymerizing olefin and method for polymerization - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a catalyst for polymerizing an olefin having an excellent olefin polymerization activity and to provide a method for polymerizing the olefin using the catalyst. <P>SOLUTION: The catalyst for polymerizing the olefin comprises a transition metal compound having one bidentate ligand having a phenolate structure and a carbonyl structure and one bidentate ligand having the phenolate structure and an imine structure a group 4 transition metal group as a central metal, respectively and (B) at least one kind of compound selected from the group consisting of (B-1) an organometallic compound, (B-2) an organoaluminumoxy compound and (B-3) a compound reactive with the transition metal compound (A) and forming an ion pair. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an olefin polymerization catalyst comprising a transition metal compound and an olefin polymerization method using the olefin polymerization catalyst.

A so-called Kaminsky catalyst is well known as an olefin polymerization catalyst. This catalyst is characterized by extremely high polymerization activity and a polymer having a narrow molecular weight distribution. Examples of the transition metal compound used in such a Kaminsky catalyst include bis (cyclopentadienyl) zirconium dichloride (see Japanese Patent Application Laid-Open No. 58-19309) and ethylene bis (4,5,6,7-tetrahydro). Indenyl) zirconium dichloride (see Japanese Patent Application Laid-Open No. 61-130314) is known. It is also known that the olefin polymerization activity and the properties of the resulting polyolefin differ greatly when the transition metal compound used in the polymerization is different. Furthermore, as a new catalyst for olefin polymerization, a transition metal compound having a bidentate ligand having a phenolate structure and a carbonyl structure (see WO9717354) has been proposed. On the other hand, transition metal compounds having a phenol moiety and a bidentate ligand having an imine structure (see European Patent 087405) have been proposed. Since these technologies, many derivatives with similar structures have been synthesized. However, transition metal compounds with a group 4 transition metal group as the central metal have a bidentate ligand with a phenolate structure and a carbonyl structure. The synthesis and use of transition metal compounds having both a phenolate structure and a bidentate ligand having an imine structure have not been reported.
JP 58-19309 A JP-A 61-130314 International Patent No. 9717354 European Published Patent No. 087405

  The present invention is a transition metal having a bidentate ligand having a phenolate structure and a carbonyl structure, and a bidentate ligand having a phenolate structure and an imine structure, each having a group 4 transition metal group as a central metal. It is an object of the present invention to provide a compound and an olefin polymerization catalyst having excellent olefin polymerization activity, and an olefin polymerization method using the catalyst.

  The present invention provides an olefin polymerization catalyst having high polymerization activity. Furthermore, according to the olefin polymerization method of the present invention, an olefin (co) polymer can be produced with high polymerization activity.

The first olefin polymerization catalyst according to the present invention comprises:
(A) a transition metal compound represented by the following formula (I):

(Ｉ)

(I)

If necessary,
(B) (B-1) Organometallic compound,
(B-2) an organoaluminum oxy compound, and
(B-3) It is characterized by comprising at least one compound selected from the group consisting of compounds that react with the transition metal compound (A) to form ion pairs.

  In the olefin polymerization catalyst according to the present invention, the transition metal compound (A), (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) a transition metal compound (A In addition to at least one compound (B) selected from the group consisting of compounds that react with) to form ion pairs, it may contain a carrier (C).

  The olefin polymerization method according to the present invention is characterized in that an olefin is polymerized or copolymerized in the presence of the catalyst as described above.

  Hereinafter, a compound that reacts with the transition metal compound (A) to form an ion pair may be referred to as an “ionized ionic compound”.

  Hereinafter, the olefin polymerization catalyst of the present invention and the olefin polymerization method using the catalyst 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 olefin polymerization catalyst of the present invention comprises:
(A) a transition metal compound represented by the formula (I),
(B) (B-1) Organometallic compound as required
(B-2) an organoaluminum oxy compound, and
(B-3) It is formed from at least one compound selected from the group consisting of compounds that react with the transition metal compound (A) to form ion pairs.

  First, components that form the catalyst used in the present invention will be described.

Transition metal compound (A)
The transition metal compound (A) is a transition metal compound represented by the following formula (I).

(Ｉ)

(I)

In the formula (I), M represents a transition metal atom of Group 4 of the periodic table, and more specifically, titanium, zirconium and hafnium are preferable. R ^{1 to} R ¹¹ may be the same as or different from each other, hydrogen atom, halogen atom, hydrocarbon group, heterocyclic compound residue, oxygen-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, sulfur-containing group A group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of these may be connected to each other to form a ring.

More specifically, R ^{1 to} R ¹¹ are a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxy group, an alkoxy group, an alkylthio group, an aryloxy group, Arylthio group, acyl group, ester group, thioester group, amide group, imide group, amino group, imino group, sulfone ester group, sulfonamide group, cyano group, nitro group, carboxyl group, sulfo group, mercapto group, aluminum-containing group Or it is preferable that it is a hydroxy group.

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

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

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

  The hydrocarbon group may have a hydrogen atom substituted with another hydrocarbon group, and examples thereof include aryl group-substituted alkyl groups such as benzyl and cumyl.

  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 group, sulfone ester , Sulfonamide groups, thiocarboxyl groups, dithiocarboxyl groups, sulfo groups, sulfonyl groups, sulfinyl groups, sulfenyl groups and other sulfur-containing groups; phosphide groups, phosphoryl groups, thiophosphoryl groups, phosphorous-containing groups such as phosphato groups, silicon You may have a containing group, a germanium containing group, or a tin containing group.

  Among these, in particular, 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, neopentyl, n-hexyl, adamantyl, etc. 20 linear or branched alkyl groups; aryl groups having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms such as phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, anthracenyl; halogen atoms to these aryl groups; A substituted aryl substituted with 1 to 5 substituents such as an alkyl group or alkoxy group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, or an aryloxy group Groups and the like are preferred.

  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.

Examples of the oxygen-containing group, nitrogen-containing group, sulfur-containing group and phosphorus-containing group shown as R ^{1 to} R ¹¹ are the same as those exemplified as the substituent which may be contained in the hydrocarbon group. .

Examples of the boron-containing group include those similar to those exemplified as the substituent which may be contained in the hydrocarbon group, alkyl group-substituted boron, aryl group-substituted boron, boron halide, alkyl group-substituted boron halide, etc. The group of is mentioned. As the alkyl group-substituted boron, (Et) ₂ B-, (iPr) ₂ B-, (iBu) ₂ B-, (Et) ₃ B, (iPr) ₃ B, (iBu) ₃ B; aryl group-substituted boron (C ₆ H ₅ ) ₂ B—, (C ₆ H ₅ ) ₃ B, (C ₆ F ₅ ) ₃ B, (3,5- (CF ₃ ) ₂ C ₆ H ₃ ) ₃ B; halogen Examples of boron halides include BCl _2- , BCl ₃ ; and alkyl group-substituted boron halides include (Et) BCl-, (iBu) BCl-, (C ₆ H ₅ ) ₂ BCl, and the like. Of these, trisubstituted boron may be in a coordinated state. Here, Et represents an ethyl group, iPr represents an isopropyl group, and iBu represents an isobutyl group.

Examples of the aluminum-containing group include groups such as alkyl group-substituted aluminum, aryl group-substituted aluminum, aluminum halide, and alkyl group-substituted aluminum halide. Alkyl group-substituted aluminum includes (Et) ₂ Al-, (iPr) ₂ Al-, (iBu) ₂ Al-, (Et) ₃ Al, (iPr) ₃ Al, (iBu) ₃ Al; (C ₆ H ₅ ) ₂ Al-; Al halides include AlCl _2- , AlCl ₃ ; Alkyl group-substituted aluminum halides include (Et) AlCl-, (iBu) AlCl-, and the like. . Of these, trisubstituted aluminum may be in a coordinated state. Here, Et represents an ethyl group, iPr represents an isopropyl group, and iBu represents an isobutyl group.

  Examples of the silicon-containing group include a silyl group, a siloxy group, a hydrocarbon-substituted silyl group, and a hydrocarbon-substituted siloxy group. Specific examples of the hydrocarbon-substituted silyl group include methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, diphenylmethylsilyl, triphenylsilyl, dimethylphenylsilyl, dimethyl-t-butylsilyl, dimethyl (pentafluoro Phenyl) silyl and the like. Among these, methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, dimethylphenylsilyl, triphenylsilyl and the like are preferable. In particular, trimethylsilyl, triethylsilyl, triphenylsilyl, and dimethylphenylsilyl are preferable. Specific examples of the hydrocarbon-substituted siloxy group include trimethylsiloxy and the like.

  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 ^{1 to} R ⁷ described above will be described more specifically.

  Among the oxygen-containing groups, alkoxy groups include methoxy, ethoxy, n-blopoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy and the like, and aryloxy groups include phenoxy, 2,6-dimethylphenoxy, 2, 4,6-trimethylphenoxy and the like are acyl groups such as formyl group, acetyl group, benzoyl group, p-chlorobenzoyl group and p-methoxybenzoyl group, and ester groups are acetyloxy, benzoyloxy and methoxycarbonyl. , Phenoxycarbonyl, p-chlorophenoxycarbonyl and the like are preferred.

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

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

R ^{1 to} R ¹¹ are two or more of these groups, preferably adjacent groups 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. These rings may further have a substituent.

  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.

Here, examples of the halogen atom include fluorine, chlorine, bromine, and iodine. Examples of the hydrocarbon group include the same ones as exemplified for R ¹ to R ¹¹ of said formula (I). Specifically, alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, octyl, nonyl, dodecyl, 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; phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, naphthyl, methylnaphthyl, anthryl, phenanthryl, and the like Examples include, but are not limited to, an aryl group. These hydrocarbon groups also include halogenated hydrocarbons, specifically, groups in which at least one hydrogen of a hydrocarbon group having 1 to 30 carbon atoms is substituted with halogen. Of these, those having 1 to 20 carbon atoms are preferred.

As the heterocyclic compound residue include the same ones as exemplified for R ¹ to R ¹¹ of said formula (I).

Examples of the oxygen-containing group include the same groups as those exemplified for R ^{1 to} R ¹¹ in the formula (I). Specific examples include hydroxy groups; alkoxy groups such as methoxy, ethoxy, propoxy, and butoxy; phenoxy Aryloxy groups such as methylphenoxy, dimethylphenoxy and naphthoxy; arylalkoxy groups such as phenylmethoxy and phenylethoxy; acetoxy groups; carbonyl groups and the like, but not limited thereto.

Examples of the sulfur-containing group include those exemplified for R ^{1 to} R ¹¹ in the formula (I), specifically, methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, Sulfonate groups such as benzyl sulfonate, p-toluene sulfonate, trimethylbenzene sulfonate, triisobutyl benzene sulfonate, p-chlorobenzene sulfonate, pentafluorobenzene sulfonate; methyl sulfinate, phenyl Sulfinate groups such as sulfinate, benzyl sulfinate, p-toluene sulfinate, trimethylbenzene sulfinate, pentafluorobenzene sulfinate; alkylthio groups; arylthio groups, etc., but are not limited thereto is not.

Specific examples of the nitrogen-containing group include those exemplified for R ^{1 to} R ¹¹ in the formula (I). Specific examples include amino groups; methylamino, dimethylamino, diethylamino, dipropyl. Alkylamino groups such as amino, dibutylamino, dicyclohexylamino; arylamino groups such as phenylamino, diphenylamino, ditolylamino, dinaphthylamino, methylphenylamino, or alkylarylamino groups; is not.

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 trialkylphosphine groups such as trimethylphosphine, tributylphosphine, and tricyclohexylphosphine; triarylphosphine groups such as triphenylphosphine and tolylphosphine; 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 the silicon-containing group include those exemplified for R ^{1 to} R ¹¹ in the formula (I), and specific examples include phenylsilyl, diphenylsilyl, trimethylsilyl, triethylsilyl, tripropyl. Hydrocarbon-substituted silyl groups such as silyl, tricyclohexylsilyl, triphenylsilyl, methyldiphenylsilyl, tolylsilylsilyl, trinaphthylsilyl; hydrocarbon-substituted silyl ether groups such as trimethylsilyl ether; silicon-substituted alkyl groups such as trimethylsilylmethyl; trimethylsilyl Examples include silicon-substituted aryl groups such as phenyl.

Specific examples of the germanium-containing group include the same groups as those exemplified for R ^{1 to} R ¹¹ in the formula (I). Specifically, a group in which silicon in the silicon-containing group is substituted with germanium is exemplified. Can be mentioned.

Examples of the tin-containing group include those exemplified as R ^{1 to} R ¹¹ in the formula (I), and more specifically, a group 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, etc.).

  In these, a halogen atom and an alkyl group are preferable, and also chlorine, bromine, and a methyl group are preferable.

  The synthesis of the transition metal compound (A) represented by the formula (I) is performed, for example, as follows.

  That is, a transition metal complex compound using a group 4 metal of the periodic table described in International Publication No. 9717354 is recrystallized in the presence of a water-containing solvent.

  As the solvent, a solvent usually used in such a reaction can be used, and among them, a polar solvent such as ether and tetrahydrofuran (THF), and a hydrocarbon solvent such as n-pentane, n-hexane, benzene and toluene are preferable. used.

  The composition and structure of the reaction product can be confirmed by analyzing by elemental analysis, X-ray crystal structure analysis, mass spectrum, NMR, IR, and the like.

  After the reaction, this reaction product can be used as a mixture without performing a purification operation, or can be used after being purified by a purification operation such as recrystallization.

  Next, each compound of (B) component used as needed is demonstrated.

(B-1) Organometallic compounds (B-1) Organometallic compounds used as necessary in the present invention are specifically the organic compounds of Groups 1 and 2 and Groups 12 and 13 of the periodic table shown below. There are metal compounds.
(B-1a) General formula R ^a _m Al (OR ^b ) _n H _p X _q
(In the formula, R ^a and R ^b each represent a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms which may be the same or different from each other, 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). Complex alkylated product.
(B-1c) General formula R ^a R ^b M ³
(In the formula, R ^a and R ^b each represent a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms which may be the same as or different from each other, and M ³ is Mg, Zn or Cd. A dialkyl compound of a Group 2 or Group 12 metal 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 each represents a hydrocarbon group having 1 to 15, preferably 1 to 4, carbon atoms which may be the same as or different from each other, 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 each represent a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms which may be the same or different from each other, X represents a halogen atom, and m represents 0 < m ≦ 3, n is 0 ≦ n <3, q is a number of 0 ≦ q <3, and m + n + q = 3).

As an organoaluminum compound belonging to (B-1a), more specifically,
Tri-n-alkylaluminums such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum;
Triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylbutylaluminum, tri-2-methylpentylaluminum, tri-3-methylpentylaluminum, tri-4 -Tri-branched alkylaluminums such as methylpentylaluminum, tri-2-methylhexylaluminum, tri-3-methylhexylaluminum, tri-2-ethylhexylaluminum;
Tricycloalkylaluminum such as tricyclohexylaluminum and tricyclooctylaluminum; triarylaluminum such as triphenylaluminum and tritylaluminum; dialkylaluminum hydride such as diethylaluminum hydride and diisobutylaluminum hydride;
_{(i-C 4 H 9)} x Al y (C 5 H 10) z ( wherein, x, y, z are each a positive number, and z ≧ 2x.) tri isoprenylaluminum represented by like Trialkenyl aluminum such as;
Alkyl aluminum alkoxides such as isobutyl aluminum methoxide, isobutyl aluminum ethoxide, isobutyl aluminum isopropoxide;
Dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide, dibutylaluminum butoxide;
Alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide;
Partially alkoxylated alkylaluminum having an average composition such as Ra _2.5 Al (OR ^b ) _0.5 ;
Diethylaluminum phenoxide, diethylaluminum (2,6-di-t-butyl-4-methylphenoxide), ethylaluminum bis (2,6-di-t-butyl-4-methylphenoxide), diisobutylaluminum (2,6- Dialkylaluminum aryloxides such as di-t-butyl-4-methylphenoxide), isobutylaluminum bis (2,6-di-t-butyl-4-methylphenoxide);
Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride;
Alkylaluminum sesquichlorides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide;
Partially halogenated alkylaluminums such as alkylaluminum dihalides such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide;
Dialkylaluminum hydrides such as diethylaluminum hydride, dibutylaluminum hydride;
Other partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as ethylaluminum dihydride, propylaluminum dihydride;
Examples include partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxychloride, butylaluminum butoxychloride, 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. As such a compound, specifically,
(C ₂ H ₅ ) ₂ AlN (C ₂ H ₅ ) Al (C ₂ H ₅ ) _{2 and the} like.

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

(B-2) Organoaluminum oxy compound The (B-2) organoaluminum oxy compound used as necessary in the present invention may be a conventionally known aluminoxane or 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 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 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 which are insoluble or hardly soluble in benzene are preferred.

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

（ｉ）

(I)

In the formula, R ¹² represents a hydrocarbon group having 1 to 10 carbon atoms.
R ¹³ represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 10 carbon atoms, which may be the same as or different from each other.

The organoaluminum oxy compound containing boron represented by the general formula (i) is an alkyl boronic acid represented by the following general formula (ii):
R ¹² -B (OH) ₂ (ii)
(Wherein R ¹² 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 (ii) include methyl boronic acid, ethyl boronic acid, isopropyl boronic acid, n-propyl boronic acid, n-butyl boronic acid, isobutyl boronic acid, and n-hexyl boronic 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.

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

(B-3) Ionized ionic compound The compound (B-3) that reacts with the transition metal compound (A) to form an ion pair used as necessary in the present invention reacts with the transition metal compound (A). Thus, the compound forms an ion pair. Therefore, what forms an ion pair by making it contact with a transition metal compound (A) at least is contained in this compound.

  Examples of such compounds include JP-A-1-501950, JP-A-1-502036, JP-A-3-179905, JP-A-3-179006, JP-A-3-207703, and JP-A-3. And Lewis acids, ionic compounds, borane compounds and carborane compounds described in Japanese Patent No. -207704 and USP-5321106. 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, Examples include tris (p-tolyl) boron, tris (o-tolyl) boron, and tris (3,5-dimethylphenyl) boron.

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

(II)

(II)

In the formula, examples of R ¹⁴ + include H ⁺ , a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptyltrienyl cation, and a ferrocenium cation having a transition metal.

R ^{15 to} R ¹⁸ are organic groups which may be the same or different from each other, 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, triethylammonium cations, tripropylammonium cations, tributylammonium cations, tri (n-butyl) ammonium cations, and the like; N, N-dimethylanilinium cations; 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 ²² 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, 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-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) borate, triphenylcarbenium pentaphenyl Examples also include cyclopentadienyl complexes, N, N-diethylanilinium pentaphenylcyclopentadienyl complexes, and boron compounds represented by the following formula (III) or (IV).

(III)
（式中、Ｅｔはエチル基を示す。）

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

(IV)

(IV)

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] undecaborate, bis [tri (n-butyl) ammonium] dodecaborate , Salts of anions such as bis [tri (n-butyl) ammonium] decachlorodecaborate, bis [tri (n-butyl) ammonium] dodecachlorododecaborate; tri (n-butyl) ammonium bis (dodecahydridododecaborate) Examples thereof include salts of metal borane anions such as cobaltate (III) and bis [tri (n-butyl) ammonium] bis (dodecahydridododecaborate) nickelate (III).

Specifically as a carborane compound, 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-dicarbaunaborane (13), 2,7-dicarbaun Decaborane (13), undecahydride-7,8-dimethyl-7,8-dicarboundecaborane, dodecahydride-11-methyl-2,7-dicarboundecarborane, tri (n-butyl) ammonium 1- Carbadecaborate, tri (n-butyl) ammonium 1-carbaundecaborate, tri (n-butyl) ammonium 1-carbadodecaborate, tri (n-butyl) ammonium 1-trimethylsilyl-1-carbadecaborate, tri ( n-butyl) ammo Nitrobromo-1-carbadodecaborate, tri (n-butyl) ammonium 6-carbadecaborate (14), tri (n-butyl) ammonium 6-carbadecaborate (12), tri (n-butyl) ammonium 7-cal Bound deborate (13), tri (n-butyl) ammonium 7,8-dicarbaundecaborate (12), tri (n-butyl) ammonium 2,9-dicarboundeborate (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 Decahydride-8-butyl-7,9-dicarboundecaborate, tri (n-butyl) ammonium undecahydride-8-allyl-7,9-dicarboundeca Borate, tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,8-dicarboundecaborate, tri (n-butyl) ammonium undecahydride-4,6-dibromo-7-carbaundecaborate, etc. Anionic salts of
Tri (n-butyl) ammonium bis (nonahydride-1,3-dicarbanonaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) Ferrate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7 , 8-Dicarbaundecaborate) nickelate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) cuprate (III), tri (n-butyl) Ammonium bis (undecahydride-7,8-dicarbaundecaborate) aurate (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarboundeca Borate) ferrate (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarboundeborate) 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) cobaltate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) nickelate (IV) Etc. Any metal carborane anion salts.

  The heteropoly compound is composed of atoms composed of silicon, phosphorus, titanium, germanium, arsenic or 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, phosphomolybniobic acid, 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, With barium etc. And organic salts such as triphenylethyl salts, and an isopoly compound may be used, not limited thereto.

  The heteropoly compound and the isopoly compound are not limited to one of the above compounds, and two or more of them can be used.

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

  If the olefin polymerization catalyst of the present invention is used, an olefin polymer can be obtained with high polymerization activity, and its molecular weight is high. For example, when an organoaluminum oxy compound (B-2) such as methylaluminoxane as a promoter component is used in combination, it exhibits a very high polymerization activity for olefin compounds. When an ionized ionic compound (B-3) such as triphenylcarbonium tetrakis (pentafluorophenyl) borate is used as a promoter component, an olefin polymer having a good activity and a very high molecular weight can be obtained.

  The olefin polymerization catalyst according to the present invention comprises a transition metal compound (A), if necessary (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) an ionized ion. In addition to at least one compound (B) selected from the active compounds, a carrier (C) as described below can be used as necessary.

(C) Carrier The carrier (C) used as necessary in the present invention is an inorganic or organic compound and is a granular or fine particle 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.

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 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. Moreover, after dissolving inorganic chloride in solvents, such as alcohol, what precipitated with the precipitation agent in the shape of fine particles can also be used.

  The clay used as a carrier in the present invention is usually composed mainly of a clay mineral. Further, the ion-exchangeable layered compound used as a carrier in the present invention is a compound having a crystal structure in which the surfaces constituted by ionic bonds and the like are stacked in parallel with a weak binding force, and the ions contained can be exchanged It is. 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 halloysite, and the ion-exchangeable layered compounds include α-Zr (HAsO ₄ ) ₂ .H ₂ O, α-Zr (HPO ₄ ) ₂ , α-Zr (KPO ₄ ) ₂ .3H ₂ O, α-Ti (HPO ₄ ) ₂ , α-Ti (HAsO ₄ ) ₂ .H ₂ O, α-Sn (HPO ₄ ) ₂ .H ₂ O, γ-Zr (HPO ₄ ) ₂ , γ-Ti (HPO ₄ ) ₂ , 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 not less than 0.1 cc / g and not less than 0.3 cc / g, as measured by mercury porosimetry. Is particularly preferred. Here, the pore volume is measured in a pore radius range of 20 to ³ × 10 ⁴ angstroms by mercury porosimetry using a mercury porosimeter. When a carrier having a pore volume with a radius of 20 angstroms 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 other large and bulky ions using the ion-exchange property. . Such bulky ions play a role of supporting pillars to support the layered structure and are usually called pillars. Moreover, introducing another substance between the layers of the layered compound in this way is called intercalation. Examples of guest compounds to be intercalated include cationic inorganic compounds such as TiCl ₄ and ZrCl ₄ , metal alkoxides such as Ti (OR) ₄ , Zr (OR) ₄ , PO (OR) ₃ , and B (OR) ₃ ( R is a hydrocarbon group), metal hydroxide ions such as [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH) ₁₄ ] ²⁺ , [Fe ₃ O (OCOCH ₃ ) ₆ ] ⁺ Etc.

  These compounds are used alone or in combination of two or more.

Further, when these compounds were intercalated, they were obtained by hydrolyzing metal alkoxides such as Si (OR) ₄ , Al (OR) ₃ , Ge (OR) ₄ (R is a hydrocarbon group, etc.). Polymers, colloidal inorganic compounds such as SiO _2, and the like can also coexist. Examples of the pillar include oxides generated by heat dehydration after intercalation of the metal hydroxide ions between layers.

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

  Among these, preferred are clays or clay minerals, and particularly preferred are montmorillonite, vermiculite, hectorite, 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 And (co) polymers produced by the main component, and their modified products.

  The catalyst for olefin polymerization according to the present invention comprises the transition metal compound (A), if necessary (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) ionized ionicity. A specific organic compound (D) as described later can be further contained as necessary together with at least one compound (B) selected from the compounds 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. Examples of such organic compounds include, but are not limited to, alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, and sulfonates.

As the alcohols and phenolic compounds, those represented by R ¹⁹ —OH are generally used (where R ¹⁹ is a hydrocarbon group having 1 to 50 carbon atoms or a halogenated group having 1 to 50 carbon atoms). Represents a hydrocarbon group), and the alcohols are preferably those wherein R ³¹ is a halogenated hydrocarbon. Moreover, as a phenolic compound, what substituted the (alpha) and (alpha) '-position of the hydroxyl group with the C1-C20 hydrocarbon is preferable.

As the carboxylic acid, one represented by R 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 (V) are used.

(Ｖ)

(V)

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

  Next, the olefin polymerization method will be described.

  The olefin polymerization method according to the present invention comprises (co) polymerizing olefins in the presence of the above catalyst.

In the polymerization, the method of adding the component (A) to the polymerization vessel, the usage method of each component, the addition method,
Although the order of addition is arbitrarily selected, the following method is exemplified.
(1) Component (A) and at least one component (B) selected from (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) an ionized ionic compound (below) And simply adding “component (B)”) to the polymerization vessel in any order.
(2) A method in which a catalyst in which the component (A) and the component (B) are contacted in advance is added to the polymerization reactor.
(3) A method in which the catalyst component in which the component (A) and the component (B) are contacted in advance, and the component (B) are added to the polymerization vessel in an arbitrary order. In this case, the component (B) may be the same or different.
(4) 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.
(5) A method in which a catalyst having components (A) and (B) supported on a carrier (C) is added to a polymerization vessel.
(6) A method in which the component (A) and the component (B) supported on the carrier (C) and the component (B) are added to the polymerization vessel in any order. In this case, the component (B) may be the same or different.
(7) 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.
(8) A method in which the catalyst component having component (B) supported on carrier (C), component (A), and component (B) are added to the polymerization vessel in any order. In this case, the component (B) may be the same or different.
(9) A method in which the component carrying component (A) on carrier (C) and the component carrying component (B) on carrier (C) are added to the polymerization vessel in any order.
(10) A method in which component (A) is supported on carrier (C), component (B) is supported on carrier (C), and component (B) is added to the polymerization vessel in any order. In this case, the component (B) may be the same or different.
(11) A method in which component (A), component (B), and organic compound component (D) are added to the polymerization vessel in any order.
(12) A method in which the component (B) and the component (D) are contacted in advance, and the component (A) are added to the polymerization vessel in any order.
(13) A method in which the component (B) and the component (D) supported on the carrier (C) and the component (A) are added to the polymerization vessel in an arbitrary order.
(14) A method in which the catalyst component in which the component (A) and the component (B) are contacted in advance, and the component (D) are added to the polymerization vessel in an arbitrary order.
(15) A method in which the component (A) and the component (B) are contacted in advance, and the component (B) and the component (D) are added to the polymerization vessel in an arbitrary order.
(16) A method in which the catalyst component in which the component (A) and the component (B) are contacted in advance, and the component in which the component (B) and the component (D) are contacted in advance are added to the polymerization vessel in an arbitrary order. (17) A method of adding the component (A) supported on the carrier (C), the component (B), and the component (D) to the polymerization vessel in any order.
(18) A method in which a component having component (A) supported on carrier (C) and a component in which component (B) and component (D) are contacted in advance are added to the polymerization vessel in any order.
(19) A method in which a catalyst component obtained by bringing the component (A), the component (B), and the component (D) into contact in advance in an arbitrary order is added to the polymerization reactor.
(20) A method in which the catalyst component in which the component (A), the component (B) and the component (D) are contacted in advance, and the component (B) are added to the polymerization vessel in an arbitrary order. In this case, the component (B) may be the same or different.
(21) A method in which a catalyst having components (A), (B) and (D) supported on a carrier (C) is added to a polymerization vessel.
(22) A method in which the component (A), the component (B) and the component (D) are supported on the carrier (C), and the component (B) is added to the polymerization vessel in any order. In this case, the component (B) may be the same or different.

  The solid catalyst component in which the component (A) and optionally the component (B) are supported on the carrier (C) may be prepolymerized with olefin.

  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, Alicyclic hydrocarbons such as methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, or mixtures thereof. It can also be used as a solvent.

When the olefin polymerization is carried out using the above olefin polymerization catalyst, the component (A) is usually 10 ⁻¹² to 10 ⁻² mol, preferably 10 ⁻¹⁰ to 10 ⁻³ , per liter of reaction volume. It is used in such an amount that it becomes a mole. In the present invention, the olefin can be polymerized with high polymerization activity even when the component (A) is used at a relatively low concentration.

  In addition, when the component (B) is used as necessary, the component (B-1) contains a molar ratio of the component (B-1) and the transition metal atom (M) in the component (A) [(B- 1) / M] is usually 0.01 to 100,000, preferably 0.05 to 50,000.

  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) 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 (D) is component (B-1), component (B), in the case of component (B-1), the molar ratio [(D) / (B-1)] is usually 0.01 to 10, preferably 0.1 In the case of component (B-2), the molar ratio [(D) / (B-2)] between component (D) and aluminum atom in component (B-2) is usually 0. 0.001 to 2, preferably 0.005 to 1 and in the case of component (B-3), the molar ratio [(D) / (B-3)] is usually 0.01 to 10, preferably Is used in an amount of 0.1-5.

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 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 α-olefins having 2 to 20 carbon atoms, such as ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1 -Hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene;
Cyclic olefins having 3 to 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;
The polar olefin in the present invention is an unsaturated hydrocarbon having a polar group. Specifically, for example, acrylic acid, 3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid, 6-heptenoic acid, 7 -Octenoic acid, 8-nonenoic acid, 9-decenoic acid, 10-undecenoic acid, 11-dodecenoic acid, 12-tridecenoic acid, 13-tetradecenoic acid, 14-pentadecenoic acid, 15-hexadecenoic acid, 16-heptadecenoic acid, 17 -Octadecenoic acid, 18-nonadecenoic acid, 19-eicosenoic acid, 20-henicosenoic acid, 21-docosenoic acid, 22-tricosenoic acid, methacrylic acid, 2-methylpentenoic acid, 2,2-dimethyl-3-butenoic acid, 2 , 2-Dimethyl-4-pentenoic acid, 3-vinylbenzoic acid, 4-vinylbenzoic acid, 2,6-heptadienoic acid, 2- (4-isopropylbenzylidene) -4-pentenoic acid, allylmalonic acid, 2- (10 -Undecenyl) malonic acid, fumaric acid, itaconic acid, bicyclo [2.2.1] -5-hepte 2-carboxylic acid, unsaturated carboxylic acids such as bicyclo [2.2.1] -5-heptene-2,3-dicarboxylic acid, and their sodium, potassium, lithium, zinc, magnesium, calcium Metal salts such as salts, and unsaturated carboxylic acid esters thereof such as methyl ester, ethyl ester, n-propyl ester, isopropyl ester, n-butyl ester, isobutyl ester, (5-norbornen-2-yl) ester ( When the unsaturated carboxylic acid is a dicarboxylic acid, it may be a monoester or a diester), and unsaturated carboxylic acid amides such as amide, N, N-dimethylamide (the unsaturated carboxylic acid) When the carboxylic acid is a dicarboxylic acid, it may be a monoamide or a diamide); for example, maleic anhydride, itaconic anhydride, allyl Succinic anhydride, isobutenyl succinic anhydride, (2,7-octadien-1-yl) succinic anhydride, tetrahydrophthalic anhydride, bicyclo [2.2.1] -5-heptene-2,3- Unsaturated carboxylic anhydrides such as dicarboxylic anhydrides; vinyl esters such as vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl trifluoroacetate; Halogenated olefins such as vinyl, vinyl fluoride, allyl bromide, allyl chloride, allyl fluoride, allyl bromide; for example, allyltrimethylsilane, diallyldimethylsilane, 3-butenyltrimethylsilane, allyltriisopropylsilane, allyltri Silylated olefins such as phenylsilane; for example, acrylonitrile, 2-cyanobicyclo [2.2.1] -5-hept Unsaturated nitriles such as ten, 2,3-dicyanobicyclo [2.2.1] -5-heptene; for example, allyl alcohol, 3-butenol, 4-pentenol, 5-hexenol, 6-hebutenol, 7-octenol, Unsaturated alcohol compounds such as 8-nonenol, 9-decenol, 10-undecenol, 11-dodecenol, 12-tridecenol, and their acetates, benzoates, propionates, caproates, caprates, lauric acids Unsaturated esters such as esters and stearic acid esters; substituted phenols such as vinylphenol and allylphenol; for example methyl vinyl ether, ethyl vinyl ether, allyl methyl ether, allyl propyl ether, allyl butyl ether, allyl methallyl ether, methoxy styrene, ethoxys Unsaturated ethers such as len; Unsaturated epoxides such as butadiene monoxide, 1,2-epoxy-7-octene, 3-vinyl 7-oxabicyclo [4.1.0] heptane; Unsaturated epoxides such as acrolein and undecenal Saturated aldehydes, and unsaturated acetals such as dimethyl acetal, diethyl acetal, etc .; for example, methyl vinyl ketone, ethyl vinyl ketone, allyl methyl ketone, allyl ethyl ketone, allyl propyl ketone, allyl butyl ketone, allyl benzyl ketone, etc. Saturated ketones, and unsaturated acetals such as dimethyl acetal and diethyl acetal; such as allyl methyl sulfide, allyl phenyl sulfide, allyl isopropyl sulfide, allyl n-propyl sulfide, 4-pentenyl phenyl sulfide, etc. Saturated thioethers; unsaturated sulfoxides such as allyl phenyl sulfoxide; unsaturated sulfones such as allyl phenyl sulfone; unsaturated phosphines such as allyl diphenyl phosphine; unsaturated phosphine oxides such as allyl diphenyl phosphine oxide Etc. Further, unsaturated hydrocarbons having the polar groups listed above, such as vinyl benzoic acid, methyl vinyl benzoate, vinyl benzyl acetate, hydroxystyrene, methyl 4- (3-butenyloxy) benzoate, allyl trifluoroacetate, o-chlorostyrene, p-chlorostyrene, divinylbenzene, glycidyl acrylate, allyl glycidyl ether, (2H-perfluoropropyl) -2-propenyl ether, linalool oxide, 3-allyloxy-1,2-propanediol, 2- ( Allyloxy) ethanol, N-allylmorpholine, allylglycine, N-vinylpyrrolidone, allyltrichlorosilane, acryltrimethylsilane, allyldimethyl (diisopropylamino) silane, 7-octenyltrimethoxysilane, allyloxytrimethylsilane, allyloxytriphenyl Silane And the like.

  Furthermore, vinylcyclohexane, diene, polyene, etc. can also be used. The diene or polyene is a cyclic or chain compound having 4 to 30, preferably 4 to 20 carbon atoms and having two or more double bonds. Specifically, butadiene, isoprene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,3-hexadiene, 1 , 3-octadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, 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-methylsterene and the like.

  The catalyst for olefin polymerization according to the present invention exhibits a high polymerization activity and can obtain a polymer having a narrow molecular weight distribution. Furthermore, when two or more olefins are copolymerized, an olefin copolymer having a narrow composition distribution can be obtained.

  The olefin polymerization catalyst according to the present invention can also be used for copolymerization of an α-olefin and a conjugated diene. Examples of the α-olefin used here include linear or branched α-olefins having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, as described above. Of these, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene and 1-octene are preferable, and ethylene and propylene are particularly preferable. These α-olefins can be used alone or in combination of two or more.

  Examples of conjugated dienes include 1,3-butadiene, isoprene, chloroprene, 1,3-cyclohexadiene, 1,3-pentadiene, 4-methyl-1,3-pentadiene, 1,3-hexadiene, 1,3- Examples thereof include aliphatic conjugated dienes having 4 to 30, preferably 4 to 20 carbon atoms such as octadiene. These conjugated dienes can be used alone or in combination of two or more.

  In the present invention, an α-olefin and a polar monomer can be copolymerized. Examples of the polar monomer used include the same ones as described above.

  In the present invention, an α-olefin and a non-conjugated diene or polyene can also be copolymerized. Non-conjugated dienes or polyenes used are 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 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, etc. Can be mentioned.

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

In addition, the structure of the compound obtained in the synthesis example is 270 MHz ¹ H-NMR (JEOL GSH-270 type), FD-mass spectrometry (FD-MS, JEOL SX-102A type), carbon, hydrogen, nitrogen The content was determined using content analysis (Heraus CHNO type), X-ray diffractometer (Rigaku RAXIS-IV) and the like. The molecular weight (Mw) and molecular weight distribution (Mw / Mn) were determined in terms of polyethylene using Waters 150-C gel permeation chromatography.
Specific examples of the synthesis of the transition metal compound according to the present invention are shown below, and specific examples of olefin polymerization are shown.

( Synthesis of raw material ligand L )
A 100 mL reactor thoroughly dried and purged with argon was charged with 3.67 g (24.7 mmol) of ethylanilide and 40 mL of dichloromethane, cooled to 0 ° C, and 5.10 g (24.7 mmol) of phosphorus pentachloride in dichloromethane (0.82 M) 30 mL was added dropwise. After stirring at room temperature for 12 hours, the solvent was removed under reduced pressure to obtain a yellow oil. Dissolve this in 20 mL of 1,2-dichloroethane, and add it to a dry, argon-substituted 200 mL reactor at 3.95 g (29.64 mmol) anhydrous aluminum chloride and 50 mL of 1,2-dichloroethane at 0 ° C. The solution was added dropwise while cooling. After the solution was stirred at 0 ° C. for 1 hour, a solution prepared by dissolving 3.65 g (22.2 mmol) of 2-tert-butyl-4-methylphenol in 20 mL of 1,2-dichloroethane was added dropwise at the same temperature. After stirring at room temperature for 18 hours, the resulting solution was poured onto 30 g of ice. After the organic layer was separated, the aqueous layer was extracted with 20 mL of dichloromethane, and the entire organic solvent solution was dried over sodium sulfate. The solvent was distilled off, and purification by column chromatography (silica gel / chloroform) was performed to obtain Compound L of the following formula (Chemical Formula 8) as yellow crystals.

¹ H-NMR (CDCl ₃ ): δ 15.12 (s, 1H), 7.42-7.12 (m, 5H), 6,93 (d, 1H, 1.3 Hz), 6.89 (d, 1H, 1.3 Hz), 2.71 ( q, 2H, 7.9 Hz), 2.32 (s, 3H), 1.45 (s, 9H), 1.20 (t, 3H, 7.9 Hz)

( Synthesis of raw material complex compound A1 )
Charge 1.40 g (4.73 mmol) of L and 35 mL of diethyl ether in a 50 mL reactor thoroughly dried and purged with argon, and add 3.0 mL of n-butyllithium / hexane solution (1.57 M) dropwise with stirring at 0 ° C. did. The obtained solution was added dropwise to 2.36 mL of a titanium tetrachloride / toluene solution (1.0 M) charged in a 50 mL reactor sufficiently dried and purged with argon while cooling to -30 ° C. After stirring for 11 hours, the solvent was distilled off under reduced pressure, and 35 mL of dichloromethane was added and allowed to stand. The solution portion was filtered through a glass filter, the mother liquor was concentrated to about 7 mL, 35 mL of n-pentane was added, and the whole was cooled to −78 ° C. The resulting precipitate was filtered through a glass filter and dried under reduced pressure to obtain Compound A1 of the following formula as a brown powder (920 mg, 55%).

（A1）
FD-MS (m/z): 706
¹H-NMR (C₆D₆): δ 7.47-6.93 (m, 10H), 6.74-6.62 (m, 2H), 6.62-6.52 (m, 2H), 2.35-2.15 (m, 4H), 1.70 (s, 18H), 0.78 (t, 6H, 7.9 Hz)
元素分析 (wt%):測定値 C, 68.32; H, 7.21; N, 4.02 計算値C, 67.90; H, 6.84; N, 3.96

(A1)
FD-MS (m / z): 706
¹ H-NMR (C ₆ D ₆ ): δ 7.47-6.93 (m, 10H), 6.74-6.62 (m, 2H), 6.62-6.52 (m, 2H), 2.35-2.15 (m, 4H), 1.70 ( s, 18H), 0.78 (t, 6H, 7.9 Hz)
Elemental analysis (wt%): measured value C, 68.32; H, 7.21; N, 4.02 calculated value C, 67.90; H, 6.84; N, 3.96

[ Synthesis of Complex Compound A2 ]
Under a nitrogen atmosphere, 12.7 mg of A1 was placed in a 1 mL glass tube that had been thoroughly dried and replaced, and 0.2 mL of benzene was added and dissolved. This tube was placed in a 30 mL Schlenk cage, and 15 mL of n-pentane previously coexisted with an equal amount of water was added to the outside of the tube, and the upper part of the Schlenk cage was sealed. After standing at room temperature for 3 days, reddish brown tabular crystals A2 adhering to the inner wall of the glass tube were collected (2.2 mg, 19%).

（A2）
FD-MS (m/z): 631
¹H-NMR (C₆D₆): δ 7.71-6.30 (m, 9H), 2.38-2.15 (m, 4H), 1.86 (s, 3H), 1.46 (s, 3H), 0.87 (t, 3H, 7.9 Hz), 0.72 (t, 3H, 7.9 Hz)
元素分析: 測定値 C, 65.01; H, 7.32; N, 2.70計算値 C, 64.57; H, 6.85; N, 2.21
X線構造解析: 三斜晶系，a = 9.9193(2) angstrom, b = 10.0822(4) angstrom , c = 17.4856(3) angstrom, α = 85.748(5) degree, β = 89.698(1) degree, γ = 76.677(7) degree, V = 1696.84(9) (angstrom)³ X線構造解析図を図１に示した。

(A2)
FD-MS (m / z): 631
¹ H-NMR (C ₆ D ₆ ): δ 7.71-6.30 (m, 9H), 2.38-2.15 (m, 4H), 1.86 (s, 3H), 1.46 (s, 3H), 0.87 (t, 3H, 7.9 Hz), 0.72 (t, 3H, 7.9 Hz)
Elemental analysis: Measured value C, 65.01; H, 7.32; N, 2.70 Calculated value C, 64.57; H, 6.85; N, 2.21
X-ray structural analysis: Triclinic system, a = 9.9193 (2) angstrom, b = 10.0822 (4) angstrom, c = 17.4856 (3) angstrom, α = 85.748 (5) degree, β = 89.698 (1) degree, γ = 76.677 (7) degree, V = 1696.84 (9) (angstrom) ^{3 An} X-ray structural analysis diagram is shown in FIG.

[ Comparative Example ] -Comparative Comparative Example-
To a glass autoclave having an internal volume of 500 mL that was sufficiently purged with nitrogen, 250 mL of toluene was placed, and the liquid phase and gas phase were saturated with ethylene at 100 liter / hr of ethylene. Thereafter, 1.25 mmol of methylaluminoxane (MAO) in terms of aluminum atom and then 0.005 mmol of compound A1 were 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, the reaction product was poured into a large amount of methanol to precipitate the whole amount of the polymer, and then hydrochloric acid was added and filtered through a glass filter. After drying the polymer under reduced pressure at 80 ° C. for 10 hours, 111 mg of polyethylene was obtained. Mn of the obtained polyethylene was 22,410 and Mw / Mn was 1.07.

-Polymerization examples-
To a glass autoclave having an internal volume of 500 mL that was sufficiently purged with nitrogen, 250 mL of toluene was placed, and the liquid phase and gas phase were saturated with ethylene at 100 liter / hr of ethylene. Thereafter, methylaluminoxane (MAO) was added in an amount of 1.25 mmol in terms of aluminum atom, and then 0.005 mmol of compound A2 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, the reaction product was poured into a large amount of methanol to precipitate the whole amount of the polymer, and then hydrochloric acid was added and filtered through a glass filter. After drying the polymer under reduced pressure at 80 ° C. for 10 hours, 22 mg of polyethylene was obtained. The molecular weight distribution of the obtained polyethylene is bimodal and consists of two peaks P ₁ and P ₂ . Mn is 225,510 (P ₁ ) and 2,120 (P ₂ ), Mw / Mn is 2.04 (P ₁ ) and 1.06 (P ₂ ), respectively, and the integral value ratio of the two peaks is 1.08 / 1 (= P ₁ / P ₂ )Met.

FIG. 6 is an X-ray structural analysis diagram of complex compound A2.

Claims (4)

The transition metal compound represented by the following general formula (I).

(I)
(In the above formula, M represents a transition metal atom of Group 4 of the periodic table, and R ^{1 to} R ¹¹ may be the same as or different from each other, a hydrogen atom, a halogen atom, a hydrocarbon group, or a heterocyclic compound residue. Group, oxygen-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium-containing group, or tin-containing group, and two or more of these are linked to each other X is 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 group A compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group, the groups represented by X may be the same or different from each other, and the groups represented by X are bonded to each other to form a ring; Also good. (A) a transition metal compound represented by the formula (I), and (B) (B-1) an organometallic compound,
(B-2) an organoaluminum oxy compound, and
(B-3) An olefin polymerization catalyst comprising at least one compound selected from the group consisting of compounds that react with the transition metal compound (A) to form ion pairs. The catalyst for olefin polymerization characterized by including a support | carrier (C) in addition to the catalyst for olefin polymerization of Claim 2. An olefin polymerization method comprising polymerizing or copolymerizing an olefin in the presence of the olefin polymerization catalyst according to any one of claims 2 to 3.

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