JPH0912618A - Olefin polymerization catalyst and production of olefin polymer using the same - Google Patents

Abstract

PURPOSE: To obtain an olefin copolymer having a sharp molecular weight distribution and a broad compositional distribution in high catalytic activity by using a catalyst comprising a specified transition metal compound containing Ti or the like, an organoaluminum compound or the like and a specified boron compound. CONSTITUTION: This olefin polymerization catalyst comprises a transition metal compound (A) of formula I (wherein M is Ti, Zr or Cf; Cp is a group of a 5-30C cyclic compound having a cyclopentadienyl skeleton; E<1> , E<2> and E<3> are each a V ligand), a compound (B) capable of forming an ionic complex with the component A, and at least one reaction product (C) of an organolauminum compound with a phenolic compound, boric acid or the like. The components B is desirably an aluminoxane or a Lewis acid, especially an ionic compound of formula II or III (wherein L<2> is M<2> , R<2> R<3> M<3> , R<4> 3 C or R<5> M3 ; L<1> is a Lewis base; D is a specified noncoordinated anion; R<1> and R<4> are each a 1-20C alkyl or the like; R<2> and R<3> are each cyclopentadienyl, indenyl or the like; R<5> is a macrocyclic ligand; (k) is 1-3; a>=1; b=(k×a);M is an element of the group 11, 12 or 13 in the periodic table or the like; and M<3> is an element of group of 7-12).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an olefin polymerization catalyst and a method for producing an olefin polymer using the same. More specifically, it provides an olefin polymer having excellent copolymerizability, a high activity per aluminum and a high activity per transition metal, a narrow molecular weight distribution and a relatively wide composition distribution, and unprecedented excellent physical properties. The present invention relates to an olefin polymerization catalyst and a method for efficiently producing an olefin polymer having the above-mentioned preferable properties, particularly an ethylene-α-olefin copolymer, using the catalyst.

[0002]

2. Description of the Related Art In recent years, a catalyst composed of a metallocene compound of a transition metal and an aluminoxane (for example, JP-A-58-19309) has attracted attention as a new olefin polymerization catalyst. Although this catalyst exhibits extremely high polymerization activity and relatively good copolymerizability, it has a problem that it requires a large amount of aluminoxane and its copolymerizability is still insufficient. Therefore, the inventors of the present invention have previously proposed, as a catalyst showing a high activity per aluminum and an extremely excellent copolymerizability, for the olefin polymerization containing a specific transition metal compound and an aluminum oxy compound in a predetermined molar ratio. Proposed a catalyst (Japanese Patent Application No. 6-75691)
issue). However, this catalyst was not always satisfactory because the activity per transition metal was still insufficient. Further, the ethylene-α-olefin copolymer obtained by using the polymerization catalyst composed of the metallocene compound of the transition metal and the aluminoxane has the characteristics that the molecular weight distribution is narrow and the composition distribution is also narrow. Therefore,
From this property, when formed into a film, it has an effect of improving heat sealability and film impact, but has a defect of low tear strength, and is not necessarily a satisfactory ethylene-α-olefin copolymer.

In order to deal with such a problem, the inventors of the present invention have previously identified, as an ethylene polymer having an excellent balance of physical properties, a specific molecular weight distribution having a narrow molecular weight distribution and a relatively wide composition distribution. An ethylene polymer was proposed (Japanese Patent Application No. 6-172643). On the other hand, a Group 4 transition metal compound containing one cyclopentadienyl ring (substantially the cyclopentadienyl ring and the σ ligand are bound to each other,
An olefin polymerization catalyst comprising a compound having a cyclic structure, a so-called constrained geometry type catalyst, an aluminoxane and a compound defined in a wide range has been disclosed (International Patent Publication 9).
3-13140). However, the polyolefin obtained with this catalyst has a narrow composition distribution and does not have sufficiently satisfactory physical properties.

[0004]

Under such circumstances, the present invention has excellent copolymerizability, high activity per aluminum and activity per transition metal, and a narrow molecular weight distribution and a relatively wide composition distribution. A catalyst for olefin polymerization which gives an olefin polymer having the above, and an olefin polymer having the above-mentioned preferable properties and excellent physical properties not hitherto, particularly an ethylene-α-olefin copolymer, can be efficiently produced by using this catalyst. It is intended to provide a method for manufacturing.

[0005]

Means for Solving the Problems As a result of intensive studies for achieving the above object, the present inventors have found that a specific cyclic compound group having a cyclopentadienyl or a substituted cyclopentadienyl skeleton has a specific cyclic compound group. The transition metal compound, by combining a compound capable of reacting with the transition metal compound or a derivative thereof to form an ionic complex, and a specific organoaluminum compound as a third component, excellent copolymerizability, And a catalyst for olefin polymerization having high activity per aluminum and high activity per transition metal, and in the presence of this catalyst, homopolymerization of olefins or polymerization of olefins with other olefins and / or other polymerizability By copolymerizing with an unsaturated compound, an olefin-based polymer having a narrow molecular weight distribution and a relatively wide composition distribution, particularly an ethylenic polymer, can be obtained. -α- olefin copolymer was found to be efficiently obtained. The present invention has been completed based on such findings. That is, the present invention
(A) General formula (I) CpME ¹ E ² E ³ ... (I) [In the formula, M represents titanium, zirconium or hafnium, and Cp is a carbon having a cyclopentadienyl or substituted cyclopentadienyl skeleton. The cyclic compound group of several 5 to 30 is shown. E ¹ , E ² and E ³ each represent a σ ligand, which may be the same or different. ] A transition metal compound represented by the following, (B) a compound capable of reacting with the transition metal compound of the component (A) or a derivative thereof, and (C) (a) an organoaluminum compound Reaction products with phenolic compounds and (b) organoaluminum compounds with general formula (II)

[0006]

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[In the formula, X, Y and Z each represent a sulfur atom or an oxygen atom, which may be the same or different. ] An olefin polymerization catalyst comprising at least one selected from the reaction products with a boron compound represented by the following. Further, the present invention is characterized by homopolymerizing olefins or copolymerizing olefins with other olefins and / or other polymerizable unsaturated compounds in the presence of the above olefin polymerization catalyst. It also provides a method for producing a united body.

The olefin polymerization catalyst of the present invention comprises (A)
A compound containing a transition metal compound, (B) a compound capable of reacting with the transition metal compound of the component (A) or a derivative thereof to form an ionic complex, and (C) a specific organoaluminum compound. is there. The transition metal compound of the component (A) is represented by the general formula (I) CpME ¹ E ² E ³ ... (I). In the general formula (I), M
Represents titanium, zirconium or hafnium. Particularly preferred M is titanium. Cp has 5 to 3 carbon atoms having a cyclopentadienyl or substituted cyclopentadienyl skeleton coordinated with M through a π bond in the η ⁵ -bonding mode.
0 is a cyclic compound group, and E ¹ , E ² and E ³ are σ ligands coordinated to M by σ bonds. Examples of this σ ligand include R ′, OR ′, SR ′, S
O ₃ R ′, NR′R ″, PR′R ″, NO ₂ , halogen atom, 1-pyrrolyl and 1-pyrrolidinyl can be preferably mentioned. Here, R'and R "are carbon numbers 1 to
20 is a hydrocarbon group or a silyl group containing a hydrocarbon group. Then, at least one of the σ ligands is preferably a halogen atom, OR ′, NR′R ″ or PR′R ″. Further, it is more preferable that all of the σ ligands are halogen atoms from the viewpoint of storage stability. Further, E ¹ , E ² and E ³ may be the same or different from each other. In addition, these E ¹ , E ² and E ³ are C
It is desirable that they do not bond with each other to form a cyclic structure.

There is one group consisting of a cyclic compound having 5 to 30 carbon atoms and having a cyclopentadienyl or substituted cyclopentadienyl skeleton coordinated by a π bond in the above M and η ⁵ -bonding mode, Further, the substituents on the substituted cyclopentadienyl skeleton may bond with each other to form a new cyclic structure. That is, a group having an indenyl skeleton, a substituted indenyl skeleton, a fluorenyl skeleton, or a substituted fluorenyl skeleton is also included in the cyclic compound group. Further, in the above R ′ and R ″, the number of carbon atoms is 1-2.
Examples of the hydrocarbon group of 0 include an alkyl group, a cycloalkyl group, an aryl group and an aralkyl group. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group,
Isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group and the like; cycloalkyl group such as cyclopentyl group and cyclohexyl group; and aryl group as aryl group For example, a phenyl group or a tolyl group can be mentioned, and as an aralkyl group, for example, a benzyl group or a phenethyl group can be mentioned. Examples of the silyl group containing a hydrocarbon group include a trimethylsilyl group and a triphenylsilyl group. Specific examples of OR ′ include methoxy group, ethoxy group, n-propoxy group,
Isopropoxy group, n-butoxy group, isobutoxy group,
sec-butoxy group, t-butoxy group, pentoxy group,
Examples thereof include alkoxy groups such as hexoxy group, octoxy group and cyclohexoxy group, aryloxy groups such as phenoxy group and the like. Specific examples of SR 'include a methylthio group, an ethylthio group, a cyclohexylthio group and a phenylthio group. Then, specific examples of SO ₃ R ′ include a methanesulfonyl group, an ethanesulfonyl group, an n-propanesulfonyl group,
Isopropanesulfonyl group, n-butanesulfonyl group,
Examples thereof include sec-butanesulfonyl group, t-butanesulfonyl group, isobutanesulfonyl group and other alkylsulfonyl groups, and benzenesulfonyl group and other arylsulfonyl groups. Further, specific examples of NR'R "include dimethylamino group, diethylamino group, di (n-propyl) amino group, diisopropylamino group,
Di (n-butyl) amino group, diisobutylamino group, di (sec-butyl) amino group, di (t-butyl) amino group, dipentylamino group, dihexylamino group, dioctylamino group, diphenylamino group, dibenzylamino Group, methylethylamino group, (t-butyl) trimethylsilylamino group, methyltrimethylsilylamino group and the like. In addition, specific examples of PR′R ″ include a dimethylphosphido group, a diethylphosphido group, a di (n-propyl) phosphido group, a diisopropylphosphido group, a di (n-butyl) phosphido group,
Diisobutylphosphido group, di (sec-butyl) phosphido group, di (t-butyl) phosphido group, dipentylphosphido group, dihexylphosphido group, dioctylphosphido group, diphenylphosphido group,
Dibenzylphosphido group, methylethylphosphido group, (t-butyl) trimethylsilylphosphido group,
Methyltrimethylsilyl sulfide group and the like can be mentioned. Further, as the halogen atom, fluorine,
Among these are chlorine, bromine and iodine.

Examples of the transition metal compound represented by the general formula (I) include cyclopentadienyl titanium trimethyl; cyclopentadienyl titanium triethyl; cyclopentadienyl titanium tri (n-propyl); cyclopentadiene. Cyclopentadienyl titanium tri (n-butyl); cyclopentadienyl titanium triisobutyl; cyclopentadienyl titanium tri (sec-butyl); cyclopentadienyl titanium tri (t-butyl); methyl 1,2-dimethylcyclopentadienyl titanium trimethyl; 1,2,4-trimethylcyclopentadienyl titanium trimethyl; 1,2,3,4-tetramethylcyclopentadienyl titanium trimethyl; Pentamethylcyclope Pentamethylcyclopentadienyl titanium triethyl; pentamethylcyclopentadienyl titanium tri (n-propyl); pentamethylcyclopentadienyl titanium triisopropyl; pentamethylcyclopentadienyl titanium tri (n-butyl) ); Pentamethylcyclopentadienyl titanium triisobutyl; pentamethylcyclopentadienyl titanium tri (sec-butyl); pentamethylcyclopentadienyl titanium tri (t-butyl); cyclopentadienyl titanium trimethoxide; cyclo Pentadienyl titanium triethoxide; Cyclopentadienyl titanium tri (n-propoxide); Cyclopentadienyl titanium triisopropoxide; Cyclopentadienyl titanium triphenoxide; Pentadienyl titanium trimethoxide; (n-butyl) cyclopentadienyl titanium trimethoxide; dimethylcyclopentadienyl titanium trimethoxide; dimethylcyclopentadienyl titanium triethoxide; dimethylcyclopentadienyl titanium tri ( n-propoxide); dimethylcyclopentadienyl titanium triisopropoxide; dimethyl cyclopentadienyl titanium triphenoxide; di (t
-Butyl) cyclopentadienyl titanium trimethoxide; di (t-butyl) cyclopentadienyl titanium triethoxide; di (t-butyl) cyclopentadienyl titanium tri (n-propoxide); di (t- Butyl) cyclopentadienyl titanium triisopropoxide; di (t
-Butyl) cyclopentadienyl titanium triphenoxide; bis (trimethylsilyl) cyclopentadienyl titanium trimethoxide; bis (trimethylsilyl) cyclopentadienyl titanium triethoxide; bis (trimethylsilyl) cyclopentadienyl titanium tri (n- Propoxide); bis (trimethylsilyl) cyclopentadienyl titanium triisopropoxide; bis (trimethylsilyl) cyclopentadienyl titanium triphenoxide; trimethylcyclopentadienyl titanium trimethoxide; trimethylcyclopentadienyl titanium triethoxide; Trimethylcyclopentadienyl titanium tri (n-propoxide); Trimethylcyclopentadienyl titanium triisopropoxide; Trimethylcyclopentadienyl titanium tri Enoxide; triethylcyclopentadienyl titanium trimethoxide; [bis (dimethylsilyl), methyl] cyclopentadienyl titanium trimethoxide; [di (t-butyl, methyl)] cyclopentadienyl titanium triethoxide; tetra Methylcyclopentadienyl titanium trimethoxide; Tetramethylcyclopentadienyl titanium triethoxide; Tetramethylcyclopentadienyl titanium tri (n-propoxide); Tetramethylcyclopentadienyl titanium triisopropoxide; Tetramethyl Cyclopentadienyl titanium tri (n-butoxide); Tetramethylcyclopentadienyl titanium triisobutoxide; Tetramethyl cyclopentadienyl titanium tri (sec-butoxide); Tetramethyl cyclopentadienyl tita Tri (t-butoxide); tetramethylcyclopentadienyl titanium triphenoxide; [tetramethyl, 4-methoxyphenyl] cyclopentadienyl titanium trimethoxide; [tetramethyl, 4-methoxyphenyl] cyclopentadienyl titanium tri Ethoxide; [Tetramethyl, 4-methoxyphenyl] cyclopentadienyl titanium tri (n-propoxide); [Tetramethyl, 4-methoxyphenyl] cyclopentadienyl titanium triisopropoxide; [Tetramethyl, 4- Methoxyphenyl] cyclopentadienyl titanium triphenoxide;
[Tetramethyl, 4-methylphenyl] cyclopentadienyl titanium trimethoxide; [Tetramethyl, 4-methylphenyl] cyclopentadienyl titanium triethoxide; [Tetramethyl, 4-methylphenyl] cyclopentadienyl titanium Tri (n-propoxide); [Tetramethyl, 4-methylphenyl] cyclopentadienyl titanium triisopropoxide; [Tetramethyl, 4-methylphenyl] cyclopentadienyl titanium triphenoxide; [Tetramethyl, benzyl] Cyclopentadienyl titanium trimethoxide; [Tetramethyl, benzyl] cyclopentadienyl titanium triethoxide; [Tetramethyl, benzyl] cyclopentadienyl titanium tri (n-propoxide); [Tetramethyl, benzyl]
Cyclopentadienyl titanium triisopropoxide;
[Tetramethyl, benzyl] cyclopentadienyl titanium triphenoxide; [Tetramethyl, 2-methoxyphenyl] cyclopentadienyl titanium trimethoxide;
[Tetramethyl, 2-methoxyphenyl] cyclopentadienyl titanium triethoxide; [Tetramethyl, 2-
Methoxyphenyl] cyclopentadienyl titanium triphenoxide; [Tetramethyl, ethyl] cyclopentadienyl titanium trimethoxide; [Tetramethyl, ethyl] cyclopentadienyl titanium triethoxide; [Tetramethyl, ethyl] cyclopentadioxide Phenyl titanium tri (n-propoxide); [tetramethyl, ethyl] cyclopentadienyl titanium triisopropoxide; [tetramethyl, ethyl] cyclopentadienyl titanium triphenoxide; [tetramethyl, n-butyl] cyclopenta Dienyl titanium trimethoxide; [tetramethyl, n
-Butyl] cyclopentadienyl titanium triethoxide; [tetramethyl, n-butyl] cyclopentadienyl titanium tri (n-propoxide); [tetramethyl,
[n-butyl] cyclopentadienyl titanium triisopropoxide; [tetramethyl, n-butyl] cyclopentadienyl titanium triphenoxide; [tetramethyl, phenyl] cyclopentadienyl titanium trimethoxide;
[Tetramethyl, phenyl] cyclopentadienyl titanium triethoxide; [Tetramethyl, phenyl] cyclopentadienyl titanium triphenoxide; [Tetramethyl, trimethylsilyl] cyclopentadienyl titanium trimethoxide; [Tetramethyl, trimethylsilyl] Cyclopentadienyl titanium triphenoxide; pentamethylcyclopentadienyl titanium trimethoxide; pentamethylcyclopentadienyl titanium triethoxide;
Pentamethylcyclopentadienyl titanium tri (n-propoxide); pentamethylcyclopentadienyl titanium triisopropoxide; pentamethylcyclopentadienyl titanium tri (n-butoxide); pentamethylcyclopentadienyl titanium triiso Butoxide; pentamethylcyclopentadienyl titanium tri (sec-butoxide); pentamethylcyclopentadienyl titanium tri (t-butoxide); pentamethylcyclopentadienyl titanium tri (cyclohexoxide); pentamethylcyclopentadienyl Titanium triphenoxide; cyclopentadienyl titanium tribenzyl; indenyl titanium trimethoxide; indenyl titanium triethoxide; indenyl titanium trimethyl; indenyl titanium tribenzyl; cyclopen Dienyl titanium tri (methanesulfonyl); trimethyl cyclopentadienyl titanium (tri benzenesulfonyl); tetramethylcyclopentadienyl titanium tri (ethanesulfonyl); pentamethylcyclopentadienyltitanium tri (methanesulfonyl);
Cyclopentadienyl titanium tris (dimethylamide); trimethylcyclopentadienyl titanium tris (dimethylamide); pentamethylcyclopentadienyl titanium tris (dibenzylamide); pentamethylcyclopentadienyl titanium tris (dimethylamide);
Pentamethylcyclopentadienyl titanium tris (diethylamide); cyclopentadienyl titanium tri (nitro); pentamethylcyclopentadienyl titanium tri (nitro), etc., and compounds in which titanium in these compounds is replaced with zirconium or hafnium Can be mentioned.

Further, cyclopentadienyl titanium dimethyl monochloride; cyclopentadienyl titanium monoethyl dichloride; cyclopentadienyl titanium di (n
-Propyl) monochloride; cyclopentadienyl titanium diisopropyl monochloride; cyclopentadienyl titanium di (n-butyl) monochloride; cyclopentadienyl titanium diisobutyl monochloride; cyclopentadienyl titanium di (sec-butyl) mono Chloride; cyclopentadienyl titanium di (t-butyl) monochloride; 1,2-dimethylcyclopentadienyl titanium dimethyl monochloride; 1,2,4-trimethylcyclopentadienyl titanium dimethyl monochloride; 3,
4-tetramethylcyclopentadienyltitanium dimethylmonochloride; pentamethylcyclopentadienyltitanium dimethylmonochloride; cyclopentadienyltitanium monochlorodimethoxide; cyclopentadienyltitaniumdichloromonomethoxide; cyclopentadienyltitaniumdichloromono Ethoxide; cyclopentadienyltitanium monochlorodioxide (n-propoxide); cyclopentadienyltitanium monochlorodithiopropoxide; cyclopentadienyltitanium monochlorodiphenoxide; dimethylcyclopentadienyltitanium monochlorodimethoxide;
Dimethylcyclopentadienyl titanium monochlorodioxide; dimethylcyclopentadienyl titanium monochlorodioxide (n-propoxide); dimethylcyclopentadienyl titanium monochlorodiisopropoxide; dimethylcyclopentadienyl titanium monochlorodiphenoxide;
Di (t-butyl) cyclopentadienyl titanium monochlorodimethoxide; Bis (trimethylsilyl) cyclopentadienyl titanium monochlorodimethoxide; Trimethylcyclopentadienyl titanium monochlorodimethoxide;
Trimethylcyclopentadienyl titanium monochlorodiphenoxide; triethylcyclopentadienyl titanium monochlorodimethoxide; [bis (dimethylsilyl), methyl] cyclopentadienyl titanium monochlorodimethoxide; tetramethylcyclopentadienyl titanium monochlorodimethoxide; tetra Methylcyclopentadienyl titanium dichloromonomethoxide; Tetramethylcyclopentadienyl titanium monochlorodi (n-butoxide);
Tetramethylcyclopentadienyl titanium monochloroisobutoxide; Tetramethylcyclopentadienyl titanium monochlorolog (sec-butoxide); Tetramethylcyclopentadienyl titanium monochlorolog (t-butoxide); [Tetramethyl, 4-methoxyphenyl ] Cyclopentadienyl titanium monochlorodimethoxide;
[Tetramethyl, 4-methylphenyl] cyclopentadienyl titanium monochlorodimethoxide; [Tetramethyl, benzyl] cyclopentadienyl titanium monochlorodimethoxide; [Tetramethyl, benzyl] cyclopentadienyl titanium monochlorodiphenoxide; [Tetra Methyl, 2-methoxyphenyl] cyclopentadienyl titanium monochlorodimethoxide; [Tetramethyl, ethyl] cyclopentadienyl titanium monochlorodimethoxide; [Tetramethyl, ethyl] cyclopentadienyl titanium monochlorodiethoxide; [Tetramethyl , N-Butyl] cyclopentadienyl titanium monochlorodiethoxide; [Tetramethyl, n-butyl] cyclopentadienyl titanium monochlorodiethyl (n-propoxide); [Tetramethyl, n-butyl ] Cyclopentadienyl titanium monochlorodiisopropoxide; [Tetramethyl, phenyl] cyclopentadienyl titanium monochlorodimethoxide; [Tetramethyl, trimethylsilyl] cyclopentadienyl titanium monochlorodimethoxide; pentamethylcyclopentadienyl titanium monochloro Dimethoxide;
Pentamethylcyclopentadienyl titanium dichloromonomethoxide; pentamethylcyclopentadienyl titanium monochlorodiethoxide; pentamethylcyclopentadienyl titanium monochlorodioxide (cyclohexoxide); pentamethylcyclopentadienyl titanium monochlorodiphenoxide; Indenyl titanium monochlorodimethoxide; cyclopentadienyl titanium monochlorodimethane (methanesulfonyl); pentamethylcyclopentadienyl titanium monochlorobis (diethylamide); pentamethylcyclopentadienyl titanium monochlorobis [di (n-butyl) amide] Pentamethylcyclopentadienyl titanium dichloro (dimethylamide); pentamethylcyclopentadienyl titanium dichloro (diphenylamide);
Pentamethylcyclopentadienyl titanium dichloro (methylethylamide); Pentamethylcyclopentadienyl titanium dichloro (t-butyltrimethylsilylamide); Pentamethylcyclopentadienyl titanium dimethoxy (diphenylamide); Pentamethylcyclopentadienyl titanium Monochlorobis (diethylphosphide); pentamethylcyclopentadienyl titanium monochlorobis [di (n-butyl) phosphide]; pentamethylcyclopentadienyl titanium dichloro (dimethylphosphide); pentamethylcyclopentadienyl titanium dimethoxy ( Dimethyl phosphide); pentamethylcyclopentadienyl titanium dichloro (diphenyl phosphide); pentamethyl cyclopentadienyl titanium dichloro (methyl ethyl) Osufido); pentamethylcyclopentadienyl titanium dichloro (t-butyl trimethylsilyl phosphinothricin de); pentamethylcyclopentadienyl titanium dimethoxy (diphenyl phosphinate de); cyclopentadienyl titanium trichloride; n-
Butylcyclopentadienyl titanium trichloride; Tetramethyl cyclopentadienyl titanium trichloride; Pentamethyl cyclopentadienyl titanium trichloride;
Pentaethylcyclopentadienyl titanium trichloride; [Tetramethyl, n-butyl] cyclopentadienyl titanium trichloride; Tetraisopropylcyclopentadienyl titanium trichloride; Tetraphenylcyclopentadienyl titanium trichloride; Novornacyclopenta Dienyl titanium trichloride; indenyl titanium trichloride; 4,5,6,7-tetrahydroindenyl titanium trichloride; [1,2,3-trimethyl, 4,
5,6,7-Tetrahydro] indenyl titanium trichloride; [1,2,3,4,5,6,7-heptamethyl]
Indenyl titanium trichloride; pentamethylcyclopentadienyl titanium trifluoride; pentamethylcyclopentadienyl titanium tribromide; pentamethylcyclopentadienyl titanium triiodide, and the like, and titanium in the compound In place of, corresponding compounds containing zirconium and hafnium are mentioned.

In the polymerization catalyst of the present invention, the transition metal compound as the component (A) may be used alone or in combination of two or more kinds. In the polymerization catalyst of the present invention, as the component (B), a compound capable of reacting with the transition metal compound of the component (A) or a derivative thereof to form an ionic complex is used.

The component (B) is (B-1)
Ionic complex that reacts with the transition metal compound of component (A)
Forming ionic compound, (B-2) aluminoxa
And (B-3) Lewis acid. (B-
As the component 1), the transition metal compound of the component (A) and
An ionic compound that reacts to form an ionic complex
Any of them can be used, but the following general formula
(III) ([L¹-R¹]^{k +})_a([D]^-)_b ... (III) and general formula (IV) ([L^Two]^{k +})_a([D]^-)_b ... At least one selected from the compounds represented by (IV) is preferred.
It is used well. Odors of the above general formulas (III) and (IV)
L^TwoIs M^Two, R^TwoR^ThreeM^Three, R^Four _ThreeC or R^Five M^Three
Indicates L¹Is a Lewis base, [D]^-Is a non-coordinating ani
On [D¹] ^-Or [D^Two]^-Is shown. Where [D¹]
^-Is an anion in which multiple groups are bound to an element, that is, [M¹
G¹G^Two... G^f]^-(Where M¹Is Periodic Table No. 5
~ Group 15 element, preferably Group 13 ~ 15 element of the Periodic Table
Is shown. G¹~ G^fAre hydrogen atom and halogen atom, respectively
Child, alkyl group having 1 to 20 carbon atoms, di group having 2 to 40 carbon atoms
Alkylamino group, C1-C20 alkoxy group, charcoal
Aryl group having 6 to 20 carbon atoms, aryl having 6 to 20 carbon atoms
Oxy group, C 7-40 alkylaryl group, carbon
C 7-20 arylalkyl group, C 1-20 ha
Rogen-substituted hydrocarbon group, acyloxy having 1 to 20 carbon atoms
Group, organic metalloid group, or hetero atom having 2 to 20 carbon atoms
A child-containing hydrocarbon group is shown. G¹~ G^fTwo or more of them
It may form a ring. f is [(central metal M¹The atom of
Value) +1]. ), [D^Two]^-Is the acid
Bren whose logarithm (pKa) of the reciprocal of the dissociation constant is -10 or less
Sted acid alone or a combination of Bronsted acid and Lewis acid
Combined conjugate base, or commonly defined as superacid
Is a conjugated base. Also, even if the Lewis base is coordinated
Good. Also, R¹Is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms
Group, aryl group having 6 to 20 carbon atoms, alkylaryl
A group or an arylalkyl group, R^TwoAnd R^ThreeIs it
Cyclopentadienyl group and substituted cyclopentadienyl group
Group, indenyl group or fluorenyl group, R^FourIs the carbon number
1-20 alkyl groups, aryl groups, alkylaryl
Represents a group or an arylalkyl group. R^Five Is Tetrapheni
Shows macrocyclic ligands such as ruporphyrin and phthalocyanine
You. k is [L¹-R¹], [L^Two] With an ion valence of 1 to
3 is an integer, a is an integer of 1 or more, and b = (k × a).
M^TwoIs an element of Groups 1 to 11, 11 to 13 and 17 of the periodic table
Including, M^ThreeIs an element of Group 7 to 12 of the periodic table
Show.

Specific examples of L ¹ include ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine,
Amines such as N, N-dimethylaniline, trimethylamine, triethylamine, tri-n-butylamine, methyldiphenylamine, pyridine, p-bromo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline, and triethylphosphine Phosphines such as triphenylphosphine and diphenylphosphine; thioethers such as tetrahydrothiophene; esters such as ethyl benzoate; and nitriles such as acetonitrile and benzonitrile.

Specific examples of R ¹ include hydrogen, a methyl group,
Examples thereof include an ethyl group, a benzyl group and a trityl group. Specific examples of R ² and R ³ include a cyclopentadienyl group, a methylcyclopentadienyl group, an ethylcyclopentadienyl group and a pentamethylcyclopenta group. A dienyl group etc. can be mentioned. As a specific example of R ⁴ ,
Examples thereof include a phenyl group, p-tolyl group, p-methoxyphenyl group, and the like. Specific examples of R ⁵ include tetraphenylporphine, phthalocyanine, allyl, methallyl and the like. In addition, specific examples of M ² include Li, Na, K, Ag, Cu, Br, I, and I ₃ , and specific examples of M ³ include Mn,
Fe, Co, Ni, Zn etc. can be mentioned.

[D ¹ ] ^- , that is, [M ¹ G ¹ G
² ... G ^f ], specific examples of M ¹ include B, A
1, Si, P, As, Sb, etc., preferably B and Al
Is mentioned. Specific examples of G ¹ and G ^{2 to} G ^f include a dimethylamino group and a diethylamino group as a dialkylamino group, a methoxy group, an ethoxy group, an n-butoxy group as an alkoxy group or an aryloxy group,
As a hydrocarbon group such as phenoxy group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group,
Fluorine, chlorine, bromine, etc. as halogen atoms such as isobutyl group, n-octyl group, n-eicosyl group, phenyl group, p-tolyl group, benzyl group, 4-t-butylphenyl group, 3,5-dimethylphenyl group. Iodine, p-fluorophenyl group as a hydrocarbon group containing a hetero atom, 3,5
-Difluorophenyl group, pentachlorophenyl group,
3,4,5-trifluorophenyl group, pentafluorophenyl group, 3,5-bis (trifluoromethyl) phenyl group, bis (trimethylsilyl) methyl group, etc. as organic metalloid group pentamethylantimony group, trimethylsilyl group, trimethyl Examples thereof include germyl group, diphenylarsine group, dicyclohexylantimony group and diphenylboron.

Further, a non-coordinating anion, that is, pKa
There -10 or less Bronsted acid alone or a combination of conjugate base of a Bronsted acid and Lewis acid [D ^{2] -} trifluoromethanesulfonic acid anion Specific examples of (CF ₃ SO ₃₎ ^-, bis (trifluoromethanesulfonyl ) Methyl anion, bis (trifluoromethanesulfonyl) benzyl anion, bis (trifluoromethanesulfonyl) amide, perchlorate anion (Cl
O ₄ ) ^- , trifluoroacetic acid anion (CF ₃ CO ₂ )
^- , Hexafluoroantimony anion (Sb
F ₆ ) ^- , Fluorosulfonate anion (FS
O ₃ ) ^- , Chlorosulfonate anion (ClS
O ₃ ) ⁻ , fluorosulfonate anion / 5-antimony fluoride (FSO ₃ / SbF ₅ ) ⁻ , fluorosulfonate anion / 5-arsenic fluoride (FSO ₃ / As
F ₅ ) ^- , trifluoromethanesulfonic acid / 5-antimony fluoride (CF ₃ SO ₃ / SbF ₅ ) ^{-, and the} like.

Specific examples of the ionic compound which reacts with the transition metal compound of the component (A) to form an ionic complex, that is, the compound of the component (B-1) are as follows.
Triethylammonium tetraphenylborate, tri-n-butylammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyl (tri-n-butyl) ammonium tetraphenylborate, benzyl tetraphenylborate (tri-n- Butyl) ammonium, dimethyl diphenyl ammonium tetraphenyl borate, triphenyl (methyl) ammonium tetraphenyl borate, trimethylanilinium tetraphenyl borate, methyl pyridinium tetraphenyl borate, benzyl pyridinium tetraphenyl borate, methyl tetraphenyl borate (2-cyanopyridinium) , Tetrakis (pentafluorophenyl) borate triethylammonium, tetrakis (pentafluorophenyl) ) Tri-n-butylammonium borate, tetrakis (pentafluorophenyl) triphenylammonium borate, tetrakis (pentafluorophenyl) tetra-n-butylammonium borate, tetraethylammonium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) Benzyl (tri-n-butyl) ammonium borate, methyldiphenylammonium tetrakis (pentafluorophenyl) borate, triphenyl (methyl) ammonium tetrakis (pentafluorophenyl) borate, methylanilinium tetrakis (pentafluorophenyl) borate, tetrakis (penta) Fluorophenyl) borate dimethylanilinium, tetrakis (pentafluorophenyl) borate trimethylanilinium, tetrakis Methylpyridinium pentafluorophenyl) borate, Benzylpyridinium tetrakis (pentafluorophenyl) borate, Methyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), Benzyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), Tetrakis ( Methyl (4-cyanopyridinium) pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) borate, dimethylanilinium tetrakis [bis (3,5-ditrifluoromethyl) phenyl] borate, ferrocenium tetraphenylborate, tetraphenyl Silver borate, trityl tetraphenylborate, tetraphenylporphyrin manganese tetraphenylborate, tetrakis (pentafluorophenyl) borate fe Rothenium, tetrakis (pentafluorophenyl)
Boric acid (1,1′-dimethylferrocenium), tetrakis (pentafluorophenyl) borate decamethylferrocenium, tetrakis (pentafluorophenyl) silver borate, tetrakis (pentafluorophenyl) trityl borate, tetrakis (pentafluorophenyl) Lithium borate, sodium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate tetraphenylporphyrin manganese, silver tetrafluoroborate, silver hexafluorophosphate, silver hexafluoroarsenate,
Examples thereof include silver perchlorate, silver trifluoroacetate, and silver trifluoromethanesulfonate. This (B-
The ionic compound which reacts with the transition metal compound of the component (A) to form an ionic complex, which is the component 1), may be used alone or in combination of two or more. On the other hand, as the aluminoxane as the component (B-2),
General formula (VII)

[0019]

Embedded image

[Wherein R ⁹ is an alkyl group, an alkenyl group, an aryl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms,
It represents a hydrocarbon group such as an arylalkyl group or a halogen atom, and w represents a degree of polymerization, and is usually an integer of 3 to 50, preferably 7 to 40. In addition, each R ⁹ may be the same or different. Represented by the chain aluminoxane,
And general formula (VIII)

[0021]

Embedded image

[In the formula, R ⁹ and w are the same as defined above. And a cyclic aluminoxane represented by the following formula: Examples of the method for producing the aluminoxane include a method in which an alkylaluminum and a condensing agent such as water are brought into contact with each other, but the means therefor is not particularly limited, and the reaction may be performed according to a known method. For example, a method in which an organoaluminum compound is dissolved in an organic solvent and then brought into contact with water, a method in which an organoaluminum compound is initially added at the time of polymerization and water is added later, water of crystallization contained in a metal salt, etc. , A method of reacting water adsorbed to an inorganic substance or an organic substance with an organoaluminum compound, a method of reacting a tetraalkyldialuminoxane with a trialkylaluminum, and further reacting with water. The aluminoxane may be toluene-insoluble.

These aluminoxanes can be classified as shown below. (A) an alkylaluminoxane produced using a single alkylaluminum (organoaluminum) compound,
For example, methylaluminoxane, ethylaluminoxane, n-propylaluminoxane, isopropylaluminoxane, n-butylaluminoxane, isobutylaluminoxane, sec-butylaluminoxane, t-butylaluminoxane and the like. (B) A mixed alkylaluminoxane in which two or more kinds are selected from the alkylaluminoxanes produced in the above (a), and these are mixed at a predetermined ratio. (C) Copolymerized alkylaluminoxane obtained by mixing two or more kinds of alkylaluminum (organoaluminum) compounds in a predetermined ratio during the production by the above-mentioned methods (1), for example, methyl-ethylaluminoxane, methyl-n-propyl. Aluminoxane, methyl-isopropylaluminoxane, methyl-n-butylaluminoxane,
Methyl-isobutylaluminoxane, ethyl-n-propylaluminoxane, ethyl-isopropylaluminoxane, ethyl-n-butylaluminoxane, ethyl-isobutylaluminoxane and the like. These aluminoxanes may be used alone or in combination of two or more. Further, among aluminoxanes, alkylaluminoxanes are particularly preferred. In addition, in the aluminoxane thus obtained, the alkylaluminum as a synthesis raw material may remain and be contained as an impurity, but in the present invention, it may be used as it is.

The component (B-3) Lewis acid is not particularly limited and may be an organic compound or a solid inorganic compound. The organic compound is a boron compound or an aluminum compound, the inorganic compound is a magnesium compound,
Aluminum compounds and the like are preferably used. Examples of the aluminum compound include aluminum oxide and aluminum chloride, and examples of the magnesium compound include magnesium chloride and diethoxymagnesium.
Examples of the boron compound include triphenylboron, tris (pentafluorophenyl) boron, tris [3,5-bis (trifluoromethyl) phenyl] boron, tris [(4-fluoromethyl) phenyl] boron, trimethylboron, triethylboron. , Tri-n-butylboron, tris (fluoromethyl) boron, tris (pentafluoroethyl) boron, tris (nonafluorobutyl) boron, tris (2,4,6-trifluorophenyl) boron, tris (3,5) -Difluoro) boron, tris [3,5-bis (trifluoromethyl) phenyl] boron, bis (pentafluorophenyl) fluoroboron, diphenylfluoroboron, bis (pentafluorophenyl) chloroboron, dimethylfluoroboron, diethylfluoroboron , The-n-
Examples thereof include butylfluoroboron, pentafluorophenyldifluoroboron, phenyldifluoroboron, pentafluorophenyldichloroboron, methyldifluoroboron, ethyldifluoroboron, n-butyldifluoroboron and the like. These Lewis acids may be used alone or in combination of two or more.

The proportion of the catalyst component (A) and the catalyst component (B) used in the catalyst for polymerization of the present invention is such that, when the compound (B-1) is used as the catalyst component (B), the catalyst activity, etc. From the aspect, it is preferable that the molar ratio is 10: 1 to 1: 100,
The range of 2: 1 to 1:10 is more preferable, and in the case of using the compound (B-2), the molar ratio is preferably 1: 1 to 1: 100,000 from the viewpoint of catalytic activity and the like.
0, more preferably in the range of 1:10 to 1: 10000. The ratio of the (A) catalyst component to the (B-3) catalyst component used is preferably 1: 0.1 to 1: 2000, more preferably 1: 0.
2 to 1: 1000, more preferably 1: 0.5 to 1: 5
A range of 00 is desirable. In the polymerization catalyst of the present invention, as the component (B), the components (B-1) and (B-
The components (2) and (B-3) may be used alone, or two or more types may be appropriately used in combination. In particular, the components (B-1) and (B-2) have catalytic activity and It is preferable in terms of properties of the polymer obtained.

In the polymerization catalyst of the present invention, for the purpose of further improving the catalytic activity and copolymerizability, etc., as the component (C), (a) a reaction product of an organoaluminum compound and a phenolic compound and / or (B) A reaction product of an organoaluminum compound and a boron compound is used.
Examples of the organoaluminum compound used as a raw material for the reaction product of the component (a) include general formula (IX) R ¹⁰ _v AlJ _{3 -v} (IX) [wherein R ¹⁰ has 1 to 20 carbon atoms]. Hydrocarbon group, preferably an alkyl group having 1 to 10 carbon atoms, J is a hydrogen atom, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or a halogen atom, and v is 1 to 3 It is an integer. ]
The compound shown by these is mentioned. Specific examples of the compound represented by the general formula (IX) include trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, methyl aluminum dichloride, ethyl aluminum dichloride, dimethyl aluminum fluoride. , Diisobutylaluminum hydride, diethylaluminium hydride, ethylaluminum sesquichloride and the like. Of these, trialkylaluminum is preferred. These organoaluminum compounds may be used alone or in combination of two or more. Further, as the phenolic compound, for example, a hydrogen atom bonded to an aromatic ring such as a benzene ring or a naphthalene ring is at least one hydroxyl group or at least one hydroxyl group and at least one substituent other than a hydroxyl group. Mention may be made of substituted compounds.

Here, examples of the substituent other than the hydroxyl group include
For example, R¹¹, OR¹¹, SR¹¹, NR¹¹R¹²， Halogen source
Child, nitro group, etc. R¹¹, R¹²Is 1 carbon
~ 20 hydrocarbon groups, alkyl groups, cycloalkyl
Groups, aryl groups, aralkyl groups and the like. Alkyl group
Are, for example, methyl group, ethyl group, n-propyl
Group, isopropyl group, n-butyl group, isobutyl group, s
ec-butyl group, t-butyl group, pentyl group, hexyl
Group, octyl group, decyl group, dodecyl group, etc.
Examples of the alkyl group include a cyclopentyl group and a cyclo group.
An aryl group such as a lohexyl group is, for example,
Examples of aralkyl groups such as phenyl and tolyl are
Examples include benzyl and phenethyl groups.
Wear. OR¹¹As specific examples of, methoxy group, ethoxy
Group, n-propoxy group, isopropoxy group, n-butoxy group
Si group, isobutoxy group, sec-butoxy group, t-but
Xy group, pentoxy group, hexoxy group, octoxy group,
Alkoxy group such as cyclohexoxy group, phenoxy group
And an aryloxy group. NR
¹¹R¹²Specific examples of are dimethylamino group, diethyl
Amino group, di (n-propyl) amino group, diisopropyi
Ruamino group, di (n-butyl) amino group, diisobutyl
Amino group, di (sec-butyl) amino group, di (t-butyl)
Cyl) amino group, dipentylamino group, dihexylamido
Group, dioctylamino group, diphenylamino group, dibe
And the like. Also halo
Examples of the gen atom include chlorine, bromine, iodine and fluorine.
Can be

As the phenolic compound, a phenolic compound substituted with a hydrocarbon group having 1 to 20 carbon atoms is preferable, and particularly, the α, α'-position of the hydroxyl group has 1 to 2 carbon atoms.
Phenolic compounds substituted with 0 hydrocarbon groups are preferred. Specific examples of the phenolic compound include phenol; 2-methylphenol; 2-ethylphenol; 2-n-propylphenol; 2-isopropylphenol; 2-n-butylphenol; 2-sec-butylphenol; 2-tert-. Butylphenol; 3
-Tert-butylphenol; 4-tert-butylphenol; 4-tert-octylphenol; 2-
n-dodecylphenol; 2-phenylphenol; 4
-Phenylphenol; 2,6-dimethylphenol;
2,6-diethylphenol; 2,6-di-tert-
Butylphenol; 2,4-di-tert-butylphenol; 2-tert-butyl-4-methylphenol; 2-tert-butyl-5-methylphenol; 2
-Tert-butyl-6-methylphenol; 2-n-
Dodecyl-4-methylphenol; 4-n-dodecyl-
2-Methylphenol; 2,6-Diphenylphenol; 2,6-Di-tert-butyl-4-methylphenol; 2,6-Di-tert-butyl-4-ethylphenol; 2,4,6-Tri- tert-Butylphenol; 2,2'-methylenebis (4-methyl-6-ter
t-butylphenol); 2,2′-methylenebis (4
-Ethyl-6-tert-butylphenol); 4,
4'-methylenebis (2,6-di-tert-butylphenol); 4,4'-butylidenebis (6-tert
-Butyl-m-cresol); 4,4′-thiobis (6
-Tert-butyl-m-cresol); α-naphthol; β-naphthol; 2-fluorophenol; 3-fluorophenol; 4-fluorophenol;
2,5-difluorophenol; 2,6-difluorophenol; 2-methoxyphenol; 3-methoxyphenol; 4-methoxyphenol; 2,6-di-tert-butyl-4-methoxyphenol; N, N -Dimethyl-3-aminophenol;
N, N-diethyl-3-aminophenol; N, N-di-n-butyl-3-aminophenol; 2,6-di-t
ert-butyl-4-dimethylaminophenol; 2-
3-Nitrophenol; 3-Nitrophenol; 4-Nitrophenol; 2-Nitro-4-methylphenol; 3-
4-nitro-3-methylphenol; 5-nitro-2-methylphenol; 5-nitro-2-methylphenol; catechol; resorcinol; hydroquinone; 3-methylcatechol; 4-methylcatechol; 4-tert-butylcatechol; 2- 5-methylresorcinol; 5-methylresorcinol; methylhydroquinone; tert-butylhydroquinone; 2,5-di-tert-butylhydroquinone; 1,2-dihydroxynaphthalene; 1,4-
Dihydroxynaphthalene; 1,5-dihydroxynaphthalene; 1,6-dihydroxynaphthalene; 1,7-dihydroxynaphthalene; 2,3-dihydroxynaphthalene; 2,7-dihydroxynaphthalene; pyrogallol;
Phloroglucinol; 1,2,4-trihydroxybenzene; hexahydroxybenzene; 4,4'-thiobis (2,6-di-tert-butylphenol); 3,5
-Di-tert-butyl-4-hydroxybenzyl chloride and the like. These phenolic compounds may be used alone or in combination of two or more.

The ratio of the phenolic compound to the organoaluminum compound used is preferably a phenolic compound / organoaluminum compound molar ratio of 0.1 to 2.5.
More preferably 0.5 to 2.2, particularly preferably 1.0 to 2.0.
Is selected in the range. The reaction conditions are not particularly limited, but a method of mixing and reacting them in a suitable inert solvent such as benzene, toluene, hexane and heptane at a temperature of 40 ° C. or less while stirring is advantageous. is there. As the reaction product of the organoaluminum compound and the phenolic compound thus obtained,
In particular, general formula (V) R ⁶ _n Al (OAr) _3-n ... (V) [In the formula, R ⁶ is a hydrocarbon group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms. , Ar has 6 to 20 carbon atoms
And n represents a real number of 1 to 2, and when there are a plurality of OArs, the plurality of OArs may be the same or different. ] Are preferred.

Specific examples of the organoaluminum compound represented by the general formula (V) include dimethyl aluminum phenoxide, methyl aluminum diphenoxide, dimethyl aluminum (2-methyl phenoxide), dimethyl aluminum (2-ethyl phenoxide) and dimethyl. Aluminum (2-n-propylphenoxide), dimethylaluminum (2-tert-butylphenoxide), dimethylaluminum (4-tert-butylphenoxide), dimethylaluminum (2,6-di-t).
tert-butylphenoxide), methylaluminummudi (2,6-di-tert-butylphenoxide), dimethylaluminum (2,4-di-tert-butylphenoxide), methylaluminum di (2,4-di-te)
rt-butylphenoxide), dimethylaluminum (2,6-di-tert-butyl-4-methylphenoxide), methylaluminum di (2,6-di-tert)
-Butyl-4-methylphenoxide), dimethylaluminum (2,6-di-tert-butyl-4-ethylphenoxide), methylaluminum di (2,6-di-t)
tert-butyl-4-ethylphenoxide), dimethylaluminum (2,4,6-tri-tert-butylphenoxide), methylaluminum di (2,4,6-tri-tert-butylphenoxide), dimethylaluminum (2 6-dimethylphenoxide), methylaluminum di (2,6-dimethylphenoxide), dimethylaluminum (2,6-diphenylphenoxide),
Methyl aluminum di (2,6-diphenylphenoxide), dimethyl aluminum (2,6-difluorophenoxide), methyl aluminum di (2,6-difluorophenoxide), methyl aluminum di (1,1-bi-2-naphthoxide), etc. And, in addition to these compounds, a methyl group bonded to aluminum in the compound is an ethyl group, an n-propyl group, an isopropyl group,
And compounds substituted with -butyl group, isobutyl group, n-hexyl group, n-octyl group and the like.

On the other hand, as the organoaluminum compound used as the raw material of the reaction product of the component (b), the same organoaluminum compound used as the raw material of the reaction product of the component (a) can be mentioned. Further, as the boron compound, a compound represented by the general formula (II)

[0032]

Embedded image

[In the formula, X, Y and Z each represent a sulfur atom or an oxygen atom, which may be the same or different from each other. ] The compound represented by these is used. Examples of the compound represented by the general formula (II) include trihydroxyboron (boric acid), dihydroxyhydrothioxyborone, hydroxydihydrothioxyboron, trihydrothioxyboron and the like. Among these, trihydroxyboron, dihydroxyhydrothioxyboron and hydroxydihydrothioxyboron are preferable, and trihydroxyboron is particularly preferable. The boron compound and the organoaluminum compound are used in a substantially stoichiometric amount, that is, a molar ratio of substantially 1: 3. The reaction of both components is usually carried out in an inert solvent under an inert gas atmosphere. Further, the contacting method of both components is not particularly limited, and various methods such as (1) adding and dissolving a boron compound in a toluene solvent and then dissolving the organoaluminum compound as it is or toluene of the organoaluminum compound A method of adding a suspension little by little, (2) a method of adding a hexane diluted solution of a boron compound to a hexane diluted solution of an organoaluminum compound, and (3) a method of diluting a boron compound and an organoaluminum compound in toluene. It is possible to use a method such as dropping at a constant speed into another container to cause a reaction. In this case, the reaction temperature and the reaction time are not particularly limited, but generally both components are mixed at a low temperature, for example, -78 to 30 ° C, preferably -78 to 10 ° C, and then gradually heated, It is desirable to set the temperature to about -10 to 80 ° C. At this time, the temperature may be raised to the boiling point of the reaction solvent, if necessary. The reaction time is usually about 2 to 48 hours.

The reaction product of the organoaluminum compound and the boron compound thus obtained is particularly represented by the general formula (VI) (R ⁷ R ⁸ AlO) ₃ B (VI) [wherein R ⁷ and R ⁸ each represent a hydrocarbon group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms, which may be the same or different.
The two R ⁷ R ⁸ AlO may be the same or different. ]
An organoaluminum compound represented by is preferable. Specific examples of the organoaluminum compound represented by the general formula (VI) include tris (dimethylaluminoxy) borane,
Tris (diethylaluminoxy) borane, Tris (di-
n-propylaluminoxy) borane, tris (diisopropylaluminoxy) borane, tris (diisobutylaluminoxy) borane, tris (di-n-hexylaluminoxy) borane, tris (di-n-octylaluminoxy) borane, tris ( Examples thereof include methylethylaluminoxy) borane and tris (ethylisobutylaluminoxy) borane.

In the polymerization catalyst of the present invention, as the component (C), one type of component (A) may be used, or two or more types may be used in combination. Further, the component (b) may be used alone or in combination of two or more. Furthermore, one or more components (a) and one or more components (b) may be used in combination. The ratio of the (A) catalyst component to the (C) catalyst component used is preferably 1: 1 to 1: 10000, more preferably 1: 5 to 1: 2000, and more preferably 1: 1 to 1: 10000 in terms of molar ratio from the viewpoint of catalytic activity. Preferably 1:10
A range of 1: 1000 is desirable.

In the olefin polymerization catalyst of the present invention, as long as the object of the present invention is not impaired, if desired,
In addition to the components (A), (B) and (C),
Other catalyst components may be included. Also, if desired,
Each catalyst component may be brought into contact with an appropriate carrier to be supported on the carrier. Examples of the carrier include inorganic oxides such as silica and alumina, inorganic halides such as magnesium chloride, inorganic alkoxides such as diethoxymagnesium, and polymers such as polystyrene.

In the method for producing an olefin polymer of the present invention, in the presence of the polymerization catalyst prepared as described above, homopolymerization of olefins or olefins with other olefins and / or other polymerizable non-polymerizable Copolymerization with a saturated compound is carried out. The olefins are not particularly limited and include, for example, ethylene; propylene; butene-1; pentene-1; hexene-1; heptene-1; octene-
1; nonene-1; decene-1; 4-phenylbutene-
1; 6-phenylhexene-1; 3-methylbutene-
1; 4-methylpentene-1; 3-methylpentene-
1; 3-methylhexene-1; 4-methylhexene-
1; 5-methylhexene-1; 3,3-dimethylpentene-1; 3,4-dimethylpentene-1; 4,4-dimethylpentene-1; 3,5,5-trimethylhexene-
1; α-olefins such as vinylcyclohexane, hexafluoropropene; tetrafluoroethylene; 2-fluoropropene; fluoroethylene; 1,1-difluoroethylene; 3-fluoropropene; trifluoroethylene; 3,4-dichlorobutene-1. And halogen-substituted α-olefins such as Further, the other olefins described above may be appropriately selected from the above olefins. In the present invention, the olefins may be used alone or in combination of two or more.

In the present invention, other polymerizable unsaturated compounds copolymerized with the above olefins include, for example, cyclic olefins, cyclic diolefins, chain conjugated diolefins, chain non-conjugated diolefins. , Aromatic vinyl compounds, unsaturated esters, lactones, lactams, epoxides and the like can be used. Examples of the cyclic olefins include cyclopentene; cyclohexene; norbornene; 5-methylnorbornene; 5
-Ethyl norbornene; 5-propyl norbornene;
5,6-dimethylnorbornene; 1-methylnorbornene; 7-methylnorbornene; 5,5,6-trimethylnorbornene; 5-phenylnorbornene; 5-benzylnorbornene and the like, and examples of cyclic diolefins include 5- Examples include ethylidene norbornene; 5-vinyl norbornene; dicyclopentadiene; norbornadiene.

As the chain conjugated diolefins,
For example, 1,3-butadiene; isoprene and the like, and as the chain non-conjugated diolefins, for example, 1,
4-hexadiene; 4-methyl-1,4-hexadiene; 5-methyl-1,4-hexadiene; 5-methyl-
1,4-dienes such as 1,4-heptadiene, 1,5
-Hexadiene; 3-methyl-1,5-hexadiene;
3-Ethyl-1,5-hexadiene; 3,4-Dimethyl-1,5-hexadiene; 1,5-heptadiene; 5-
Methyl-1,5-heptadiene; 6-methyl-1,5-
Heptadiene; 1,5-octadiene; 5-methyl-
1,5-octadiene; 1,5-dienes such as 6-methyl-1,5-octadiene, 1,6-octadiene;
6-methyl-1,6-octadiene; 7-methyl-1,
6-octadiene; 7-ethyl-1,6-octadiene; 1,6-nonadiene; 7-methyl-1,6-nonadiene; 4-methyl-1,6-nonadiene and the like 1,6-
Dienes, 1,7-octadiene; 3-methyl-1,7
-Octadiene; 3-ethyl-1,7-octadiene;
3,4-Dimethyl-1,7-octadiene; 3,5-Dimethyl-1,7-octadiene; 1,7-Nonadiene;
Examples thereof include 1,7-dienes such as 8-methyl-1,7-nonadiene, 1,11-dodecadiene and 1,13-tetradecadiene.

Examples of the aromatic vinyl compound include styrene and α-methylstyrene, p-methylstyrene; m-methylstyrene; o-methylstyrene; pt-butylstyrene; p-phenylstyrene. Alkyl or aryl styrenes, p-methoxystyrene; m-methoxystyrene; p-ethoxystyrene; pn-propoxystyrene; alkoxystyrenes such as pn-butoxystyrene, p-chlorostyrene; p-bromostyrene Halogenated styrenes such as p-iodostyrene, p-trimethylsilylstyrene;
m-trimethylsilylstyrene; o-trimethylsilylstyrene; p-dimethylphenylsilylstyrene; p-
Methyldiphenylsilylstyrene; alkyl- or aryl-group-containing silylstyrenes such as p-triphenylsilylstyrene, p-dimethylchlorosilylstyrene; p
-Methyldichlorosilylstyrene; halogen-containing silylstyrenes such as p-trichlorosilylstyrene, p-
(2-propenyl) styrene; m- (2-propenyl)
Styrene; p- (3-butenyl) styrene; m- (3-
Butenyl) styrene; o- (3-butenyl) styrene;
Alkenyl styrenes such as p- (3-butenyl) -α-methylstyrene, and further 4-vinylbiphenyl; 3
-Vinyl biphenyl; vinyl biphenyls such as 2-vinyl biphenyl; 1- (4-vinylphenyl) naphthalene; vinylphenyl naphthalene such as 2- (3-vinylphenyl) naphthalene; 1- (4-vinylphenyl)
Anthracene; vinylphenylanthracenes such as 2- (4-vinylphenyl) anthracene; 1- (4-vinylphenyl) phenanthrene; vinylphenylphenanthrenes such as 2- (4-vinylphenyl) phenanthrene; 1- (4-vinyl Phenyl) pyrene; 2- (4
Examples thereof include vinylphenylpyrenes such as -vinylphenyl) pyrene.

Next, examples of the unsaturated esters include ethyl acrylate and methyl methacrylate, and examples of the lactones include β-propiolactone and β.
-Butyrolactone, γ-butyrolactone and the like, lactams such as ε-caprolactam and δ-valerolactam and the like, and epoxides such as epoxypropane and 1,2-epoxybutane. In the present invention, the polymerizable unsaturated compound to be copolymerized with the olefin may be used alone, or may be used in combination of two or more kinds, and may be used in combination with the above-mentioned other α-olefins. .

The polymerization method in the present invention is not particularly limited, and any polymerization method such as slurry polymerization method, high temperature solution polymerization method, gas phase polymerization method, bulk polymerization method and the like can be adopted. When a polymerization solvent is used, the solvent is, for example, an inert solvent such as an aliphatic hydrocarbon having 5 to 18 carbon atoms, an alicyclic hydrocarbon, or an aromatic hydrocarbon having 6 to 20 carbon atoms, specifically n. -Pentane, isopentane,
Hexane, heptane, octane, nonane, decane, tetradecane, cyclohexane, benzene, toluene, xylene, ethylbenzene and the like can be mentioned. These may be used alone or in combination of two or more.
Further, the polymerization temperature is not particularly limited, but is usually 0.
To 350 ° C, preferably 20 to 250 ° C. On the other hand, the polymerization pressure is not particularly limited, but is usually selected in the range of 0 to 150 kg / cm ² G, preferably 0 to 100 kg / cm ² G. The polymerization time is usually about 5 minutes to 10 hours. The method for controlling the molecular weight of the polymer includes the selection of the type and amount of each catalyst component, the polymerization temperature, and further the polymerization in the presence of hydrogen. The olefin-based polymer thus obtained has a narrow molecular weight distribution and a relatively wide composition distribution and has excellent physical properties that have never been obtained. The method of the present invention is particularly useful for ethylene-α-olefin copolymerization. Suitable for polymer production.

[0043]

EXAMPLES The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples. Example 1 (1) Preparation of components (C)-(a) 2,6-di-ter was added to 5 ml of a toluene solution having a concentration of 2.0 mol / liter of triisobutylaluminum.
20 ml of a toluene solution having a concentration of 0.5 mol / l of t-butyl-4-ethylphenol was added dropwise at room temperature over 5 minutes, and stirring was continued for 1 hour to complete the reaction. Generation of gas and heat generation were observed during the reaction. The reaction product was determined by proton nuclear magnetic resonance spectroscopy ( ¹ H-NMR) to have no OH group, and diisobutylaluminum (2,6-di-tert-butyl-4-ethylphenoxide) was produced. It was confirmed. (2) Copolymerization of ethylene and 1-octene After replacing the inside of a dry 1 liter polymerization reactor equipped with a stirrer with dry nitrogen, 390 ml of dried n-hexane and 10 ml of 1-octene were added. Then, the (C)-(a) component produced in the above (1) is replaced with Al
0.3 mmol in terms of atom, dimethylanilinium tetrakis (pentafluorophenyl) borate as component (B) 1.5 micromol, pentamethylcyclopentadienyl titanium trimethoxide as component (A) 1.0 micromol After adding a mole and raising the temperature to 80 ° C., introducing ethylene gas,
Polymerization was carried out at 80 ° C. for 10 minutes while maintaining the total pressure at 8 kg / cm ² G.

Immediately after the completion of the polymerization, the pressure was released and methanol was added to the polymerization reactor to stop the polymerization. The contents of the polymerization reactor were put into a large amount of a mixed solution of methanol / hydrochloric acid for deashing. The polymer was separated by filtration and dried under reduced pressure at 80 ° C. for 4 hours to obtain 6.7 g of an ethylene-1-octene copolymer.
The activity was 140 kg / g-Ti. This copolymer has a melting point of 86.3 as measured by a differential scanning calorimeter (DSC).
℃, intrinsic viscosity (135 ℃, in decalin) [η] is 2.28
It was deciliter / g. The molecular weight distribution Mw / Mn (weight average molecular weight / number average molecular weight) determined by gel permeation chromatography (GPC) method is 1.
The peak was as narrow as 97, and the peak of the composition distribution curve determined by the temperature rising fractionation method was 55.5 ° C, and the half-width was as wide as 22.0 ° C.

The method of measuring the molecular weight distribution and the method of measuring the composition distribution are as follows. (1) Measuring method of molecular weight distribution Device: Waters ALC / GPC 150C, column: TSK HM + GMH6 × 2, flow rate: 1.0 ml / min, solvent: 1,2,4-trichlorobenzene, polyethylene by GPC method under the conditions The converted weight average molecular weight Mw and number average molecular weight Mn are calculated, and the molecular weight distribution Mw / M
n was calculated. (2) Method for measuring composition distribution Chromosorb PNAN as a column packing material
A polymer solution of o-dichlorobenzene adjusted to a concentration of about 6 g / liter at 135 ° C. is injected into a column having an inner diameter of 10 mm and a length of 250 mm filled with (80/100 mesh) with a metering pump. This is cooled to room temperature at a rate of 10 ° C./hour to adsorb and crystallize the polymer on the filler.
Thereafter, o-dichlorobenzene is fed at a rate of 2 cc / min at a temperature rising rate of 20 ° C./hour. The eluted polymer is an infrared detector (device: 1-AFox Boro
The concentration was measured by CVF, cell: CaF ₂ ) to obtain a composition distribution curve with respect to the elution temperature, and the temperature position of the main peak and the half-value width of the main peak were obtained.

Example 2 Example 1- (2) was repeated except that the amount of the component (C)-(a) used in Example 1- (2) was changed to 0.5 mmol in terms of Al atom. Copolymerization of ethylene and 1-octene was carried out, and ethylene-1-octene copolymer 6.4g
I got The activity was 133 kg / g-Ti. This copolymer had a melting point of 86.7 ° C. as measured by DSC.

Comparative Example 1 In the same manner as in Example 1- (2), except that 0.5 mmol of triisobutylaluminum was used in place of the component (C)-(a) in Example 1- (2). , Ethylene and 1
-Copolymerization with octene was carried out to obtain 0.3 g of ethylene-1-octene copolymer. The activity was 7 kg / g-Ti. This copolymer has a melting point of 10 6 as measured by DSC.
5 ° C.

Example 3 (1) Preparation of components (C)-(a) 2.6-di-tert-butyl-4-ethylphenol was added to 5 ml of a toluene solution having a concentration of 2.0 mol / liter of triethylaluminum. 20 ml of a toluene solution having a concentration of 0.5 mol / liter was added dropwise at room temperature over 5 minutes, and stirring was continued for 1 hour to complete the reaction. Generation of gas and heat generation were observed during the reaction. (2) Copolymerization of ethylene and 1-octene In Example 1- (2), the component obtained in the above (1) was used as the component (C)-(a) for 0.3 mmol in terms of Al atom. Except for the above, copolymerization of ethylene and 1-octene was carried out in the same manner as in Example 1- (2), and ethylene-
1.1 g of 1-octene copolymer was obtained. 24 kg / activity
g-Ti. This copolymer had a melting point of 97.4 ° C. as measured by DSC.

Example 4 (1) Preparation of components (C)-(a) 2,6-di-ter was added to 5 ml of a toluene solution having a concentration of 2.0 mol / l of triisobutylaluminum.
14 ml of a toluene solution having a concentration of 0.5 mol / l of t-butyl-4-ethylphenol was added at room temperature to 5 ml.
The mixture was added dropwise over a period of 1 minute, and the stirring was continued for another 1 hour.
The component (a) was manufactured. (2) Copolymerization of ethylene and 1-octene After replacing the inside of a dry 1 liter polymerization reactor equipped with a stirrer with dry nitrogen, 480 ml of dried toluene and 20 ml of 1-octene were added. Then
The component (C)-(a) produced in the above (1) is 0.5 mmol in terms of Al atom, 10 micromoles of tetrakis (pentafluorophenyl) borate dimethylanilium as the component (B), and the component (A) as the component (A). 5 μmol of pentamethylcyclopentadienyl titanium trichloride was added,
After raising the temperature to 90 ° C, introduce ethylene gas to bring the total pressure to 7 kg.
Polymerization was carried out at 90 ° C. for 1 hour while maintaining the same at / cm ² G.

Thereafter, the same treatment as in Example 1 was carried out to obtain 18.5 g of an ethylene-1-octene copolymer. 77 activity
It was kg / g-Ti. This copolymer had a melting point measured by DSC of 83.6 ° C. and an intrinsic viscosity [η] of 2.49 deciliter / g.

Example 5 The inside of a dried 1 liter polymerization reactor equipped with a stirrer was replaced with dry nitrogen, and then 390 ml of dried n-hexane and 10 ml of 1-octene were added. Then, the (C)-(a) component produced in Example 1- (1)
0.5 mmol in terms of Al atom, methylaluminoxane (manufactured by Albemarl) as component (B) in terms of Al atom
1.0 micromol of pentamethylcyclopentadienyl titanium trimethoxide was added as a component of 0.2 mmol (A), the temperature was raised to 80 ° C., ethylene gas was introduced, and the total pressure was adjusted to 8
Polymerization was carried out at 80 ° C. for 10 minutes while maintaining kg / cm ² G. Thereafter, the same treatment as in Example 1 was carried out to obtain ethylene-
3.2 g of 1-octene copolymer was obtained. 67 kg / activity
g-Ti. This copolymer had a melting point of 94.3 ° C. as measured by DSC.

Comparative Example 2 Copolymerization of ethylene with 1-octene was carried out in the same manner as in Example 5 except that the components (C)-(a) were not used. 0.4 g of 1-octene copolymer was obtained. The activity was 9 kg / g-Ti. This copolymer has a melting point of 99.7 ° C. measured by DSC.
Met.

Comparative Example 3 Ethylene and 1-octene were prepared in the same manner as in Example 5, except that 0.5 mmol of diisobutylaluminum methoxide was used instead of the component (C)-(a). Copolymerization was carried out, but no polymer was obtained.

Example 6 (1) Production of components (C)-(B) In a Schlenk tube having a volume of 100 ml and replaced with nitrogen,
50 ml of fully dehydrated and deoxygenated toluene and triisobutylaluminum (manufactured by Tosoh Aguzo) 1
9.8 g (100 mmol) were introduced. Boric acid (manufactured by Junsei Kagaku Co., Ltd.), which was kept at room temperature, thoroughly crushed and dried in advance.
2.0 g (33 mmol) was added in small portions. After the addition was completed, the temperature was gradually raised to 90 ° C. over 1 hour. On this occasion,
It is essential to continue mechanical stirring. As the reaction proceeded, the dissolution disappearance of solid boric acid was observed. While maintaining this temperature, heating and stirring was continued for 12 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and unreacted boric acid was filtered off. The filtrate is a slightly pale yellow solution. When the solvent was distilled off under reduced pressure, 9.6 g of a solid product [tris (diisobutylaluminoxy) borane] was obtained.

(2) Copolymerization of ethylene and 1-octene After the inside of a dry 1 liter polymerization reactor equipped with a stirrer was replaced with dry nitrogen, 390 ml of dried n-hexane and 10 ml of 1-octene were added. . Then, the (C)-(b) component produced in the above (1) is replaced with Al
0.5 mmol in terms of atoms, 3 micromoles of dimethylanilium tetrakis (pentafluorophenyl) borate as the component (B), and 2 micromoles of pentamethylcyclopentadienyl titanium trimethoxide as the component (A), After the temperature was raised to 0 ° C, ethylene gas was introduced, and polymerization was carried out at 80 ° C for 10 minutes while maintaining the total pressure at 8 kg / cm ² G. Thereafter, the same treatment as in Example 1 was carried out to obtain ethylene-
10.1 g of 1-octene copolymer was obtained. Activity is 105k
It was g / g-Ti. This copolymer had a melting point of 102.3 ° C. as measured by DSC and an intrinsic viscosity [η] of 4.44 deciliter / g. Further, the molecular weight distribution Mw / Mn measured by the GPC method is as narrow as 2.15, the peak top of the composition distribution curve obtained by the temperature rising fractionation method is 78 ° C, and the half-width is as wide as 11.5 ° C. It was

Example 7 After the inside of a dry 1 liter polymerization reactor equipped with a stirrer was replaced with dry nitrogen, 390 ml of dry toluene and 10 ml of 1-octene were added. Then
The component (C)-(b) produced in Example 6- (1) was replaced with A
1.0 mmol in terms of 1 atom, dimethylanilinium tetrakis (pentafluorophenyl) borate as component (B) 1.5 μmol, pentamethylcyclopentadienyl titanium trimethoxide as component (A) 1.0 Micromolar was added, the temperature was raised to 80 ° C., ethylene gas was introduced, and the total pressure was maintained at 8 kg / cm ² G, and the temperature was adjusted to 1 at 80 ° C.
Polymerization was performed for 0 minutes. Then, the same treatment as in Example 1 was carried out to obtain 4.2 g of an ethylene-1-octene copolymer. The activity was 87 kg / g-Ti. This copolymer is DSC
Melting point 97.0 ° C, intrinsic viscosity [η] is 4.11
It was deciliter / g.

Comparative Example 4 In Example 7, except that 1.0 mmol of triisobutylaluminum was used in place of the components (C)-(B),
Copolymerization of ethylene and 1-octene was carried out in the same manner as in Example 7 to obtain 0.5 g of an ethylene-1-octene copolymer. The activity was 10 kg / g-Ti. This copolymer had a melting point of 105.4 ° C. as measured by DSC and an intrinsic viscosity [η] of 2.21 deciliter / g.

Example 8 In Example 7, as the component (B), methylaluminoxane (manufactured by Albemarle) was used in an amount of 0.2 mmol in terms of Al atom, and (C) -produced in Example 6- (1).
Copolymerization of ethylene and 1-octene was carried out in the same manner as in Example 7 except that the component (b) was used in an amount of 0.5 mmol in terms of Al atom, and ethylene-1-octene copolymerization (2.1 g) was carried out.
I got The activity was 44 kg / g-Ti. This copolymer had a melting point of 99.5 ° C. as measured by DSC and an intrinsic viscosity [η] of 6.44 deciliter / g.

Reference Example 1 Copolymerization of ethylene and 1-octene was carried out using a typical single site catalyst (metallocene catalyst). After replacing the inside of the dried polymerization reactor equipped with a stirrer with dry nitrogen, 360 ml of dried toluene and 40 ml of 1-octene were added. Then, methylaluminoxane (0.75 mmol in terms of Al atom) and dicyclopentadienylzirconium dichloride (0.5 micromol) were added, and the ethylene partial pressure was 8 kg / cm ² G, the temperature was 80 ° C., and the polymerization time was 10 minutes. Copolymerization was carried out. 59.9 g of ethylene-1-octene copolymer was obtained. This copolymer has a molecular weight distribution M measured by the GPC method.
w / Mn was 2.4, which was narrow. Further, the peak top of the composition distribution curve obtained by the temperature rising fractionation method was 73.0 ° C, and the full width at half maximum was as narrow as 8.0 ° C.

[0060]

EFFECT OF THE INVENTION The olefin polymerization catalyst of the present invention has excellent copolymerizability, high activity per aluminum and activity per transition metal, and has a narrow molecular weight distribution and a relatively wide composition distribution, which is unprecedented. It is possible to provide an olefin polymer having excellent physical properties, particularly an ethylene-α-olefin copolymer.

Claims (6)

[Claims] 1. (A) General formula (I) CpME ¹ E ² E ³ ... (I) [wherein M represents titanium, zirconium or hafnium, and Cp is cyclopentadienyl or substituted cyclopentadiene. It shows a cyclic compound group having 5 to 30 carbon atoms having an enyl skeleton. E ¹ , E ² and E ³ each represent a σ ligand, which may be the same or different. ] A transition metal compound represented by the following, (B) a compound capable of reacting with the transition metal compound of the component (A) or a derivative thereof, and (C) (a) an organoaluminum compound Reaction products with phenolic compounds and (b) organoaluminum compounds with general formula (II) [In the formula, X, Y and Z each represent a sulfur atom or an oxygen atom, which may be the same or different from each other. ] An olefin polymerization catalyst comprising at least one selected from the reaction products with a boron compound represented by: 2. The catalyst for olefin polymerization according to claim 1, wherein the component (B) is a chain and / or cyclic aluminoxane. 3. The component (B) has the general formula (III) ([L¹-R¹]^{k +})_a([D]^-)_b ... (III) and general formula (IV) ([L^Two]^{k +})_a([D]^-)_b ... (IV) [wherein L^TwoIs M^Two, R^TwoR^ThreeM^Three, R^Four _ThreeC or R^Five 
M^ThreeIndicates L¹Is a Lewis base, [D]^-Is non-coordinating
Anion [D¹]^-Or [D^Two]^-Is shown. [D ¹]^-
Is an anion in which multiple groups are bound to an element, that is, [M¹G
¹G^Two... G^f]^-(However, M¹Is Periodic Table No. 5
Group 15 elements are shown. G¹~ G^fAre hydrogen and ha
Rogen atom, C1-C20 alkyl group, C2-C2
40 dialkylamino groups, alkoxy having 1 to 20 carbon atoms
Si group, aryl group having 6 to 20 carbon atoms, 6 to 20 carbon atoms
Aryloxy group, alkylaryl having 7 to 40 carbon atoms
Group, arylalkyl group having 7 to 40 carbon atoms, 1 to carbon number
20 halogen-substituted hydrocarbon groups, 1 to 20 carbon atoms
Luoxy group, organic metalloid group, or C2-20
A hydrocarbon group containing a hetero atom is shown. G¹~ G^f2 out of
One or more may form a ring. f is [(central metal M
¹Valence of +1)]. ), [D^Two]
^-Means that the logarithm (pKa) of the reciprocal of the acid dissociation constant is -10 or less
Of Bronsted acid alone or Brønsted acid and Louis
Is defined as the conjugate base of a combination of sulphonic acid, or superacid
Is a conjugated base. Also, even if the Lewis base is coordinated
Good. R ¹Is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms,
An aryl group having 6 to 20 carbon atoms, an alkylaryl group or
Represents an arylalkyl group, R^TwoAnd R^ThreeAre each
Clopentadienyl group, substituted cyclopentadienyl group,
Indenyl group or fluorenyl group, R^FourHas 1 to 2 carbon atoms
0 alkyl group, aryl group, alkylaryl group or
Represents an arylalkyl group, R^Five Indicates a macrocyclic ligand
You. k is [L¹-R¹], [L^Two] With an ion valence of 1 to
3 is an integer, a is an integer of 1 or more, and b = (k × a).
M^TwoIs an element of Groups 1 to 11, 11 to 13 and 17 of the periodic table
Including, M^ThreeIs an element of Group 7 to 12 of the periodic table
Show. ] Selected from among ionic compounds represented by
The olefin polymerization catalyst according to claim 1, which is at least one kind.
Medium. 4. The component (C) (a) is represented by the general formula (V) R ⁶ _n Al (OAr) _3-n (V) [wherein R ⁶ is a hydrocarbon having 1 to 20 carbon atoms]. Group, Ar is an aryl group having 6 to 20 carbon atoms, n is a real number of 1 to 2,
When there are a plurality of OArs, the plurality of OArs may be the same or different. ] The catalyst for olefin polymerization according to claim 1, which is an organoaluminum compound represented by the following formula. 5. The component (C) (b) is represented by the general formula (VI) (R ⁷ R ⁸ AlO) ₃ B (VI) [wherein R ⁷ and R ⁸ each have 1 to 10 carbon atoms]. 20 hydrocarbon groups are shown, which may be the same or different from each other, and the three R ⁷ R ⁸ AlO may be the same or different. ] The catalyst for olefin polymerization according to claim 1, which is an organoaluminum compound represented by the following formula. 6. In the presence of the catalyst for olefin polymerization according to claim 1, olefins are homopolymerized or olefins are copolymerized with other olefins and / or other polymerizable unsaturated compounds. A method for producing an olefin-based polymer, comprising: