JPH05247128A - Method for polymerizing olefin and catalyst for olefin polymerization - Google Patents

Abstract

PURPOSE:To efficiently produce an olefinic polymer having excellent properties, namely a spherical olefinic polymer having high bulk density and an excellent particle diameter distribution without using a large amount of an organoaluminum compound. CONSTITUTION:An olefin is polymerized by using a catalyst consisting of the following compounds (A) and (B) as main components wherein at least one of the components (A) and (B) is supported on a carrier (C) and an organoaluminum compound (D). The compound (A) is a transition metal compound containing a transition metal selected from the group IVB of the periodic table. The component B is a compound to be reacted with the transition metal compound to form an ionic complex.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an olefin polymerization method and an olefin polymerization catalyst for efficiently producing an olefin homopolymer or copolymer.

[0002]

2. Description of the Related Art As a soluble olefin polymerization catalyst, a Kaminsky catalyst containing a transition metal compound and an aluminoxane has been known. For example, in the polymerization of α-olefins, a catalyst composed of a zirconium compound and an aluminoxane exhibits high polymerization activity (JP-A-58-19309), and a compound in which two indenyl groups are bonded via an ethylene group is arranged. Production of stereoregular polypropylene using a catalyst composed of a zirconium compound as a ligand and aluminoxane (Japanese Patent Laid-Open No. 61-13 / 1986)
No. 0314) and the like are known. According to this Kaminsky catalyst, for example, in the polymerization of propylene, it is said that any of isotactic polypropylene, atactic polypropylene and syndiotactic polypropylene can be produced (Makromol. Chem., R
apid Commun. 4,417-421 (1983); Angew.Chem.Int.Ed.Eng
l.24,507-508 (1985); J.Am.Chem.Soc.109,6544-6545 (198
7); J. Am. Chem. Soc. 110, 6255-6256 (1988)).

In this case, as the transition metal compound for producing the isotactic polyolefin, a transition metal compound having an ethylenebis (indenyl) ligand (Japanese Patent Laid-Open Nos. 61-264010 and 64-51408).
No., JP-A-64-66216), R. by Yuen et al.
(C ₅ (R ′) ₄ ) ₂ MeQp type metallocene compound (JP-A-63-251405, JP-A-63-295607)
JP-A-64-74202), metallocene compounds crosslinked with silicon and the like (JP-A-3-12406), and the like. Further, a metallocene compound for producing a stereo block polymer is also known (JP-A-63-142004).
No. 63-2005).

[0004]

However, in the above-mentioned polymerization method, there is a problem that the cost becomes high because sufficient activity cannot be obtained unless a large amount of expensive aluminoxane is used. Further, since a large amount of aluminoxane is used, a large amount of metal remains in the product after polymerization, which causes deterioration of the polymer, coloring, and the like. Therefore, there is a problem in productivity such that the product must be sufficiently deashed after the polymerization. Furthermore, aluminoxane is required to react highly reactive trimethylaluminum with water in the production thereof, which is dangerous, and
Since the reaction product is a mixture of various substances including unreacted raw materials, and it is very difficult to isolate a single substance, it is difficult to control the catalyst to obtain a product having stable physical properties. Extremely difficult.

On the other hand, a method for polymerizing an α-olefin using a boron complex containing a specific amine and a metallocene compound as a catalyst is also disclosed (Japanese Patent Publication No. 1-5020).
36). However, the catalyst used in the above method has remarkably low polymerization activity. Moreover, the resulting polymer has problems such as poor shape and extremely low bulk density, and it is difficult to industrially utilize this method.

Further, a method for polymerizing an olefin using a catalyst in which one or both of a transition metal compound and an aluminoxane is supported on a particulate polymer or an inorganic particulate carrier is disclosed (Japanese Patent Laid-Open No. 3-74411 and Japanese Patent Laid-Open No. 74441/1993). 3-74412). However, these methods use a large amount of aluminoxane, and are industrially unfavorable for the same reason as described above. Further, a catalyst for olefin polymerization in which a specific transition metal compound or the like is supported on a carrier has been proposed (International Publication No. 91/09882, JP-A-3-2347).
09). However, these catalysts have limited catalyst components and are not always satisfactory in industrial use.

The present invention has been made in view of the above circumstances, and an olefin polymer having excellent properties, that is, a spherical olefin polymer having a high bulk density and a good particle size distribution,
It is an object of the present invention to provide an olefin polymerization method which can be efficiently produced without using a large amount of an organoaluminum compound. Moreover, it aims at providing the catalyst for olefin polymerization which enables such a polymerization.

[0008]

In order to achieve the above-mentioned object, the present invention is a catalyst comprising the following compounds (A) and (B) as main components, which are compounds (A) and (B): There is provided a method for polymerizing an olefin, which comprises using a catalyst in which at least one of the above is supported on a carrier and an organoaluminum compound. (A) Transition metal compound containing a transition metal selected from Group IVB of the periodic table (B) Compound which reacts with a transition metal compound to form an ionic complex

Further, the present invention is characterized by containing the following compounds (A ') and (B) as main components and carrying at least one of the compounds (A') and (B) on a carrier. A polymerization catalyst is provided. (A ′) a transition metal compound represented by the following formula (IV) containing a transition metal selected from Group IVB of the periodic table: M ¹ R ¹ _a R ² _b R ³ _c R ⁴ _d (IV) [wherein , M ¹ is a Ti, Zr or Hf atom, R ¹ _a , R
² _b , R ³ _c and R ⁴ _d each represent a σ-bonding ligand, a chelating ligand or a Lewis base, which may be the same as or different from each other. Often, a, b, c and d each represent an integer of 0-4. ] (B) Compound that reacts with a transition metal compound to form an ionic complex

The present invention will be described in more detail below.
In the present invention, the compound (A) is represented by IV in the periodic table.
A transition metal selected from Group B, namely titanium (T
Any compound containing i), zirconium (Zr) or hafnium (Hf) can be used, but in particular, a cyclopentadienyl compound represented by the following general formula (I), (II) or (III) Alternatively, a derivative thereof, a compound represented by the following general formula (IV) or a derivative thereof is suitable. ^{_{CpM 1 R 1 a R 2 b}} R 3 c ... (I) Cp 2 M 1 R 1 a R 2 b ... (II) (Cp-A e -Cp) M 1 R 1 a R 2 b ... (III) M ¹ R ¹ _a R ² _b R ³ _c R ⁴ _d (IV) [(I) to (IV) In the formula, M ¹ represents a Ti, Zr or Hf atom, and Cp represents a cyclopentadienyl group or a substituted cyclopentadienyl group. A cyclic unsaturated hydrocarbon group-containing group such as a pentadienyl group, an indenyl group, a substituted indenyl group, a tetrahydroindenyl group, a substituted tetrahydroindenyl group, a fluorenyl group or a substituted fluorenyl group is shown. R ¹ , R ² , R ³ and R ⁴
Are σ-bonding ligands, chelating ligands, and Lewis base ligands, respectively. Specific examples of the σ-bonding ligands include hydrogen atom, oxygen atom, halogen atom, Alkyl group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, alkylaryl group or arylalkyl group, 1 to 20 carbon atoms
Examples thereof include an acyloxy group, an allyl group, a substituted allyl group, and a substituent containing a silicon atom, and examples of the chelating ligand include an acetylacetonato group and a substituted acetylacetonate group. A indicates crosslinking by covalent bond. a, b, c and d are each an integer of 0 to 4, and e is 0.
Indicates an integer of ˜6. Two or more of R ¹ , R ² , R ³ and R ⁴ may combine with each other to form a ring. Cp above
Has a substituent, the substituent has 1 to 2 carbon atoms.
An alkyl group of 0 is preferred. In the formulas (II) and (III), the two Cp's may be the same or different from each other. ]

Examples of the substituted cyclopentadienyl group in the above formulas (I) to (III) include methylcyclopentadienyl group, ethylcyclopentadienyl group, isopropylcyclopentadienyl group, 1,2-dimethyl. Cyclopentadienyl group, tetramethylcyclopentadienyl group, 1,3-dimethylcyclopentadienyl group, 1,
2,3-trimethylcyclopentadienyl group, 1,2,
4-trimethylcyclopentadienyl group, pentamethylcyclopentadienyl group, trimethylsilylcyclopentadienyl group and the like can be mentioned. In addition, (I) ~ (I
Specific examples of R ^{1 to} R ^{4 in} the formula V) include, for example, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom as a halogen atom; a methyl group, an ethyl group and n-propyl as an alkyl group having 1 to 20 carbon atoms. Group, iso-propyl group,
n-butyl group, octyl group, 2-ethylhexyl group; methoxy group, ethoxy group, propoxy group, butoxy group, phenoxy group as alkoxy group having 1 to 20 carbon atoms; aryl group having 6 to 20 carbon atoms, alkylaryl group or Phenyl group, tolyl group, xylyl group, benzyl group as arylalkyl group; heptadecylcarbonyloxy group as acyloxy group having 1 to 20 carbon atoms; trimethylsilyl group as substituent containing silicon atom, (trimethylsilyl) methyl group: as Lewis base Dimethyl ether,
Ethers such as diethyl ether and tetrahydrofuran, thioethers such as tetrahydrothiophene, esters such as ethylbenzoate, nitriles such as acetonitrile and benzonitrile, trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, pyridine, 2, Amines such as 2'-bipyridine and phenanthroline; phosphines such as triethylphosphine and triphenylphosphine; ethylene, butadiene, 1-pentene, isoprene, pentadiene, 1-hexene and their derivatives as chain unsaturated hydrocarbons;
Examples of the cyclic unsaturated hydrocarbon include benzene, toluene, xylene, cycloheptatriene, cyclooctadiene, cyclooctatriene, cyclooctatetraene and derivatives thereof. Examples of the cross-linking by the covalent bond of A in the formula (III) include methylene cross-link, dimethyl methylene cross-link, ethylene cross-link, 1,1′-
Examples thereof include cyclohexylene crosslinks, dimethylsilylene crosslinks, dimethylgermylene crosslinks, and dimethylstannylene crosslinks.

Examples of such compounds include the following compounds and compounds obtained by substituting zirconium of these compounds with titanium or hafnium. Compound of formula (I) (pentamethylcyclopentadienyl) zirconium trimethyl, (pentamethylcyclopentadienyl) zirconium triphenyl, (pentamethylcyclopentadienyl) zirconium tribenzyl, (pentamethylcyclopentadienyl) zirconium Trichloride, (pentamethylcyclopentadienyl) zirconium trimethoxide, (cyclopentadienyl) zirconium trimethyl, (cyclopentadienyl) zirconium triphenyl, (cyclopentadienyl) zirconium tribenzyl, (cyclopentadienyl) ) Zirconium trichloride, (cyclopentadienyl) zirconium trimethoxide, (cyclopentadienyl) zirconium dimethylmethoxide, (methylcyclopentadienyl) zirco Trimethyl trimethyl, (methylcyclopentadienyl)
Zirconium triphenyl, (methylcyclopentadienyl) zirconium tribenzyl, (methylcyclopentadienyl) zirconium trichloride, (methylcyclopentadienyl) zirconium dimethylmethoxide,
(Dimethylcyclopentadienyl) zirconium trichloride, (trimethylcyclopentadienyl) zirconium trichloride, (trimethylsilylcyclopentadienyl) zirconium trimethyl, (tetramethylcyclopentadienyl) zirconium trichloride,

Compound of formula (II) bis (cyclopentadienyl) zirconium dimethyl
, Bis (cyclopentadienyl) zirconium diphenyl, bis (cyclopentadienyl) zirconium diethyl, bis (cyclopentadienyl) zirconium dibenzyl, bis (cyclopentadienyl) zirconium dimethoxide, bis (cyclopentadienyl) Zirconium dichloride, bis (cyclopentadienyl) zirconium methoxy chloride Bis (cyclopentadienyl) zirconium dihydride, bis (cyclopentadienyl)
Zirconium chloride hydride, bis (methylcyclopentadienyl) zirconium dimethyl, bis (methylcyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dibenzyl, bis (pentamethylcyclopentadienyl) zirconium dimethyl, Bis (pentamethylcyclopentadienyl) zirconium dichloride, Bis (pentamethylcyclopentadienyl) zirconium dibenzyl, Bis (pentamethylcyclopentadienyl) zirconium methyl chloride, Bis (pentamethylcyclopentadienyl) zirconium methylhydride , (Cyclopentadienyl) (pentamethylcyclopentadienyl) zirconium dichloride,

A compound of the formula (III) ethylenebis (indenyl) zirconium dimethyl,
Ethylene bis (indenyl) zirconium dichloride,
Ethylenebis (tetrahydroindenyl) zirconium dimethyl, ethylenebis (tetrahydroindenyl) zirconium dichloride, dimethylsilylenebis (cyclopentadienyl) zirconium dimethyl, dimethylsilylenebis (cyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadiene) (Enyl) (9
-Fluorenyl) zirconium dimethyl, isopropylidene (cyclopentadienyl) (9-fluorenyl) zirconium dichloride, [phenyl (methyl) methylene] (9-fluorenyl) (cyclopentadienyl) zirconium dimethyl, diphenylmethylene (cyclopentadienyl) ) (9-Fluorenyl) zirconium dimethyl, ethylene (9-fluorenyl) (cyclopentadienyl) zirconium dimethyl, cyclohexylidene (9
-Fluorenyl) (cyclopentadienyl) zirconium dimethyl, cyclopentylidene (9-fluorenyl)
(Cyclopentadienyl) zirconium dimethyl, cyclobutylidene (9-fluorenyl) (cyclopentadienyl) zirconium dimethyl, dimethylsilylene (9-
Fluorenyl) (cyclopentadienyl) zirconium dimethyl, dimethylsilylene bis (2,3,5-trimethylcyclopentadienyl) zirconium dichloride,
Dimethyl silylene bis (2,3,5-trimethylcyclopentadienyl) zirconium dimethyl, dimethyl silylene bis (indenyl) zirconium dichloride,

Compound of formula (IV) zirconium tetramethyl, zirconium tetrabenzyl, zirconium tetramethoxide, zirconium tetraethoxide, zirconium tetrabutoxide, zirconium tetrachloride, zirconium tetrabromide,
Zirconium butoxy trichloride, zirconium dibutoxy dichloride, bis (2,5-di-t-butylphenoxy) zirconium dimethyl, bis (2,5-di-t
-Butylphenoxy) zirconium dichloride, zirconium bis (acetylacetonate), and thus, when the compound of the formula (IV) is used as the compound (A '), an olefin polymer can be industrially produced without using a special compound. Can be advantageously manufactured.

Further, in the present invention, the compound (A)
As substituted or unsubstituted 2 in the formula (III)
Conjugated cycloalkadienyl groups (provided that at least 1
Is a substituted cycloalkadienyl group) in the periodic table
A Group IVB transition metal compound having a ligand of a multidentate coordination compound bonded to each other through an element selected from Group IVA can be preferably used, which has a high isotacticity, a high molecular weight, and a high molecular weight. An isotactic polyolefin having a melting point can be obtained. Examples of such compounds include compounds represented by the following general formula (V) or derivatives thereof.

[0017]

[Chemical 1] [In the formula (V), Y is a carbon, silicon, germanium or tin atom, R ⁵ _t -C ₅ H _4-t and R ⁵ _u -C ₅ H _4-u are substituted cyclopentadienyl groups and t And u represents an integer of 1 to 4. Here, R ⁵ represents a hydrogen atom, a silyl group or a hydrocarbon group, and may be the same or different.
Further, at least one cyclopentadienyl ring,
There is R ⁵ on at least one carbon next to the carbon bonded to Y. R ⁶ represents 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 an arylalkyl group. M ² is T
i, Zr or Hf atom, X is a hydrogen atom, a halogen atom,
An alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group or an arylalkyl group, or an alkoxy group having 1 to 20 carbon atoms is shown. X's may be the same as or different from each other, and R ^6's may be the same or different from each other.

Examples of the substituted cyclopentadienyl group in the above formula (V) include methylcyclopentadienyl group, ethylcyclopentadienyl group, isopropylcyclopentadienyl group, 1,2-dimethylcyclopentadienyl group. Group, 1,3-dimethylcyclopentadienyl group, 1,2,3-trimethylcyclopentadienyl group,
Examples include 1,2,4-trimethylcyclopentadienyl group. Specific examples of X include, for example, F, Cl, Br and I as halogen atoms; methyl group, ethyl group, n-propyl group and is as alkyl groups having 1 to 20 carbon atoms.
o-propyl group, n-butyl group, octyl group, 2-ethylhexyl group; methoxy group, ethoxy group, propoxy group, butoxy group, phenoxy group as alkoxy group having 1 to 20 carbon atoms; aryl group having 6 to 20 carbon atoms Examples of the alkylaryl group or arylalkyl group include a phenyl group, a tolyl group, a xylyl group and a benzyl group. Specific examples of R ⁶ include a methyl group, an ethyl group, a phenyl group, a tolyl group, a xylyl group and a benzyl group.

Examples of the compound of the formula (V) include the following compounds and compounds in which zirconium of these compounds is replaced with titanium or hafnium. Compound of formula (V) dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) hafnium dichloride

Any compound that reacts with the transition metal compound (A) to form an ionic complex can be used as the compound (B). A compound consisting of a bound anion, that is, compound (B) is a group IIIB, VB or VIB of the periodic table.
Tribe, VIIB, VIII, IA, IB, IIA, IIB, IVA
A cation containing an element selected from group VIIA and group VIIA is a group VB, VIB, VIIB, VIII, IB, I of the periodic table.
A compound composed of an anion bonded to an element selected from Group IB, IIIA, IVA and VA, particularly a coordination complex compound composed of a cation and an anion in which a plurality of groups are bonded to an element, is preferably used. it can. As the compound composed of such a cation and an anion in which a plurality of groups are bound to an element, a compound represented by the following formula (VI) or (VII) can be preferably used. ([L ¹ −R ⁷ ] ^{k +} ) _p ([M ³ Z ¹ Z ² … Z ⁿ ] ^(nm)- ) _q … (VI) ([L ² ] ^{k +} ) _p ([M ⁴ Z ¹ Z ² …. Z ⁿ ] ^(nm)- ) _q (VII) (where L ² is M ⁵ , R ⁸ R ⁹ M ⁶ , R ¹⁰ ₃ C or R ¹¹ M ⁶ )

[In the formulas (VI) and (VII), L¹ Is Lewis salt
Group, M³And M^FourAre VB group, VIB group and V of the periodic table, respectively.
IIB, VIII, IB, IIB, IIIA, IVA and
Element selected from VA group, preferably IIIA group, IVA group
And elements selected from VA group, M ^FiveAnd M⁶Each is a lap
Periodic Table IIIB, IVB, VB, VIB, VIIB, V
From Group III, Group IA, Group IB, Group IIA, Group IIB and Group VIIA
Selected element, Z¹~ ZⁿAre hydrogen atom and dialki respectively
Lumino group, C1-20 alkoxy group, C6
~ 20 aryloxy group, C1-20 alkyl
Group, aryl group having 6 to 20 carbon atoms, alkylaryl
Group, arylalkyl group, halogen unit having 1 to 20 carbon atoms
Substituted hydrocarbon group, acyloxy group having 1 to 20 carbon atoms, organic
Represents a metalloid group or a halogen atom, Z¹~ ZⁿIs that
Two or more may combine with each other to form a ring. R⁷
Is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and a carbon number of 6 to
20 aryl groups, alkylaryl groups or aryl groups
R is a group, R⁸And R⁹Are each cyclopentadi
Enyl group, substituted cyclopentadienyl group, indenyl group
Or a fluorenyl group, R^TenIs alkyl having 1 to 20 carbons
Group, aryl group, alkylaryl group or arylal
Indicates a kill group. R¹¹Is tetraphenylporphyrin,
A macrocyclic ligand such as phthalocyanine is shown. m is M³ , M
^FourIs an integer of 1 to 7, n is an integer of 2 to 8 and k is
[L¹-R⁷], [L²] With an ionic valence number of 1 to 7,
p is an integer of 1 or more, q = (p × k) / (nm)
It ]

Specific examples of the Lewis base include ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine,
Amine such as trimethylamine, triethylamine, tri-n-butylamine, N, N-dimethylaniline, methyldiphenylamine, pyridine, p-promo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline, triethylphosphine Phosphines such as fin, triphenylphosphine and diphenylphosphine,
Examples thereof include ethers such as dimethyl ether, diethyl ether, tetrahydrofuran and dioxane, thioethers such as diethyl thioether and tetrahydrothiophene, and esters such as ethyl benzoate. Specific examples of M ³ and M ⁴ include B, Al, Si, P, As and Sb.
Etc., preferably B or P, and specific examples of M ⁵ are Li,
Specific examples of Na, Ag, Cu, Br, I, I _3, etc. and M ⁶ include Mn, Fe, Co, Ni, Zn and the like.

Specific examples of Z ^{1 to} Z ⁿ include, for example, 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 having 1 to 20 carbon atoms; and a carbon number of 6 A phenoxy group, a 2,6-dimethylphenoxy group, a naphthyloxy group as an aryloxy group having 20 to 20 carbon atoms, a methyl group, an ethyl group, an n-propyl group having an alkyl group having 1 to 20 carbon atoms,
iso-propyl group, n-butyl group, n-octyl group,
2-ethylhexyl group; aryl group having 6 to 20 carbon atoms,
As an alkylaryl group or an arylalkyl group, a phenyl group, a p-tolyl group, a benzyl group, a 4-tert-butylphenyl group, a 2,6-dimethylphenyl group,
3,5-dimethylphenyl group, 2,4-dimethylphenyl group, 2,3-dimethylphenyl group; p-fluorophenyl group, 3,5-difluorophenyl group as a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, Pentachlorophenyl group, 3,4,5-trifluorophenyl group, pentafluorophenyl group, 3,5-di (trifluoromethyl) phenyl group; F, Cl, Br as halogen atoms
I: Examples of the organic metalloid group include pentamethylantimony group, trimethylsilyl group, trimethylgermyl group, diphenylarsine group, dicyclohexylantimony group and diphenylboron group. Specific examples of R ⁷ and R ¹⁰ include:
Examples are the same as those listed above. R ⁸ and R ⁹
Specific examples of the substituted cyclopentadienyl group include those substituted with an alkyl group such as a methylcyclopentadienyl group, a butylcyclopentadienyl group, and a pentamethylcyclopentadienyl group. Here, the alkyl group usually has 1 to 6 carbon atoms, and the number of substituted alkyl groups can be selected by an integer of 1 to 5. (VI), (VI
Among the compounds of formula I), those in which M ³ and M ⁴ are boron are more preferable.

Among the compounds of the formulas (VI) and (VII), the following can be used particularly preferably. Compound of formula (VI) triethylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyltri (n-butyl) ammonium tetraphenylborate, benzyltriphenylphenylborate (N-butyl) ammonium, dimethyldiphenylammonium tetraphenylborate, methyltriphenylammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate, methyl tetraphenylborate (2-cyanopyridinium) ), Trimethylsulfonium tetraphenylborate, benzyl dimethylsulfonium tetraphenylborate ,

Triethylammonium tetra (pentafluorophenyl) borate, tri (n-butyl) ammonium tetra (pentafluorophenyl) borate, triphenylammonium tetra (pentafluorophenyl) borate, tetrabutylammonium tetra (pentafluorophenyl) borate, Tetra (pentafluorophenyl) borate (tetraethylammonium), tetra (pentafluorophenyl) borate (methyltri (n-butyl) ammonium), tetra (pentafluorophenyl) borate (benzyltri (n-butyl) ammonium), tetra (pentafluoro) Phenyl) methyl diphenylammonium borate, tetra (pentafluorophenyl) methyl triphenylammonium borate Dimethyl diphenyl (pentafluorophenyl) borate Phenylammonium, anilinium tetra (pentafluorophenyl) borate, methylanilinium tetra (pentafluorophenyl) borate, dimethylanilinium tetra (pentafluorophenyl) borate, trimethylanilinium tetra (pentafluorophenyl) borate, tetra (pentafluorophenyl) ) Dimethyl borate (m-nitroanilinium), dimethyl tetra (pentafluorophenyl) borate (p-bromoanilinium),

Pyridinium tetra (pentafluorophenyl) borate, tetra (pentafluorophenyl) borate (p-cyanopyridinium), tetra (pentafluorophenyl) borate (N-methylpyridinium), tetra (pentafluorophenyl) borate (N- Benzylpyridinium), tetra (pentafluorophenyl) boric acid (O
-Cyano-N-methylpyridinium), tetra (pentafluorophenyl) borate (p-cyano-N-methylpyridinium), tetra (pentafluorophenyl) borate (p-cyano-N-benzylpyridinium), tetra (pentafluorophenyl) ) Trimethylsulfonium borate, benzyldimethylsulfonium tetra (pentafluorophenyl) borate, tetraphenylphosphonium tetra (pentafluorophenyl) borate, triphenylphosphonium tetra (pentafluorophenyl) borate, tetra (3,5-ditrifluoromethylphenyl) borate Dimethylanilinium, triethylammonium hexafluoroarsenate,

Compound of formula (VII) : ferrocenium tetraphenylborate, silver tetraphenylborate, trityl tetraphenylborate, tetraphenylborate (tetraphenylporphyrin-manganese), ferrocenium tetra (pentafluorophenyl) borate, tetra (pentafluorophenyl) borate (1,1′-Dimethylferrocenium) tetra (pentafluorophenyl) decamethylferrocenium borate, acetylferrocenium tetra (pentafluorophenyl) borate, formylferrocenium tetra (pentafluorophenyl) borate, tetra ( Cyanoferrocenium pentafluorophenyl) borate, silver tetra (pentafluorophenyl) borate, trityl tetra (pentafluorophenyl) borate,
Lithium tetra (pentafluorophenyl) borate, Sodium tetra (pentafluorophenyl) borate, Tetra (pentafluorophenyl) boric acid (Tetraphenylporphyrin manganese), Tetra (pentafluorophenyl) boric acid (Tetraphenylporphyrin iron chloride), Tetra (penta Fluorophenyl) boric acid (tetraphenylporphyrin zinc), silver tetrafluoroborate,
Silver hexafluoroarsenate, silver hexafluoroantimonate,

Among the compounds of the formulas (VI) and (VII), preferred are the compounds of the formula (VI) in which [L ¹ -R ⁷ ] has no proton, that is, quaternary ammonium salts, -Grade oxonium salts, tertiary thionium salts, etc., and these are excellent in long-term storage stability. Also, (VI),
Compounds other than formula (VII), such as tri (pentafluorophenyl) boron, tri (3,5-di (trifluoromethyl) phenyl) boron, triphenylboron, etc., can also be used.

In the present invention, the type of carrier (C) is not limited, and any of an inorganic carrier, an inorganic oxide carrier and an organic carrier can be used, but an inorganic carrier or an inorganic oxide carrier is particularly preferable. Specific examples of the inorganic carrier include magnesium compounds such as MgCl ₂ and Mg (OEt) ₂ and complex salts thereof, and organomagnesium compounds represented by MgR ¹³ _X X ¹ _Y. Here, R ¹³ represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and X ¹ represents a halogen atom or an alkyl group having 1 to 20 carbon atoms, x is 0
~ 2, y is 0-2. As the inorganic oxide carrier, S
iO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , Fe ₂ O
Examples include ₃ , B ₂ O ₃ , CaO, ZnO, BaO, ThO _2, and mixtures thereof such as silica alumina, zeolite, ferrite, and glass fiber. Among these, SiO ₂ and Al ₂ O ₃ are particularly preferable. The inorganic oxide carrier may contain a small amount of carbonate, nitrate, sulfate or the like. Examples of the organic carrier include polymers such as polystyrene, polyethylene, polypropylene, substituted polystyrene and polyarylate, starch, carbon and the like.

The carrier (C) used in the present invention is Mg
Cl ₂ , MgCl (OC ₂ H ₅ ), Mg (OC ₂ H ₅ ) ₂ , S
iO ₂ , Al ₂ O _{3 and the} like are preferable, and the average particle size is usually 1 to 300, although the properties thereof vary depending on the type and manufacturing method.
μm, preferably 10 to 200 μm, more preferably 2
It is 0 to 100 μm. When the particle size is small, fine powder in the polymer increases, and when the particle size is large, coarse particles in the polymer increase, which causes a decrease in bulk density and clogging of the hopper. The specific surface area of the carrier (C) is usually 1 to 1,000 m ^2.
/ G, preferably 50 to 500 m ² / g, the pore volume is
Usually 0.1 to ⁵ cm ³ / g, preferably 0.3 to ³ cm ³
/ G. If either the specific surface area or the pore volume deviates from the above range, the catalytic activity may decrease. The specific surface area and the pore volume can be determined, for example, from the volume of nitrogen gas adsorbed according to the BET method [“Journal of American Chemical Society (J. Am. Chem. Soc.)”]. Volume 60, page 309 (1
983)]]. Further, the carrier (C) is usually 15
It is desirable to use by firing at 0 to 1000 ° C, preferably 200 to 800 ° C.

The olefin polymerization catalyst of the present invention contains the compounds (A) and (B) as main components, and at least one of the compounds (A) and (B), preferably the compound (A).
Both (1) and (B) are supported on the carrier (C).
The method of supporting at least one of the compounds (A) and (B) on the carrier (C) is not particularly limited, but the following methods (1) to (4) can be exemplified. A method of mixing at least one of the compounds (A) and (B) with the carrier (C). A method in which the carrier (C) is treated with an organoaluminum compound or a halogen-containing silicon compound and then mixed with at least one of the compounds (A) and (B) in an inert solvent. A method of reacting the carrier (C) with the compound (A) and / or (B) with an organoaluminum compound or a halogen-containing silicon compound. A method in which the compound (A) or (B) is supported on the carrier (C) and then mixed with the compound (B) or (A). A method of mixing a contact reaction product of a compound (A) and a compound (B) with a carrier (C). A method in which the carrier (C) is allowed to coexist during the contact reaction between the compound (A) and the compound (B). In addition, in the reaction of the above and, it is also possible to add an organoaluminum compound (D) described later.

The catalyst thus obtained may be used for the polymerization after the solvent is once distilled off and taken out as a solid, or may be used for the polymerization as it is. Further, in the present invention, the catalyst can be produced by carrying out the loading operation of at least one of the compounds (A) and (B) on the carrier (C) in the polymerization system. As such a method, for example, an inert solvent is put in an autoclave, at least one of the compounds (A) and (B), a carrier (C) and optionally a compound (D) described later are added, and an olefin such as ethylene is added. Normal pressure ~ 20Kg / cm ² added,-
There is a method of preliminarily polymerizing at 20 to 100 ° C. for 1 minute to 2 hours to generate catalyst particles. In the present invention, the mixing ratio (weight ratio) of the compound (B) and the carrier (C) is 1: 5.
It is preferable to be ˜1: 10000, particularly 1:10 to 1: 500. The mixing ratio (weight ratio) of the compound (A) and the carrier (C) is preferably 1: 5 to 1: 10000, and particularly preferably 1:10 to 1: 500. If the mixing ratio of the compound (B) and the carrier (C) or the mixing ratio of the compound (A) and the carrier (C) is out of the above range, the activity may decrease.

The olefin polymerization catalyst of the present invention prepared as described above has an average particle size of usually 2 to 200 μm,
Preferably 10 to 150 μm, particularly preferably 20 to 1
00 μm, and the specific surface area is usually 20 to 1000 m ^2.
/ G, preferably 50 to 500 m ² / g. If the average particle size is less than 2 μm, the fine powder in the polymer may increase, and if it exceeds 200 μm, the coarse particles in the polymer may increase. If the specific surface area is less than 20 m ² / g, the activity may decrease, and if it exceeds 1000 m ² / g, the bulk density of the polymer may decrease. In the catalyst of the present invention, the amount of transition metal in 100 g of the carrier is usually 0.05 to 10 g, and preferably 0.1 to 2 g. If the amount of the transition metal is out of the range, the activity may decrease.

The olefin polymerization method of the present invention is characterized by carrying out homopolymerization of olefins or copolymerization of two or more kinds of olefins using the above-mentioned catalyst for olefin polymerization of the present invention. In this case, the type of olefin is not particularly limited, but α-olefin having 2 to 20 carbon atoms is preferable. Specifically, ethylene, propylene, 1-butene,
3-methyl-1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene And the like can be preferably used. In the present invention, two or more α
-When copolymerizing olefins, the above-mentioned monomers can be combined in any combination. Ethylene and carbon number 3
When copolymerizing 10 α-olefins, the copolymerization ratio of ethylene and α-olefins having 3 to 10 carbon atoms is
Usually, the molar ratio is 99.9: 0.1-60.0: 40.0.
It is preferably 99.5: 0.5 to 75.0: 25.0.

In the method of the present invention, in addition to the above olefins, other unsaturated compounds, for example, vinyl aromatic compounds such as styrene, p-methylstyrene, isopropylstyrene and t-butylstyrene, butadiene, isoprene, 1,5.
-Chain diolefins such as hexadiene, norbornene, 1,4,5,8-dimethano-1,2,3,4,4
Copolymerization can be performed using cyclic olefins such as a, 5,8,8a-octahydronaphthalene and cyclic diolefins such as norbornadiene and ethylidene norbornene. Usually, other unsaturated compounds are 20 mol% or less with respect to the olefin. In this case, one or more olefins can be preferably used.

In the olefin polymerization method of the present invention, the olefin polymerization or copolymerization is carried out by using the organoaluminum compound (D) together with the above-mentioned catalyst for olefin polymerization of the present invention, thereby improving the polymerization activity. be able to. Here, the organoaluminum compound (D)
Examples thereof include those represented by the following general formula (VIII), (IX) or (X). R ¹⁴ _r AlQ _3-r (VIII) (R ¹⁴ is a hydrocarbon group such as an alkyl group, an alkenyl group, an aryl group and an arylalkyl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, Q is a hydrogen atom, It represents an alkoxy group having 1 to 20 carbon atoms or a halogen atom, and r is in the range of 1 ≦ r ≦ 3.) Specific examples of the compound of formula (VIII) include trimethylaluminum, triethylaluminum, and triisopropyl. Aluminum, triisobutyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, methyl aluminum dichloride, ethyl aluminum dichloride, dimethyl aluminum fluoride, diisobutyl aluminum hydride, diethyl aluminum hydride, ethyl aluminum sesquichloride and the like can be mentioned. (R ¹⁴ is the formula (VI
Same as II). s indicates the degree of polymerization, usually 3 to 5
It is 0, preferably 7-40. )

[0037]

[Chemical 2] A chain aluminoxane represented by. (R ¹⁴ has the same meaning as in the formula (VIII), s denotes the degree of polymerization, and the preferred number of repeating units is 3 to 50, preferably 7 to 40.)

[0038]

[Chemical 3] A cyclic alkylaluminoxane having a repeating unit represented by: Among the compounds of the formulas (VIII) to (X), the alkyl group-containing aluminum compound or aluminoxane having at least one alkyl group having 3 or more carbon atoms, and particularly having at least one branched alkyl group is preferable. Particularly preferred is triisobutylaluminum or aluminoxane having a degree of polymerization of 7 or more. When this triisobutylaluminum, aluminoxane having a degree of polymerization of 7 or more, or a mixture thereof is used, high activity can be obtained.

As a method for producing the aluminoxane, there may be mentioned 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 carried out according to a known method. For example, a method in which an organoaluminum compound is dissolved in an organic solvent and 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. There are a method of reacting water adsorbed on 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 insoluble in toluene.

When the component (D) is used, the amount used is usually 1 to 2,000 mol per 1 mol of the component (A),
Preferably 5 to 1,000 mol, particularly preferably 10 to
It is 500 mol. When the component (D) is used, the polymerization activity can be improved, but if it is too much, the organoaluminum compound is wasted and a large amount remains in the polymer, which is not preferable. The component (D) may be used in contact with the catalyst of the present invention. The contact may be made in advance or in the polymerization system.

In the present invention, the polymerization method is not particularly limited, and any method such as slurry polymerization method, gas phase polymerization method, bulk polymerization method, solution polymerization method and suspension polymerization method may be used. The legal method and the gas phase polymerization method are particularly preferable. Regarding the polymerization conditions, the polymerization temperature is usually -100 to 250 ° C, preferably -50 to 200 ° C, more preferably 0 to 130 ° C.
Is. The ratio of the catalyst to the reaction raw material is such that the raw material monomer / the above-mentioned component (A) (molar ratio) or the raw material monomer / the above-mentioned (B) component (molar ratio) is 1 to 10 ⁸ , and particularly 100 to 10 ^5. Is preferred. Further, the polymerization time is usually 5 minutes to 10 hours, and the reaction pressure is atmospheric pressure to 100 Kg.
/ Cm ² G, preferably atmospheric pressure to 30 Kg / cm ² G.

The method for controlling the molecular weight of the polymer may be based on the amount of each catalyst component used, the selection of the polymerization temperature, and the polymerization reaction in the presence of hydrogen. When a polymerization solvent is used, for example, aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclohexane, aliphatic hydrocarbons such as pentane, hexane, heptane and octane. , Halogenated hydrocarbons such as chloroform and dichloromethane can be used. These solvents may be used alone or in combination of two or more. Further, a monomer such as α-olefin may be used as a solvent. The polymerization may be carried out without solvent.

In the polymerization method of the present invention, preliminary polymerization can be carried out using the catalyst of the present invention. Prepolymerization is
It can be carried out by contacting a small amount of olefin with the solid catalyst component, but the method is not particularly limited,
Known methods can be used. The olefin used in the prepolymerization is not limited, and examples thereof include the same ones as described above, for example, ethylene, C _{3 to} C ₂₀ α-olefins, or a mixture thereof. It is preferable to use. The prepolymerization temperature is usually -20 to 100 ° C, preferably -10 to 70 ° C, more preferably 0 to 50 ° C.

In the prepolymerization, an inert hydrocarbon, an aliphatic hydrocarbon, an aromatic hydrocarbon, a monomer or the like can be used as a solvent. Of these, particularly preferred are aliphatic hydrocarbons. Further, the prepolymerization may be carried out without a solvent. In the prepolymerization, the intrinsic viscosity [η] of the prepolymerized product (measured in decalin at 135 ° C.) was 0.2.
dl / g or more, particularly 0.5 dl / g or more, and the conditions are adjusted so that the amount of the prepolymerized product per mmol of the transition metal component in the catalyst is 1 to 10,000 g, particularly 10 to 1,000 g. Preferably.

According to the present invention, an olefin homopolymer or copolymer having a granular shape, a high bulk density and a good particle size distribution and excellent properties can be efficiently produced without using a large amount of an organometallic compound. it can.

[0046]

EXAMPLES Next, the present invention will be illustrated concretely by examples, but the present invention is not limited to the following examples. In the following examples and comparative examples, physical properties were measured as follows. Intrinsic viscosity [η] Measured in decalin at 135 ° C. Bulk density Measured according to JIS K6721. In addition, Example 1
Table 1 shows the compound components for the preparation of the solid catalyst of Example 50.
~ Table 3 shows the polymerization conditions in Tables 4 ~ 6.

Example 1 Silica (average particle size 70 μm, specific surface area 260 m ² / g, pore volume 1.5
cm ³ / g) baked at 300 ° C. for 4 hours 2.3
g, toluene solution of bis (cyclopentadienyl) zirconium dichloride (0.01 mol / liter) 100
ml, triisobutylaluminum (TIBA) 5 mmol, tetrakis (pentafluorophenyl) borate dimethylanilinium 2 mmol, and the mixture was treated at room temperature for 30 minutes with stirring, and then toluene was distilled off under reduced pressure.
A solid catalyst was obtained. Then, add toluene 4 to the autoclave.
0.003 mmol of zirconium equivalent of the solid catalyst obtained above together with 00 ml of 0.6 mmol of TIBA was added, and ethylene was continuously supplied at 90 ° C. at a pressure of 9 Kg / cm ² to the autoclave, and polymerization was carried out for 30 minutes. As a result, 104 g of a polymer was obtained. The intrinsic viscosity [η] of the obtained polymer was 2.13 dl / g. The bulk density of the polymer was 0.36 g / cm ³ , and the polymer was a spherical polymer having a good particle size distribution.

Example 2 Example 2 was repeated except that bis (cyclopentadienyl) zirconium dimethyl was used in place of bis (cyclopentadienyl) zirconium dichloride and triisobutylaluminum (TIBA) was not used. A solid catalyst was prepared in the same manner as in Example 1. Then, polymerization was carried out under the same conditions as in Example 1. As a result, the intrinsic viscosity [η] was 2.09 dl / g and the bulk density was 0.34 g / c.
101 g of a spherical polymer having a particle size distribution of m ³ was obtained.

Example 3 Example 3 was repeated except that ferrocenium tetrakis (pentafluorophenyl) borate was used in place of dimethylanilinium tetrakis (pentafluorophenyl) borate and triisobutylaluminum (TIBA) was not used. A solid catalyst was prepared in the same manner as in Example 1. Then, polymerization was carried out under the same conditions as in Example 1. As a result, 120 g of a spherical polymer having an intrinsic viscosity [η] of 2.02 dl / g, a bulk density of 0.35 g / cm ³ and a good particle size distribution was obtained.

Examples 4 to 29 The compounds shown in Table 1 and Table 2 were used as the compounds (A), (B) and (C), and a solid catalyst was prepared in the same manner as in Example 1. Then, polymerization was carried out in the same manner as in Example 1 under the conditions shown in Tables 4 and 5. The results are shown in Tables 4 and 5. From Tables 4 and 5, it can be seen that according to the present invention, a spherical polymer having a high bulk density can be obtained. In addition, Example 9,
Regarding 11, 17, 18, 24, and 25, it is found that organoaluminum is not used at the time of polymerization, but it is effective as a catalyst for olefin polymerization.

Example 30 Commercially available anhydrous magnesium chloride 3 which was thoroughly dried under reduced pressure
g was mixed with 1 mmol of bis (cyclopentadienyl) zirconium dichloride, 5 mmol of triisobutylaluminum (TIBA), and 2 mmol of dimethylanilinium tetrakis (pentafluorophenyl) borate in toluene (100 ml) in a ball mill for 6 hours. After crushing by crushing, washing with toluene gave a solid catalyst. Example 1 except that the solid catalyst was changed from one using silica as a carrier to one using the above anhydrous magnesium chloride as a carrier.
Polymerization was carried out in the same manner as in. The compound composition is shown in Table 2 and the polymerization result is shown in Table 5.

Example 31 Polymerization was carried out in the same manner as in Example 30 except that the carrier was changed from anhydrous magnesium chloride to 3 g of alumina. The compound composition is shown in Table 2 and the polymerization result is shown in Table 5.

Example 3 2 Polymerization was carried out in the same manner as in Example 30 except that bis (cyclopentadienyl) zirconium methoxychloride was used in place of bis (cyclopentadienyl) zirconium dichloride. The compound composition is shown in Table 2 and the polymerization result is shown in Table 5.

Examples 33 to 50 Using the compounds shown in Table 3 as the compounds (A), (B), (C) and (D), a solid catalyst was prepared in the same manner as in Example 30. Then, Example 30 was performed under the conditions shown in Table 6.
Polymerization was carried out in the same manner as in. The polymerization results are shown in Table 6.

Example 51 Using the solid catalyst prepared in Example 2, ethylene 1-
Gas-phase copolymerization of butene was performed. Stirrer (anchor type blade)
Stainless steel autoclave (with internal volume 4.
Into 5 liters), 30 g of powder of ethylene / 1-butene copolymer was added and dried under vacuum at 90 ° C. At that temperature, the pressure was restored to atmospheric pressure with nitrogen. Furthermore, 1-butene 2.0 kg / cm ² , ethylene 10.0 kg / cm ²
Was introduced to bring the total pressure to 12.0 kg / cm ² . 1.0 ml of triisobutylaluminum in 30 ml of dry heptane
The solid catalyst prepared in Example 2 and 0.006 mmol in terms of zirconium were added and immediately charged into the reactor to start the reaction. Ethylene was continuously supplied while maintaining the reaction temperature and pressure. After reacting for 1 hour, the pressure was released and 26
0 g of copolymer was obtained. Polymer bulk density is 0.35 g /
It was cm ³ .

Example 52 A solid catalyst was prepared in the same manner as in Example 2 except that bis (cyclopentadienyl) zirconium dimethoxide was used instead of bis (cyclopentadienyl) zirconium dimethyl. Then, polymerization was carried out under the same conditions as in Example 51. As a result, 158 g of a spherical polymer having a bulk density of 0.37 g / cm ³ was obtained.

Example 53 A solid catalyst was prepared in the same manner as in Example 2 except that zirconium tetrachloride was used instead of bis (cyclopentadienyl) zirconium dichloride. Then, polymerization was carried out under the same conditions as in Example 51. as a result,
A spherical copolymer having a bulk density of 0.35 g / cm ³ was obtained.

Comparative Example 1 Example 1 except that the carrier silica was not used.
The catalyst was prepared and polymerized in the same manner as in. The properties of the obtained polymer were unfavorable because they had a cotton-like shape with a significantly low bulk density.

[0059]

[Table 1]

[0060]

[Table 2]

[0061]

[Table 3]

[0062]

[Table 4]

[0063]

[Table 5]

[0064]

[Table 6]

[0065]

As described above, according to the present invention, an olefin polymer having excellent properties, that is, a spherical olefin polymer having a high bulk density and a good particle size distribution,
It can be efficiently produced without using a large amount of organoaluminum compound.

Claims (6)

[Claims] 1. A catalyst mainly comprising the following compounds (A) and (B), in which at least one of the compounds (A) and (B) is supported on a carrier (C), and an organoaluminum compound: (D) is used, The olefin polymerization method characterized by using. (A) Transition metal compound containing a transition metal selected from Group IVB of the periodic table (B) Compound which reacts with a transition metal compound to form an ionic complex 2. The method for polymerizing an olefin according to claim 1, wherein the compound (A) is a transition metal compound (A ′) represented by the following formula (IV). M ¹ R ¹ _a R ² _b R ³ _c R ⁴ _d (IV) [wherein, M ¹ is a Ti, Zr or Hf atom, R ¹ _a , R
² _b , R ³ _c and R ⁴ _d each represent a σ-bonding ligand, a chelating ligand or a Lewis base, which may be the same as or different from each other. Often, a, b, c and d each represent an integer of 0-4. ] 3. The compound (B) is a group IIIB group, VB group of the periodic table.
Tribe, VIB, VIIB, VIII, IA, IB, IIA, IIB
A cation containing an element selected from Group IVA, Group VIIA, and multiple groups are group VB, VIB, VIIB, VIII of the periodic table.
3. The method for polymerizing an olefin according to claim 1 or 2, which is a compound comprising an anion bonded to an element selected from Group I, Group IB, Group IIB, Group IIIA, Group IVA and Group VA. 4. The organoaluminum compound (D) is
4. The method for producing an olefin according to claim 1, wherein the alkyl group-containing aluminum compound or aluminoxane having at least one branched alkyl group having 3 or more carbon atoms is an aluminoxane. 5. The following compounds (A) and (B): (A) a transition metal compound containing a transition metal selected from Group IVB of the periodic table (B) an ionic complex by reacting with a transition metal compound. The compound (A) and (B) whose main component is the compound to be formed
An olefin polymerization catalyst in which at least one of the above is supported on a carrier (C), wherein the compound (A) is a transition metal compound represented by the following formula (IV): .. M ¹ R ¹ _a R ² _b R ³ _c R ⁴ _d (IV) [wherein, M ¹ is a Ti, Zr or Hf atom, R ¹ _a , R
² _b , R ³ _c and R ⁴ _d each represent a σ-bonding ligand, a chelating ligand or a Lewis base, which may be the same as or different from each other. Often, a, b, c and d each represent an integer of 0-4. ] 6. The compound (B) is a group IIIB or VB group of the periodic table.
Tribe, VIB, VIIB, VIII, IA, IB, IIA, IIB
A cation containing an element selected from Group IVA, Group VIIA, and multiple groups are group VB, VIB, VIIB, VIII of the periodic table.
The catalyst for olefin polymerization according to claim 5, which is a compound comprising an anion bonded to an element selected from Group I, Group IB, Group IIB, Group IIIA, Group IVA and Group VA.