JPH1160628A - Olefin polymerization catalyst using organometal lic complex and preparation of polyolerin using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produec an olefin polymn. catalyst which can produce a homogeneous polyolefin having a high mol.wt. and narrow mol.wt. distribution and compsn. distribution in a cost-effective manner by incorporating a specified org. transition metal compd. and an activation co-catalyst. SOLUTION: This olefin polymn. catalyst comprises a combination of a transition metal compd. represented by formula I or II [wherein M<1> and M<2> represent each a group 4, 5, or 6 transition metal of the periodic table; L<1> and L<3> represent each a cyclopentadienyl deriv.; L<2> and L<4> represent each a ligand represented by formula III or IV; Y<1> to Y<4> represent each an (un)substd. arom. hydrocarbon group or an (un) substd. heterocylic group; Z<1> represents a hydrocarbon group a hydrocarbon group contg. a hetero atom; Z<2> represents carbon or a hydrocarbon group (contg. a hetero atom); L<5> represents a hydrocarbon group (contg. a hetero atom); X<1> and X<2> represent each H, a halogen, a hydrocarbon group (contg. a hetero atom) or the like; and (n) is 2 to 4] with an activation cocatalyst represented by formulae V to VIII [wherein H represents a proton; E represents B or Al; L<6> represents a Lewis base; L<7> represents L<6> or a (un)substd. cyclopentadienyl; A represents Li, Fe, or Ag; D represents a carbonium cation or the like; Ar represents an (un)substd. aryl or the like; and (m) is 0 to 2) or the like].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a catalyst for olefin polymerization using an organic transition metal complex and a method for producing a polyolefin. More specifically, the present invention relates to an olefin polymerization catalyst characterized by an organic transition metal complex as a main catalyst, and a method for producing a polyolefin using the same.

[0002]

2. Description of the Related Art Until now, industrially, heterogeneous Ziegler catalysts mainly comprising titanium chloride or chromium oxide have been mainly used for polymerization of olefins.

[0003] However, recently, homogeneous catalysts for producing polyolefins using transition metal compounds or organic transition metal compounds have been actively studied, and many reports have been made on the possibility of complex catalysts, especially soluble complex catalysts.

[0004] However, most of them are organic transition metal compounds having two or more cyclopentadienyl derivatives collectively referred to as metallocene compounds as substituents, such as bis (cyclopentadienyl) zirconium dichloride and bis (substituted cyclopentadienyl). (Pentadienyl) zirconium dichloride is a typical compound (JP-A-58-1).
No. 9309). However, these complex catalysts have a limit in copolymerizability, and there is a demand for the development of a complex catalyst having higher copolymerizability. As a complex catalyst with significantly improved copolymerizability, a complex having a constrained geometric structure in which a cyclopentadienyl derivative and an amide ligand are crosslinked with a silyl atom has been reported, but there are problems with the stability and polymerization activity of the complex. (Japanese Unexamined Patent Publication (Kokai) No. 3-163088).

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and has as its object a novel structure which has not been found in a wide variety of olefin polymerization technical fields. Provide catalysts for olefin polymerization, manufacture new catalysts in this technical field,
An object of the present invention is to provide a method for producing a polyolefin more economically by using it for development.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to solve the above problems, and as a result, have found that a new catalyst for olefin polymerization and a method for producing polyolefin using the same can be provided. Was completed.

That is, the present invention provides the following general formula (1) or (2)

[0008]

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(Where M ¹ and M ² are transition metals of groups 4, 5 or 6 of the periodic table, L ¹ and L ³ are cyclopentadienyl derivatives, L ² and L ⁴ are the following general formula (3) or
(4)

[0010]

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A ligand represented by the formula: Y ¹ , Y ² , Y ³
And Y ^{4, which} may be the same or different, are a substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted heterocyclic group, and Z ¹ is a hydrocarbon group or a hetero atom-containing hydrocarbon group; ² is carbon, a hydrocarbon group or a hetero atom-containing hydrocarbon group, L ⁵ is a hydrocarbon group or a hetero atom-containing hydrocarbon group, X ¹ and X ² may be the same or different, and may be hydrogen, halogen, hydrocarbon A hetero atom-containing hydrocarbon group, or an alkoxy group or an amide group having a hydrocarbon group or a hetero atom-containing hydrocarbon group, and n is 2, 3 or 4. )) And an organic transition metal compound (A) represented by the following general formula (5)
Or (8) [HL ⁶ ] [E (Ar) ₄ ] (5) [AL ⁷ _m ] [E (Ar) ₄ ] (6) [D] [E (Ar) ₄ ] (7) E (Ar) ₃ (8) (where H is a proton, E is boron or aluminum. L ⁶ is a Lewis base, L ⁷ is a Lewis base or a substituted or unsubstituted cyclopentadienyl group. A is lithium , Iron or silver, D is a carbonium cation or a tropylium cation, Ar is the same or different and is a substituted or unsubstituted aryl group or a substituted or unsubstituted aralkyl group, and m is 0, 1 or 2), one or more activating cocatalysts (B) selected from aluminoxane, clay minerals and magnesium chloride.
Alternatively, the present invention relates to an olefin polymerization catalyst comprising (A) an organic transition metal compound, (B) an activating co-catalyst, and (C) an organoaluminum compound, and a method for producing a polyolefin using the same.

Further, this olefin polymerization catalyst is referred to as (D)
A solid catalyst for olefin polymerization characterized by being supported on a solid carrier, or (E) an olefin polymerization catalyst obtained by prepolymerizing an olefin using a catalyst for olefin polymerization or a solid catalyst for olefin polymerization; Olefin polymerization catalyst comprising the above-mentioned olefin polymerization catalyst or olefin polymerization solid catalyst obtained according to the present invention and (F) one or more selected from organolithium compounds, organomagnesium compounds and organoaluminum compounds, and polyolefins using them And a method for producing the same.

Hereinafter, the present invention will be described in detail.

The organic transition metal compound (A) used as the main catalyst of the catalyst for olefin polymerization of the present invention is represented by the following Periodic Tables 4 and 5:
Or a polydentate ligand having a group 6 transition metal, a cyclopentadienyl derivative, an aromatic hydrocarbon group and / or a heterocyclic group as a basic skeleton, and represented by the general formula (1) or (2). It is.

L ¹ and L ³ in formulas (1) and (2) are cyclopentadienyl derivatives, for example, cyclopentadienyl, indenyl, fluorenyl, hydrocarbon or heteroatom-containing hydrocarbon groups. A cyclopentadienyl group, an indenyl group or a fluorenyl group substituted with a cyclopentadienyl group, an indenyl group or a fluorenyl group substituted with a silyl group having a hydrocarbon group or a heteroatom-containing hydrocarbon group; Examples of the group and the hetero atom-containing hydrocarbon group include a methyl group, an ethyl group, an isopropyl group, an n-propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a cyclopentyl group, a cyclohexyl group, and a trimethylsilylmethyl group. Alkyl groups such as dimethylphenylsilylmethyl group, Aralkyl groups such as benzyl group, methoxybenzyl group, dimethylaminobenzyl group, phenyl group, o
-Tolyl group, m-tolyl group, p-tolyl group, o-ethylphenyl group, m-ethylphenyl group, p-ethylphenyl group, o-isopropylphenyl group, m-isopropylphenyl group, p-isopropylphenyl group, o-butylphenyl group, m-butylphenyl group, p-butylphenyl group, o- (t-butyl) phenyl group, m- (t-butyl) phenyl group, p- (t-butyl) phenyl group, o-
Methoxyphenyl group, m-methoxyphenyl group, p-methoxyphenyl group, o-dimethylaminophenyl group, m
-Dimethylamino group, p-dimethylamino group, 2,6-
Dimethylphenyl group, 2,6-diethylphenyl group,
2,6-dipropylphenyl group, 2,6-diisopropylphenyl group, 2,6-di (n-butyl) phenyl group,
2,6-di (t-butyl) phenyl group, 2,6-di (s
ec-butyl) phenyl group, 2,6-diphenylphenyl group, 2,6-dimethoxyphenyl group, 2,6-bis (dimethylamino) phenyl group, 2,6-difluorophenyl group, 2,4,6-trimethyl Phenyl group, 2,
4,6-triethylphenyl group, 2,4,6-tripropylphenyl group, 2,4,6-tri (isopropyl) phenyl group, 2,4,6-tri (n-butyl) phenyl group, 2,4 , 6-tri (t-butyl) phenyl group, 2,
4,6-tri (sec-butyl) phenyl group, 2,4
Aryl groups such as a 6-triphenylphenyl group, a 2,4,6-trimethoxyphenyl group, a 2,4,6-tri (dimethylamino) phenyl group, and a 2,4,6-trifluorophenyl group may be mentioned. Examples of the silyl group having a hydrocarbon group or a hetero atom-containing hydrocarbon group as a substituent include trimethylsilyl, triethylsilyl, triisopropylsilyl, tris (tributylmethyl) silyl, triphenylsilyl, and dimethyl. Examples include a methoxysilyl group and a dimethylphenylsilyl group.

Preferred examples of L ¹ and L ³ include cyclopentadienyl group, methylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, tetramethylcyclopentadienyl group and ethylcyclopentane. Dienyl group, isopropylcyclopentadienyl group, n-butylcyclopentadienyl group, methylethylcyclopentadienyl group, trimethylsilylcyclopentadienyl group, indenyl group, methylindenyl group, t-butylindenyl group, Trimethylsilylindenyl group, dimethylaminoindenyl group, methoxyindenyl group, methylfluorenyl group, 2,7-dimethylfluorenyl group, 2,7-di (t-butyl) fluorenyl group, methoxyfluorenyl group A 2,7-dimethoxyfluorenyl group, a di Methylaminofluorenyl group, 2,7
A dimethylaminofluorenyl group and the above cyclopentadienyl derivative in which L ⁵ is introduced as a substituent, or L ¹ is a pentamethylcyclopentadienyl group, a pentaphenylcyclopentadienyl group or the like; Can be mentioned.

L ² and L ⁴ are represented by the general formula (3) or (4)
And has a monovalent negative charge, and at least two or more atoms of Y ¹ , Y ² , Y ³ , Y ⁴ , Z ¹ , and Z ² form a transition metal. A ligand exhibiting an interaction, wherein Y ¹ , Y ² , Y ³ , and Y ⁴ may be the same or different from each other, and may be a substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted heterocyclic group; It is.

Specific examples include phenyl, toluyl, dimethylaminophenyl, methoxyphenyl,
A naphthyl group, a pyridyl group, a quinolyl group, an isoquinolyl group, a pyridazinyl group, a pyrimidinyl group, a thiophenyl group, a furyl group, a pyrrolyl group, and the like. Examples include a naphthyl group, a pyridyl group or a methylpyridyl group.

Z ¹ and Z ² are Y ¹ and Y ² or Y ³
And Y ⁴ , wherein Z ¹ is a hydrocarbon group or a hetero atom-containing hydrocarbon group, and Z ² is a carbon, hydrocarbon group or a hetero atom-containing hydrocarbon group, for example, a methylidine group, a methylene group , Ethylidene group, ethylene group, vinylene group, dimethylvinylene group, isopropylidene group, propylidene group, phenylmethylidene group, trimethylsilylmethylidene group, methylsilyl group, phenylsilyl group, dimethylsilyl group, methylphenylsilyl group,
Examples include a diphenylsilyl group. Preferred are carbon, methylidene, ethylidene, phenylmethylidene and trimethylsilylmethylidene.

M ¹ and M ² are titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum or tungsten, preferably titanium, zirconium or hafnium.

X ¹ and X ² may be the same or different from each other, and may be hydrogen, halogen, hydrocarbon, a hetero atom-containing hydrocarbon group, or an alkoxy group or amide group having a hydrocarbon group or a hetero atom-containing hydrocarbon group. And examples of the hydrocarbon group and the hetero atom-containing hydrocarbon group include methyl group, ethyl group, isopropyl group, n-propyl group, n-butyl group, sec-butyl group, t-butyl group, cyclopentyl group, and cyclohexyl. Group, trimethylsilylmethyl group, alkyl group such as dimethylphenylsilylmethyl group, benzyl group, methoxybenzyl group, aralkyl group such as dimethylaminobenzyl group, phenyl group, o
-Tolyl group, m-tolyl group, p-tolyl group, o-ethylphenyl group, m-ethylphenyl group, p-ethylphenyl group, o-isopropylphenyl group, m-isopropylphenyl group, p-isopropylphenyl group, o-butylphenyl group, m-butylphenyl group, p-butylphenyl group, o- (t-butyl) phenyl group, m- (t-butyl) phenyl group, p- (t-butyl) phenyl group, o
-Methoxyphenyl group, m-methoxyphenyl group, p-
Methoxyphenyl group, o-dimethylaminophenyl group,
m-dimethylamino group, p-dimethylamino group, 2,6
-Dimethylphenyl group, 2,6-diethylphenyl group,
2,6-dipropylphenyl group, 2,6-diisopropylphenyl group, 2,6-di (n-butyl) phenyl group,
2,6-di (t-butyl) phenyl group, 2,6-di (s
ec-butyl) phenyl group, 2,6-diphenylphenyl group, 2,6-dimethoxyphenyl group, 2,6-bis (dimethylamino) phenyl group, 2,6-difluorophenyl group, 2,4,6-trimethyl Phenyl group, 2,
4,6-triethylphenyl group, 2,4,6-tripropylphenyl group, 2,4,6-tri (isopropyl) phenyl group, 2,4,6-tri (n-butyl) phenyl group, 2,4 , 6-tri (t-butyl) phenyl group, 2,
4,6-tri (sec-butyl) phenyl group, 2,4
Aryl groups such as a 6-triphenylphenyl group, a 2,4,6-trimethoxyphenyl group, a 2,4,6-tri (dimethylamino) phenyl group, and a 2,4,6-trifluorophenyl group may be mentioned. Examples of the alkoxy group and the amide group include those having the above-described hydrocarbon group or heteroatom-containing hydrocarbon group as a substituent.

As specific examples of the organic transition metal compound,
(Cyclopentadienyl) (dipyridylmethyl) zirconium dichloride, (methylcyclopentadienyl)
(Dipyridylmethyl) zirconium dichloride, (t
-Butyl-cyclopentadienyl) (dipyridylmethyl) zirconium dichloride, (trimethylsilylcyclopentadienyl) (dipyridylmethyl) zirconium dichloride, (indenyl) (dipyridylmethyl)
Zirconium dichloride, (fluorenyl) (dipyridylmethyl) zirconium dichloride, (pentamethylcyclopentadienyl) (dipyridylmethyl) zirconium dichloride, (cyclopentadienyl) (phenyldipyridylmethyl) zirconium dichloride,
(Methylcyclopentadienyl) (phenyldipyridylmethyl) zirconium dichloride, (t-butyl-cyclopentadienyl) (phenyldipyridylmethyl) zirconium dichloride, (trimethylsilylcyclopentadienyl) (phenyldipyridylmethyl) zirconium dichloride, (indenyl) ) (Phenyldipyridylmethyl) zirconium dichloride, (fluorenyl) (phenyldipyridylmethyl) zirconium dichloride, (pentamethylcyclopentadienyl) (phenyldipyridylmethyl) zirconium dichloride,
[(Cyclopentadienyl) (dipyridylmethylene) dimethylsilyl] zirconium dichloride, [(methylcyclopentadienyl) (dipyridylmethylene) dimethylsilyl] zirconium dichloride, [(t-butyl-cyclopentadienyl) (dipyridylmethylene) [Dimethylsilyl] zirconium dichloride, [(trimethylsilylcyclopentadienyl) (dipyridylmethylene) dimethylisyl] zirconium dichloride,
[(Indenyl) (dipyridylmethylene) dimethylsilyl] zirconium dichloride, [(fluorenyl)
((Dipyridylmethylene) dimethylsilyl] zirconium dichloride, [(cyclopentadienyl) (dipyridylmethylene) dimethylmethylene] zirconium dichloride, [(methylcyclopentadienyl) (dipyridylmethylene) dimethylmethylene] zirconium dichloride, [(t-butyl -Cyclopentadienyl) (dipyridylmethylene) dimethylmethylene] zirconium dichloride, [(trimethylsilylcyclopentadienyl)
((Dipyridylmethylene) dimethylmethylene] zirconium dichloride, [(indenyl) (dipyridylmethylene) dimethylmethylene] zirconium dichloride,
[(Fluorenyl) (dipyridylmethylene) dimethylmethylene] zirconium dichloride, [(cyclopentadienyl) (dipyridylmethylene) diphenylmethylene] zirconium dichloride, [(methylcyclopentadienyl) (dipyridylmethylene) diphenylmethylene] zirconium dichloride, [ (T-butyl-cyclopentadienyl) (dipyridylmethylene) diphenylmethylene] zirconium dichloride, [(trimethylsilylcyclopentadienyl) (dipyridylmethylene)
Diphenylmethylene] zirconium dichloride,
[(Indenyl) (dipyridylmethylene) diphenylmethylene] zirconium dichloride, [(fluorenyl) (dipyridylmethylene) diphenylmethylene] zirconium dichloride, and compounds in which the central metal is replaced with titanium or hafnium from zirconium can be mentioned. It is not limited.

The (B) activating co-catalyst, which is one of the components of the olefin polymerization catalyst in the present invention, is (A) the organic transition metal compound itself, which is the main catalyst of the present invention, or (A) the organic transition metal compound itself. It refers to a compound that forms an active species capable of producing a polyolefin by an action or reaction between a transition metal compound and a product obtained by reacting the organoaluminum compound (C).

These compounds include the following general formula (5)
Any of the protonic acid represented by the general formula (6), the ionized ionic compound represented by the general formula (6), the Lewis acid represented by the general formula (7) and the Lewis acidic compound represented by the general formula (8) [HL ⁶ ] [E (Ar) ₄ ] (5) [AL ⁷ _m ] [E (Ar) ₄ ] (6) [D] [E (Ar) ₄ ] (7) E (Ar) ₃ (8) wherein H is a proton, E is boron or aluminum, L ⁶ is a Lewis base, L ⁷ is a Lewis base or a substituted or unsubstituted cyclopentadienyl group, A is lithium, D is a carbonium cation or a tropylium cation, and Ar is the same or different and is a substituted or unsubstituted aryl group or a substituted or unsubstituted aralkyl group, and m is 0. , 1 or 2 Some.), It can be shown aluminoxane, clay mineral or a magnesium chloride compound.

Specific examples of the protonic acid represented by the general formula (5) include diethyloxonium tetrakis (pentafluorophenyl) borate, dimethyloxonium tetrakis (pentafluorophenyl) borate, tetramethyleneoxonium tetrakis (pentafluorophenyl) ) Borate, hydronium tetrakis (pentafluorophenyl) borate, trimethylammonium tetrakis (pentafluorophenyl) borate, tri (n-
Butyl) ammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, diethyloxonium tetrakis (pentafluorophenyl) aluminate, dimethyloxonium tetrakis (pentafluorophenyl) aluminate, Tetramethyleneoxonium tetrakis (pentafluorophenyl) aluminate, hydronium tetrakis (pentafluorophenyl) aluminate, N, N-dimethylaniliniumtetrakis (pentafluorophenyl) aluminate, tri (n-butyl) ammonium tetrakis (pentane) Fluorophenyl) aluminate and the like,
It is not limited to these.

Specific examples of the ionized ionic compound represented by the general formula (6) include lithium salts such as lithium tetrakis (pentafluorophenyl) borate and lithium tetrakis (pentafluorophenyl) aluminate, and ether complexes thereof. , Ferrocenium salts such as ferrocenium tetrakis (pentafluorophenyl) borate and ferrocenium tetrakis (pentafluorophenyl) aluminate, and silver salts such as silver tetrakis (pentafluorophenyl) borate and silver tetrakis (pentafluorophenyl) aluminate And the like, but are not limited thereto.

As the Lewis acid represented by the general formula (7), specifically, trityltetrakis (pentafluorophenyl) borate, trityltetrakis (pentafluorophenyl) aluminate, tropylium tetrakis (pentafluorophenyl) borate, Examples include, but are not limited to, tropylium tetrakis (pentafluorophenyl) aluminate.

Specific examples of the Lewis acidic compound represented by the general formula (8) include tris (pentafluorophenyl) borane, tris (2,3,5,6-tetrafluorophenyl) borane, tris (2 3,4,5-tetraphenylphenyl) borane, tris (3,4,5-trifluorophenyl) borane, phenylbis (perfluorophenyl) borane, tris (3,4,5-trifluorophenyl) aluminum and the like But are not limited to these.

On the other hand, when the activating polymerization catalyst (B), which is a component of the catalyst for olefin polymerization of the present invention, is aluminoxane, it is represented by the following general formula (9) or (10).

[0030]

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(In the formula, R ⁸ may be the same or different, and is hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, and q is 2 to 60.) In addition to the shape or ring structure,
It may have a partially or entirely clustered structure of aluminum, oxygen and alkyl groups. This aluminoxane can be generally obtained by reacting an organic aluminum compound and water in an organic solvent or an organic aluminum compound and a salt or oxide hydrate in an organic solvent, and is produced by a known method. Can be used.

In the general formulas (9) and (10), R
⁸ may be the same or different from each other, and specific examples include hydrogen or a hydrocarbon group having 1 to 20 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an isobutyl group, and a tert-butyl group. be able to.

When the activating polymerization catalyst (B) which is a component of the catalyst for olefin polymerization of the present invention is magnesium chloride, magnesium chloride may be prepared by a known method, and (A) an organic transition metal There is no particular limitation on the amount used per compound.

Further, when the activating polymerization catalyst (B), which is a component of the olefin polymerization catalyst of the present invention, is a clay mineral, the clay mineral is fine particles mainly composed of microcrystalline silicate. . Most of the clay minerals have a layered structure as a structural feature, and include various sizes of negative charges in the layer. When the clay mineral is classified according to the magnitude of the negative charge, the negative charge per chemical formula is 0.
Pyophyllite, kaolinite, dickarite and talc groups, smectite group whose negative charge is 0.25 to 0.6, vermiculite group which is 0.6 to 0.9, mica group of about 1 Each group shown here contains various minerals, and clay minerals belonging to smectite include montmorillonite, beidellite, saponite, hectorite, and the like. . In addition, these clay minerals exist naturally, but can be obtained by artificial synthesis with few impurities. In the present invention, all of the natural clay minerals shown here and clay minerals obtained by artificial synthesis can be used, and even those not exemplified above, all those belonging to the definition of clay minerals can be used. it can.

Further, clay minerals modified by introducing a cationic compound between the layers of the above clay minerals can also be used. In modifying the clay mineral, it is preferable that the cationic compound be used in an amount equal to or more than the cation exchange amount of the clay mineral.

The organoaluminum compound (C) which can be used together with (A) the organic transition metal compound and (B) the activating co-catalyst is not particularly limited, but may be represented by the following general formula (11). Compounds.

(R ⁹ ) ₃ Al (11) (wherein, R ⁹ may be the same or different and each represents hydrogen, halogen, a hydrocarbon group, an amide group, an alkoxy group,
An amide group substituted with a hydrocarbon group or an alkoxy group substituted with a hydrocarbon group, at least one of
One is a hydrocarbon group. ) Such compounds include trimethylaluminum,
Examples thereof include triethylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, diisobutylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, isobutylaluminum dichloride and the like.

In the preparation of the catalyst, the amount ratio of (A) the organic transition metal compound and (B) the activating co-catalyst is such that (B) the activating co-catalyst has the general formula (5), (6), (7) or (8) In the case of the compound represented by the formula (A), (A) :( B) = 10: 1 to 1: 1000 at a molar ratio per metal atom of (A) the organic transition metal compound and (B) the activation promoter. Is preferably used, and particularly preferably in the range of 3: 1 to 1: 100. The ratio of the (A) organic transition metal compound to the (C) organic aluminum compound when the (C) organic aluminum compound is used is not particularly limited. (A component) :( C component) = 100: 1 to 1:
The range of 100,000 is preferably used, particularly preferably in the range of 1: 1 to 1: 10000.

(B) The activating co-catalyst is aluminoxane,
For example, when represented by the general formula (9) or (10), (A)
(A component) :( B component) = 100: 1 to 1 mole ratio of the organic transition metal compound and the (B) activation co-catalyst per metal atom.
1: 1,000,000 is preferably used, and particularly preferably in the range of 1: 1 to 1: 100,000. Also,
The ratio of the (A) organic transition metal compound to the (C) organoaluminum compound is not particularly limited, but the molar ratio of the (A) organic transition metal compound to the (C) organoaluminum compound per metal atom is (A component): (Component C) = 100: 1 to 1: 1
The range of 00000 is preferably used, particularly preferably in the range of 1: 1 to 1: 10000.

Further, when (B) the activating co-catalyst is a clay mineral, the molar ratio of (A) the organic transition metal compound to (B) the activating co-catalyst is not particularly limited. It is desirable to add a sufficient amount of clay mineral to react with the clay mineral.

In the present invention, the method for preparing the catalyst is not particularly limited, and examples of the preparation method include a method in which a solvent or monomer inert to each component is used as a solvent and mixed. Also, there is no particular limitation on the order in which the above-mentioned catalyst components are reacted, and there is no particular limitation on the temperature and the processing time for this treatment.

The olefin polymerization catalyst of the present invention can be used in any of ordinary polymerization methods, that is, slurry polymerization, gas phase polymerization, high pressure polymerization, solution polymerization, bulk polymerization and the like.

In the present specification, polymerization is used to mean not only homopolymerization but also copolymerization, and the polyolefin produced by these polymerizations includes not only homopolymers but also copolymers. I have.

Further, the present invention shows a method for stably producing a polyolefin while substantially forming polymer particles using the catalyst system described above.

When a polyolefin is produced using the olefin polymerization catalyst or the olefin polymerization solid catalyst of the present invention in the presence of an olefin polymerization catalyst obtained by prepolymerizing (E) an olefin, the resulting polyolefin has a high bulk density. The polyolefin does not adhere to the walls of the reactor, and stable production is realized particularly by gas phase polymerization or slurry polymerization.

The above (A) organic transition metal compound and (B) activation co-catalyst, or (A) an organic transition metal compound, (B) activation co-catalyst and (C) organoaluminum compound, It can be supported on a carrier and used as a solid catalyst for olefin polymerization. The solid support (D) used as a component of the solid component for olefin polymerization is an inorganic or organic compound, and specific examples of the inorganic compound include an inorganic oxide and an inorganic halide. More specifically, examples of inorganic oxides include oxides of typical elements such as alumina, silica and magnesia, transition metal oxides such as titania and zirconia, and composite oxides such as silica-alumina and silica-magnesia. Can be Examples of inorganic halides include magnesium chloride, aluminum chloride and the like. These compounds usually contain, as impurities, salts such as carbonates and sulfates of alkali metals and alkaline earth metals such as potassium carbonate and barium sulfate, and particularly, inorganic halides include hydroxides and oxides. ing. The above-mentioned inorganic oxides or inorganic halides can be used in a form containing these impurities, but they can also be used after previously performing an operation of removing or reducing these impurities. Examples of the organic carrier include polyolefins such as polyethylene, polypropylene, polybutene, and polystyrene; polar polymers such as polyethyl methacrylate, polyester, and polyimide; and mixtures of polyolefins and polar polymers. Further, an ethylene-vinyl acetate copolymer which is a copolymer of an olefin and a polar monomer may be used.

The shape of the solid carrier (D) used in the present invention is not limited. However, in consideration of a range in which the catalyst shows high activity and is easy to handle in the process, the particle diameter is 0.1 to 1
It is preferably in the form of granules or fine particles having a diameter of 000 μm and a pore diameter of 1 to 1000 nm.

When (F) an organolithium compound, an organomagnesium compound or an organoaluminum compound is used as a component of the catalyst for olefin polymerization of the present invention, it is represented by the general formulas (12), (13) and (14). Compounds.

R ¹⁰ Li (12) (wherein, R ¹⁰ is hydrogen, an amide group or an alkoxy group having a hydrocarbon group or a hetero atom-containing hydrocarbon group,
Or a hydrocarbon group. (R ¹¹ ) ₂ Mg (13) wherein R ¹¹ may be the same as or different from each other, and may be hydrogen, halogen, an amide group or an alkoxy group having a hydrocarbon group or a heteroatom-containing hydrocarbon group, or a carbon atom. A hydrogen group, at least one of which is a hydrocarbon group.) (R ¹² ) ₃ Al (14) (wherein R ¹² may be the same or different, and may be hydrogen, halogen, a hydrocarbon group or An amide group or an alkoxy group having a hetero atom-containing hydrocarbon group, or a hydrocarbon group, at least one of which is a hydrocarbon group.) Represented by general formulas (12), (13) and (14) Examples of compounds include methyl lithium, butyl lithium, methyl magnesium chloride, dimethyl magnesium,
Examples include diethyl magnesium, butyl methyl magnesium, dibutyl magnesium, benzyl magnesium chloride, methyl magnesium bromide, trimethyl aluminum, triethyl aluminum or triisobutyl aluminum.

The olefin (E) which is a component of the solid catalyst for olefin polymerization prepared by prepolymerization using the catalyst for olefin polymerization or the solid catalyst for olefin polymerization of the present invention is not particularly limited, but has 2 to 16 carbon atoms. Α-olefins or cyclic olefins are preferred, and α-olefins such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene and styrene; butadiene, 1,4-hexadiene, 5 -Ethylidene-2
-Norbornene, dicyclopentadiene, 4-methyl-
Conjugated and non-conjugated dienes such as 1,4-hexadiene and 7-methyl-1,6-octadiene; and cyclic olefins such as cyclobutene and cyclopentene. These may be used alone or as a mixture of two or more.

When prepolymerization is carried out using two or more olefins, they are sequentially or simultaneously added to the reaction system.
Prepolymerization can be performed.

The prepolymerization method using the catalyst for olefin polymerization or the solid catalyst for olefin polymerization of the present invention is carried out as long as the catalyst for olefin polymerization or the solid catalyst for olefin polymerization can be polymerized with the olefin (E). Although not particularly limited, the reaction temperature is −50 to 100 ° C.,
Preferably -20 to 60 ° C, more preferably -10 to 4
In the temperature range of 0 ° C., the reaction pressure can be carried out under normal pressure or under pressure. When the reaction is carried out in a gaseous phase, it is preferred that the contact be carried out sufficiently under flow conditions, and when the reaction is carried out in a liquid phase, it is preferred that the contact be carried out sufficiently under stirring conditions.

The olefin used for the polymerization in the present invention includes α-olefins such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene and styrene; butadiene, 1,4- Hexadiene, 5-ethylidene-2-norbornene, dicyclopentadiene, 4-methyl-1,4-hexadiene, 7-
Conjugated and non-conjugated dienes such as methyl-1,6-octadiene; cyclic olefins such as cyclobutene and cyclopentene; and ethylene and propylene;
-Two or more kinds of components such as butene, or three or more kinds of components such as ethylene and propylene and styrene, ethylene and 1-hexene and styrene, and ethylene and propylene and ethylidene norbornene can be mixed and polymerized.

In the present invention, it is possible to carry out the polymerization using two or more kinds of the organic transition metal compounds (A). In particular, when expanding the molecular weight distribution or the composition distribution, it is preferable to use a plurality of (A) organic transition metal compounds.

In the present invention, the olefin polymerization can be carried out in a gas phase or a liquid phase. In particular, when the olefin polymerization is carried out in a gas phase, an olefin polymer having a uniform particle shape can be produced efficiently and stably. Can be. When the polymerization is carried out in the liquid phase, the solvent used may be any organic solvent generally used, and specifically, benzene, toluene, xylene, propane, isobutane, pentane, heptane,
Cyclohexane, gasoline and the like, propylene,
An olefin itself such as 1-butene, 1-hexene, 1-octene and the like can also be used as a solvent.

In producing an olefin polymer using the method of the present invention, there are no particular restrictions on polymerization conditions such as polymerization temperature, polymerization time, polymerization pressure and monomer concentration.
The polymerization temperature is −100 to 300 ° C., and considering the productivity, 2
0 to 300 ° C., particularly preferably 120 to 300 ° C. when the ethylene copolymer is produced by a high pressure method, -10 to 260 ° C. for solution polymerization, and 6 to 6 for slurry polymerization and gas phase polymerization.
It is preferable to carry out in the range of 0 to 120 ° C. The polymerization time varies depending on each process, but is usually performed in the range of 10 seconds to 20 hours, and the polymerization pressure varies depending on the process, but can be performed in the range of normal pressure to 3000 kg / cm ² G. It is also possible to adjust the molecular weight using hydrogen or the like during polymerization. Polymerization is batch, semi-continuous,
It is possible to carry out by any method of a continuous type, and it is also possible to carry out in two or more stages by changing the polymerization conditions.
Further, the polyolefin obtained after the completion of the polymerization can be separated and recovered from the polymerization solvent by a conventionally known method, and can be obtained by drying.

[0057]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which are only for illustrating the outline of the present invention and the present invention is not limited to these Examples. .

All the reactions were carried out in an atmosphere of an inert gas such as dried or purified nitrogen or argon, and the solvents used for the reactions were all “Purimon” manufactured by Pergamon.
fiction of Laboratory Ch
Purification, drying, or deoxygenation was carried out by a known method described in “Electrics 2nd Edition” and the like. The identification of the organic transition metal compound was performed using ¹ H-NMR (GPX-400 type NMR measuring apparatus manufactured by JEOL Ltd.).

Synthesis Example 1 Synthesis of (C ₅ H ₅ ) ((C ₅ H ₄ N) ₂ CH) ZrCl ₂
0.73 g of dipyridylmethane is added to 30 parts of tetrahydrofuran.
Then, 2.6 ml of a 1.6 M hexane solution of n-BuLi was reacted at −78 ° C., and the temperature was slowly raised to room temperature. 1.13 g of cyclopentadienyl zirconium trichloride dissolved in 50 ml of toluene
Was mixed at −78 ° C. with a solution suspended in 20 ml of toluene, and the temperature was slowly raised to room temperature. The reaction mixture was evaporated under reduced pressure to give a yellow-orange solid. By purifying and recrystallizing this reaction mixture, the desired compound 1.
02 g were obtained.

¹ H-NMR (CDCl ₃ : ppm)
84 (s), 6.49 (s), 7.00 (ddd),
7.18 (dd), 7.63 (ddd), 8.43 (d
d) Example 1 [Preparation of Catalyst] 0.5% of the organic transition metal compound (C ₅ H ₅ ) ((C ₅ H ₄ N) ₂ CH) ZrCl ₂ obtained in Synthesis Example 1 described above.
Methylaluminoxane diluted with 10 ml of a mol / l toluene solution and 10 ml of toluene (Tosoh Akzo Co., Ltd.)
The mixture was stirred at room temperature under a nitrogen stream at room temperature and stirred for 20 minutes to obtain a polymerization catalyst.

[Ethylene polymerization] 1000 ml of toluene was placed in a 2 liter autoclave sufficiently purged with dry nitrogen.
50 ml of 1-hexene was sequentially introduced, and ethylene was introduced into the autoclave so that the total pressure became 4 kg / cm ² . 40. The above-mentioned catalyst component was injected thereinto, and polymerization was carried out at 80 ° C. for 20 minutes while continuously supplying ethylene.
74 g of polymer were obtained.

[0062]

According to the present invention, it is possible to provide an olefin polymerization catalyst mainly comprising an organic transition metal complex having a novel structure. Thus, a homogeneous polyolefin having a narrow molecular weight distribution and a narrow composition distribution can be produced economically.

Claims (6)

[Claims] 1. A compound represented by the following general formula (1) or (2): (Where M ¹ and M ² are transition metals of Group 4, 5 or 6 of the periodic table, L ¹ and L ³ are cyclopentadienyl derivatives,
L ² and L ⁴ are represented by the following general formula (3) or (4): Wherein Y ¹ , Y ² , Y ³ and Y ⁴ may be the same or different, and each represents a substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted heterocyclic group. Wherein Z ¹ is a hydrocarbon group or a hetero atom-containing hydrocarbon group, Z ² is carbon, a hydrocarbon group or a hetero atom-containing hydrocarbon group, L ⁵ is a hydrocarbon group or a hetero atom-containing hydrocarbon group, X ¹ and X ² may be the same or different, and is hydrogen, halogen, hydrocarbon, a hetero atom-containing hydrocarbon group, or an alkoxy group or amide group having a hydrocarbon group or a hetero atom-containing hydrocarbon group; , 3 or 4. ) And the following general formulas (5) to (8) [HL ⁶ ] [E (Ar) ₄ ] (5) [AL ⁷ _m ] [E (Ar) ₄ ] ( 6) [D] [E (Ar) ₄ ] (7) E (Ar) ₃ (8) wherein H is a proton, E is boron or aluminum, L ⁶ is a Lewis base, and L ⁷ is A Lewis base or a substituted or unsubstituted cyclopentadienyl group, A is lithium, iron or silver, D is a carbonium cation or a tropylium cation, Ar may be the same or different from each other, Or an unsubstituted aryl group or a substituted or unsubstituted aralkyl group; m is 0, 1 or 2), an aluminoxane, a clay mineral, and at least one activity selected from magnesium chloride. Chemical assistant Olefin polymerization catalyst, comprising the medium (B). 2. An olefin polymerization catalyst comprising: (A) the organic transition metal compound according to claim 1; (B) an activating co-catalyst; and (C) an organoaluminum compound. 3. A solid catalyst for olefin polymerization, wherein the catalyst for olefin polymerization according to claim 1 or 2 is carried on a solid carrier (D). 4. An olefin polymerization catalyst obtained by prepolymerizing (E) an olefin using the olefin polymerization catalyst or the olefin polymerization solid catalyst according to any one of claims 1 to 3. 5. An olefin polymerization catalyst or an olefin polymerization solid catalyst according to any one of claims 1 to 4, and (F) at least one selected from organolithium compounds, organomagnesium compounds and organoaluminum compounds. A catalyst for olefin polymerization characterized by the following. 6. A method for producing a polyolefin, comprising polymerizing an olefin using the catalyst for olefin polymerization or the solid catalyst for olefin polymerization according to any one of claims 1 to 5.