JPH06340704A - Polymerization catalyst and production of polymer - Google Patents

Abstract

PURPOSE:To provide a new highly active polymerization catalyst comprising an activation auxiliary catalyst and a transition metal compound containing hetero atom-containing cyclopentadienyl groups, and giving polymers each having a large mol.wt. and a narrow mol.wt. distribution. CONSTITUTION:A polymerization catalyst having a high activity and giving polymers each having a large mol.wt., an uniform composition and a narrow mol.wt. distribution comprises (A) a cyclopentadienyl group-containing transition metal compound of the formula [M is the 3-10th group metal or the lanthanoid metal in the periodic table; X is the element of the 13-15th group, etc.; R is H, halogen, 1-20C hydrocarbon, oxygen-containing group, silicon-containing group; a is 0,1; b is an integer of 1 to the atomic valency number of M; Y is a sigma-bonding ligand, a chelating ligand, a Lewis base; c is 0 to an integer equal to (the atomic valency of M-b)], wherein the cyclopentadienyl group contains at least one hetero atom, (B) an activation auxiliary catalyst comprising a compound capable of forming a cation species from the component A or its derivative, etc., and (C) an organic Al compound.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel and useful polymerization catalyst, and a method for producing a polymer using the same. More specifically, it relates to a polymerization catalyst particularly useful as an olefin polymerization catalyst, and a method for producing a polyolefin-based polymer using the same.

[0002]

2. Description of the Related Art Heretofore, a catalyst comprising a combination of a transition metal compound and an aluminoxane has been known as a highly active soluble olefin polymerization catalyst (JP-A-58-1930).
9 and JP-A-60-217209). Further, it has been proposed that a cationic species is useful as an active species of a soluble olefin polymerization catalyst [J. Am. Chem. Soc. 81, 81 (1
959), J.Am.Chem.Soc.82,1953 (1960), J.Am.Chem.Soc.
107, 7219 (1985)]. As an example of isolating this active species and applying it to olefin polymerization, J. Am. Chem. Soc. 108, 7410 (1
986), Tokushuhei 01-502636, JP-A-03-13.
9504, European Patent Publication 468651 and the like, and examples of the active species used in combination with an organoaluminum compound include JP-A 03-207704 and International Patent Publication 92-1723.

[0003]

However, the polymer produced by the complex having a cyclopentadienyl type ligand used in these prior arts has a reaction temperature of 70 to 70% which is efficient in an industrial process. When the polymerization was carried out at 100 ° C. or higher, there was a problem that the molecular weight of the obtained polymer was small.

The present invention has been made in view of the above-mentioned problems, and it is highly active as a polymerization catalyst, and the obtained polymer or copolymer has a large molecular weight and a uniform composition, and further has a molecular weight. It is an object of the present invention to provide a polymerization catalyst whose distribution range can be controlled narrowly and a method for producing a polymer using the same.

[0005]

To achieve the above object, the present invention provides a polymerization catalyst containing the following compounds (A) and (B). (A) a transition metal compound containing a cyclopentadienyl group containing at least one heteroatom (B) an activating cocatalyst, such as a transition metal compound (A) or a derivative of (A) forming a cationic species And a compound (A),
Provided is a polymerization catalyst containing (B) and (C). (A) Transition metal compound containing cyclopentadienyl group containing at least one hetero atom (B) Activation co-catalyst (C) Organoaluminum compound Further, in the presence of the above-mentioned polymerization catalyst, for example, olefins alone are used. There is provided a method for producing an olefin-based (co) polymer, which comprises polymerizing or copolymerizing an olefin with another olefin or another monomer. Other objects and other advantages of the present invention will be apparent from the following description.

The present invention will be specifically described below. 1. A transition metal compound (A) containing a cyclopentadienyl group containing at least one hetero atom (A) As a transition metal compound (A) containing a cyclopentadienyl group containing at least one hetero atom used in the present invention, Although not particularly limited, specific examples thereof include compounds of the following formula (I).

[0007]

[Chemical 1]

[In the formula, M represents a metal of Group 3 to 10 of the periodic table or a lanthanoid series metal. X is 13th group, 14th
An element of Group 15 or Group 15 is shown. Each X may be the same or different, but at least one of the 5 × b Xs contains an element other than carbon. R is a hydrogen atom, a halogen atom,
Alternatively, it represents a hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, or a silicon-containing group. Each R may be the same or different, and Rs may be crosslinked. Further, R and M may be crosslinked. a represents 0 or 1. b represents an integer not less than 1 and not more than the valence number of M. Each [((R) _a ) ₅
The X ₅ ] groups may be the same or different. Y represents a σ-bonding ligand, a chelating ligand or a Lewis base. Each Y may be the same or different. [((R)
_{The a} ) ₅ X ₅ ] group and Y may be crosslinked. c is
The integer which is 0 or more and is equal to (valence of M-b) is shown. ]

As the hetero atom contained in the compound (A) at least one, a phosphorus atom (P), a nitrogen atom (N), an aluminum atom (Al) and a boron atom (B).
One or more atoms selected from the group consisting of can be preferably used. Specific examples thereof include those using one type of phosphorus atom (P) or the like, or two types using a combination of nitrogen atom (N) and boron atom (B). Specific examples of such compounds include the following, and zirconium substituted with hafnium, titanium, vanadium, or another metal of Group 3 to 10 of the periodic table or a lanthanoid series metal.

Bis (1-phospha-2,3,4,5-tetramethylcyclopentadienyl) zirconium dichloride, bis (1-phospha-2,3,4,5-tetramethylcyclopentadienyl) zirconium dichloride Bromide,
Bis (1-phospha-2,3,4,5-tetramethylcyclopentadienyl) zirconium dimethyl, bis (1
-Phospha-2,3,4,5-tetramethylcyclopentadienyl) zirconium dibenzyl, bis (1-phospha-2,3,4,5-tetramethylcyclopentadienyl) zirconium chloride hydride, bis (1 -Phospha-2,3,4,5-tetramethylcyclopentadienyl) zirconium dihydride, bis (1-phospha-
2,3,4,5-tetramethylcyclopentadienyl)
Bis (dimethylamino) zirconium, bis (1-phospha-2,3,4,5-tetramethylcyclopentadienyl) zirconium dimethoxide, bis (1-phospha-2,3,4,5-tetramethylcyclopenta) Dienyl) zirconium diphenoxide, bis (1-phospha-2,3,4,5-tetramethylcyclopentadienyl) zirconium, bis (1-phospha-3,4-diphenylcyclopentadienyl) zirconium dichloride, bis (1-phospha-3,4-diphenylcyclopentadienyl) zirconium dimethyl, bis (1-phospha-3,4-diphenylcyclopentadienyl) zirconium dibenzyl, bis (1-phospha-3,4-diphenylcyclo) Pentadienyl) zirconium chloride hydride, bis (1-pho Fan-3,4-diphenyl-cyclopentadienyl) zirconium dihydride, bis (1-phospha-3,4-dimethyl-cyclopentadienyl) zirconium dichloride, bis (1-phospha -
2,5-Dimethylcyclopentadienyl) zirconium dichloride, bis (1-phospha-2,5-diphenylcyclopentadienyl) zirconium dichloride, bis (1-phospha-cyclopentadienyl) zirconium dichloride, bis (1- Phosfinedenyl) zirconium dichloride, bis (1-phospha-2,3,4,5)
-Tetramethylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, bis (1-phospha-2,3,4,5-tetramethylcyclopentadienyl) (pentamethylcyclopentadienyl) zirconium dichloride, ( 9-phosphafluorenyl) (cyclopentadienyl) zirconium dichloride, (1-phosfindenyl) (indenyl) zirconium dichloride, bis (1-phospha-3-methoxycarbonylcyclopentadienyl) zirconium dichloride, ethylene Bis (3-phosphinedenyl) zirconium dichloride, dimethylsilylene (3-phosfinedenyl) zirconium dichloride, dimethylsilylene (3-phospha-4-methylcyclopentadienyl) zirconium dichloride, bis (1 3-diphospha-4,5-diphenylcyclopentadienyl) zirconium dichloride, bis (1,2,3-triphospha-4,5-diphenylcyclopentadienyl) zirconium dichloride, bis (1,2,4-triphospha) 3,5-diphenylcyclopentadienyl) zirconium dichloride, bis (1,2,3,4-tetraphospha-5-phenylcyclopentadienyl) zirconium dichloride, bis (pentaphosphacyclopentadienyl) zirconium dichloride, bis (1-phospha-3-benzoyloxycyclopentadienyl) zirconium dichloride, (1-
Phospha-2,3,4,5-tetramethylcyclopentadienyl) zirconium trichloride, (1-phospha-2,3,4,5-tetramethylcyclopentadienyl) zirconium trimethyl, (1-phospha-2) ，
3,4,5-Tetramethylcyclopentadienyl) zirconium tribenzyl, (1-phospha-2,3,4,
5-tetramethylcyclopentadienyl) zirconium methyl dichloride, (1-phospha-2,3,4,5-
Tetramethylcyclopentadienyl) zirconium trihydride, (1-phospha-3,4-diphenylcyclopentadienyl) zirconium trichloride, (1-phospha-3,4-diphenylcyclopentadienyl) zirconium trimethyl, (1 -Phospha-3,4-diphenylcyclopentadienyl) zirconium tribenzyl, (1-phospha-3,4-diphenylcyclopentadienyl) zirconium methyl dichloride, (1-phospha-3,4-diphenylcyclopentadienyl) ) Zirconium trihydride, (1-phospha-3,4-dimethylcyclopentadienyl) zirconium trichloride, (1-phosfindenyl) zirconium trichloride, (1-phospha-3-methoxycarbonylcyclopentadienyl) The Benzalkonium trichloride, (1,3
-Diphospha-4,5-diphenylcyclopentadienyl) zirconium trichloride, (1,2,3-triphospha-4,5-diphenylcyclopentadienyl) zirconium trichloride, (1,2,4-triphospha-3) , 5-Diphenylcyclopentadienyl) zirconium trichloride, (1,2,3,4-tetraphospha-5-phenylcyclopentadienyl) zirconium trichloride, (pentaphosphacyclopentadienyl)
Zirconium trichloride, (1-phospha-3-benzoyloxycyclopentadienyl) zirconium trichloride, bis (imidazolyl) zirconium dichloride, bis (pyrrolyl) zirconium dichloride, bis (2,5-dimethylpyrrolyl) zirconium dichloride, bis (Pyrrolyl) zirconium dimethyl, bis (pyrrolyl) zirconium dibenzyl, bis (pyrrolyl) zirconium chloride hydride, bis (pyrrolyl) zirconium dihydride, bis (pyrazolyl) zirconium dichloride, bis (1,2,3-triazolyl) zirconium dichloride, Bis (1,2,4-triazolyl) zirconium dichloride, bis (tetrazolyl) zirconium dichloride, bis (pentazolyl) zirconium dichloride, (imidazo Le) zirconium trichloride, (imidazolyl) zirconium trimethyl, (imidazolyl) zirconium tribenzyl, (imidazolyl) zirconium methyl dichloride, (imidazolyl)
Zirconium trihydride, (bilazolyl) zirconium trichloride, (1,2,3-triazolyl) zirconium trichloride, (1,2,4-triazolyl) zirconium trichloride, (tetrazolyl) zirconium trichloride, (pentazolyl) zirconium trichloride , Bis (2,3,4,5-tetramethylarsolyl) zirconium dichloride, bis (2,3,4,5-
Tetramethylarsolyl) zirconium dimethyl,
(2,3,4,5-Tetramethylarsolyl) zirconium trichloride, bis (1-sila-pentamethylcyclopentadienyl) zirconium dichloride, bis (1
-Bora-2,3,4,5-tetramethylcyclopentadienyl) zirconium dichloride, bis (1-alumina-2,3,4,5-tetramethylcyclopentadienyl) zirconium dichloride, bis (1-trimethylsilyl) 2-Methyl-1H-1,2-azaborolyl) zirconium dichloride, bis (1-tert-butyl-2)
-Methyl-1H-1,2-azaborolyl) zirconium dichloride, bis (2-methyl-1H-1,2-azaborolyl) zirconium dichloride, (cyclopentadienyl) (1-trimethylsilyl-2-methyl-1H-
1,2-azaborolyl) zirconium dichloride, N,
N '-(dimethylsilylene) bis (2-methyl-1H-
1,2-Azaborolyl) zirconium dichloride, dimethylsilylene bis (1-trimethylsilyl-2-methyl 1H-1,2-azaborolyl) zirconium dichloride, (cyclopentadiene-1,1-diyl) dimethylsilylene (1-trimethylsilyl-2- Methyl 1H-
1,2-azaborolyl) zirconium dichloride, bis (1-phenyl-2-methyl-1-phospha-2-aluminacyclopentadienyl) zirconium dichloride,

2. Activation Cocatalyst (B) The activation cocatalyst (B) used in the present invention is not particularly limited, but for example, a cation species is formed from the transition metal compound (A) or a derivative of (A). The compound (B ') which can be mentioned is mentioned. As the compound (B ′), specifically, a compound (B-1) which reacts with the transition metal compound (A) to form an ionic complex,
Examples thereof include aluminoxane (B-2) and Lewis acid (B-3).

Here, as the ionic compound (B-1) which reacts with the transition metal compound (A) to form an ionic complex, an ionic complex which reacts with the transition metal compound (A) is formed. Any ionic compound can be used as long as it can be formed, and those having the following general formulas (II) and (III) can be preferably used. ([L ¹ −R ¹ ] ^{k +} ) _p ([Z] ⁻ ) _q … (II) ([L ² ] ^{k +} ) _p ([Z] ⁻ ) _q … (III) (where L ² is M ² , R ² R ³ M ³ , R ⁴ ₃ C or R
⁵ M ³ . ) [(II), (III) In the formula, [Z] ⁻ represents a non-coordinating anion [Z ¹ ] ⁻ or [Z ² ] ^−, and
¹ ] ⁻ is an anion in which a plurality of groups are bound to an element, that is, [M ¹ A ¹ A ² ... ^An ] ⁻ (where M ¹ is 5 to 15).
A group element, preferably a group 13 to 15 element is shown. A ¹ ~ A
ⁿ represents a hydrogen atom, a dialkylamino group, an oxygen-containing group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms, an organic metalloid group, a halogen atom, or a halogen-substituted hydrocarbon group, and two or more are rings. It may be formed. n is an integer of [(valence of central metal M ¹ ) +1], at least one of which is an anion in which a plurality of groups are bonded to an element selected from Groups 13 to 15 of the periodic table. Indicates a coordinating anion. [Z ² ] ⁻ represents a conjugate base of Bronsted acid alone or a combination of Bronsted acid and Lewis acid having an acid dissociation constant (pKa) of −10 or less, or a conjugate base of what is generally defined as a super strong acid. . A Lewis base may be coordinated. Anion in which a plurality of groups are bonded to an element [Z ^{1] -,} i.e. specific examples of ^{[M 1 A 1 A 2 ···} A n] is, B as ^{M 1, Al, Si, P} , A
s and Sb, preferably B, Al and A ^{1 to An} , dialkylamino group: dimethylamino group, diethylamino group, oxygen-containing group having 1 to 20 carbon atoms: methoxy group, ethoxy group, n-butoxy group, phenoxy group Group, 2,6-di-t
-Butyl-4-methylphenoxy group, hydrocarbon group having 1 to 20 carbon atoms: methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-octyl group, n-eicosyl group , Phenyl group, p-tolyl group, benzyl group, 4-t-butylphenyl group, 3,5-
Dimethylphenyl group, halogen atom: fluorine, chlorine, bromine, iodine, halogen-substituted hydrocarbon group having 1 to 20 carbon atoms: p-fluorophenyl group, 3,5-difluorophenyl group, pentachlorophenyl group, 3,4,5 -Trifluorophenyl group, pentafluorophenyl group, 3,5
-Di (trifluoromethyl) phenyl group, organic metalloid group: pentamethylantimony group, trimethylsilyl group, trimethylgermyl group, diphenylarsine group, dicyclohexylantimony group, diphenylboron group. A non-coordinating anion, that is, a conjugate base of a Bronsted acid alone or a combination of a Bronsted acid and a Lewis acid having an acid dissociation constant (pKa) of -10 or less, or a conjugate base of what is generally defined as a super strong acid [ Specific examples of Z ² ] ⁻ include trifluoromethanesulfonic acid anion (CF ₃ SO ₃ ) ⁻ , bis (trifluoromethanesulfonyl) methyl anion, bis (trifluoromethanesulfonyl) benzyl anion, bis (trifluoromethanesulfonyl) amide, and Chlorate anion (ClO ₄ ) ^- , trifluoroacetate anion (CF ₃ C
O ₂ ) ^- , hexafluoroantimony anion (SbF
₆₎ ^-, fluorosulfonic acid anion (FSO ₃₎ ^- chlorosulfonic acid anion (ClSO ₃₎ ^-, fluorosulfonic acid anion / antimony pentafluoride (FSO ₃ -
SbF ₅₎ ^-, fluorosulfonic acid anion / 5- fluoride arsenic (FSO ₃ -AsF ₅₎ ^-, trifluoromethyl meth acid / antimony pentafluoride (CF ₃ -SO ₃ / S
bF ₅₎ ^- can be mentioned. L ¹ is a Lewis base,
R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ² and R ³ represent a cyclopentadienyl group or a substituted cyclopentadienyl group (each Cp may be the same or different). 2 or more Cp may have a crosslinked structure). R ⁴ represents a hydrocarbon group having 1 to 20 carbon atoms or an oxygen-containing group having 1 to 20 carbon atoms.
k is the ionic valence of [L ¹ -R ¹ ] and [L ² ] and is 1 to 3.
, P is an integer of 1 or more, and q = p × k. M ² includes elements of groups ¹ to 11, 11 to 13 and 17 and M ³ represents elements of group 7 to 12. R ⁵ represents porphines, phthalocyanines, allyl group derivatives and the like. ]

Specific examples of the Lewis base (L ¹ ) include amines: ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, N, N-dimethylaniline,
Trimethylamine, triethylamine, tri-n-butylamine, methyldiphenylamine, pyridine, p-bromo-N, N-dimethylaniline, p-nitro-N, N
-Dimethylaniline, phosphines: triethylphosphine, triphenylphosphine, diphenylphosphine, thioethers: tetrahydrothiophene, esters: ethyl benzoate, nitriles: acetonitrile,
Mention may be made of benzonitrile. Specific examples of R ¹ include hydrogen, methyl group, ethyl group, benzyl group and trityl group. Specific examples of R ² and R ³ include a cyclopentadienyl group, a methylcyclopentadienyl group, an ethylcyclopentadienyl group, and a pentamethylcyclopentadienyl group. Specific examples of R ⁴ include phenyl, p-tolyl, p-methoxyphenyl and the like. Specific examples of R ⁵ include tetraphenylporphyrin, phthalocyanine, allyl and methallyl. Specific examples of M ² include Li, Na, K, Ag, Cu, Br, I and I ₃ . Specific examples of M ³ include Mn and F
e, Co, Ni, Zn, etc. can be mentioned.

Ionic compound (B-1) which reacts with such a transition metal compound (A) to form an ionic complex
As specific examples of, triethylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyl (tri-n-butyl) ammonium tetraphenylborate, tetraphenyl Benzyl (tri-n-butyl) ammonium borate, dimethyldiphenylammonium tetraphenylborate, triphenyl (methyl) ammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate, tetraphenylborate Methyl (2-cyanopyridinium), tetrakis (pentafluorophenyl) triethylammonium borate, tetrakis ( Pentafluorophenyl) borate tri (n- butyl) ammonium tetrakis (pentafluorophenyl) borate triphenyl ammonium, tetrakis (pentafluorophenyl) borate tetra -n-
Butylammonium, tetraethylammonium tetrakis (pentafluorophenyl) borate, benzyl (tri-n-butyl) ammonium tetrakis (pentafluorophenyl) borate, methyldiphenylammonium tetrakis (pentafluorophenyl) borate, trikis (pentafluorophenyl) borate tri Phenyl (methyl) ammonium, tetrakis (pentafluorophenyl) borate methylanilinium, tetrakis (pentafluorophenyl) borate dimethylanilinium, tetrakis (pentafluorophenyl) borate trimethylanilinium, tetrakis (pentafluorophenyl) borate methylpyridinium, tetrakis (Pentafluorophenyl)
Benzylpyridinium borate, methyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium),
Benzyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), methyl tetrakis (pentafluorophenyl) borate (4-cyanopyridinium), triphenylphosphonium tetrakis (pentafluorophenyl) borate, tetrakis [bis (3,5-ditritri]) Fluoromethyl) phenyl] dimethylanilinium borate, ferrocenium tetraphenylborate, silver tetraphenylborate, trityl tetraphenylborate, tetraphenylporphyrin manganese tetraphenylborate, ferrocenium tetrakis (pentafluorophenyl) borate,
Tetrakis (pentafluorophenyl) boric acid (1,1 '
-Dimethylferrocenium), tetrakis (pentafluorophenyl) decamethylferrocenium borate, silver tetrakis (pentafluorophenyl) borate, trityl tetrakis (pentafluorophenyl) borate, lithium tetrakis (pentafluorophenyl) borate, tetrakis (penta) Sodium fluorophenyl) borate, tetrakis (pentafluorophenyl) borate tetraphenylporphyrin manganese, silver tetrafluoroborate, silver hexafluorophosphate, silver hexafluoroarsenate, silver perchlorate,
Mention may be made of silver trifluoroacetate and silver trifluoromethanesulfonate.

The following can be mentioned as examples of the aluminoxane (B-2).

[Chemical 2]

(R ⁶ has 1 to 20 carbon atoms, preferably 1 to
12 represents a hydrocarbon group such as an alkyl group, an alkenyl group, an aryl group and an arylalkyl group, and a halogen atom, which may be the same or different. Also, s
Represents the degree of polymerization, and the preferred number of repeating units is 3 to 50,
More preferably, it is 7-40. ) A chain aluminoxane represented by.

[0017]

[Chemical 3]

(R ⁶ is the same as in the formula (IV), s is the degree of polymerization, and the preferred number of repeating units is 3 to
50, and more preferably 7-40. ) A cyclic alkylaluminoxane having a repeating unit represented by the formula: Examples of the method for producing the aluminoxane include a method in which an alkylaluminum (one or more kinds) is contacted with a condensing agent such as water, but the means is not particularly limited, and the reaction can be performed according to a known method. Good. For example, a method in which an organoaluminum compound is dissolved in an organic solvent and then brought into contact with water, a method in which an organoaluminum compound is initially added at the time of polymerization, and water is added later, water of crystallization contained in a metal salt, etc. 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. In addition,
The aluminoxane may be insoluble in toluene.

The Lewis acid (B-3) is not particularly limited, and may be an organic substance or a solid inorganic substance. A boron compound and an aluminum compound are preferably used as the organic substance, and a magnesium compound and an aluminum compound are suitably used as the inorganic substance. Examples of the aluminum compound include bis (2,6-di-t-butyl-4-methylphenoxy) aluminum methyl and (1,1′-bi-2-naphthoxy).
Aluminum methyl and magnesium compounds include magnesium chloride and diethoxymagnesium, aluminum compounds include aluminum oxide and aluminum chloride, and boron compounds include triphenylboron, tris (pentafluorophenyl) boron, and tris [3,5-bis (3,5-bis) bis (trifluoro)). (Trifluoromethyl) phenyl] boron, tris [(4-fluoromethyl) phenyl] boron, trimethylboron, triethylboron, tri (n-butyl) boron, tris (fluoromethyl) boron, tris (pentafluoroethyl) boron, Tris (nonafluorobutyl) boron, tris (2,4,6-trifluorophenyl) boron, tris [3,5-bis (trifluoromethyl) phenyl] boron, tris (3,5-difluorophenyl) boron, bis (Pentafluorophenyl Fluoro boron, diphenyl fluoro boron, bis (pentafluorophenyl) chloro boron, dimethyl fluoro boron, diethyl fluoro boron,
Di (n-butyl) fluoroboron, (pentafluorophenyl) difluoroboron, phenyldifluoroboron, (pentafluorophenyl) difluoroboron, phenyldifluoroboron, (pentafluorophenyl) dichloroboron, methyldifluoroboron, ethyldifluoroboron,
Mention may be made of (n-butyl) difluoroboron.

Here, the mixing ratio (molar ratio) of the compound (A) and the compound (B) is the same as that of the compound (B).
-1) is used, 10: 1 to 1: 100, preferably 2: 1 to 1:10, and compound (B-2) is used, 1: 1 to 1: 100,000, preferably 1 : 10
It is 1: 10,000.

The mixing ratio (molar ratio) of the compound (A) and the compound (B-3) is 1: 0.1 to 1: 2,000, preferably 1: 0.2 to 1: 1,000, and particularly Preferably 1:
It is 0.5 to 1: 500. Further, as the compound (B), (B-1), (B-2), (B-3) and the like can be used alone, or two or more kinds of them can be used in combination.

3. Organoaluminum Compound (C) As described above, the polymerization catalyst of the present invention contains the organoaluminum compound (C) as a main component in addition to the compounds (A) and (B) as its components. May be. Polymerization or copolymerization using this catalyst can improve the polymerization activity.

Examples of the organoaluminum compound (C) include those represented by the following general formula (VI). ^{_{R 7 r AlQ 3-r ...}} (VI) (R 7 is a hydrocarbon group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 12 carbon atoms, Q is a hydrogen atom, a halogen atom, having 1 to 20 carbon atoms Alkoxy group or C6-20
The aryl group of is shown. r is an integer of 0-3. ) Specific examples of the compound of the formula (VI) include trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride,
Examples thereof include methyl aluminum dichloride, ethyl aluminum dichloride, dimethyl aluminum fluoride, diisobutyl aluminum hydride, diethyl aluminum hydride and ethyl aluminum sesquichloride. Among the compounds of the formula (VI), preferred are alkyl group-containing aluminum compounds having an alkyl group having 3 or more carbon atoms, and particularly at least one branched alkyl group. Particularly preferred is triisobutylaluminum. High activity can be obtained with this triisobutylaluminum or a mixture thereof.

The mixing ratio (molar ratio) of the compound (A) and the compound (C) is 1: 1 to 1: 2,000, preferably 1 :.
5 to 1: 1,000, particularly preferably 1:10 to 1: 5
00. By using the compound (C), the polymerization activity per transition metal 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.

4. Carrier [Compound (D)] The polymerization catalyst of the present invention may contain a carrier as a catalyst component. The type of the carrier [compound (D)] 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. Specifically, as the inorganic carrier, MgCl ₂ , MgCl (OEt), Mg (OE
t) A magnesium compound such as ₂ or a complex salt thereof, or Mg
Examples thereof include organomagnesium compounds represented by R ⁸ _X X ¹ _Y. Here, R ⁸ is 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, X ¹ represents a halogen atom or an alkyl group having 1 to 20 carbon atoms, x is 0 to 2 and y is 0 to 2.

As the inorganic oxide carrier, SiO ₂ , Al
₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , Fe ₂ O ₃ , B
₂ O ₃ , CaO, ZnO, BaO, ThO ₂ and mixtures thereof such as silica alumina, zeolite, ferrite and glass fiber can be exemplified.
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. As the organic carrier, polymers such as polystyrene, styrene-divinylbenzene copolymer, polyethylene, linear low-density polyethylene, polypropylene, poly-4-methyl-1-pentene, substituted polystyrene and polyarylate, and starch are used. , Carbon, etc. can be exemplified.

Carrier used in the present invention [compound (D)]
The average particle size is usually 1 to 300 μm, preferably 10 to 200 μm, though it varies depending on its type and production method.
More preferably, it is 20 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 [compound (D)] is usually 1 to 1,000 m ² / g, preferably 50 to 5
00 m ² / g, the pore volume is usually 0.1 to ⁵ cm ³ / g,
It is 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 obtained, for example, from the volume of nitrogen gas adsorbed according to the BET method [“Journal of American Chemical Society (J.Am.Chem.Soc.)”]. 6
0, p. 309 (1983)]. Further, the carrier [compound (D)] is usually 150 to 1,000 ° C.
It is preferable to use it after baking at 200 to 800 ° C.

The polymerization catalyst of the present invention comprises the above-mentioned compounds (A) and (B) as main components, and at least one of the compounds (A) and (B), preferably the compounds (A) and (B). Both can be supported on the carrier [compound (D)]. Compound (A) on carrier [compound (D)]
The method of supporting at least one of (B) and (B) 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 a carrier [compound (D)]. A method in which a carrier [compound (D)] 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 a carrier [compound (D)] with a compound (A) and / or (B) and an organoaluminum compound or a halogen-containing silicon compound. A method in which the compound (A) or (B) is supported on a carrier [compound (D)] 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 [compound (D)]. A method of allowing a carrier [compound (D)] to coexist during the contact reaction between the compound (A) and the compound (B). The organoaluminum compound (C) may be added in the above reactions. 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.

In the present invention, the catalyst can also be produced by carrying out the loading operation of at least one of the compounds (A) and (B) on the carrier (E) in the polymerization system. At least one of the compounds (A) and (B) and a carrier [compound (D)], and if necessary, an organoaluminum compound (C) are added, and an olefin such as ethylene is added at atmospheric pressure to 20 Kg / cm ² , 1 at -20 to 100 ° C
There is a method of preliminarily polymerizing for 2 minutes to 2 hours to generate catalyst particles.

In the present invention, the mixing ratio (weight ratio) of the compound (B-1) and the carrier [compound (D)] is 1: 5.
It is preferably 1: 10,000, particularly preferably 1:10 to 1: 500. The mixing ratio (weight ratio) of the compound (B-2) and the carrier [compound (D)] is 1: 0.5 to 1:
It is preferably 1,000, and particularly preferably 1: 1 to 1:50. The mixing ratio (weight ratio) of the compound (A) and the carrier [compound (D)] is preferably 1: 5 to 1: 10,000, and particularly preferably 1:10 to 1: 500. The mixing ratio of the compounds (B), ((B-1) and (B-2)) and the carrier [compound (D)] or the mixing ratio of the compound (A) and the carrier [compound (D)] is within the above range. If it is out of the range, the activity may decrease. The average particle size of the polymerization catalyst of the present invention prepared as described above is usually 2 to 200 μm, preferably 10 to 150 μm, and particularly preferably 20 to 100 μm.
μm, and the specific surface area is usually 20 to 1,000 m ² /
g, preferably 50 to 500 m ² / g. If the average particle diameter is less than 2 μm, fine powder in the polymer may increase, and if it exceeds 200 μm, 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 1,000 m ² / g, the bulk density of the polymer may decrease.

Further, in the catalyst of the present invention, the carrier 100
The amount of transition metal in g is usually 0.05 to 10 g, and especially 0.
It is preferably 1 to 2 g. If the amount of the transition metal is out of the range, the activity may decrease. By thus supporting the polymer on the carrier [compound (D)], a polymer having industrially advantageous high bulk density and excellent particle size distribution can be obtained.

6. Method for producing polymer According to the method for producing a polymer of the present invention, by using the above-mentioned polymerization catalyst of the present invention, for example, homopolymerization of olefin or olefin and ethylene, other olefin or other unsaturated compound. Can be suitably copolymerized. 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-
Styrenes such as styrene, p-methylstyrene, p-chlorostyrene, p-t-butylstyrene, p-phenylstyrene, p-methylsilylstyrene, p-trimethylsilylmethylstyrene, etc., such as octadecene and 1-eicosene are suitable. Can be used.

In the present invention, when the copolymerization of two or more olefins is carried out, the above-mentioned monomers can be arbitrarily combined. For example, when propylene and ethylene or ethylene and an α-olefin having 3 to 10 carbon atoms are copolymerized, the copolymerization ratio of propylene and ethylene or ethylene and the α-olefin 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.

The method for producing a polymer of the present invention is particularly suitable for the polymerization of olefins, but other unsaturated compounds such as butadiene, isoprene, and chain diolefins such as 1,5-hexadiene. , Norbornene,
1,4,5,8-dimethano-1,2,3,4,4a,
Cyclic olefins such as 5,8,8a-octahydronaphthalene, cyclic diolefins such as norbornadiene and ethylidene norbornene, unsaturated esters such as ethyl acrylate and methyl methacrylate, β-propiolactone, β-butyrolactone, It can also be used for the polymerization of lactones such as γ-butyrolactone or the copolymerization of these unsaturated compounds with olefins.

In the method for producing the polymer of the present invention, the polymerization method is not particularly limited, and slurry polymerization method, gas phase polymerization method,
Any method such as a bulk polymerization method, a solution polymerization method and a suspension polymerization method may be used, but a slurry polymerization method and a gas phase polymerization method are particularly preferable. Regarding the polymerization conditions, the polymerization temperature is usually -100.
-250 degreeC, Preferably it is -50-200 degreeC, More preferably, it is 0-130 degreeC. Further, the ratio of the catalyst used 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 includes the selection of the type and amount of each catalyst component, the polymerization temperature, and further the polymerization 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 performed without a solvent.

In the method for producing a polymer of the present invention, prepolymerization can be carried out using the polymerization catalyst of the present invention. The prepolymerization can be carried out by contacting the solid catalyst component with, for example, a small amount of olefin.
The method is not particularly limited, and a known method 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 −
20-100 degreeC, Preferably it is -10-70 degreeC, More preferably, it is 0-50 degreeC. 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, aliphatic hydrocarbons are particularly preferable. 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.) is 0.2 dl / g or more, particularly 0.5 dl / g or more,
The amount of the prepolymerized product is 1 to 10,000 g, particularly 10 to 1,000 per 1 mmol of the transition metal component in the catalyst.
It is preferable to adjust the conditions so that it becomes 0 g.

[0037]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the invention is not limited to the following examples and comparative examples. Example 1 (1) Catalyst component (A): Bis (1-phospha-2,3,3)
Synthesis of 4,5-tetramethylcyclopentadienyl) zirconium dichloride It was synthesized according to the literature: Organometallics 7, p921 (1988).

(2) Preparation of catalyst Bisch (1-phospha-2,3,4,5-tetramethylcyclopentadienyl) zirconium dichloride [(Me ₄ C
₄ P) ₂ ZrCl ₂ ] 0.0383g (0.087mm
ol), and 8.7 ml of purified toluene was added to it,
A 0.01M toluene solution of (Me ₄ C ₄ P) ₂ ZrCl ₂ was prepared. In a nitrogen atmosphere, a Schlenk that has been sufficiently substituted with nitrogen is used as a catalyst component (B): tetrakis (pentafluorophenyl) borate N, N-dimethylanilinium ([PhNMe ₂ H]
[B (C ₆ F ₅ ) ₄ ]) 0.0876 g (0.109 m
mol), 10.9 ml of purified toluene was added thereto, and 0.0 of [PhNMe ₂ H] [B (C ₆ F ₅ ) ₄ ] was added.
A 1M toluene solution was prepared.

(3) Polymerization 400 ml of purified toluene was introduced into a 1 liter autoclave with a stirring blade, which had been sufficiently replaced with nitrogen, under a nitrogen atmosphere, and triisobutylaluminum (TIBA) was introduced under a nitrogen atmosphere.
0.6 ml of 1.0 M toluene solution (0.06 mmo
l) added and kept at 20 ° C. After 1 hour, 0.3 ml (3.0 μmol) of (Me ₄ C ₄ P) ₂ ZrCl ₂ prepared in (2) was added under a nitrogen atmosphere, and then [PhNMe ₂ prepared in (2) under a nitrogen atmosphere. H] [B (C ₆
F ₅ ) ₄ ] was added in an amount of 0.3 ml (3.0 μmol).
Ethylene was introduced into this while stirring, and polymerization was carried out for 1 hour while continuously introducing ethylene so that the pressure was kept constant at 3 atm.

As a result, as shown in Table 2, 9.6 g of polyethylene was obtained. Also, the molecular weight of this polymer
Regarding the molecular weight distribution, in terms of polyethylene, the weight average molecular weight (Mw) is 574,000, and the number average molecular weight (Mn) is
139,000, Mw / Mn is 4.13, Tm is 136
It was ℃. The measurement conditions of GPC were as follows. Apparatus: Waters ALC / GPS 150C Column: Tosoh Corp. TSK HM + GMH6 × 2 Solvent: 1,2,4-trichlorobenzene Temperature: 135 ° C. Tm (melting point) was measured under the following conditions. Apparatus: 7 series DSC manufactured by Perkin Elmer Inc. Temperature rising rate: 10 ° C / min Temperature range: -50 ° C to 150 ° C [η] (intrinsic viscosity) was measured at 135 ° C in decalin.

Examples 2 to 9 and Comparative Example 1 Example 1 was repeated except that the conditions shown in Table 1 were used. The results are shown in Table 2. In addition, the synthesis of the catalyst component (A): tetrakis (2,5-dimethylpyrrolyl) zirconium in Examples 4 and 7 is described in Reference: Can. J. Chem. 64, p1306 (19
86).

[0042]

[Table 1]

[Table 2] ─────────────────────────────────── No. Yield g Mw (× 10 ⁻⁴ ) Mw / Mn [η] Tm ─────────────────────────────────── Example 1 9.6 57.4 4.13 7.54 136 Example 2 8.7 30.5 3.22 7.05 137 Example 3 24.6 14.7 3.42 2.78 128 Implementation Example 4 0.03 --- --Example 5 12.9 --- 7.61 137 Example 6 29.6 24.7 3.26 3.98 126 Example 7 1.3 30.2 2.426 .76 120 Example 8 3.2 −−−− Example 9 1.0 7.91 6.18 2.28 132 Comparative Example 1 53.6 16.4 2.78 2.69 137 ───── ──────────────────────────────

Example 10 (1) Catalyst component (A) + catalyst component (B): Preparation of bis (1-phospha-2,3,4,5-tetramethylcyclopentadienyl) zirconium ditriflate Bis (1 −
Phospha-2,3,4,5-tetramethylcyclopentadienyl) zirconium dichloride [(Me ₄ C ₄ P)
₂ ZrCl ₂ ] 0.088 g (0.20 mmol) was dissolved in 10 ml of dry nitrogen-substituted toluene,
0.020 mol of solution A was prepared. Next, 0.103 g (0.40 mmol) of silver trifluoromethanesulfonate
Was dissolved in 10 ml of dry nitrogen-substituted toluene to prepare 0.040 mol of solution B. Solution B was added dropwise to solution A while stirring solution A at room temperature. The formed silver chloride precipitate was filtered off, and bis (1-phospha-2,
3,4,5-tetramethyl-cyclopentadienyl) zirconium triflate _{[(Me 4 C 4 P)} 2 Zr]
A 0.010 molar solution of [OTf] ₂ was prepared. (2) Polymerization It was carried out according to Example 1 except that the conditions shown in Table 3 were carried out. The results are shown in Table 4.

Examples 11 to 13 It was carried out according to Example 1 except that the conditions were shown in Table 3. The results are shown in Table 4.

Example 14 (1) Catalyst component (A): Bis (1-phospha-3,4-)
Synthesis of dimethylcyclopentadienyl) zirconium dichloride Reference: Synthesis p983 (1981) and Reference: J. Organomet. Chem. 193p
It was synthesized according to C13 (1980). (2) Polymerization It was carried out according to Example 1 except that the conditions shown in Table 3 were carried out. The results are shown in Table 4.

Example 15 The procedure of Example 1 was repeated except that the conditions shown in Table 3 were used. The results are shown in Table 4.

[0048]

[Table 3]

[Table 4] ─────────────────────────────────── No. Yield g Mw (× 10 ⁻⁴ ) Mw / Mn [η] Tm ─────────────────────────────────── -Example 10 0.23 33.3 5.27-133 Example 11 23.9 22.4 1.91-137 Example 12 2.0 37.3 5.10-134 Example 13 2.4 32 .6 3.50 4.29 126 Example 14 14.7 44.6 2.15 4.45 135 Example 15 8.9 16.2 1.82 2.90 123 123 ────────── ──────────────────────────

Example 16 Copolymerization of ethylene and 2-norbornene 400 ml of toluene, 1.2 mmol of triisobutylaluminum (TIBA), bis (1-) in a 1 liter autoclave at room temperature under a nitrogen atmosphere.
Phospha-3,4-dimethylcyclopentadienyl) zirconium dichloride (4 micromoles) and tetrakis (pentafluorophenyl) anilinium borate (8 micromoles) were added in this order, followed by 75 ml of a toluene solution containing 70% by weight of 2-norbornene. (0.4 mol as 2-norbornene) was added. After the temperature was raised to 120 ° C., the reaction was carried out for 30 minutes while continuously introducing ethylene so that the ethylene partial pressure became 6 kg / cm ² . After the reaction was completed, the polymer solution was poured into 1 liter of methanol to precipitate the polymer. This polymer was collected by filtration and dried to obtain a cyclic olefin-based copolymer. The yield of the cyclic olefin-based copolymer was 2.68 g.
The polymerization activity was 7 kg / gZr. The physical properties of the obtained cyclic olefin-based copolymer were as follows. ¹³ C-
The sum of the peak derived from ethylene and the peak derived from methylene at the 5- and 6-positions of norbornene appearing at around 30 ppm in NMR and 7 of norbornene appearing near 32.5 ppm.
The norbornene content determined from the ratio with the peak based on the methylene group at position was 7.5 mol%. Intrinsic viscosity [η]
Was 1.08 dl / g, and the crystallinity determined by X-ray diffractometry was 2.6%. Orientec's Leo-Vibron DDV-II type was used as a measuring device, and the width was 45 m.
A measuring piece of m, length 40 mm, and thickness 0.1 mm was measured at a temperature rising rate of 3 ° C./min and a frequency of 3.5 Hz, and the glass transition temperature (Tg) was obtained from the peak of this loss elastic modulus (E ″). As a result, Tg was 0 ° C. When the weight average molecular weight Mw, the number average molecular weight Mn, and the molecular weight distribution (Mw / Mn) were determined, Mw was 45,300, Mn was 19,600,
Mw / Mn was 2.31. Tm was 85 ° C. (broad peak).

Example 17 Copolymerization of ethylene and 1,5-hexadiene In Example 1- (3), 1,5-
An ethylene copolymer was produced in the same manner except that 0.1 ml of hexadiene was added. As a result, 6.8 g of a polymer was obtained. The melting point of this product is 135 ℃
The weight average molecular weight (Mw) is 726,000, and the molecular weight distribution (Mw)
/ Mn) was 6.5.

Example 18 (1) Catalyst component (A) Magnesium chloride (average particle size: 70 μm, specific surface area: 260 m ² / g, pore volume: 260 cc / g) was placed in a 200 ml flask substituted with nitrogen at 300 ° C. for 4 hours. 2.0 g of the calcined product was dispersed in 53.2 ml of toluene, and a toluene solution of bis (tetramethylphosphacyclopentadienyl) zirconium dichloride (0.02 mol / l) was prepared.
After adding 8 ml and reacting at room temperature for 24 hours with stirring, toluene was removed by filtration, further washed with toluene and dried under reduced pressure to obtain 1.91 g of a solid catalyst. The amount carried by elemental analysis was 2.8 mg of zirconium element per 1 g of the carrier.

(2) Polymerization A 1 liter autoclave with a stirring blade, which was sufficiently replaced with nitrogen, was dried under a nitrogen atmosphere and toluene 40 was replaced with nitrogen.
The solid catalyst obtained above together with 0 ml and 6.0 mmol of methylaluminoxane was 4.6 μm in terms of zirconium.
Ol at a temperature of 80 ° C and ethylene pressure of 8 kg /
It was continuously supplied to the autoclave at cm ² , and the polymerization was carried out for 1 hour to obtain 46.0 g of a particulate polymer. The reduced viscosity measured in decalin at 135 ° C. at a concentration of 0.2 g / deciliter was 4.9.

Example 19 In a 1 liter autoclave equipped with a stirring blade, which had been sufficiently replaced with nitrogen, under a nitrogen atmosphere, toluene 3 which had been dried and replaced with nitrogen was used.
After introducing 60 ml, 40 ml of 1-octene which had been dried and replaced with nitrogen was added, and then 1.0 ml (1.0 mmol) of a 1.0 M toluene solution of triisobutylaluminum was added under a nitrogen atmosphere. This was heated to 60 ° C., and a 0.010 M toluene solution of bis (3,4-dimethyl-1-phosphacyclopentadienyl) zirconium dichloride was added to 0.20 milliliter (2.0 μmol) under a nitrogen atmosphere. Then, 0.20 ml (2.0 micromol) of a 0.010 M toluene solution of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate was added under a nitrogen atmosphere. To this solution, 1.0 ml (10 μmol) of 0.010 M toluene solution of tris (pentafluorophenyl) boron was added. This was heated to 80 ° C., ethylene was introduced while stirring, and polymerization was carried out for 1 hour while continuously introducing ethylene so that the pressure was kept constant at 8 atm. As a result, 3.8 g of polyethylene was obtained.
The reduced viscosity measured in decalin at 135 ° C. at a concentration of 0.2 g / deciliter was 5.2 deciliter / g.

Example 20 In a 1 liter autoclave with a stirring blade, which had been sufficiently replaced with nitrogen, under a nitrogen atmosphere, toluene 5 which had been dried and replaced with nitrogen was used.
20 ml was introduced, followed by dry nitrogen replacement 1
-Octene (180 ml) and triisobutylaluminum 1.0 M toluene solution (1.50 ml (1.50 mmol)) were added, the temperature was raised to 150 ° C, and the ethylene pressure was kept at 24 atm. Into the catalyst charging pipe which is connected to this autoclave and which is fully replaced with nitrogen,
In a nitrogen atmosphere, 20 ml of toluene that had been dried and replaced with nitrogen was introduced, and 1.0 ml of a 0.010 M toluene solution of bis (3,4-dimethyl-1-phosphacyclopentadienyl) zirconium dichloride was added (10 ml).
Micromol), and then 1.2 ml (12 micromol) of a 0.010 M toluene solution of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate was added under a nitrogen atmosphere. This was charged into the above 1 liter autoclave by ethylene pressure while stirring the inside of the autoclave, and polymerization was carried out for 1 hour while continuously introducing ethylene so that the pressure inside the autoclave was kept constant at 24 atm. As a result, an ethylene-1-octene copolymer was obtained.

[0056]

As described above, the polymerization catalyst of the present invention is highly active, and the polymer or copolymer obtained by using this catalyst for the production of polyolefin or the like has a large molecular weight. In addition, its composition is uniform, and its molecular weight and molecular weight distribution can be controlled. Without using a large amount of organometallic compounds,
It is possible to efficiently produce a polymer or copolymer having excellent properties.

Claims (13)

[Claims] 1. A polymerization catalyst containing the following compounds (A) and (B). (A) Transition metal compound containing cyclopentadienyl group containing at least one hetero atom (B) Activation promoter 2. The following compounds (A), (B) and (C)
A catalyst for polymerization, which comprises: (A) Transition metal compound containing cyclopentadienyl group containing at least one hetero atom (B) Activation promoter (C) Organoaluminum compound 3. The polymerization according to claim 1, wherein the compound (B) is a transition metal compound (A) or a compound (B ′) capable of forming a cationic species from a derivative of (A). Catalyst. 4. The polymerization catalyst according to claim 1, wherein the compound (A) is a compound represented by the following formula (I). [Chemical 1] [In the formula, M represents a metal of Groups 3 to 10 of the periodic table or a lanthanoid series. X represents an element of group 13, group 14 or group 15. Each X may be the same or different, but at least one of the 5 × b Xs contains an element other than carbon. R represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group or a silicon-containing group. Each R may be the same or different, and Rs may be crosslinked. Further, R and M may be crosslinked. a represents 0 or 1. b represents an integer not less than 1 and not more than the valence number of M. Each [((R) _a ) ₅ X ₅ ] group may be the same or different. Y represents a σ-bonding ligand, a chelating ligand or a Lewis base. Each Y
May be the same or different. [((R) _a ) ₅ X
₅ ] group and Y may be crosslinked. c is 0 or more and represents an integer equal to (valence of M-b). ] 5. The compound (A) as the hetero atom, one or more atoms selected from the group consisting of a phosphorus atom (P), a nitrogen atom (N), an aluminum atom (Al) and a boron atom (B). The polymerization catalyst according to any one of claims 1 to 4, which is a transition metal compound containing. 6. The polymerization catalyst according to claim 1, wherein the compound (A) is a transition metal compound containing a metal of Group 4 of the periodic table. 7. The ionic compound (B-1), wherein the compound (B ′) is an ionic compound (B-1) which reacts with the transition metal compound (A) or a derivative thereof to form an ionic complex. The catalyst for polymerization according to any one of claims 1. 8. The polymerization catalyst according to claim 3, wherein the compound (B ′) is an aluminoxane (B-2). 9. The compound (B ′) is a Lewis acid (B-
The catalyst for polymerization according to any one of claims 3 to 6, which is 3). 10. The compound (B ′) is composed of two or more compounds selected from the group consisting of the compounds (B-1), (B-2) and (B-3). Item 7. A polymerization catalyst according to any one of items 3 to 6. 11. The compounds (A), (B) and (C)
11. The polymerization catalyst according to claim 2, wherein at least one of the above is supported on a carrier [compound (D)]. 12. A method for producing a polymer, which comprises homopolymerizing or copolymerizing a monomer in the presence of the polymerization catalyst according to any one of claims 1 to 11. 13. Homopolymerization of olefins, or copolymerization of olefins with other olefins or other monomers in the presence of the polymerization catalyst according to any one of claims 1 to 11. A method for producing a polymer, comprising: