JPH07133308A - Olefin polymerization catalyst and production of olefin polymer using the catalyst - Google Patents

Abstract

PURPOSE:To obtain a high-mol. olefin polymer having a uniform composition and a narrow mol.wt. distribution by using a soluble catalyst comprising a specific transition metal compound, an activated promoter, and an organoaluminum compound. CONSTITUTION:The catalyst is produced by fixing to an appropriate support a combination of a transition metal compound (A) represented by the formula (M is a metal Groups 3 to 10 of the Periodic Table or the lanthanide series; Cp is a cyclic unsaturated hydrocarbon group; a is 0-2; b, which is (the valence of M)-a-l, is 0-5; X is a sigma-bonding ligand; Y is a Lewis base; c is 0-3; R<1> is H, a 1-20C hydrocarbon group, an acyl, etc.; and R<2> is a 1-20C hydrocarbon group, an alkoxy, etc.) and an activated promoter capable of forming an ionic complex through reaction with the compound (A). Trimethylaluminum or the like may be optionally fixed to the support. M in the formula is preferably Ti, Zr, or Hf. Preferred examples of X include halogens and alkyls. Examples of Y include amines and phosphines. Examples of the promoter include triethylammonium tetraphenylborate, aluminoxanes, and Lewis acids.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an olefin polymerization catalyst and a method for producing an olefin polymer using the catalyst. More specifically, the present invention provides a highly active soluble polymerization catalyst that gives an olefin polymer having a high molecular weight, a uniform composition, and a narrow molecular weight distribution, and a catalyst for polymerization having the above properties. The present invention relates to a method for efficiently producing an olefin polymer.

[0002]

2. Description of the Related Art Conventionally, as a highly active soluble olefin polymerization catalyst, one comprising a combination of a transition metal compound and an aluminoxane is known (Japanese Patent Laid-Open No. 58-193).
09, JP-A-60-217209). Also, it has been reported that cationic species are useful as active species for soluble olefin polymerization catalysts ["Journal of the American Chemical Society".
(J. Am. Chem. Soc.) "Vol. 81, Page 81 (1959
Year), vol. 82, p. 1953 (1960), ten.
Volume 7, page 7219 (1985)]. Also, as an example of isolating this active species and applying it to olefin polymerization,
"Journal of the American Chemical Society (J. Am. Chem. Soc.)", Volume 108, 7410.
Page (1986), Japanese Patent Laid-Open No. 1-502636, Japanese Patent Laid-Open No. 3-139504, European Published Patent No. 4
Japanese Patent Application Laid-Open No. 3-20770, which is an example in which an organoaluminum compound is used in combination with 68651 and the like,
4 and International Patent Publication No. 92-1723.

Further, a method for polymerizing olefins using a catalyst composed of a specific transition metal compound and aluminoxane,
International Patent Publication No. 87-2370, JP-A-4-18561
No. 4 publication. However, a catalyst system composed of a combination of a transition metal compound and an aluminoxane is dangerous and expensive for trialkylaluminum, which is a raw material for synthesizing an aluminoxane, and a large amount must be used for the transition metal compound. Has drawbacks,
It was not necessarily industrially suitable in terms of productivity. In addition, examples of isolating active species and applying them to olefin polymerization,
In the case where the active species and the organoaluminum compound are used in combination, there is a problem that a large amount of aluminoxane must be used.

Further, the polymer produced by the complex having a cyclopentadienyl-based ligand used in these conventional techniques is polymerized at a reaction temperature of 70 to 100 ° C., which is efficient in an industrial process, or higher. When carried out, there was a problem that the molecular weight of the obtained polymer was small.

[0005]

Under the circumstances described above, the present invention provides a novel highly active soluble system polymerization which gives an olefin polymer having a high molecular weight, a uniform composition and a narrow molecular weight distribution. The present invention has been made for the purpose of providing a catalyst and a method for efficiently producing an olefin polymer having the above-mentioned properties by using this polymerization catalyst.

[0006]

Means for Solving the Problems As a result of intensive studies for achieving the above-mentioned object, the present inventors have found that a specific transition metal compound, an activating cocatalyst, and optionally an organoaluminum compound are contained. It was found that the purpose can be achieved by using a polymerization catalyst. The present invention has been completed based on such findings. That is, the present invention provides (A)
General formula (I)

[0007]

[Chemical 2]

[In the formula, M is a metal element of Group 3 to 10 of the periodic table or a lanthanoid series, Cp is a cyclic unsaturated hydrocarbon group, a is an integer of 0 to 2, and when a is 2, Two Cp's may be the same or different, and may form a multi-bridged structure, X is a σ-bonding ligand, and b is [(M
Valence) -a-1], and when there are a plurality of Xs, the plurality of Xs may be the same or different, and X and Cp form a crosslinked structure. Good. Y represents a Lewis base, c represents an integer of 0 to 3, and when there are a plurality of Ys, the plurality of Ys may be the same or different. R ¹ is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or 1 to 2 carbon atoms
An acyl group having 0, an arylcarbonyl group having 7 to 20 carbon atoms or a silicon-containing group, R ² is a hydrocarbon group having 1 to 20 carbon atoms,
It represents an alkoxy group having 1 to 20 carbon atoms or an aryloxy group having 6 to 20 carbon atoms, and each R ² may be the same or different. ] The olefin polymerization catalyst containing the transition metal compound represented by the following, (B) activation cocatalyst, and (C) organoaluminum compound optionally, and olefins alone in the presence of the olefin polymerization catalyst The present invention provides a method for producing an olefin polymer, which comprises polymerizing or copolymerizing an olefin with another olefin and / or another polymerizable unsaturated compound.

In the polymerization catalyst of the present invention, the component (A) is represented by the general formula (I)

[0010]

[Chemical 3]

A transition metal compound represented by the following is used.
In the general formula (I), M represents a metal element of Groups 3 to 10 of the periodic table or a lanthanoid series, and specific examples thereof include titanium, zirconium, hafnium, yttrium, vanadium, chromium, manganese, nickel, cobalt, Palladium and lanthanoid-based metals may be mentioned, but among these, titanium, zirconium and hafnium are preferable. Cp represents a cyclic unsaturated hydrocarbon group, specifically, a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a tetrahydroindenyl group, a substituted tetrahydroindenyl group, a fluorenyl group, Examples thereof include a substituted fluorenyl group. a represents an integer of 0 to 2 and a is 2
In the case of, the two Cp may be the same or different,
Further, a multi-crosslinked structure may be formed.

X is a sigma-bonding ligand, b is [(valence of M) -a-1] and is an integer of 0 to 5, and when there are a plurality of Xs, the plurality of Xs are the same or different. Alternatively, X and Cp or Y may form a crosslinked structure. Specific examples of X include a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and 6 to 2 carbon atoms.
0 aryloxy group, C1-20 amide group, C1-20 silicon-containing group, C1-20 phosphide group, C1-20 sulfide group, C1-20
And the like. Preferred examples thereof include halogen atoms of fluorine, chlorine, bromine and iodine, alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group and isobutyl group, Arylalkyl group such as benzyl group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, alkoxy group such as isobutoxy group, trimethylsilyl group,
Examples thereof include silicon-containing groups such as trimethylsilylmethyl group. On the other hand, Y represents a Lewis base, and c is 0.
Is an integer from 3 to 3, and when there are a plurality of Ys, the plurality of Ys may be the same or different. Specific examples of the Lewis base of Y include amines, ethers, phosphines and thioethers. R ¹ represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an acyl group having 1 to 20 carbon atoms, an arylcarbonyl group having 7 to 20 carbon atoms, or a silicon-containing group, and R ² has 1 to 20 carbon atoms. Hydrocarbon radical,
It shows an alkoxy group having 1 to 20 carbon atoms or an aryloxy group having 6 to 20 carbon atoms. Further, each R ² may be the same or different. Specific examples of R ¹ include hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n
-Butyl group, isobutyl group, octyl group, 2-ethylhexyl group, phenyl group, benzyl group, acetyl group, propionyl group, benzoyl group and the like, and specific examples of R ² include methyl group, ethyl group, n-propyl group. , Isopropyl group, n-butyl group, isobutyl group, octyl group, 2-
Examples thereof include ethylhexyl group, phenyl group, benzyl group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, butoxy group, phenoxy group and benzyloxy group.

The transition metal compound represented by the above general formula (I)
Examples of the product include bis (cyclopentadienyl) ti
Tankolide (triphenylphosphorus methyl iri
De) [Cp₂TiCl (-CH = PPh₃)〕,Screw
(Cyclopentadienyl) titanium methyl (triphenyl
Phosphorus methyl ylide) [Cp₂TiMe (-CH
= PPh₃)], Bis (cyclopentadienyl) titanium
Benzyl (triphenylphosphorus methyl ylide)
[Cp₂TiBz (-CH = PPh₃)], Screw (meth)
Rucyclopentadienyl) titanium methyl (triphenyl
Phosphorus methyl ylide [(MeCp)₂TiMe
(-CH = PPh₃)], Bis (n-butylcyclopene)
Tadienyl) titanium methyl (triphenylphosphorus)
Methyl ylide) [(n-BuCp)₂TiMe (-CH
= PPh₃)], Ethylene bis (indenyl) titanium
Chill (triphenylphosphorus methyl ylide) [(C
₂H_Four(Ind)₂TiMe (-CH = PPh₃)],
Isopropylidene (cyclopentadienyl, 1-fluor
Renyl) titanium methyl (triphenylphosphorus methyl)
Louislide) [i-C₃H₆(Cp, 1-Flu) TiM
e (-CH = PPh₃)], Dimethyl silylene bis (shi
Clopentadienyl) titanium methyl (triphenylphosphine
Forasmethyl ylide) [Me₂Si (Cp)₂TiM
e (-CH = PPh₃)], (Cyclopentadienyl)
Titanium dichloride (triphenylphosphorus methyl group
Lido) [CpTiCl₂(-CH = PPh₃)], (
Clopentadienyl) titanium dimethyl (triphenylpho
Sphorus methyl ylide) [CpTiMe₂(-CH =
PPh₃)], (Pentamethylcyclopentadienyl)
Titanium dichloride (triphenylphosphorus methyl group
Lido) [(C_FiveMe_Five) TiCl ₂(-CH = PP
h₃)], (Pentamethylcyclopentadienyl) tita
Dimethyl (triphenylphosphorus methyl ylide)
[(C_FiveMe_Five) TiMe₂(-CH = PPh₃)],
Bis (cyclopentadienyl) titanium methyl (trimethyl
Luphosphorus methyl ylide) [Cp₂TiMe (-C
H = PMe₃)], Bis (cyclopentadienyl) tita
Methyl (triethoxyphosphorus methyl ylide)
(Cp₂TiMe [-CH = P (OE_t)₃〕),Screw
(Cyclopentadienyl) titanium methyl (triphenyl
Phosphorus acetonyl ylide) (Cp₂TiMe [-
C (CH₃CO) = PPh₃)] Etc.
Zirconium or hafnium for titanium in compound
Can be mentioned. Of course this
It is not limited to these. Also, other tribes or lanta
It may be a compound similar to a metal element of the series of noids. Na
In the above compound, Cp = cyclopentadienyl
Group, Ph = phenyl group, Me = methyl group, Bz = benzyl
Group, Bu = butyl group, Ind = indenyl group, Flu
== fluorenyl group, Et = ethyl group. Said (A)
Minute transition metal compounds may be used alone or in combination of two or more.
You may use in combination.

In the polymerization catalyst of the present invention, (B)
An activation promoter is used as a component. This activation co-catalyst
Examples of the transition metal compound or the transition metal compound of the component (A)
Can react with its derivatives to form ionic complexes
Compounds can be preferably mentioned. The ionic complex
The compound capable of forming a compound includes a transition of the component (B-1) (A)
Ions that react with metal compounds to form ionic complexes
Compounds, (B-2) aluminoxane, (B-3) Louis
There is soot. As the component (B-1), the above-mentioned component (A)
Reacts with transition metal compounds to form ionic complexes
Any ionic compound can be used
However, the following general formulas (II) and (III) ([L¹-R³]^{k +})_p([Z]^-)_q ... (II) ([L²]^{k +})_p([Z]^-)_q ... (III) [However, L²Is M², R^FourR^FiveM³, R⁶ ₃C or R⁷
M³Is. ] [(II), (III) In Formula, L¹Is a Lewis base, [Z]
^-Is a non-coordinating anion [Z ¹]^-Or [Z²]^-, This
Here [Z¹]^-Is an anion in which multiple groups are bound to an element.
Nawachi [M¹A¹A²... Aⁿ]^-(Where M¹Is
Periodic Table Group 5 to 15 elements, preferably Periodic Table 13
~ Group 15 elements are shown. A¹~ AⁿIs the hydrogen source
Child, halogen atom, alkyl group having 1 to 20 carbon atoms, carbon
A dialkylamino group having 2 to 40 carbon atoms and an alkyl group having 1 to 20 carbon atoms
Lucoxy group, aryl group having 6 to 20 carbon atoms, 6 to carbon atoms
20 aryloxy groups, C 7-40 alkyl groups
Reel group, arylalkyl group having 7 to 40 carbon atoms, carbon
Halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, 1 to 20 carbon atoms
Acyloxy group, organic metalloid group, or carbon number 2
20 represents a heteroatom-containing hydrocarbon group. A¹~ Aⁿof
Two or more of them may form a ring. n is [(center
Metal M¹Valence of +1)]. ), [Z²]
^-Has a logarithm (pKa) of the reciprocal of the acid dissociation constant of -10 or less.
Bronsted acid alone or Bronsted acid and Rui
With a conjugate base of a combination of sulphonic acids, or, in general, superacids
The defined conjugate base is shown. Also, the Lewis base coordinates
May be. Also, R³Is a hydrogen atom, having 1 to 20 carbon atoms
Alkyl group, aryl group having 6 to 20 carbon atoms, alkyl
An aryl group or an arylalkyl group, R^FourAnd R
^FiveAre a cyclopentadienyl group and a substituted cyclopentyl group, respectively.
Entadienyl group, indenyl group or fluorenyl group, R
⁶Is an alkyl group, aryl group, or alkyl group having 1 to 20 carbon atoms.
A ruaryl group or an arylalkyl group is shown. R⁷Is
Macrocycles such as traphenylporphyrin and phthalocyanine
Indicates a ligand. k is [L¹-R³], [L²] Ion
The valence is an integer of 1 to 3, p is an integer of 1 or more, q = (k ×
p). M²Is the periodic table 1 to 3, 11 to 13,
Contains Group 17 elements, M³Is Periodic Table No. 7-
Group 12 elements are shown. ] Those represented by are preferably used
be able to.

Specific examples of L ¹ include ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine,
Amines such as N, N-dimethylaniline, trimethylamine, triethylamine, tri-n-butylamine, methyldiphenylamine, pyridine, p-bromo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline, triethylphosphine , Phosphines such as triphenylphosphine and diphenylphosphine, thioethers such as tetrahydrothiophene, esters such as ethyl benzoate, nitriles such as acetonitrile and benzonitrile. Specific examples of R ³ include hydrogen, methyl group, ethyl group, benzyl group and trityl group, and specific examples of R ⁴ and R ⁵ include cyclopentadienyl group and methylcyclopentadienyl group. , Ethylcyclopentadienyl group,
Examples thereof include a pentamethylcyclopentadienyl group. Specific examples of R ⁶ include phenyl group, p-tolyl group and p-methoxyphenyl group, and specific examples of R ⁷ include tetraphenylporphine,
Examples thereof include phthalocyanine, allyl and methallyl. Further, specific examples of M ² include Li, Na,
K, Ag, Cu, Br, I, I _{3 and the} like can be cited, and specific examples of M ³ include Mn, Fe, Co, Ni,
Zn etc. can be mentioned.

[Z ¹ ] ^- , that is, [M ¹ A ¹ A
² ... A ⁿ ] ^- , specific examples of M ¹ include B,
Al, Si, P, As, Sb, etc., preferably B and A
1 can be mentioned. Specific examples of A ¹ and A ^{2 to} A ⁿ include dimethylamino group and diethylamino group as dialkylamino group, methoxy group, ethoxy group, n-butoxy group and phenoxy group as alkoxy group or aryloxy group, and the like. 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 as a hydrocarbon group −
Butylphenyl group, 3,5-dimethylphenyl group, etc.
Fluorine, chlorine, bromine, iodine as a halogen atom, p-fluorophenyl group as a hydrocarbon group containing a hetero atom,
3,5-difluorophenyl group, pentachlorophenyl group, 3,4,5-trifluorophenyl group, pentafluorophenyl group, 3,5-bis (trifluoromethyl)
Phenyl group, bis (trimethylsilyl) methyl group, etc.
Examples of the organic metalloid group include pentamethylantimony group, trimethylsilyl group, trimethylgermyl group, diphenylarsine group, dicyclohexylantimony group and the like.

Further, a non-coordinating anion, that is, pKa
With Brönsted acid of -10 or less
Conjugate base [Z²]^-Ingredient
As an example, trifluoromethane sulfonate anion
(CF₃SO₃)^-, Bis (trifluoromethanesulfone
Nyl) methyl anion, bis (trifluoromethanesulfur)
Honyl) benzyl anion, bis (trifluoromethane)
Sulfonyl) amide, perchlorate anion (Cl
O_Four)^-, Trifluoroacetic acid anion (CF₃CO₂)
^-, Hexafluoroantimony anion (Sb
F₆)^-, Fluorosulfonate anion (FS
O₃)^-, Chlorosulfonate anion (ClS
O₃)^-, Fluorosulfonate anion / 5-fluorinated acid
Nchimon (FSO₃/ SbF_Five)^-, Fluorosulfone
Acid anion / 5-arsenic fluoride (FSO₃/ As
F_Five)^-, Trifluoromethanesulfonate anion / 5
-Antimony fluoride (CF₃SO₃/ SbF_Five) ^-Such
Can be mentioned.

Specific examples of the ionic compound which reacts with the transition metal compound of the component (A) to form an ionic complex, that is, the compound of the component (B-1) are as follows.
Triethylammonium tetraphenylborate, tri-n-butylammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyl (tri-n-butyl) ammonium tetraphenylborate, benzyl tetraphenylborate (tri-n- Butyl) ammonium, dimethyldiphenylammonium tetraphenylborate, triphenyl (methyl) ammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate, methyl tetraphenylborate (2-cyanopyridinium) , Tetrakis (pentafluorophenyl) borate triethylammonium, tetrakis (pentafluorophenyl) ) Tri-n-butylammonium borate, tetrakis (pentafluorophenyl) triphenylammonium borate, tetrakis (pentafluorophenyl) tetra-n-butylammonium borate, tetrakis (pentafluorophenyl) tetraethylammonium borate, tetrakis (pentafluorophenyl) Benzyl (tri-n-butyl) ammonium borate, Methyldiphenylammonium tetrakis (pentafluorophenyl) borate, Triphenyl (methyl) ammonium tetrakis (pentafluorophenyl) borate, Methylanilinium tetrakis (pentafluorophenyl) borate, Tetrakis (penta) Fluorophenyl) borate dimethylanilinium, tetrakis (pentafluorophenyl) borate trimethylanilinium, tetrakis Methylpyridinium pentafluorophenyl) borate, Benzylpyridinium tetrakis (pentafluorophenyl) borate, Methyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), Benzyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), Tetrakis ( Methyl (4-cyanopyridinium) pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) borate, dimethylanilinium tetrakis [bis (3,5-ditrifluoromethyl) phenyl] borate, ferrocenium tetraphenylborate, tetraphenyl Silver borate, trityl tetraphenylborate, tetraphenylporphyrin manganese tetraphenylborate, tetrakis (pentafluorophenyl) borate fe Rothenium, tetrakis (pentafluorophenyl)
Boric acid (1,1′-dimethylferrocenium), tetrakis (pentafluorophenyl) borate decamethylferrocenium, tetrakis (pentafluorophenyl) silver borate, tetrakis (pentafluorophenyl) trityl borate, tetrakis (pentafluorophenyl) Lithium borate, sodium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate theoraphenylporphyrin manganese, silver tetrafluoroborate, silver hexafluorophosphate, silver hexafluoroarsenate,
Examples thereof include silver perchlorate, silver trifluoroacetate, and silver trifluoromethanesulfonate.

The ionic compound which is the component (B-1) and which reacts with the transition metal compound of the component (A) to form an ionic complex may be used alone or in combination of two or more kinds. You may use it. On the other hand, the aluminoxane as the component (B-2) is represented by the general formula (IV)

[0020]

[Chemical 4]

[In the formula, each R ⁸ independently has 1 to 1 carbon atoms.
20, preferably 1 to 12 hydrocarbon groups 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. s represents the degree of polymerization, and is usually an integer of 3 to 50, preferably 7 to 40. ] The chain | strand-shaped aluminoxane shown by these, and general formula (V)

[0022]

[Chemical 5]

[In the formula, R ⁸ and s are as defined above. ] The cyclic aluminoxane shown by these can be mentioned. Examples of the method for producing the aluminoxane include a method in which an alkylaluminum and a condensing agent such as water are brought into contact with each other, but the means therefor is not particularly limited, and the reaction may be performed according to a known method. For example, a method in which an organoaluminum compound is dissolved in an organic solvent and then brought into contact with water, a method in which an organoaluminum compound is initially added during polymerization and then water is added, water of crystallization contained in a metal salt, etc. , A method of reacting water adsorbed to an inorganic substance or an organic substance with an organoaluminum compound, a method of reacting a tetraalkyldialuminoxane with a trialkylaluminum, and further reacting with water. The aluminoxane may be insoluble in toluene. These aluminoxanes may be used alone or in combination of two or more.

The component (B-3) Lewis acid is not particularly limited and may be an organic compound or a solid inorganic compound. Organic boron compounds and organic aluminum compounds are preferably used as the organic compounds, and magnesium compounds, aluminum compounds and the like are preferably used as the inorganic compounds. Examples of the organic aluminum compound include bis (2,6-di-t-butyl-4-methylphenoxy) aluminum methyl and (1,1-bi-2-naphthoxy) aluminum methyl, and examples of the magnesium compound include Magnesium chloride, diethoxymagnesium, etc., aluminum compounds such as aluminum oxide and aluminum chloride, and organic boron compounds such as triphenylboron, tris (pentafluorophenyl) boron, tris [3,5-bis (trifluoro) Methyl) phenyl] boron, tris [(4-fluoromethyl) phenyl] boron, trimethylboron, triethylboron, tri-n-butylboron, tris (fluoromethyl)
Boron, tris (pentafluoroethyl) boron, tris (nonafluorobutyl) boron, tris (2,4,6-trifluorophenyl) boron, tris (3,5-difluoro) boron, tris [3,5-bis ( Trifluoromethyl) phenyl] boron, bis (pentafluorophenyl)
Fluoroboron, diphenylfluoroboron, bis (pentafluorophenyl) chloroboron, dimethylfluoroboron, diethylfluoroboron, di-n-butylfluoroboron, pentafluorophenyldifluoroboron, phenyldifluoroboron, pentafluorophenyldichloroboron, methyldifluoro Boron, ethyldifluoroboron, n
-Butyldifluoroboron, boron trifluoride, etc. may be mentioned. These Lewis acids may be used alone or in combination of two or more.

The ratio of the catalyst component (A) to the catalyst component (B) used in the polymerization catalyst of the present invention is preferably a molar ratio when the compound (B-1) is used as the catalyst component (B). Is 10: 1 to 1: 100, more preferably 2: 1 to
The range of 1:10 is desirable, and when the compound (B-2) is used, the molar ratio is preferably 1: 1 to 1: 100.
The range of 0000, more preferably 1:10 to 1: 10000 is desirable. The ratio of the (A) catalyst component to the (B-3) catalyst component used is a molar ratio, preferably 1: 0.1-
1: 2000, more preferably 1: 0.2 to 1: 100
The range of 0, more preferably 1: 0.5 to 1: 500 is desirable. Further, as the catalyst component (B), (B-1),
(B-2), (B-3) and the like can be used alone or in combination of two or more kinds. The polymerization catalyst of the present invention,
It may contain the above-mentioned components (A) and (B) as main components, or may contain the above-mentioned components (A), (B) and (C) organoaluminum compounds as main components. May be Here, the organoaluminum compound as the component (C) is represented by the general formula (VI) R ⁹ _r AlQ _3-r (VI) [wherein, R ⁹ is an alkyl group having 1 to 10 carbon atoms, and Q is Hydrogen atom, alkoxy group having 1 to 20 carbon atoms, 6 to 20 carbon atoms
Represents an aryl group or a halogen atom, and r is an integer of 1 to 3. ] The compound shown by these is used.

Specific examples of the compound represented by the general formula (VI) include trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, methyl aluminum dichloride, ethyl aluminum dichloride, dimethyl. Aluminum fluoride, diisobutyl aluminum hydride, diethyl aluminum hydride, ethyl aluminum sesquichloride and the like can be mentioned. These organoaluminum compounds may be used alone or in combination of two or more. The (A) catalyst component and (C) catalyst component are preferably used in a molar ratio of 1: 1 to 1: 100.
00, more preferably 1: 5 to 1: 2000, further preferably 1:10 to 1: 1000. By using the (C) catalyst component, 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.

In the present invention, at least one of the catalyst components can be used by supporting it on a suitable carrier. There is no particular limitation on the type of the carrier, an inorganic oxide carrier,
Although any other inorganic carrier or organic carrier can be used, an inorganic oxide carrier or another inorganic carrier is particularly preferable. Specific examples of the inorganic oxide carrier include SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ and TiO ₂ .
₂ , Fe ₂ O ₃ , B ₂ O ₃ , CaO, ZnO, BaO,
Examples include ThO ₂ and mixtures thereof, such as silica alumina, zeolite, ferrite, and glass fiber. Of these, SiO ₂ and Al ₂ O ₃ are particularly preferable. The inorganic oxide carrier is a small amount of carbonate,
It may contain nitrates, sulfates and the like. On the other hand, as a carrier other than the above, a general formula MgR ¹⁰ _X typified by a magnesium compound such as MgCl ₂ or Mg (OC ₂ H ₅ ) ₂ is used.
Examples thereof include magnesium compounds represented by X ¹ _y and complex salts thereof. Here, R ¹⁰ represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and X ¹ represents a halogen atom or an alkyl group having 1 to 20 carbon atoms, x is 0-2, y is 0-2
And x + y = 2. Each R ¹⁰ and each X ¹ may be the same or different.

As the organic carrier, polystyrene,
Examples thereof include polymers such as styrene-divinylstyrene copolymer, substituted polystyrene, polyethylene, polypropylene and polyarylate, starch and carbon. As the carrier used in the present invention, MgC
l ₂ , MgCl (OC ₂ H ₅ ), Mg (OC ₂ H ₅ ) ₂ ,
SiO ₂ , Al ₂ O _{3 and the} like are preferable. The properties of the carrier vary depending on the type and production method, but the average particle size is usually 1 to 300 μm, preferably 10 to 200 μm, and more preferably 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 is usually 1 to 1000 m ² /
g, preferably 50 to 500 m ² / g, the pore volume is usually
It is 0.1 to ⁵ cm ³ / g, preferably 0.3 to ³ cm ³ / g. If either the specific surface area or the pore volume deviates from the above range, the catalytic activity may decrease. The specific surface area and the pore volume can be obtained from the volume of nitrogen gas adsorbed according to, for example, the BET method (Journal of the American Chemical Society, Volume 60, page 309 (1983)). reference). Furthermore, it is desirable that the above-mentioned carrier is usually calcined at 150 to 1000 ° C., preferably 200 to 800 ° C. before use.

When at least one catalyst component is supported on the carrier, at least one of (A) catalyst component and (B) catalyst component, preferably (A) catalyst component and (B).
It is desirable to support both catalyst components. In the carrier,
The method of supporting at least one of the component (A) and the component (B) is not particularly limited. For example, a method of mixing at least one of the component (A) and the component (B) with a carrier, an organoaluminum compound as a carrier. Alternatively, a method of treating with a halogen-containing silicon compound and then mixing with at least one of the components (A) and (B) in an inert solvent, a carrier, a component (A) and / or a component (B) and an organoaluminum compound, or Method of reacting with halogen-containing silicon compound, method of loading component (A) or component (B) on carrier and then mixing with component (B) or component (A), component (A) and component (B) It is possible to use a method of mixing a reaction product of contact with the carrier with a carrier, a method of allowing a carrier to coexist in the contact reaction between the component (A) and the component (B), and the like. In the above reaction and
It is also possible to add an organoaluminum compound as the component (C).

The catalyst thus obtained may be used for the polymerization after the solvent is once distilled off and taken out as a solid, or may be used for the polymerization as it is. Further, in the present invention, the catalyst can be produced by carrying out the loading operation of at least one of the component (A) and the component (B) on the carrier in the polymerization system. For example, at least one of the component (A) and the component (B), a carrier, and, if necessary, the organoaluminum compound of the component (C) are added, and an olefin such as ethylene is added at atmospheric pressure to 20 kg / cm ² to obtain −20 to 200. It is possible to use a method in which catalyst particles are produced by carrying out prepolymerization at a temperature of 1 minute to 2 hours.

In the present invention, the compound (B-1)
The ratio of the component to the carrier used is preferably 1: 5 by weight.
˜1: 10000, more preferably 1:10 to 1:50
0 is desirable, and the ratio of the component (B-2) to the carrier is preferably 1: 0.5 to 1: 1000 by weight.
More preferably, the ratio is 1: 1 to 1:50,
The weight ratio of the component (B-3) to the carrier is preferably 1: 5 to 1: 10000, more preferably 1:10.
It is desirable to be set to about 1: 500. When two or more kinds of catalyst components (B) are mixed and used, it is desirable that the weight ratio of each component (B) to the carrier be within the above range. The ratio of the component (A) to the carrier is preferably 1: 5 to 1: 10000, more preferably 1:10 to 1: 500 by weight. The (B)
Component [(B-1) component, (B-2) component or (B-3)
If the ratio of the component] to the carrier or the ratio of the component (A) to the carrier deviates from the above range, the activity may decrease. The average particle size of the polymerization catalyst of the present invention thus prepared is usually 2 to 200 μm, preferably 10 to
150 μm, particularly preferably 20 to 100 μm,
The specific surface area is usually 20 to 1000 m ² / g, preferably 50 to 500 m ² / g. If the average particle size is less than 2 μm, the fine powder in the polymer may increase.
If it exceeds m, coarse particles in the polymer may increase. If the specific surface area is less than 20 m ² / g, the activity may decrease, and if it exceeds 1000 m ² / g, the bulk density of the polymer may decrease. Further, in the catalyst of the present invention, the amount of transition metal in 100 g of the carrier is usually 0.05 to 10
g, particularly 0.1 to 2 g is preferable. If the amount of transition metal is out of the above range, the activity may decrease. By thus supporting on a carrier, a polymer having a high bulk density industrially advantageous and an excellent particle size distribution can be obtained.

According to the method for producing an olefin-based polymer of the present invention, the above-mentioned polymerization catalyst is used to homopolymerize olefins or olefins and other olefins and / or
Or copolymerization with other monomers (ie, copolymerization with different olefins, copolymerization with olefins and other monomers, or with different olefins and other monomers) (Copolymerization) can be suitably performed. The olefins are not particularly limited, but α-olefins having 2 to 20 carbon atoms are preferable. Examples of this α-olefin include ethylene, propylene, 1-butene, and 3-methyl-1.
-Butene, 1-pentene, 1-hexene, 4-methyl-
1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene, p -T
-Butyl styrene, p-phenyl styrene, p-methyl silyl styrene, p-trimethyl silyl styrene etc. can be mentioned. Further, the other olefins described above may be appropriately selected from the above olefins.

In the present invention, the above olefins may be used alone or in combination of two or more. When copolymerizing two or more olefins, the above olefins can be combined arbitrarily. In that case, for example, when propylene and ethylene, or ethylene and an α-olefin having 3 to 10 carbon atoms are copolymerized, the ratio of propylene and ethylene, or ethylene and an α-olefin having 3 to 10 carbon atoms is used. Polymerization ratio (molar ratio)
Is usually 99.9: 0.1 to 0.1: 99.9, preferably 99.9.
It is selected in the range of 5: 0.5 to 75.0: 25.0. In the present invention, the above-mentioned olefins may be copolymerized with another monomer, and examples of the other monomer used at this time include a chain of butadiene; isoprene; 1,5-hexadiene and the like. Diolefins, norbornene; 1,
4,5,8-Dimethano-1,2,3,4,4a, 5
8,8a-Octahydronaphthalene; cyclic olefins such as 2-norbornene, cyclic diolefins such as norbornadiene, 5-ethylidene norbornene, 5-vinyl norbornene and dicyclopentadiene, unsaturated such as ethyl acrylate and methyl methacrylate Esters,
Lactones such as β-propiolactone, β-butyrolactone, γ-butyrolactone, ε-caprolactam, δ
Examples thereof include lactams such as valerolactam, epoxy propane, and epoxides such as 1,2-epoxybutane. The polymerization catalyst of the present invention can be used not only for polymerization of the above-mentioned olefins but also for polymerization of other than olefins.

In the present invention, the polymerization method is not particularly limited.
No, slurry polymerization method, gas phase polymerization method, bulk polymerization method, solution weight
Any method such as legal method or suspension polymerization method may be used
However, the slurry polymerization method and the gas phase polymerization method are particularly preferable. polymerization
Regarding the conditions, the polymerization temperature is usually −100 to 250 ° C.,
Preferably -50 to 200 ° C, more preferably 0 to 13
It is 0 ° C. Also, the ratio of catalyst used to the reaction raw materials
Is preferably the raw material monomer / the above-mentioned component (A) (molar ratio)
Kuha 1-10 ⁸, Especially from 10 to 10^FiveLike to be
Good Furthermore, the polymerization time is usually 5 minutes to 10 hours, and the reaction pressure is
Force is preferably normal pressure to 200 kg / cm²G, especially preferred
Normal pressure to 100 kg / cm²G. Polymer content
As the method for adjusting the amount of impurities, the type of each catalyst component, the amount used,
The selection of the polymerization temperature, the polymerization in the presence of hydrogen, etc.
It When a polymerization solvent is used, for example, benzene or toluene
Aromatic hydrocarbons such as benzene, xylene, ethylbenzene,
Cyclopentane, cyclohexane, methylcyclohexa
Alicyclic hydrocarbons such as benzene, pentane, hexane, hepta
Aliphatic hydrocarbons such as octane and octane, chloroform, diene
Do not use halogenated hydrocarbons such as chloromethane.
You can These solvents may be used alone.
Alternatively, two or more kinds may be combined. Also, α-
Monomers such as olefins may be used as a solvent.
Depending on the polymerization method, it can be carried out without a solvent.
The molecular weight of the polymer thus obtained is not particularly limited.
However, the intrinsic viscosity [η] (135 ° C
Measurement), 0.1 dL / g or more is preferable.
Especially, 0.2 deciliter / g or more is preferable.

In the present invention, prepolymerization can be carried out using the above-mentioned polymerization catalyst. The prepolymerization can be carried out by contacting the solid catalyst component with, for example, a small amount of olefin, but the method is not particularly limited,
A known method can be used. The olefin used in the prepolymerization is not particularly limited, and the same olefins as those exemplified above, for example, ethylene, α having 3 to 20 carbon atoms
-Olefin, or a mixture thereof can be mentioned, but it is advantageous to use the same olefin as that used in the polymerization. The prepolymerization temperature is usually -20 to 200 ° C, preferably -10 to 1
It is 30 ° C, more preferably 0 to 80 ° C. In the prepolymerization, an inert hydrocarbon, an aliphatic hydrocarbon, an aromatic hydrocarbon, a monomer or the like can be used as a solvent. Of these, aliphatic hydrocarbons are particularly preferable. Further, the prepolymerization may be carried out without a solvent. In the prepolymerization, the intrinsic viscosity [η] (135) of the prepolymerized product is
C. decalin) of 0.2 deciliter / g or more, especially 0.5 deciliter / g or more, transition metal component 1 in the catalyst 1
The amount of prepolymerized product per millimole is 1 to 10
It is desirable to adjust the conditions so that the amount is 000 g, particularly 10 to 1000 g.

[0036]

The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The physical properties of the polymer were measured as follows. (1) Weight average molecular weight (Mw) Using 1,2,4-trichlorobenzene as a solvent, 1
Gel permeation chromatography (GPC) at 35 ° C (apparatus: Waters ALC / GPC
150C, column: Tosoh TSK HM + GMH6
× 2, flow rate: 1.0 ml / min) was calculated in terms of polyethylene. (2) Melting point The melting point was measured by DSC (differential scanning calorimeter) analysis. Measurement conditions: Fast heating: Room temperature to 190
℃, 10 ℃ / min, 3min hold Fast cooling: 190 ℃ to room temperature, 10 ℃ / min, 3min hold Second heating: Room temperature to 190 ℃, 10 ℃ / m
in

Production Example 1 Bis (cyclopentadienyl) titanium methyl (triphenylphosphorus methyl ylide) [Cp ₂ TiMe (-
CH = PPh ₃ )] Into 100 ml of a tetrahydrofuran solution of 0.1 mol of methyltriphenylphosphonium bromide, 0.1 mol of n-butyllithium (1.5 M-hexane solution) was slowly added at -78 ° C. The mixture was added dropwise, the temperature was gradually raised, and stirring was continued at 0 ° C. for another hour. This solution was slowly added dropwise to 100 ml of a tetrahydrofuran solution containing 0.05 mol of bis (cyclopentadienyl) titanium dichloride at −78 ° C., the temperature was gradually raised, and stirring was continued at 0 ° C. for another hour. Next, 0.1 mol of methyllithium (1.0 M-tetrahydrofuran solution) was slowly added dropwise to this solution at -78 ° C, the temperature was gradually raised, and stirring was continued at 0 ° C for another hour. From this reaction product, bis (cyclopentadienyl) titanium methyl (triphenylphosphorus methyl ylide) (complex a) was taken out as a toluene-soluble component insoluble in hexane. Yield 62%. ¹ H-NMR of complex a
The measurement results are shown below. ¹ H-NMR (90 MHz, solvent C ₆ D ₆ ) δ 0.32
(3H, s, CH ₃ ), 5.61 (10H, s, Cp ),
6.95-7.20 (9H, m, benzene ring), 7.45-7.
80 (7H, m, benzene ring 6H, -CH = P)

Example 1 400 ml of toluene and 1 mmol of triisobutylaluminum (TIBA) were put into a 1 liter autoclave which was dried under heating and reduced pressure at room temperature in a nitrogen atmosphere.
The temperature of the solution was raised to 60 ° C. with stirring, and then 60
1 micromol of the complex a obtained in Production Example 1 and 1 micromol of N, N'-dimethylanilinium tetrakis (pentafluorophenyl) borate were added at 0 ° C, and the temperature was raised to 80 ° C. Polymerization was carried out at 80 ° C. for 1 hour while continuously maintaining ethylene at 8 atm. After completion of the reaction, the reaction product was thoroughly stirred in a methanol-hydrochloric acid solution and then filtered off,
The polymer was thoroughly washed with methanol and then dried to obtain a polymer. For the obtained polymer, yield (g), melting point (° C), weight average molecular weight (Mw) and Q
(Mw / Mn) was measured. The results are shown in Table 1.

Example 2 360 ml of toluene, 40 ml of 1-octene and 1 mmol of TIBA were placed in a 1 liter autoclave which was dried under heating under reduced pressure at room temperature in a nitrogen atmosphere.
The temperature of the solution was raised to 60 ° C. with stirring, and then 60
1 micromol of the complex a obtained in Production Example 1 and 1 micromol of N, N'-dimethylanilinium tetrakis (pentafluorophenyl) borate were added at 0 ° C, and the temperature was raised to 80 ° C. Polymerization was carried out at 80 ° C. for 1 hour while continuously maintaining ethylene at 8 atm. After completion of the reaction, the reaction product was thoroughly stirred in a methanol-hydrochloric acid solution and separated,
The polymer was thoroughly washed with methanol and then dried to obtain a polymer. The results are shown in Table 1.

Example 3 Example 1 was repeated except that 6 mmol of methylaluminoxane was used in place of 1 mmol of TIBA and N, N'-dimethylanilinium tetrakis (pentafluorophenyl) borate was not used. It carried out similarly to. The results are shown in Table 1.

Example 4 Example 2 was repeated except that 6 mmol of methylaluminoxane was used in place of 1 mmol of TIBA and N, N'-dimethylanilinium tetrakis (pentafluorophenyl) borate was not used. It carried out similarly to. The results are shown in Table 1.

[0042]

[Table 1]

[0043]

The olefin polymerization catalyst of the present invention is a highly active soluble catalyst, and by using this catalyst,
An olefin-based polymer having a high molecular weight, uniform and narrow molecular weight distribution can be efficiently obtained.

Claims (4)

[Claims] 1. (A) General formula (I): [In the formula, M is a metal element of Groups 3 to 10 of the periodic table or a lanthanoid series, Cp is a cyclic unsaturated hydrocarbon group, and a is 0 to
In the case where a is 2, two Cp may be the same or different and may form a multi-bridged structure, X is a σ-bonding ligand, and b is [ (Valence of M)-
a-1] represents an integer of 0 to 5, and when there are a plurality of Xs,
A plurality of X may be the same or different, and X and Cp may form a crosslinked structure. Y is Lewis base, c
Represents an integer of 0 to 3, and when there are plural Ys, plural Ys
May be the same or different. R ¹ is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an acyl group having 1 to 20 carbon atoms,
C 7-20 arylcarbonyl group or silicon-containing group, R ² is a C 1-20 hydrocarbon group, C 1-2
0 represents an alkoxy group or an aryloxy group having 6 to 20 carbon atoms, and each R ² may be the same or different. ] The olefin polymerization catalyst containing the transition metal compound represented by these, and (B) activation cocatalyst. 2. An olefin polymerization catalyst comprising (A) a transition metal compound represented by the general formula (I), (B) an activation co-catalyst, and (C) an organoaluminum compound. 3. The activating cocatalyst of the component (B) is a compound capable of reacting with the transition metal compound of the component (A) or a derivative thereof to form an ionic complex. Olefin polymerization catalyst. 4. In the presence of the olefin polymerization catalyst according to claim 1, olefins are homopolymerized or olefins are copolymerized with other olefins and / or other polymerizable unsaturated compounds. A method for producing an olefin-based polymer, comprising: