JPH0770222A - Olefin polymerization catalyst and production of polyolefin using the catalyst - Google Patents

Abstract

PURPOSE:To obtain an olefin polymerization catalyst composed mainly of a specific transition metal compound and a specific compound capable of forming an ionic complex, having high activity and capable of producing a polyolefin having high molecular weight in high efficiency. CONSTITUTION:This catalyst is composed mainly of (A) a transition metal compound of the formula [M is the group 3-5 or lanthanoid metal element of the Periodic Table; X is a (chelating) ligand; Y is a bivalent ligand; Z is a Lewis base, (b) is 1 or 2; (a+2b) is atomic valence of M; (c) is 0-4] such as (B9C2H11)ZrCl2 and (B) a compound capable of forming an ionic complex from the transition metal compound (or its derivative) such as triethylammonium tetraphenyl-borate. A polyolefin is produced by homopolymerizing an olefin or copolymerizing an olefin and other olefins and/or other monomers in the presence of the catalyst.

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 a polyolefin using the catalyst. More specifically, the present invention uses a catalyst for high activity polymerization which gives a high molecular weight olefin homopolymer or a high molecular weight and good copolymerizable olefin copolymer, and a catalyst having the above-mentioned properties. The present invention relates to a method for efficiently producing an olefin homopolymer or copolymer.

[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). Further, it has been reported that a cationic species is useful as an active species of a soluble olefin polymerization catalyst ["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.

However, 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 200 ° 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. On the other hand, "Journal of the American Chemical Society (J. Am. Chem. Soc.)", Volume 113, page 1455 (1991), US Patent No. 5,
162,466 and U.S. Pat. No. 5,214,173 describe synthesis of a complex having a carborane ligand and polymerization of an olefin using the same. Then, as a complex having the carborane ligand, (Cp) (C ₂ B
₉ H ₁₁ ) M (CH ₃ ), [(Cp) (C ₂ B ₉ H ₁₁ ).
M] _{2 - (μ-CH 2)} ( where, Cp is a cyclopentadienyl-based ligand, M is a transition metal) are illustrated. However, the polymers obtained by using the complexes having these carborane ligands and cyclopentadienyl-based ligands are not sufficiently high in molecular weight as described above.

[0004]

Under the circumstances described above, the present invention provides a high-activity olefin homopolymer or a high-activity polymerizing olefin copolymer which provides a high-molecular-weight and good copolymerizable olefin copolymer. The object of the present invention is to provide a catalyst and a method for efficiently producing an olefin homopolymer or copolymer having the above-mentioned properties using the catalyst for polymerization.

[0005]

Means for Solving the Problems As a result of intensive studies to achieve the above-mentioned object, the present inventors have identified a specific transition metal compound and an ionic complex from the transition metal compound or a derivative thereof. It was found that the object can be achieved by a polymerization catalyst containing a compound capable of forming as a main component. The present invention has been completed based on such findings.

That is, the present invention provides (A) general formula (I) MX _a Y _b Z _c (I) (wherein, M is a metal element of Groups 3 to 5 of the periodic table or a lanthanoid series, X is a σ-bonding ligand or chelating ligand, Y is a π-bonding divalent ligand containing at least a boron atom and a carbon atom, Z is a Lewis base, b is 1 or 2, (A + 2b) is a valence of M, c is an integer of 0 to 4, and when each of X, Y and Z is plural, each X, each Y
And each Z may be the same or different. In the presence of a transition metal compound represented by the above) and (B) a compound capable of forming an ionic complex from the transition metal compound or a derivative thereof as a main component, and the catalyst for olefin polymerization, The present invention provides a method for producing a polyolefin, which comprises homopolymerizing olefins or copolymerizing olefins and / or other monomers.

In the polymerization catalyst of the present invention, a transition metal compound represented by the general formula (I) MX _a Y _b Z _c (I) is used as the component (A). In the above general formula (I), M represents a metal element of Groups 3 to 5 of the periodic table or a lanthanoid series. Specific examples of M include titanium, zirconium, hafnium, vanadium and niobium. X represents a σ-bonding ligand or a chelating ligand, and specific examples thereof include halogen compounds of fluorine, chlorine, bromine and iodine, methyl group, ethyl group, n
-Propyl group, isopropyl group, n-butyl group, alkyl group such as isobutyl group, methoxy group, ethoxy group, n
-Propoxy group, isopropoxy group, n-butoxy group,
Examples thereof include alkoxy groups such as isobutoxy group.
Y represents a π-bonding divalent ligand containing at least a boron atom and a carbon atom, and specific examples thereof include B ₉ C ₂ H ₁₁ and B ₄
C ₂ H ₆ , B ₃ C ₂ H ₇ , B ₂ C ₂ SH ₄ , BC
_{4 H 5, B 2 C 4} H 6 may be a group derived from carborane represented by like. A specific structural formula is shown in FIG. Z represents a Lewis base, and specific examples thereof include ethers such as dimethyl ether, diethyl ether and tetrahydrofuran, thioethers such as tetrahydrothiophene, esters such as ethylbenzoate, acetonitrile; nitriles such as benzonitrile, trimethylamine; triethylamine; triethylamine. Butylamine; N, N-dimethylaniline; pyridine; 2,
2'-bipyridine; amines such as phenanthroline,
Triethylphosphine; phosphines such as triphenylphosphine, ethylene; butadiene; 1-pentene;
Chain unsaturated hydrocarbons such as isoprene; pentadiene; 1-hexene and their derivatives, benzene; toluene; xylene; cycloheptatriene; cyclooctadiene; cyclooctatriene; cyclooctatetraene and cyclic derivatives such as their derivatives. Examples include saturated hydrocarbons. b is 1 or 2, (a + 2b) is the valence of M,
c shows the integer of 0-4. Further, when there are a plurality of Xs, Ys and Zs, each X, each Y and each Z may be the same or different.

A transition metal compound represented by the above general formula (I)
For example, (B₉C₂H₁₁) ZrCl₂, (B
₉C₂H₁₁) ZrMe₂, (B₉C₂H₁₁) Zr (CH
₂Ph)₂, (B₉C₂H₁₁) Zr (OMe)₂, (B
₉C₂H₁₁) Zr (O-iPr)₂, (B_FourC₂H₆)
ZrCl₂, (B_FourC₂H₆) ZrMe₂, (B_FourC ₂
H₆) Zr (CH₂Ph)₂, (B_FourC₂H₆) Zr
(OMe)₂, (B_FourC ₂H₆) Zr (O-iPr)₂
Etc. and 1 to 4 Lewis bases coordinate to these compounds
And in these, zirconium
Compounds in which is replaced by titanium or hafnium
It Of course, it is not limited to these,
With similar compounds of other group or lanthanide series metal elements
It may be. In the above compound, Ph is phenyl
Group, Me is a methyl group, and iPr is an isopropyl group.
You Use one kind of these transition metal compounds (A)
Or, two or more kinds may be used in combination.

In the polymerization catalyst of the present invention, (B)
Ions from the transition metal compounds or their derivatives as
A compound capable of forming a volatile complex is used. This (B)
As a component, a transition metal compound of (B-1) (A) component
An ionic compound that reacts with to form an ionic complex,
Examples of (B-2) aluminoxane and (B-3) Lewis acid
You can As the component (B-1), the above (A)
Reacts with the transition metal compounds of the components to form ionic complexes
Any ionic compound can be used
However, the following general formulas (II) and (III) ([L¹-R¹]^{k +})_p([Z]^-)_q ... (II) ([L²]^{k +})_p([Z]^-)_q ... (III) (However, L²Is M², R²R³M³, R^Four ₃C or R^Five
M³Is. ) [In the formulas (II) and (III), L¹Is a Lewis base, [Z]
^-Is a non-coordinating anion [Z ¹]^-And [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~ AⁿAre hydrogen atoms,
Halogen atom, C1-20 alkyl group, C2
~ 40 dialkylamino group, C1-20 alco
Xy group, aryl group having 6 to 20 carbon atoms, 6 to 20 carbon atoms
Aryloxy group of 7 to 40 carbon atoms
Group, arylalkyl group having 7 to 40 carbon atoms, 1 carbon atom
~ 20 halogen-substituted hydrocarbon groups, C 1-20
Syloxy group, organic metalloid group, or 2 to 20 carbon atoms
The heteroatom-containing hydrocarbon group of is shown. A¹~ AⁿOut of
Two or more may form a ring. n is [(central 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, R¹Is 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, R²And R
³Are cyclopentadienyl group and substituted cyclopenes, respectively.
Tadienyl group, indenyl group or fluorenyl group, R^Four
Is an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkyl
An aryl group or an arylalkyl group is shown. R^FiveIs Tet
Macrocyclic compounds such as laphenylporphyrin and phthalocyanine
Show the order. k is [L¹-R¹], [L²] Ion value of
Number is an integer of 1 to 3, p is an integer of 1 or more, q = (k × p)
Is. M²Is Periodic Table Nos. 1-3, 11-13, 17
It contains a group element, M³Is the 7th to 12th periodic table
Indicates a group element. ] Use preferably those represented by
You can

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

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

Specific examples of the ionic compound which reacts with the transition metal compound of the component (A) to form an ionic complex, that is, the compound of the component (B-1) are as follows:
Triethylammonium tetraphenylborate, tri-n-butylammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyl (tri-n-butyl) ammonium tetraphenylborate, benzyl tetraphenylborate (tri-n- Butyl) ammonium, 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.

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

[0015]

[Chemical 1]

(In the formula, each R ⁶ independently has 1 carbon atom.
To 20, preferably 1 to 12 hydrocarbon groups such as an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, and an arylalkyl group, and a halogen atom, s represents a degree of polymerization, and usually 3 to 50, preferably A chain aluminoxane represented by the formula (7 to 40), and the general formula (V)

[0017]

[Chemical 2]

The cyclic aluminoxane represented by the formula (wherein R ⁶ and s are the same as above) 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.

Further, the Lewis acid as the component (B-3) is not particularly limited and may be an organic compound or a solid inorganic compound. A boron compound or an aluminum compound is preferably used as the organic compound, and a magnesium compound or an aluminum compound is preferably used as the inorganic compound.
Examples of the aluminum compound include bis (2,6-di-t-butyl-4-methylphenoxy) aluminum methyl, (1,1-bi-2-naphthoxy) aluminum methyl, and examples of the magnesium compound include magnesium chloride, Diethoxymagnesium and the like, aluminum compounds such as aluminum oxide and aluminum chloride, and boron compounds such as triphenylboron, tris (pentafluorophenyl) boron and tris [3,5-bis (trifluoromethyl) phenyl] boron. , Tris [(4-fluoromethyl) phenyl] boron,
Trimethylboron, triethylboron, tri-n-butylboron, tris (fluoromethyl) boron, tris (pentafluoroethyl) boron, tris (nonafluorobutyl) boron, tris (2,4,6-trifluorophenyl) boron, Tris (3,5-difluoro) boron, Tris [3,3
5-bis (trifluoromethyl) phenyl] boron, bis (pentafluorophenyl) fluoroboron, diphenylfluoroboron, bis (pentafluorophenyl) chloroboron, dimethylfluoroboron, diethylfluoroboron,
Examples thereof include di-n-butylfluoroboron, pentafluorophenyldifluoroboron, phenyldifluoroboron, pentafluorophenyldichloroboron, methyldifluoroboron, ethyldifluoroboron, n-butyldifluoroboron and boron trifluoride. These Lewis acids may be used alone or in combination of two or more.

The use ratio of the (A) catalyst component and the (B) catalyst component in the polymerization catalyst of the present invention is preferably a molar ratio when the (B-1) compound is used as the (B) catalyst component. Is 10: 1 to 1: 100, more preferably 2: 1 to
The range of 1:10 is more preferable, and the range of 1: 1 to 1: 5 is preferable, and when the compound (B-2) is used, the molar ratio is preferably 1:20 to 1: 10000, and more preferably 1 The range of: 100 to 1: 2000 is desirable. When the compound (B-3) is used, the molar ratio is preferably 10: 1 to 1: 2000, more preferably 5: 1 to 1: 1.
The range of 1: 1000, more preferably 2: 1 to 1: 500 is desirable. Further, as the component (B), (B-1),
(B-2) and (B-3) may be used alone or in combination of two or more kinds. The polymerization catalyst may contain the above-mentioned component (A) and component (B) as main components, and may also contain the components (A), (B) and (C) organoaluminum compound. It may be contained as the main component. Here, the organoaluminum compound as the component (C) is represented by the general formula (VI) R ⁷ _r AlQ _3-r (VI) (wherein, R ⁷ is an alkyl group having 1 to 10 carbon atoms, and Q is Hydrogen atom, C1-C20 alkoxy group, C6-C20
Is an aryl group or a halogen atom, and r is an integer of 1 to 3).

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: 200.
The range of 0, more preferably 1: 5 to 1: 1000, and further preferably 1:10 to 1: 500 is desirable. 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 method of the present invention, a small amount of catalyst components is used.
Use at least one supported on a suitable inorganic or organic carrier
You can As the inorganic carrier, for example, SiO₂，
Al ₂O₃, MgO, ZrO₂, TiO₂, Fe
₂O₃, B₂O₃, CaO, ZnO, BaO, ThO₂
And mixtures of these, such as silica-alumina, zeoli
G, ferrite, sepiolite, glass fiber
But also MgCl₂And Mg (OC₂H_Five)₂Such as
Examples thereof include a gnesium compound. On the other hand, with an organic carrier
For example, polystyrene, styrene-divinylben
Zen copolymer, polyethylene, polypropylene, substitution
Polymer such as styrene, polyarylate, starch,
Examples include carbon. Among these carriers, especially
MgCl₂, Mg (OC₂H_Five)₂, SiO₂, Al₂O
₃Etc. are suitable. The average particle size of the carrier is 1 to 30.
0 μm, preferably 10 to 200 μm, more preferably
The range of 20 to 100 μm is desirable.

According to the method for producing a polyolefin of the present invention, homopolymerization of olefins or copolymerization of olefins with other olefins and / or other monomers (that is, with the above-mentioned polymerization catalyst) , Copolymerization of different olefins, copolymerization of olefins with other monomers,
Alternatively, copolymerization of different olefins with other monomers) can be suitably carried out. The olefins are not particularly limited, but α-olefins having 2 to 20 carbon atoms are preferable. Examples of the α-olefin include ethylene, propylene, 1-butene, 3-methyl-1-
Butene, 1-pentene, 1-hexene, 4-methyl-1
-Pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene and vinyl aroma such as styrene, p-methylstyrene, isopropylstyrene and t-butylstyrene. Group compounds can be mentioned. Also,
The other olefins described above may be appropriately selected from the above olefins.

In the present invention, the olefins may be used alone or in combination of two or more. 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. Further, in the present invention, the above-mentioned olefins may be copolymerized with other monomers, and examples of the other monomer used at this time include butadiene; isoprene; 1,5-hexadiene and the like. Chain 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, dicyclopentadiene, and 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.
Intrinsic viscosity [η] (135 ° C decalin
(Measured in) is preferably 0.1 deciliter / g or more,
Particularly, 0.2 to 30 deciliter / g 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 and α having 3 to 20 carbon atoms can be used.
-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.

[0027]

EXAMPLES The present invention will now be described in more detail by way of examples, which should not be construed as limiting the invention thereto. Example 1 (Production of ethylene-1-octene copolymer) In a 1 liter autoclave dried under heating and reduced pressure, at room temperature under a nitrogen atmosphere, 360 ml of toluene, 40 ml of 1-octene, and methylaluminoxane (MA).
(O) 5 mmol, and the temperature of the solution was adjusted to 6 while stirring.
The temperature was raised to 0 ° C. Then, at 60 ° C (B ₉ C ₂ H ₁₁ )
ZrCl ₂ [See FIG. 1] Add 5 μmol of complex,
The temperature was raised to 80 ° C. with stirring. Then, polymerization was carried out at 80 ° C. for 1 hour while continuously introducing 8 atm of ethylene. After completion of the reaction, the reaction solution was poured into a methanol-hydrochloric acid solution, and the obtained polymer was washed with methanol three times and dried under reduced pressure. Polymer (ethylene-1-octene copolymer)
Yield 3.0g, melting point 127 ° C, intrinsic viscosity [η]
(Measured in decalin at 135 ° C.) was 2.80 deciliters / g.

Example 2 (Production of ethylene-1-octene copolymer) In Example 1, 1 mmol of triisobutylaluminum and [PhMe ₂ NH] [B (C ₆ F ₅ ) ₄ were used in place of 5 mmol of methylaluminoxane. Polymerization was carried out in the same manner as in Example 1 except that 5 μmol was used,
0.06 g of an ethylene-1-octene copolymer was obtained. This polymer has a melting point of 122 ° C. and an intrinsic viscosity [η] of 10.04.
It was deciliter / g. .

Example 3 In Example 1, the main catalyst was (C ₂ B ₉ H ₁₁ ) TiCl 2.
Polymerization was performed in the same manner as in Example 1 except that the amount was changed to ₂ , to obtain 0.26 g of an ethylene-1-octene copolymer.
This polymer has a melting point of 119 ° C. and an intrinsic viscosity [η]
Was 2.1 deciliter / g.

Comparative Example 1 Polymerization was carried out in the same manner as in Example 2 except that the main catalyst was changed to Cp _z ZrCl ₂ to obtain 65 g of an ethylene-1-octene copolymer. The melting point of this polymer was 117 ° C., and the intrinsic viscosity [η] was 2.80 deciliter / g.

[0031]

EFFECT OF THE INVENTION By using the olefin polymerization catalyst of the present invention, a high molecular weight olefin homopolymer or a high molecular weight and good copolymerizable olefin copolymer can be efficiently obtained.

[Brief description of drawings]

FIG. 1 shows a specific structural formula of carborane.

Claims (2)

[Claims] 1. (A) General formula (I) MX _a Y _b Z _c (I) (wherein, M is a metal element of Group 3 to 5 of the periodic table or a lanthanoid series, and X is a σ bond. Or a chelating ligand, Y is a π-bonding divalent ligand containing at least a boron atom and a carbon atom, Z is a Lewis base, b is 1 or 2, and (a + 2b) is The valence of M, c is an integer of 0 to 4, and when X, Y and Z are respectively plural, each X and each Y
And each Z may be the same or different. ) A catalyst for olefin polymerization comprising a transition metal compound represented by the formula (B) and (B) a compound capable of forming an ionic complex from the transition metal compound or a derivative thereof. 2. A polyolefin characterized by homopolymerizing olefins or copolymerizing olefins with other olefins and / or other monomers in the presence of the olefin polymerization catalyst according to claim 1. Manufacturing method.