JP3371920B2 - Olefin polymerization catalyst and method for producing olefin polymer using the catalyst - Google Patents

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). 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 Publication No. 1-502636, Japanese Unexamined Patent Publication 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]

[Wherein M is a transition metal element of Group 4 of the periodic table, Cp is a cyclic unsaturated hydrocarbon group, b is 1 or 2, and when b is 2, two Cp's are the same or different. Or X may be a halo.
Gen atom, hydrocarbon group having 1 to 20 carbon atoms, 1 to 2 carbon atoms
0 alkoxy group, aryloxy having 6 to 20 carbon atoms
Group, amide group having 1 to 20 carbon atoms, silicon having 1 to 20 carbon atoms
Containing group, phosphide group having 1 to 20 carbon atoms, 1 to 2 carbon atoms
0 represents a sulfide group or an acyl group having 1 to 20 carbon atoms , each X may be the same or different, and X and Cp may form a crosslinked structure . R has 1 to 30 carbon atoms
A represents an integer of 1 to 3, and when there are a plurality of Rs, the plurality of Rs may be the same or different. ] An olefin polymerization catalyst comprising a transition metal compound represented by: (B) an activation co-catalyst, and optionally (C) an organoaluminum compound, 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, as the component (A), a compound represented by the general formula (I)

[0009]

[Chemical 3]

A transition metal compound represented by the following is used.

In the above general formula (I), M represents a transition metal element of Group 4 of the periodic table, specifically titanium, zirconium or hafnium. Cp represents a cyclic unsaturated hydrocarbon group, specifically, cyclopentadienyl group, substituted cyclopentadienyl group, indenyl group, substituted indenyl group, tetrahydroindenyl group, substituted tetrahydroindenyl group, fluorenyl group, substituted Fluorenyl group etc. can be mentioned. b represents 1 or 2, and when b is 2, two Cp's may be the same or different, and may form a multi-bridged structure. X represents a σ-bonding ligand, each X may be the same or different, and X and Cp 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, an aryloxy group having 6 to 20 carbon atoms, an amide group having 1 to 20 carbon atoms, and carbon. C1-C20 silicon-containing groups, C1-C20 phosphide groups, C1-C20 sulfide groups, C1-C20 acyl groups, and the like, preferably halogen atoms of fluorine, chlorine, bromine, and iodine. , An alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group and an isobutyl group, an arylalkyl group such as a benzyl group,
Examples thereof include alkoxy groups such as methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group and isobutoxy group, and silicon-containing groups such as trimethylsilyl group and trimethylsilylmethyl group. On the other hand, Y represents a Lewis base, c is an integer of 0 to 3, and when there are plural Ys, the plural Ys may be the same or different. The Y
As specific examples of the Lewis base, there can be mentioned amines, ethers, phosphines, thioethers and the like.

R is a hydrocarbon group having 1 to 30 carbon atoms, for example, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkylaryl group having 7 to 30 carbon atoms, and 7 to 30 carbon atoms. And an arylalkyl group thereof. Specific examples of R include methyl group, ethyl group, n-propyl group,
Isopropyl group, n-butyl group, isobutyl group, octyl group, 2-ethylhexyl group, phenyl group, tolyl group,
Examples thereof include a xylyl group, a benzyl group, and a phenethyl group. a represents an integer of 1 to 3, and when there are a plurality of Rs, the plurality of Rs may be the same or different.

Examples of the transition metal compound represented by the above general formula (I) include bis (methoxycarbonylcyclopentadienyl) titanium dichloride, bis (ethoxycarbonylcyclopentadienyl) titanium dichloride and bis (phenoxycarbonylcyclo). Pentadienyl) titanium dichloride, bis (ethoxycarbonylcyclopentadienyl) titanium dimethyl, bis (ethoxycarbonylcyclopentadienyl) titanium dibenzyl, bis (ethoxycarbonylcyclopentadienyl) titanium bis (trimethylsilylmethyl), meso-bis (1-Ethoxycarbonyl-2-methylcyclopentadienyl) titanium dichloride, racemic-bis (1-ethoxycarbonyl-2)
-Methylcyclopentadienyl) titanium dichloride, meso-bis (1-ethoxycarbonyl-3-methylcyclopentadienyl) titanium dichloride, racemic-bis (1
-Ethoxycarbonyl-3-methylcyclopentadienyl) titanium dichloride, meso-bis (1-ethoxycarbonyl-2,3-dimethylcyclopentadienyl) titanium dichloride, racemic-bis (1-ethoxycarbonyl-2,3- Dimethylcyclopentadienyl) titanium dichloride, meso-bis (1-ethoxycarbonyl-2,4
-Dimethylcyclopentadienyl) titanium dichloride,
Racemic-bis (1-ethoxycarbonyl-2,4, dimethylcyclopentadienyl) titanium dichloride, bis (1-ethoxycarbonyl-2,5-dimethylcyclopentadienyl) titanium dichloride, bis (1-ethoxycarbonyl-3) , 4-dimethylcyclopentadienyl)
Titanium dichloride, meso-bis (1-ethoxycarbonyl-2,3,4-trimethylcyclopentadienyl) titanium dichloride, racemic-bis (1-ethoxycarbonyl-2,3,4-trimethylcyclopentadienyl) titanium dichloride , Meso-bis (1-ethoxycarbonyl-2,3,5-trimethylcyclopentadienyl) titanium dichloride, racemic-bis (1-ethoxycarbonyl-2,3,5-trimethylcyclopentadienyl) titanium dichloride, bis (1-ethoxycarbonyl-2,
3,4,5-Tetramethylcyclopentadienyl) titanium dichloride, racemic-bis (1-ethoxy-3-trimethylsilylcyclopentadienyl) titanium dichloride, racemic-bis (1-ethoxy-3-t-butylcyclopenta) Dienyl) titanium dichloride, bis (1,3-
Diethoxycarbonylcyclopentadienyl) titanium dichloride, racemic-dimethylsilylenebis (3-ethoxycarbonylcyclopentadienyl) titanium dichloride, racemic-dimethylsilylenebis (3-ethoxycarbonyl-5-methylcyclopentadienyl) titanium dichloride , Racemic-ethylenebis (3-ethoxycarbonyl-5-methylcyclopentadienyl) titanium dichloride, racemic-isopropylidene bis (3-ethoxycarbonyl-5-methylcyclopentadienyl) titanium dichloride, (methoxycarbonylcyclopentadiene Enil)
Titanium trichloride, (ethoxycarbonylcyclopentadienyl) titanium trichloride, (phenoxycarbonylcyclopentadienyl) titanium trichloride, (ethoxycarbonylcyclopentadienyl) titanium trimethyl, (ethoxycarbonylcyclopentadienyl) titanium tribenzyl , (Ethoxycarbonylcyclopentadienyl) titanium tris (trimethylsilylmethyl),
(1-Ethoxycarbonyl-2-methylcyclopentadienyl) titanium trichloride, (1-ethoxycarbonyl-3-methylcyclopentadienyl) titanium trichloride, (1-ethoxycarbonyl-2,3-dimethylcyclopentadiene) (Enyl) titanium trichloride, (1-ethoxycarbonyl-2,4-dimethylcyclopentadienyl) titanium trichloride, (1-ethoxycarbonyl-
2,5-Dimethylcyclopentadienyl) titanium trichloride, (1-ethoxycarbonyl-3,4-dimethylcyclopentadienyl) titanium trichloride, (1-ethoxycarbonyl-2,3,4-trimethylcyclopentadiene (Enyl) titanium trichloride, (1-ethoxycarbonyl-2,3,5-trimethylcyclopentadienyl) titanium trichloride, (1-ethoxycarbonyl-
2,3,4,5-tetramethylcyclopentadienyl)
Titanium trichloride, (1-ethoxycarbonyl-3-
Trimethylsilylcyclopentadienyl) titanium trichloride, (1-ethoxycarbonyl-3-t-butylcyclopentadienyl) titanium trichloride, (1,3-
Examples thereof include diethoxycarbonylcyclopentadienyl) titanium trichloride, and compounds in which these titaniums are replaced with zirconium or hafnium.
Of course, it is not limited to these. The (A)
The component transition metal compound may be used alone or in combination of two or more.

In the polymerization catalyst of the present invention, an activation promoter is used as the component (B). The activation cocatalyst is not particularly limited and, for example, a compound capable of reacting with the transition metal compound of the component (A) or a derivative thereof to form an ionic complex can be preferably mentioned.
The compound capable of forming the ionic complex includes (B-1)
There are ionic compounds (B-2) aluminoxane and (B-3) Lewis acid which react with the transition metal compound of the component (A) to form an ionic complex.

As the component (B-1), the above-mentioned component (A) is used.
Reacts with transition metal compounds to form ionic complexes
Any ionic compound can be used
However, the following general formula (II), (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]^-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~ 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 methylcyclopenta group. Examples thereof include a dienyl group, an ethylcyclopentadienyl group and 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, phthalocyanine, allyl, methallyl and the like. . Further, specific examples of M ² include Li, Na, K, Ag, Cu, Br, I, and I ₃ , and specific examples of M ³ include Mn and F.
e, 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 kind 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 kinds thereof 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)

[0022]

[Chemical 4]

[In the formula, each R ⁶ independently has 1 to 1 carbon atoms.
20, preferably a hydrocarbon group such as an alkyl group, an alkenyl group, an aryl group and an arylalkyl group having 1 to 12 or a halogen atom, which may be the same or different. s represents a degree of polymerization, and is usually an integer of 3 to 50, preferably 7 to 40], and a general formula (V)

[0024]

[Chemical 5]

[In the formula, R ⁶ and s are the same as described 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. (B-
The Lewis acid as the component 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, 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 [3,5-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 (A) catalyst component to the (B) catalyst component used 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 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 ⁷ _r AlQ _3-r (VI) (wherein, R ⁷ 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
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: 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 ⁸ _X typified by magnesium compounds such as MgCl ₂ and Mg (OC ₂ H ₅ ) ₂ is used.
Examples thereof include magnesium compounds represented by X ¹ _y and complex salts thereof. Here, R ⁸ 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 ⁸ and each X ¹ may be the same or different.

As the organic carrier, polystyrene,
Examples thereof include polymers such as styrene-divinylbenzene 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 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 polymer of the present invention, the above-mentioned polymerization catalyst is used to homopolymerize an olefin, or an olefin is mixed with another olefin and / or another polymerizable unsaturated compound. Copolymerization can be suitably performed. 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-eicosene, styrene, p-methylstyrene, p-chlorostyrene, pt-butylstyrene, p-phenylstyrene, p-methylsilylstyrene, p -Trimethylsilylstyrene and the like can be mentioned. Further, 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. In the present invention, the above-mentioned olefins may be copolymerized with another monomer (polymerizable unsaturated compound). Examples of the other monomer used at this time include butadiene; isoprene; , 5-hexadiene and other chain diolefins, norbornene; 1,4,5,8-dimethano-1,
2,3,4,4a, 5,8,8a-octahydronaphthalene; cyclic olefins such as 2-norbornene, norbornadiene, 5-ethylidene norbornene, 5-vinyl norbornene, dicyclopentadiene and other cyclic diolefins, acrylic Unsaturated esters such as ethyl acid and methyl methacrylate, lactones such as β-propiolactone, β-butyrolactone and γ-butyrolactone,
Examples thereof include lactams such as ε-caprolactam and δ-valerolactam, epoxypropane; and epoxides such as 1,2-epoxybutane. The polymerization catalyst of the present invention can be used not only for polymerization or copolymerization of the above-mentioned olefins, but also for homopolymerization or copolymerization 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 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 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.

[0037]

The present invention will be further described in detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In the examples and comparative examples, the physical properties of polymers were measured as follows. (1) Intrinsic viscosity [η] Measured in decalin at 135 ° C. (2) Melting point DSC (differential scanning calorimeter) analysis was performed. Measurement conditions Fast heating: Room temperature to 190 ℃, 10 ℃ /
Hold for min, 3min Fast cooling: 190 ℃ to room temperature, 10 ℃ / m
In, 3min holding second heating: room temperature to 190 ℃, 10 ℃ / m
in

Production Example 1 Bis (ethoxycarbonylcyclopentadienyl) zirconium dichloride ([C ₅ H ₄ (COOC ₂ H ₅ )])
₂ ZrCl ₂ ) Tl [C ₅ H ₄ (COOC ₂ H ₅ )] [[Journal
Of Organometal Chemistry (J. Organometal
Chem.) ”, Vol. 396, p. 279 (1990). ] 4.4 g (12.9 mmol) and 1.5 g (6.5 mmol) of zirconium tetrachloride were mixed in 100 ml of toluene and stirred at room temperature for 20 hours. Then, the solvent was distilled off, the solid was washed with 100 ml of hexane, extracted with 100 ml of dichloromethane, and the extract was concentrated to give yellow crystals of bis (ethoxycarbonylcyclopentadienyl) zirconium dichloride (complex a). Was obtained with a yield of 38%.

Example 1 400 ml of toluene and 1 mmol of triisobutylaluminum (TIBA) were placed at room temperature in a nitrogen atmosphere at room temperature in a 1 liter autoclave which was dried under reduced pressure by heating, and the temperature of the solution was raised to 60 ° C. with stirring. 60 ° C
1 micromol of the complex a obtained in Production Example 1 and 1 micromol of N, N′-dimethylanilinium tetrakis (pentafluorophenyl) borate were added, 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 and separated in a methanol-hydrochloric acid solution, further thoroughly washed with methanol, and then dried to obtain a polymer. The results are shown in Table 1.

Comparative Example 1 Example 1 was repeated except that zirconocene dichloride was used in place of the complex a. 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 nitrogen atmosphere at room temperature in a 1 liter autoclave which was dried under reduced pressure by heating, and the temperature of the solution was raised to 60 ° C. with stirring. 60 ° C
1 micromol of the complex a obtained in Production Example 1 and 1 micromol of N, N′-dimethylanilinium tetrakis (pentafluorophenyl) borate were added, 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 and separated in a methanol-hydrochloric acid solution, further thoroughly washed with methanol, and then dried to obtain a polymer. The results are shown in Table 1.

Comparative Example 2 The procedure of Example 2 was repeated, except that zirconocene dichloride was used instead of the complex a. The results are shown in Table 1.

Example 3 Example 2 was repeated except that 6 mmol of methylaluminoxane was used instead 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.

[0044]

[Table 1]

Example 4 2 g of atactic polypropylene was obtained in the same manner as in Example 1 except that propylene was used instead of ethylene.

[0046]

EFFECT OF THE INVENTION The olefin polymerization catalyst of the present invention is a highly active soluble catalyst, and by using this catalyst, an olefin polymer having a high molecular weight, uniform and narrow molecular weight distribution can be efficiently obtained. .

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Narutoshi Takahashi 7-18 Jinmeicho, Izumiotsu-shi, Osaka (56) Reference JP-A-6-239916 (JP, A) JP-A-7-10927 (JP, A ) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08F 4/64-4/658

Claims (4)

(57) [Claims] 1. (A) General formula (I): [In the formula, M is a transition metal element of Group 4 of the periodic table, Cp is a cyclic unsaturated hydrocarbon group, b is 1 or 2, and when b is 2, two Cp's may be the same or different. X may be a halogen atom or carbon.
C1-C20 hydrocarbon group, C1-C20 alkoxy
Group, aryloxy group having 6 to 20 carbon atoms, 1 to 2 carbon atoms
0 amide group, silicon-containing group having 1 to 20 carbon atoms, 1 carbon atom
~ 20 phosphide group, C1-20 sulfide group
Alternatively, it represents an acyl group having 1 to 20 carbon atoms , each X may be the same or different, and X and Cp may form a crosslinked structure . R represents a hydrocarbon group having 1 to 30 carbon atoms, a represents an integer of 1 to 3, and when there are a plurality of Rs, the plurality of Rs may be the same or different. ] The catalyst for olefin polymerization 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: