JP2994517B2 - Olefin polymerization catalyst and method for producing olefin polymer - 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 olefin polymerization using the catalyst.

[0002]

2. Description of the Related Art Conventionally, in producing an olefin polymer by polymerizing an olefin in the presence of a catalyst, a method using (1) a metallocene and (2) an aluminoxane as a catalyst. Is widely known (JP-A-58-19309,
JP-A-2-167307).

A polymerization method using these catalysts has a very high polymerization activity per transition metal and a high molecular weight distribution as compared with a method using a Ziegler-Natta catalyst comprising a titanium compound or a vanadium compound and an organoaluminum compound. The characteristic feature is that a polymer having a narrow particle size is obtained. However, these catalysts cannot be said to have a sufficiently high polymerization activity per aluminum, are not only uneconomical, but also require a step of removing catalyst residues from the produced polymer.

On the other hand, a method has been proposed in which an olefin is polymerized with a catalyst in which the above-mentioned transition metal compound or aluminoxane is supported on an inorganic oxide such as silica or alumina (Japanese Patent Application Laid-Open No. 60-135408; 61-108
610, 61-296008, JP-A-Hei 3
-74412, JP-A-3-74415, etc.). Further, a method of polymerizing an olefin with a catalyst in which a transition metal compound or an organoaluminum compound is supported on an inorganic oxide or an organic substance such as silica or alumina has been proposed (JP-A-1-101303, JP-A-1-101303).
207303, 3-234709, and 3
JP-A-234710, JP-A-3-501869, and the like.

In the method proposed here, the polymerization activity per aluminum is improved to some extent, but the polymerization activity per carrier is insufficient, and the amount of catalyst residue in the polymer cannot be ignored. Met.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above problems, and as a result, have found a catalyst having a high polymerization activity per aluminum and a high polymerization activity per carrier, and reached the present invention. did. That is, the present invention provides (A) a metallocene-based transition metal compound, (B) a lanthanoid compound, and (C) a catalyst for olefin polymerization comprising a product obtained by contacting with an organoaluminum compound; A) A method for producing an olefin polymer, comprising homopolymerizing or copolymerizing an olefin in the presence of an organoaluminum compound.

Hereinafter, the present invention will be described in detail. Catalytic metallocene transition metal compound used in the present invention, i.e. (A) Ingredient is a compound represented by the general formula or below SL.

[0008]

## STR2 ## ^{_{(C 5 R 1 a H 5}} -a) p (C 5 R 2 b H 5-b) q MR 3 r ... ^{_{[(C 5 R 1 a H 5}} -a) p (C 5 R 2 _{b H 5-b) q MR} 3 r L m ] ^{n +} [R ^{4] n-...} (, ^{_{wherein, C 5 R 1 a H 5}} -a cyclopentadienyl group
Represents a derivative of R ¹ and R ² are substituted with 1 to 20 carbon atoms
Hydrocarbon group, silicon-containing substituent, phosphorus-containing
A substituent or a nitrogen-containing substituent. R ³ has 1 carbon atom
To 20 optionally substituted hydrocarbon groups, hydrogen, halo
Gen, silicon-containing substituent, alkoxy group, aryloxy
A silyl group, an amide group, or a thioalkoxy group. M is
Titanium, zirconium, or hafnium.
L represents an electrically neutral ligand. [R ⁴ ] ^n- is n-valent
Is an anion. a and b are integers of 0-5. Also,
p, q, and r are as follows when the valence of M is s.
Is a non-negative integer satisfying p + q + r = s, and
Is a non-negative integer satisfying p + q + r = s−n
You. )

R ¹ and R ² are an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing substituent, a phosphorus-containing substituent, and a nitrogen-containing substituent. Good. Specifically, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-
Butyl group, pentyl group, isopentyl group, hexyl group,
Alkyl group such as heptyl group, octyl group, nonyl group, decyl group, phenyl group, p-tolyl group, o-tolyl group, m
-Aryl group such as tolyl group, fluoromethyl group, fluoroethyl group, fluorophenyl group, chloromethyl group, chloroethyl group, chlorophenyl group, bromomethyl group, bromoethyl group, bromophenyl group, iodomethyl group, iodoethyl group, iodophenyl group, etc. And a silicon-containing substituent such as a halo-substituted hydrocarbon group, trimethylsilyl group, triethylsilyl group and triphenylsilyl group.

Further, R ¹ and R ² may be bonded to each other to form a crosslinking group. Specifically, methylene group, alkylene group such as ethylene group, ethylidene group, propylidene group, isopropylidene group, phenylmethylidene group, alkylidene group such as diphenylmethylidene group, dimethylsilylene group, diethylsilylene group, dipropyl group Silylene group, diisopropylsilylene group, diphenylsilylene group, methylethylsilylene group, methylphenylsilylene group, methylisopropylsilylene group, silicon-containing cross-linking group such as methyl-t-butylsilylene group, dimethylgermylene group, diethylgermylene group, Dipropylgermylene group, diisopropylgermylene group, diphenylgermylene group, methylethylgermylene group, methylphenylgermylene group, methylisopropylgermylene group, methyl-
germanium-containing crosslinking groups such as t-butylgermylene groups,
Examples include amines and phosphines.

Further, R ¹ and R ² may be mutually bonded to form a ring. Specific examples include an indenyl group, a tetrahydroindenyl group, a fluorenyl group and an octahydrofluorenyl group. R ³
Is an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, hydrogen, halogen, a silicon-containing substituent, an alkoxy group, an aryloxy group, an amide group, or a thioalkoxy group. Group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-
Butyl group, pentyl group, isopentyl group, hexyl group,
Alkyl group such as heptyl group, octyl group, nonyl group, decyl group, phenyl group, p-tolyl group, o-tolyl group, m
-Aryl group such as tolyl group, fluoromethyl group, fluoroethyl group, fluorophenyl group, chloromethyl group, chloroethyl group, chlorophenyl group, bromomethyl group, bromoethyl group, bromophenyl group, iodomethyl group, iodoethyl group, iodophenyl group Halo-substituted hydrocarbon groups, such as fluorine, chlorine, bromine and iodine, silicon-containing substituents such as trimethylsilyl group, triethylsilyl group, triphenylsilyl group, methoxy group, ethoxy group, propoxy group, isopropoxy group , Butoxy group, isobutoxy group, alkoxy group such as t-butoxy group, phenoxy group, p-tolyloxy group, m-tolyloxy group, aryloxy group such as o-tolyloxy group, amide group, dimethylamide group, diethylamide group, Propylamide group, diiso An amide group such as a propylamide group, a diisopropylamide group, a bis (trimethylsilyl) amide group, a methylthioalkoxy group, an ethylthioalkoxy group, a propylthioalkoxy group, a butylthioalkoxy group, a t-butylthioalkoxy group, a phenylthioalkoxy group; And thioalkoxy groups.

Also, R^ThreeIs R¹Or R^TwoCombined with
Examples of such ligands include C_FiveH
_Four(CH_Two)_nO^-(1 ≦ n ≦ 5), C_FiveMe_Four(CH
_Two) _nO^-(1 ≦ n ≦ 5), C_FiveH_Four(Me_TwoSi)
(T-Bu) N^-, C_FiveMe_Four(Me_TwoSi) (t-B
u) N^-And the like. Further, R^ThreeAre interconnected
To form a bidentate ligand. Such R^ThreeConcrete
For example,^-OCH_TwoO^-,^-OCH_TwoCH_TwoO^-,
^-O (o-C₆H _Four) O^-And the like.

[0013] M is a Chi Taniumu, zirconium or c <br/> Funiumu.

These may be used as a mixture. L
Represents an electrically neutral ligand, specifically, ethers such as diethyl ether, tetrahydrofuran, dioxane, nitriles such as acetonitrile, amides such as dimethylformamide, and trimethylphosphine. Examples include phosphines and amines such as trimethylamine.

[R ⁴ ] ^n- is an n-valent anion, specifically, tetraphenyl borate, tetra (p-tolyl) borate, carbadodecaborate, tetrakis (pentafluorophenyl) borate, tetrafluoroborate, Hexafluorophosphate and the like can be mentioned. a and b are integers of 0-5. Also, p, q,
r is a non-negative integer that satisfies p + q + r = s when the metallocene-based transition metal compound is a formula when the valence of M is s, and p + q + r = when the metallocene-based transition metal compound is a formula. It is a non-negative integer satisfying sn.

Specific examples of the compound represented by the formula include bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dimethyl, bis (cyclopentadienyl) zirconium diphenyl, and (methylcyclopentadienyl). ) (Cyclopentadienyl) zirconium dichloride, (methylcyclopentadienyl) (cyclopentadienyl) zirconium dimethyl, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dimethyl, (Trimethylsilylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride, (trimethylsilylcyclopentadienyl) (cyclopentadienyl) zirconium dimethyl, bis Cyclopentadienyl) zirconium dihydride, bis (cyclopentadienyl) zirconium difluoride, bis (cyclopentadienyl) zirconium bis (trimethylsilyl), bis (cyclopentadienyl) zirconium dimethoxide, bis (cyclopentane Dienyl) zirconium diphenoxide, bis (cyclopentadienyl) zirconium bis (dimethylamide), bis (cyclopentadienyl) zirconium bis (methylthiolate), bis (cyclopentadienyl) zirconium bis (phenylthiolate), [(Η5: η1-3- (2,3,4,5-tetramethylpentadienyl) propoxy] zirconium dichloride, (biscyclopentadienyl) zirconium (η2-1,2-benzenedioxide), Tylenebis (cyclopentadienyl) zirconium dichloride, ethylenebis (cyclopentadienyl) zirconium dichloride, isopropylidenebis (cyclopentadienyl) zirconium dichloride, diphenylmethylidenebis (cyclopentadienyl) zirconium dichloride, ethylenebis (indenyl) ) Zirconium dichloride, ethylenebis (tetrahydroindenyl) zirconium dichloride, dimethylsilylenebis (cyclopentadienyl) zirconium dichloride,
Dimethylsilylenebis (trimethylcyclopentadienyl) zirconium dichloride , dimethylgermylenebis (cyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (1-
Fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (1-fluorenyl)
Zirconium dimethyl and dimethylsilylene (cyclopentadienyl) (1-fluorenyl) zirconium dichloride are exemplified.

Specific examples of the compound represented by the formula include bis (cyclopentadienyl) zirconium methyltetraphenylborate, bis (cyclopentadienyl) zirconiumphenyltetraphenylborate,
Bis (cyclopentadienyl) zirconium methyltetrakis (pentafluorophenyl) borate, bis (cyclopentadienyl) zirconiumphenyltetrakis (pentafluorophenyl) borate, (methylcyclopentadienyl) (cyclopentadienyl) zirconium methyltetra Phenyl borate, bis (pentamethylcyclopentadienyl) zirconium methyltetraphenylborate, bis (pentamethylcyclopentadienyl) zirconium methyltetrakis (pentafluorophenyl) borate, (trimethylsilylcyclopentadienyl) (cyclopentadienyl) Zirconium methyltetraphenyl borate, [(η5: η1-3- (2,
3,4,5-tetramethylpentadienyl) propoxy] zirconium methyltetraphenylborate, methylenebis (cyclopentadienyl) zirconiummethyltetraphenylborate, ethylenebis (cyclopentadienyl) zirconiummethyltetraphenylborate, ethylenebis ( Cyclopentadienyl) zirconium methyltetrakis (pentafluorophenyl) borate, isopropylidenebis (cyclopentadienyl) zirconiummethyltetraphenylborate, diphenylmethylidenebis (cyclopentadienyl) zirconium methyltetraphenylborate, ethylenebis (indenyl) ) Zirconium methyltetraphenylborate, ethylenebis (indenyl) zirconiummethyltetrakis Nyl) borate, ethylenebis (tetrahydroindenyl) zirconium methyltetraphenylborate, ethylenebis (tetrahydroindenyl) zirconiummethyltetrakis (pentanephenyl) borate, dimethylsilylenebis (cyclopentadienyl) zirconiummethyltetraphenylborate, dimethyl Silylenebis (trimethylcyclopentadienyl) zirconium methyltetraphenylborate, dimethylsilylenebis (trimethylcyclopentadienyl) zirconiummethyltetrakis (pentafluorophenyl) borate, isopropylidene (cyclopentadienyl) (1-fluorenyl) zirconiummethyl Tetraphenylborate, isopropylidene (cyclopentadienyl) (1-fluorenyl) zyl Iodonium tetrakis (pentafluorophenyl) borate, dimethylsilylene (cyclopentadienyl) (1-fluorenyl) zirconium methyl tetraphenylborate,
Bis (cyclopentadienyl) zirconium methyl tetraphenylborate tetrahydrofuran complex, bis (cyclopentadienyl) zirconium phenyl tetraphenylborate tetrahydrofuran complex, (methylcyclopentadienyl) (cyclopentadienyl zirconium methyl tetraphenylborate tetrahydrofuran complex, Bis (pentamethylcyclopentadienyl) zirconium methyltetraphenylborate tetrahydrofuran complex, (trimethylsilylcyclopentadienyl)
(Cyclopentadienyl) zirconium methyl tetraphenyl borate tetrahydrofuran complex, methylene bis (cyclopentadienyl) zirconium methyl tetraphenyl borate tetrahydrofuran complex, ethylene bis (cyclopentadienyl) zirconium methyl tetraphenyl borate tetrahydrofuran complex, isopropylidene bis (cyclo (Pentadienyl) zirconium methyltetraphenylborate tetrahydrofuran complex, diphenylmethylidenebis (cyclopentadienyl) zirconium methyltetraphenylborate tetrahydrofuran complex, ethylenebis (indenyl) zirconium methyltetraphenylborate tetrahydrofuran complex, ethylenebis (tetrahydroindenyl) Zirconium methyltetraphenyl Borate tetrahydrofuran complex,
Dimethylsilylenebis (cyclopentadienyl) zirconiummethyltetraphenylborate tetrahydrofuran complex, dimethylsilylenebis (trimethylcyclopentadienyl) zirconiummethyltetraphenylborate tetrahydrofuran complex, isopropylidene (cyclopentadienyl) (1-fluorenyl) zirconium Methyltetraphenylborate tetrahydrofuran complex,
And dimethylsilylene (cyclopentadienyl) (1-fluorenyl) zirconiummethyltetraphenylborate tetrahydrofuran complex.

[0018] For metals other than zirconium, corresponding compounds can be mentioned. As the lanthanoid compound as the component (B) used in the present invention, a compound comprising a cation and an anion of a lanthanoid is preferably used, and lanthanum oxide, lanthanum sulfide, lanthanum fluoride, lanthanum chloride, lanthanum cerium bromide,
Inorganic salts such as lanthanum iodide, lanthanum hydroxide, lanthanum nitrate, and lanthanum nitrite; double salts of lanthanum sulfate, lanthanum carbonate, lanthanum oxalate, lanthanum cyanide, etc .; lanthanum acetate; lanthanum trimethoxide; lanthanum triethoxide And salts containing organic substances such as lanthanum triisopropoxide. In addition, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium can also include corresponding compounds. Among these compounds, oxides or chlorides are particularly preferably used.

These salts may be used without any particular treatment, or may be used after having been subjected to treatments such as ball milling and sieving. Further, it may be used after water is newly added and adsorbed or subjected to a heat dehydration treatment. Further, they may be used alone or as a mixture of two or more lanthanoid salts. Any shape may be used, but a pore having a radius of 20 ° or more measured by a mercury intrusion method and having a pore volume of 0.1 cc / g or more is preferably used. The pore volume described in the examples was measured using Auto Pore 9200 manufactured by Shimadzu Corporation (measurement range: pore radius = 20 to 30,000 °).

The component (C) used in the present invention, that is, the organoaluminum compound, has a general formula of AlR ⁵ _j X
_3-j (wherein, R ⁵ is a hydrocarbon group having 1 to 20 carbon atoms, X
Represents hydrogen, a halogen, an alkoxy group, and j is 0 <j
≤3. Or a low polymer of an organoaluminum compound in which aluminum atoms are bonded to each other via oxygen or nitrogen.
These may be used alone or as a mixture.

More specifically, halogen-containing organoaluminum compounds such as trialkylaluminums such as trimethylaluminum, triethylaluminum, tripropylaluminum and triisobutylaluminum, diethylaluminum chloride, di-n-propylaluminum chloride and diisobutylaluminum chloride;
Dimethylaluminum methoxide, alkoxide-containing organoaluminum compounds such as diethylaluminum methoxide, dimethylaluminum hydride, hydride-containing organoaluminum compounds such as diethylaluminum hydride, methylaluminoxane, ethylaluminoxane, aluminoxane such as isobutylaluminoxane, among these , Trialkylaluminum or aluminoxane is preferably used, and particularly preferably, trialkylaluminum is used.

The order and method of contacting the components (A) to (C) are optional. Specifically, the component (C) is added after the component (A) is brought into contact with the component (B). After the component (A) and the component (C) are brought into contact, the component (B) is added. After the components (B) and (C) are brought into contact, the component (A) is added. (A) (B) (C) The three components are brought into contact simultaneously. Is used.

The contact is performed in an inert gas such as nitrogen or argon.
It can be carried out in an inert hydrocarbon solvent such as butane, pentane, hexane, heptane, toluene, xylene and the like.
The contact temperature is preferably between -20 ° C and the boiling point of the solvent. There is no particular limitation on the quantitative ratio of each component,
The components (A), (B) and (C) are brought into contact with each other in a weight ratio of 1: 1 to 10,000: 0.1 to 1,000,000, preferably 1: 1 to 1000: 1 to 10,000.

The olefin used in the polymerization includes ethylene, propylene, 1-butene, 1-hexene,
Methyl-1-butene, 3-methyl-1-pentene, 4-
Α-olefins such as methyl-1-pentene, vinylcyclohexane and styrene; internal olefins such as 2-butene, 2-pentene, cyclopentene and cyclohexene; and derivatives thereof. These may be polymerized singly or may be used for generally known random copolymerization or block copolymerization.

If necessary, the polymerization may be carried out in the presence of an organoaluminum compound (hereinafter referred to as component (D)). As the organoaluminum compound used at this time, the same compound as the component (C) can be used. There is no particular limitation on the amount of the component (D),
Good results can be obtained by setting the molar ratio of the transition metal in the component (A) to the organoaluminum used here to be 1: 0.01 to 100,000.

Known processes can be used for the polymerization. That is, slurry polymerization using an inert hydrocarbon such as n-hexane as a solvent, bulk polymerization using a monomer itself such as liquid propylene as a solvent, and a liquid phase such as an inert hydrocarbon or liquid propylene are substantially performed. Non-existent gas phase polymerization or the like is used. Further, these processes can be used in combination. The reaction system may be a batch system or a continuous system. The reaction is usually 1-20
Performed at a pressure of 00 atm and in a range of -50 to 250 ° C.,
A known molecular weight regulator such as hydrogen can be appropriately used.

Further, the catalyst according to claim 1 and, if necessary, an organic aluminum compound are combined to prepolymerize an olefin to form a catalyst, and the catalyst is formed in the presence of the catalyst and, if necessary, an organic aluminum compound. Olefin polymerization may be performed. The prepolymerization is carried out using an inert solvent such as n-hexane, heptane, toluene, etc.
A catalyst comprising the components (B) and (C) and, if necessary, an organoaluminum compound are added, and ethylene, propylene, 1-butene, 1-hexene, and 3-methyl-1 are added thereto.
-Butene, 3-methyl-1-pentene, 4-methyl-1
-By contacting an α-olefin such as pentene, vinylcyclohexane and styrene, an internal olefin such as 2-butene, 2-pentene, cyclopentene and cyclohexene, or a mixture thereof. The olefin to be brought into contact with the catalyst at the time of prepolymerization and the olefin used at the time of polymerization may be the same or different. Here, as the organoaluminum compound used as necessary, the same compound as the component (C) can be used. The obtained prepolymerization catalyst component may be used for polymerization after being washed with an inert hydrocarbon such as n-hexane, or may be used as it is without washing.

[0028]

Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited by these examples unless departing from the gist of the present invention.

Example 1 (1) Synthesis of catalyst A commercially available biscyclopentadienyl zirconium dichloride 1.46 was placed in a 100 ml round bottom flask purged with nitrogen.
mg was collected and used as a toluene solution. 1.3 mmol of trimethylaluminum was added to this solution while stirring at room temperature.
Was added.

In a separate 100 ml round bottom flask, lanthanum oxide (pore volume with a radius of 20 ° or more measured by a mercury intrusion method = 0.294 cc / g, water content 23.1 wt%)
After collecting 32 g, the inside of the flask was sufficiently purged with nitrogen, and 47 ml of toluene was added to obtain a slurry. 3.6 ml of this slurry was added to the above contact product of biscyclopentadienyl zirconium dichloride and trimethylaluminum at room temperature. After completion of the addition, the mixture was stirred at room temperature for 1 hour to obtain a catalyst slurry.

(2) Copolymerization of Ethylene-Propylene 300 ml of n-hexane and 25 μmol of trimethylaluminum were introduced at room temperature under a nitrogen gas stream into a nitrogen-purged 21-induction stirring autoclave.
The entire amount of the catalyst slurry obtained in (1) was added. Further, 600 ml of liquid propylene was introduced at room temperature.

After the temperature of the mixture was raised to 70 ° C., ethylene was introduced so that the ethylene partial pressure became 7.6 kgf / cm ^2, and polymerization was carried out for 1 hour. Thereafter, the supply of ethylene was stopped, and the polymerization was stopped with ethanol to obtain 104 g of an ethylene-propylene copolymer. The amount of copolymer produced per 1 g of zirconium was 2.3 × 10 ⁵ g, the amount of copolymer produced per 1 g of aluminum derived from trimethylaluminum was 2.9 × 10 ³ g, and the amount of copolymer per 1 g of lanthanum oxide was obtained. The production amount was 1.3 × 10 ³ g.

Comparative Example 1 (1) Synthesis of Catalyst The same operation as in Example 1 (1) was carried out except that lanthanum oxide was not used, to obtain a toluene solution of the catalyst. (2) Copolymerization of ethylene-propylene Polymerization was carried out in the same manner as in Example 1 (2), except that the catalyst obtained in Comparative Example 1 (1) was used as a catalyst. The obtained polymer was in a trace amount.

Comparative Example 2 (1) Synthesis of Catalyst A commercially available biscyclopentadienyl zirconium dichloride 0.72 was placed in a 100 ml round bottom flask purged with nitrogen.
mg was collected and used as a toluene solution. To this solution was added 3.7 mmol of a toluene solution of methylaluminoxane (molecular weight: 1232; manufactured by Tosoh Akzo) in terms of Al atoms while stirring at room temperature. After completion of the addition, the mixture was stirred at room temperature for 1 hour to obtain a catalyst.

(2) Copolymerization of ethylene-propylene Example 1 was repeated except that the catalyst synthesized in Comparative Example 2 (1) was used without using trimethylaluminum.
Polymerization was carried out in the same manner as in (2) to obtain 8.3 g of an ethylene-propylene copolymer. The amount of copolymer produced per 1 g of zirconium was 3.7 × 10 ⁴ g. The amount of the copolymer produced per g of aluminum derived from methylaluminoxane was 83 g.

Example 2 (1) Synthesis of catalyst A commercially available biscyclopentadienyl zirconium dichloride 1.44 was placed in a 100 ml round-bottom flask purged with nitrogen.
mg was collected and used as a toluene solution. 1.3 mmol of trimethylaluminum was added to this solution while stirring at room temperature.
Was added.

In another 100 ml round-bottom flask, 0.39 g of lanthanum chloride heptahydrate (pore volume with a radius of 20 ° or more = 0.250 cc / g measured by a mercury intrusion method) was collected, and the inside of the flask was sufficiently purged with nitrogen. After that, 35 ml of toluene was added to obtain a slurry. 6.1 ml of this slurry was added to the above contact product of biscyclopentadienyl zirconium dichloride and trimethylaluminum at room temperature. After completion of the addition, the mixture was stirred at room temperature for 1 hour to obtain a catalyst slurry.

(2) Copolymerization of ethylene-propylene Polymerization was carried out in the same manner as in Example 1 (2), except that the catalyst synthesized in Example 2 (1) was used as a catalyst. 58 g were obtained. 1 g of zirconium
The amount of copolymer produced per unit was 1.3 × 10 ⁵ g. Further, the amount of copolymer produced per 1 g of aluminum derived from trimethylaluminum was 1.6 × 10 ³ g,
Also, the amount of copolymer produced per gram of lanthanum chloride is
1.3 x 10 ³ g.

Comparative Example 3 (1) Synthesis of Catalyst A commercially available biscyclopentadienyl zirconium dichloride 1.46 was placed in a 100 ml round bottom flask purged with nitrogen.
mg was collected and used as a toluene solution. 1.3 mmol of trimethylaluminum was added to this solution while stirring at room temperature.
Was added.

In another 100 ml round bottom flask, put silica (Fuji Davidson 952; water content: 15.1 wt.)
%), And the inside of the flask was sufficiently purged with nitrogen. Then, 42 ml of toluene was added to obtain a slurry. 5.0 ml of this slurry was added to the above contact product of biscyclopentadienyl zirconium dichloride and trimethylaluminum at room temperature. After completion of the addition, the mixture was stirred at room temperature for 1 hour to obtain a catalyst slurry.

(2) Copolymerization of ethylene-propylene Polymerization was carried out in the same manner as in Example 1 (2) except that the catalyst synthesized in Comparative Example 3 (1) was used as a catalyst. 33 g were obtained. 1 g of zirconium
The amount of the copolymer formed per unit was 7.2 × 10 ⁴ g. Further, the amount of copolymer produced per 1 g of aluminum derived from trimethylaluminum was 9.4 × 10 ² g,
The amount of copolymer produced per gram of silica was 2.5 ×
Was 10 ² g.

Example 3 (1) Copolymerization of ethylene-propylene Except that trimethylaluminum was not added,
Polymerization was performed in the same manner as in Example 1 (2) to obtain 17 g of an ethylene-propylene copolymer. The amount of copolymer produced per 1 g of zirconium was 3.7 × 10 ⁴ g, the amount of copolymer produced per 1 g of aluminum derived from trimethylaluminum was 4.9 × 10 ² g, and the weight of copolymer was 1 g of lanthanum oxide. The combined amount was 220 g.

[0043]

According to the method of the present invention, the polymerization activity per aluminum is high, and the polymerization activity per carrier is also high. Therefore, it is not necessary to remove the catalyst residue from the obtained polymer, and it is industrially useful. is there.

[Brief description of the drawings]

FIG. 1 is a flowchart illustrating one embodiment of the present invention.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Fumihiko Shimizu 1000 Kamoshita-cho, Midori-ku, Yokohama-shi, Yokohama, Japan Within Mitsubishi Chemical Research Institute (58) Fields investigated (Int. Cl. ⁶ , DB name) C08F 4 / 60-4/70

Claims (2)

(57) [Claims] 1. An olefin polymerization catalyst comprising a product obtained by contacting (A ) a metallocene transition metal compound represented by the following general formula or (B) a lanthanoid compound and (C) an organoaluminum compound. ## STR1 ## ^{_{(C 5 R 1 a H 5}} -a) p (C 5 R 2 b H 5-b) q MR 3 r ... ^{_{[(C 5 R 1 a H 5}} -a) p (C 5 R 2 _{b H 5-b) q MR} 3 r L m ] ^{n +} [R ^{4] n-...} (, ^{_{wherein, C 5 R 1 a H 5}} -a cyclopentadienyl group
Represents a derivative of R ¹ and R ² are substituted with 1 to 20 carbon atoms
Hydrocarbon group, silicon-containing substituent, phosphorus-containing
A substituent or a nitrogen-containing substituent. R ³ has 1 carbon atom
To 20 optionally substituted hydrocarbon groups, hydrogen, halo
Gen, silicon-containing substituent, alkoxy group, aryloxy
A silyl group, an amide group, or a thioalkoxy group. M is
Titanium, zirconium, or hafnium.
L represents an electrically neutral ligand. [R ⁴ ] ^n- is n-valent
Is an anion. a and b are integers of 0-5. Also,
p, q, and r are as follows when the valence of M is s.
Is a non-negative integer satisfying p + q + r = s, and
Is a non-negative integer satisfying p + q + r = s−n
You. ) 2. A method for producing an olefin polymer, comprising homopolymerizing or copolymerizing an olefin in the presence of the catalyst according to claim 1 and (D) an organoaluminum compound as required.