JP2012140606A - Method for producing olefin polymerization catalyst, olefin polymerization catalyst, and polymerization method of olefin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an olefin polymerization catalyst with high activity and excellent storage stability by improving, in a metallocene-supported catalyst using an inorganic oxide having specified particle size and pore capacity, the slurrying step of a catalyst component, an olefin polymerization catalyst obtained by the method, and a polymerization method of olefin.SOLUTION: The method for producing an olefin polymerization catalyst comprises: adding the following component (B) to the following component (A) to obtain the catalyst component. The component (B) is dissolved or dispersed in hydrocarbon of an amount three times or more the pore capacity, measured by BET method, of the component (A). Component (A): an inorganic oxide component having an average particle size of 5-25 μm and a pore capacity of 0.1-3.0 ml/g. Component (B) is a transition metal compound of 3-12 group in the periodic table.

Description

  The present invention relates to a method for producing an olefin polymerization catalyst, an olefin polymerization catalyst, and an olefin polymerization method, and more particularly, in a metallocene-supported catalyst using an inorganic oxide having a specific structure having a specific particle size and pore volume. The present invention relates to a method for producing an olefin polymerization catalyst having high activity and excellent storage stability by improving the slurrying process of the components, and the olefin polymerization catalyst and olefin polymerization method obtained.

Conventionally, it is known that polyolefins can be produced with an olefin polymerization catalyst comprising a combination of a metallocene compound and an organoaluminum oxy compound or boron compound (for example, Patent Documents 1 to 4). In addition, in order to solve the problem that the polymer adheres to the inner wall of the reactor during the polymerization, a catalyst in which a promoter such as a metallocene compound or an organoaluminum oxy compound is supported on a fine particle carrier such as silica gel is used. It is known that olefins can be polymerized (for example, Patent Documents 5 to 7).
In these patents, a silica carrier having a particle size of about 30 to 50 μm is generally used. By supporting the metallocene compound and the cocatalyst component on the fine particle carrier in this way, the resulting polymer is in the form of particles and the productivity of the polymer is improved, but the polymerization activity inherent to the metallocene catalyst is not fully exhibited by the support. There was a problem.

In order to solve this problem, it has been studied to apply an inorganic oxide having a small particle size. Patent Document 8 discloses a method in which an alumoxane cocatalyst is immobilized on the outer surface of spherical silica particles having an average particle size of 10 to 15 μm, and a metallocene compound is supported under specific conditions. Patent Document 9 discloses a metallocene-supported catalyst using a silica support having a specific surface area and pore volume and an average particle diameter of 2 to 10 μm. Patent Document 10 discloses a metallocene-supported catalyst using a particulate carrier having a specific specific surface area and pore volume and an average particle diameter of 20 μm or less.
Although the polymerization activity is improved by using such a small particle size silica as a carrier, there is a disadvantage that the fluidity is deteriorated when the silica is a small particle size powder. Therefore, the catalyst preparation method for improving the activity, which was effective when using silica having a particle size of several tens of μm, may not be applicable to silica having a particle size of about 10 μm. For this reason, a method for improving the activity of a metallocene-supported catalyst suitable for a fine particle carrier having a small particle diameter is required.

JP 58-19309 A JP-A-60-35006 JP-T-1-501950 Japanese translation of PCT publication No. 1-502036 JP-A-61-108610 JP 63-66206 A JP-A-2-173104 JP 2002-275207 A JP 2004-91498 A JP 2004-238520 A

  In view of the state of the prior art, the object of the present invention is to improve the slurry process of the catalyst component in the metallocene-supported catalyst using the inorganic oxide having a specific structure having a specific particle size and pore volume, It is to provide a method for producing an olefin polymerization catalyst having high activity and excellent storage stability, an olefin polymerization catalyst to be obtained, and an olefin polymerization method.

  As a result of intensive studies on an ideal olefin polymerization catalyst component capable of solving the above-described problems of the prior art, the present inventors have found that silica having a specific property having a specific particle size and pore volume as an inorganic oxide. And the like, and through the manufacturing process of slurrying with a specific amount of hydrocarbon, the inventors have reached the knowledge that an olefin polymerization catalyst with improved polymerization activity can be obtained, and the present invention has been completed.

That is, according to the first invention of the present invention, in the method for producing an olefin polymerization catalyst, the component (B) is obtained by adding the following component (B) to the following component (A). Provides a method for producing an olefin polymerization catalyst characterized by being dissolved or dispersed in a hydrocarbon in an amount of 3 or more times the pore volume measured by the BET method of component (A).
Component (A): Inorganic oxide component having an average particle diameter of 5 to 25 μm and a pore volume of 0.1 to 3.0 ml / g (B): Transition metal compound of Groups 3 to 12 of the periodic table

According to the second aspect of the present invention, in the method for producing an olefin polymerization catalyst, the following component (B) and component (C) are added to the following component (A): There is provided a method for producing an olefin polymerization catalyst, which comprises dissolving or dispersing in a hydrocarbon in an amount of 3 or more times the pore volume measured by the BET method of component (A).
Component (A): Inorganic oxide component having an average particle diameter of 5 to 25 μm and a pore volume of 0.1 to 3.0 ml / g (B): Transition metal compound component of group 3 to 12 of the periodic table (C ): Compound that reacts with component (B) to form a cationic complex

According to the third invention of the present invention, there is provided a method for producing an olefin polymerization catalyst, wherein the component (A) is used in the form of powder in the first or second invention.
According to a fourth aspect of the present invention, in any one of the first to third aspects, the component (A) is used after being slurried with a hydrocarbon solvent. Is provided.
According to the fifth aspect of the present invention, in any one of the first to fourth aspects, after adding the component (B) and / or the component (C) to the component (A), the hydrocarbon is removed. A method for producing an olefin polymerization catalyst is provided.
According to a sixth aspect of the present invention, there is provided the method for producing an olefin polymerization catalyst according to any one of the first to fifth aspects, wherein the component (A) is silica.
According to a seventh aspect of the present invention, there is provided the method for producing an olefin polymerization catalyst according to any one of the first to sixth aspects, wherein the component (B) is a metallocene compound.
According to an eighth aspect of the present invention, in any one of the first to seventh aspects, the component (B) is a metallocene compound having a heterocyclic aromatic group as a substituent. A method for producing an olefin polymerization catalyst is provided.
Furthermore, according to the ninth aspect of the present invention, there is provided the method for producing an olefin polymerization catalyst, wherein in any one of the first to eighth aspects, the component (C) is an alumoxane.

  On the other hand, according to the tenth aspect of the present invention, there is provided an olefin polymerization catalyst obtained by the production methods of the first to ninth aspects.

Furthermore, according to the eleventh aspect of the present invention, there is provided an olefin polymerization method characterized by polymerizing an olefin using the olefin polymerization catalyst of the tenth aspect.
According to a twelfth aspect of the present invention, there is provided an olefin polymerization method according to the tenth aspect, wherein the olefin is slurry-polymerized using an olefin polymerization catalyst.

According to the present invention, a solution or slurry of a catalyst component diluted with a specific amount of solvent with respect to the pore volume of the fine particle support is added to the powder of the fine particle support having a specific average particle diameter and a specific pore volume. Therefore, a supported olefin polymerization catalyst having good polymerization activity and good particle properties of the resulting polymer can be obtained.
Further, by using such an olefin polymerization catalyst, it is possible to efficiently polymerize olefins and obtain high-quality polyolefins. That is, the polyolefin obtained improves the flowability and bulk density of the powder and suppresses the generation of a fine powder polymer.

  Next, the manufacturing method of the olefin polymerization catalyst of the present invention, the olefin polymerization catalyst and the olefin polymerization method will be described in detail. That is, the present invention is a method for producing a metallocene-supported catalyst using a specific inorganic oxide and an olefin polymerization method using the same.

1. Component (A): Inorganic oxide Examples of the inorganic oxide that is the component (A) of the present invention include single oxides or complex oxides of elements of Groups 1 to 14 of the periodic table. For example, SiO ₂ , Al ₂ O ₃ , MgO, CaO, B ₂ O ₃ , TiO ₂ , ZrO ₂ , Fe ₂ O ₃ , ZnO, Al ₂ O ₃ —MgO, Al ₂ O ₃ —CaO, SiO ₂ —MgO, SiO ₂ —Al ₂ O ₃ , SiO ₂ —TiO ₂ , SiO ₂ —V ₂ O ₅ , SiO ₂ —Cr ₂ O ₃ , SiO ₂ —TiO ₂ —MgO, Al ₂ O ₃ —MgO—CaO, Al ₂ O ₃ —MgO—SiO ₂ And various natural or synthetic single oxides or composite oxides such as Al ₂ O ₃ —CuO, Al ₂ O ₃ —Fe ₂ O ₃ , and Al ₂ O ₃ —NiO.

  Here, the above formula is not a molecular formula but represents only the composition, and the structure and component ratio of the composite oxide used in the present invention are not particularly limited.

An inorganic silicate can also be used as the inorganic oxide. As the inorganic silicate, clay, clay mineral, zeolite, diatomaceous earth, or the like can be used. A synthetic product may be used for these, and the mineral produced naturally may be used.
Specific examples of clays and clay minerals include allophanes such as allophane, kaolins such as dickite, nacrite, kaolinite and anorcite, halloysites such as metahalloysite and halloysite, and serpentine such as chrysotile, lizardite and antigolite. Stone group, montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite and other smectites, vermiculite and other vermiculite minerals, illite, sericite and sea chlorite and other mica minerals, attapulgite, sepiolite, pigolite, bentonite, wood Examples include knot clay, gyrome clay, hysingelite, pyrophyllite, and ryokdee stones. These may form a mixed layer.
Examples of the artificial compound include synthetic mica, synthetic hectorite, synthetic saponite, and synthetic teniolite.

  Among these specific examples, preferably, kaolins such as dickite, nacrite, kaolinite, anorcite, halosites such as metahalosite, halosite, chrysotile, lizardite, serpentine such as antigolite, montmorillonite, Examples include smectites, such as sauconite, beidellite, nontronite, saponite, hectorite, vermiculite minerals such as vermiculite, mica minerals such as illite, sericite, and sea chlorite, synthetic mica, synthetic hectorite, synthetic saponite, and synthetic teniolite. Smectite such as montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, vermiculite mineral such as vermiculite, synthetic mica, synthetic hectorite, Adult saponite, synthetic taeniolite.

These inorganic silicates may be used as they are, but acid treatment with hydrochloric acid, nitric acid, sulfuric acid, etc. and / or LiCl, NaCl, KCl, CaCl ₂ , MgCl ₂ , Li ₂ SO ₄ , MgSO ₄ , ZnSO ₄ , Ti (SO ₄ ) ₂ , Zr (SO ₄ ) ₂ , Al ₂ (SO ₄ ) ₃ or the like may be subjected to salt treatment. In the treatment, the corresponding acid and base may be mixed to produce a salt in the reaction system, and the treatment may be performed, or shape control such as pulverization and granulation and drying treatment may be performed.

Among these inorganic silicates, those containing SiO ₂ or Al ₂ O ₃ as a main component are preferable, and SiO ₂ is more preferable.
In addition, the inorganic silicate used in the present invention may absorb a small amount of moisture or may contain a small amount of impurities.

The inorganic oxide used as the component (A) is usually dried at 150 to 800 ° C., preferably 200 to 650 ° C. in the air or in an inert gas such as nitrogen or argon. The average particle diameter is 5 to 25 μm, preferably 8 to 15 μm. When the average particle size of the inorganic oxide of component (A) is out of the above range, the catalytic activity tends to decrease.
The pore volume of the inorganic oxide of component (A) is 0.1 to 3.0 ml / g, preferably 0.5 to 2.5 ml / g, more preferably 1.0 to 2.0 ml. / G. When the pore volume is too small, the amount of the catalyst component impregnated with the catalyst component is reduced, so that the catalyst component supported on one particle is reduced and the polymerization activity is lowered. Further, since the particle strength is also increased, the component (A) does not collapse during the olefin polymerization, and the polymerization does not continue. On the other hand, if the pore volume is too large, the particle strength of the component (A) is insufficient, so that an olefin polymer having a good shape cannot be obtained.

Further, the surface area measured by the BET method of the inorganic oxide component (A), is usually 150~1000m ² / g, preferably 200-700 ² / g, more preferably 200 to 500 m ² / g It is.
Bulk densities either measured by gravity method is usually 0.05~0.30g / cm ^3, preferably 0.08~0.20g / cm ^3, more preferably 0.10~0.18g / Cm ³ .

The average particle diameter of the inorganic oxide of the component (A) can be measured by a method for measuring a normal particle diameter. Specifically, using a laser diffraction / scattering particle size distribution measuring device, measurement is performed under the conditions of a dispersion solvent: ethanol, a refractive index of 1.0, and a shape factor of 1.0, and a median diameter value is obtained as an average particle size. be able to.
Further, the pore volume and specific surface area of the inorganic oxide of component (A) can be specifically measured as follows. That is, each sample can be subjected to sufficient pretreatment under heating and reduced pressure, and then nitrogen adsorption isotherm can be measured at a liquid temperature using a BET measuring device. The specific surface area can be calculated by performing a BET multipoint analysis on the pore volume from the adsorption amount of the obtained adsorption isotherm at a relative pressure of 0.95. Furthermore, assuming that the pore structure is a cylinder, the average pore diameter can be calculated according to the equation (i). In this equation, Dave represents the average pore diameter, Vtotal represents the pore volume, and SBET represents the specific surface area by the BET multipoint method. Furthermore, mesopore distribution can be obtained by BJH method analysis, and the pore volume within a specified range can be calculated.
Dave = 4Vtotal / SBET Formula (i)
In addition, the bulk density of the inorganic oxide of component (A) can be calculated by, for example, measuring the weight of silica when it is naturally dropped from a height of 5 cm and filled into a 20 ml container. .

  Of course, the above-mentioned inorganic oxides can be used as they are, but as a pretreatment, these carriers are used as trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, tripropylaluminum, tributylaluminum, trioctylaluminum, tridecylaluminum. It can be used after contact with an organoaluminum compound such as diisobutylaluminum hydride or an organoaluminum oxy compound containing an Al—O—Al bond.

2. Component (B): Transition Metal Compound of Groups 3-12 of Periodic Table Component (B) used in the present invention is a transition metal compound of Groups 3-12 of the periodic table. Specifically, a Group 3-10 transition metal halide, a Group 3-6 transition metal metallocene compound, a Group 4 transition metal bisamide or bisalkoxide compound, a Group 8-10 transition metal bisimide compound, Examples thereof include phenoxyimine compounds of Group 3-11 transition metals.

  Among these, metallocene compounds of Group 4 transition metals are preferred, and specifically, compounds represented by the following general formulas (I) to (VI) are used.

^{_{(C 5 H 5-a R}} 1 a) (C 5 H 5-b R 2 b) MXY ··· (I)
^{_{Q (C 5 H 4-c}} R 1 c) (C 5 H 4-d R 2 d) MXY ··· (II)
^{_{Q '(C 5 H 4-}} e R 3 e) ZMXY ··· (III)
^{_{(C 5 H 5-f R}} 3 f) ZMXY ··· (IV)
^{_{(C 5 H 5-f R}} 3 f) MXYW ··· (V)
Q ″ (C ₅ H _5-g R ⁴ _g ) (C ₅ H _5-h R ⁵ _h ) MXY (VI)

Here, Q is a bonding group that bridges two conjugated five-membered ring ligands, Q ′ is a bonding group that bridges the conjugated five-membered ring ligand and the Z group, and Q ″ is R ⁴ and R. ⁵ is a bonding group that crosslinks ⁵ ; M is a group 3-12 transition metal of the periodic table; X, Y, and W are each independently hydrogen, halogen, a hydrocarbon group having 1 to 20 carbon atoms, An oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, a phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms, or a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, Z is oxygen , A sulfur-containing ligand, a silicon-containing hydrocarbon group having 1 to 40 carbon atoms, a nitrogen-containing hydrocarbon group having 1 to 40 carbon atoms, or a phosphorus-containing hydrocarbon group having 1 to 40 carbon atoms. Group 4 transition metals such as Zr, Zr and Hf are preferred.

R ^{1 to} R ⁵ are each independently a hydrocarbon group having 1 to 20 carbon atoms, a halogen group, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group, an aryloxy group, an oxygen-containing hydrocarbon group, silicon A hydrocarbon-containing group, a phosphorus-containing hydrocarbon group, a nitrogen-containing hydrocarbon group or a boron-containing hydrocarbon group; Among these, it is preferable that at least one of R ^{1 to} R ⁵ is a heterocyclic aromatic group. Among the heterocyclic aromatic groups, a furyl group, a benzofuryl group, a thienyl group, and a benzothienyl group are preferable, and a furyl group and a benzofuryl group are more preferable. These heterocyclic aromatic groups include hydrocarbon groups having 1 to 20 carbon atoms, halogen groups, halogen-containing hydrocarbon groups having 1 to 20 carbon atoms, oxygen-containing hydrocarbon groups, silicon-containing hydrocarbon groups, and phosphorus-containing carbon groups. Although it may have a hydrogen group, a nitrogen-containing hydrocarbon group or a boron-containing hydrocarbon group, in that case, a hydrocarbon group having 1 to 20 carbon atoms and a silicon-containing hydrocarbon group are preferable. Two adjacent R ¹ , 2 R ² , 2 R ³ , 2 R ⁴ , or 2 R ⁵ are bonded to each other to form a ring having 4 to 10 carbon atoms. You may have. a, b, c, d, e, f, g and h are respectively 0 ≦ a ≦ 5, 0 ≦ b ≦ 5, 0 ≦ c ≦ 4, 0 ≦ d ≦ 4, 0 ≦ e ≦ 4, 0 ≦ It is an integer that satisfies f ≦ 5, 0 ≦ g ≦ 5, and 0 ≦ h ≦ 5.

A bonding group Q that bridges between two conjugated five-membered ring ligands, a bonding group Q ′ that bridges a conjugated five-membered ring ligand and a Z group, and bridges R ⁴ and R ⁵ Specific examples of Q ″ include the following: alkylene groups such as methylene groups and ethylene groups, ethylidene groups, propylidene groups, isopropylidene groups, phenylmethylidene groups, and diphenylmethylidene groups. Silicon such as alkylidene group, dimethylsilylene group, diethylsilylene group, dipropylsilylene group, diphenylsilylene group, methylethylsilylene group, methylphenylsilylene group, methyl-t-butylsilylene group, disilylene group, tetramethyldisiylene group -Containing crosslinking group, germanium-containing crosslinking group, alkylphosphine, amine, etc. Among these, alkylene group, alkylidene group, silica Containing crosslinking groups and germanium-containing crosslinking group are particularly preferably used.

  Specific Zr complexes represented by the above general formulas (I), (II), (III), (IV), (V) and (VI) are exemplified below, but Zr is replaced with Hf or Ti. The same compounds can be used as well. In addition, the component (B) represented by the general formulas (I), (II), (III), (IV), (V) and (VI) may be a compound represented by the same general formula or a different general formula. It can be used as a mixture of two or more of the compounds shown.

Compounds of general formula (I) Biscyclopentadienylzirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, bis (2-methylindenyl) zirconium dichloride, bis (2-methyl-4,5-benzoin Denyl) zirconium dichloride, bisfluorenylzirconium dichloride, bis (4H-azurenyl) zirconium dichloride, bis (2-methyl-4H-azurenyl) cyclopentadienylzirconium dichloride, bis (2-methylbiscyclopentadienylzirconium) Dichloride, bis (2-methyl-4-phenyl-4H-azurenyl) zirconium dichloride, bis (2-methyl-4- (4-chlorophenyl) -4H-azurenyl) zirconium dichloride.
Bis (2-furylcyclopentadienyl) zirconium dichloride, bis (2-furylindenyl) zirconium dichloride, bis (2-furyl-4,5-benzoindenyl) zirconium dichloride.

Compounds of general formula (II) Dimethylsilylene bis (1,1′-cyclopentadienyl) zirconium dichloride, dimethylsilylene bis [1,1 ′-(2-methylindenyl)] zirconium dichloride, dimethylsilylene bis [1, 1 '-(2-methyl-4-phenyl-indenyl)] zirconium dichloride, ethylene bis [1,1'-(2-methyl-4,5-benzoindenyl)] zirconium dichloride, dimethylsilylene bis [1,1 '-(2-Methyl-4H-azurenyl)] zirconium dichloride, dimethylsilylenebis [1,1'-(2-methyl-4-phenyl-4H-azurenyl)] zirconium dichloride, dimethylsilylenebis {1,1'- [2-Methyl-4- (4-chlorophenyl) -4H-azurenyl]} zirconium dic Lido, dimethylsilylene bis [1,1 '- (2-ethyl-4-phenyl -4H- azulenyl)] zirconium dichloride, ethylene bis [1,1' - (2-methyl -4H- azulenyl)] zirconium dichloride.
Dimethylsilylenebis [1,1 ′-(2-furylcyclopentadienyl)] zirconium dichloride, dimethylsilylenebis {1,1 ′-[2- (2-furyl) -4,5-dimethyl-cyclopentadienyl] ]} Zirconium dichloride, dimethylsilylenebis {1,1 ′-{2- [2- (5-trimethylsilyl) furyl] -4,5-dimethyl-cyclopentadienyl}} zirconium dichloride, dimethylsilylenebis {1,1 '-[2- (2-furyl) indenyl]} zirconium dichloride, dimethylsilylenebis {1,1'-[2- (2-furyl) -4-phenyl-indenyl]} zirconium dichloride, dimethylsilylenebis {1, 1 ′-[2- (2- (2- (5-methyl) furyl) -4-phenyl-indenyl]} zirconium dichloride, di Tylsilylenebis {1,1 ′-[2- (2- (5-methyl) furyl) -4- (4-isopropyl) phenyl-indenyl]} zirconium dichloride, isopropylidene (cyclopentadienyl) (9-fluorenyl) zirconium Dichloride, isopropylidene (cyclopentadienyl) [9- (2,7-t-butyl) fluorenyl] zirconium dichloride, diphenylmethylene (cyclopentadienyl) [9- (2,7-t-butyl) fluorenyl] zirconium Dichloride, diphenylmethylene (cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) [9- (2,7-t-butyl) fluorenyl] zirconium dichloride, dimethylsilylene (cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylsilylene (cyclopentadienyl) [9- (2, 7-t-butyl) fluorenyl] zirconium dichloride.

Compound of general formula (III) (t-Butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediylzirconium dichloride, (methylamide)-(tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediyl-zirconium dichloride, (ethylamide) (tetramethyl-η ⁵ -cyclopentadienyl) -methylenezirconium dichloride, (t-butylamido) dimethyl- (tetramethyl-η ⁵ -cyclopentadienyl) silane Zirconium dichloride, (t-butylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silane zirconium dibenzyl, (benzylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silane zirconium dichloride, (phenyl) Ruphosphide) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silane zirconium dibenzyl.

Compound of general formula (IV) (cyclopentadienyl) (phenoxy) zirconium dichloride, (2,3-dimethylcyclopentadienyl) (phenoxy) zirconium dichloride, (pentamethylcyclopentadienyl) (phenoxy) zirconium dichloride, (Cyclopentadienyl) (2,6-di-t-butylphenoxy) zirconium dichloride, (pentamethylcyclopentadienyl) (2,6-di-i-propylphenoxy) zirconium dichloride.

Compounds of general formula (V) (cyclopentadienyl) zirconium trichloride, (2,3-dimethylcyclopentadienyl) zirconium trichloride, (pentamethylcyclopentadienyl) zirconium trichloride, (cyclopentadienyl) Zirconium triisopropoxide, (pentamethylcyclopentadienyl) zirconium triisopropoxide.

Compound of general formula (VI) Ethylene bis (7,7'-indenyl) zirconium dichloride, dimethylsilylene bis {7,7 '-(1-methyl-3-phenylindenyl)} zirconium dichloride, dimethylsilylene bis {7, 7 ′-[1-methyl-4- (1-naphthyl) indenyl]} zirconium dichloride, dimethylsilylenebis [7,7 ′-(1-ethyl-3-phenylindenyl)] zirconium dichloride, dimethylsilylenebis {7 , 7 '-[1-Isopropyl-3- (4-chlorophenyl) indenyl]} zirconium dichloride.

In addition, the compound which replaced the silylene group of the compound of these specific examples with the germylene group is illustrated as a suitable compound.
As specific examples of the metallocene compounds, JP-A-7-188335, Journal of American Chemical Society, 1996, Vol. Transition metal compounds having a ligand containing one or more elements other than carbon in a 5-membered ring or 6-membered ring disclosed in 118, 2291 can also be used.
An example of a metallocene compound having a heterocyclic hydrocarbon group as a substituent is disclosed in Japanese Patent No. 3675509.

  Suitable examples of the bisamide compounds belonging to Group 4 of the periodic table include those described in Macromolecules, Vol. 29, 5241 (1996) and Journal of American Chemical Society, Vol. 119, no. 16, 3830 (1997), Journal of American Chemical Society, Vol. 121, no. 24, 5798 (1999), a bridged transition metal compound having a bulky substituent on the nitrogen atom can be given.

  Further, suitable examples of the bisalkoxide compounds belonging to Group 4 of the periodic table include transition metal compounds belonging to Group 4 of the periodic table disclosed in WO 87/02370, preferably two aryloxy ligands. Can be bonded by a bridging group, and more preferred is a bridging transition metal compound in which the bridging group can coordinate to a transition metal.

  Further, bisimide compounds of Group 8 to 10 transition metals in the periodic table can be found in Journal of American Chemical Society, Vol. 117, 6414, WO96 / 23010, Chemical Communication, page 849, Journal of American Chemical Society, Vol. 120, 4049, WO98 / 27124, a bridged transition metal bisimide compound having a bulky substituent on the nitrogen atom can be cited as a suitable example.

  In addition, as a suitable example of the phenoxyimine compound of Group 3-10 transition metal of a periodic table, the compound currently disclosed by Unexamined-Japanese-Patent No. 11-315109 can be mentioned.

  Furthermore, these components (B) can be used as a mixture of two or more. In addition, a plurality of types can be used in combination with the above-mentioned periodic table group 3-12 metallocene compound.

In the present invention, the transition metal compound of Group 3-12 of the periodic table as component (B) is preferably a metallocene compound, particularly a metallocene compound having a heterocyclic aromatic group as a substituent. If the said compound is used, the effect of this invention can be exhibited in the more outstanding form.
Among metallocene compounds having a heterocyclic aromatic group as a substituent, it is more preferable to use a compound of general formula (II), a compound of general formula (III), and a compound of general formula (VI), Most preferred are compounds of general formula (II). Moreover, what has a furyl group and a thienyl group is still more preferable.

3. Component (C): Compound that reacts with component (B) to form a cationic complex Component (C) used in the present invention is a compound that reacts with component (B) to form a cationic complex. Preferably, organoaluminum compounds, borane compounds, and borate compounds represented by the following general formulas (1) to (4) are used.

In the above general formulas, R ¹ represents a hydrogen atom or a hydrocarbon residue, preferably a hydrocarbon residue having 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms. Moreover, several R < ¹ > may be same or different, respectively. P represents an integer of 0 to 40, preferably 2 to 30.
The compounds represented by the above formulas (1) and (2) are also called aluminoxanes. Among these, methylaluminoxane or methylisobutylaluminoxane is preferable. The above aluminoxanes can be used in combination within a group and between groups. And said aluminoxane can be prepared on well-known various conditions.
Moreover, the compound represented by Formula (3) is 10: 1 of one type of trialkylaluminum or two or more types of trialkylaluminum and an alkylboronic acid represented by the general formula R ² B (OH) _2. It can be obtained by a reaction of ˜1: 1 (molar ratio). In the general formula, R ¹ and R ² represent a hydrocarbon residue having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms.

Other specific examples of the compound (C) that reacts with the metallocene compound (B) to form a cationic metallocene compound include borane compounds and borate compounds.
More specifically, the borane compound is triphenylborane, tri (o-tolyl) borane, tri (p-tolyl) borane, tri (m-tolyl) borane, tri (o-fluorophenyl) borane, tris ( p-fluorophenyl) borane, tris (m-fluorophenyl) borane, tris (2,5-difluorophenyl) borane, tris (3,5-difluorophenyl) borane, tris (4-trifluoromethylphenyl) borane, tris (3,5-ditrifluoromethylphenyl) borane, tris (2,6-ditrifluoromethylphenyl) borane, tris (pentafluorophenyl) borane, tris (perfluoronaphthyl) borane, tris (perfluorobiphenyl), tris ( Perfluoroanthryl) borane, tris (perfluorobi) Fuchiru) such as borane and the like.

  Among these, tris (3,5-ditrifluoromethylphenyl) borane, tris (2,6-ditrifluoromethylphenyl) borane, tris (pentafluorophenyl) borane, tris (perfluoronaphthyl) borane, tris (perfluoro) Biphenyl) borane, tris (perfluoroanthryl) borane, and tris (perfluorobinaphthyl) borane are preferable, and tris (2,6-ditrifluoromethylphenyl) borane, tris (pentafluorophenyl) borane, and tris (perfluoro). Naphthyl) borane and tris (perfluorobiphenyl) borane are exemplified as more preferred compounds.

When the borate compound is specifically represented, the first example is a compound represented by the following general formula (4).
^{[L 1 -H] + [BR} 6 R 7 X 4 X 5] - ··· Equation (4)

In Formula (4), L ¹ is a neutral Lewis base, H is a hydrogen atom, and [L ¹ -H] is a Bronsted acid such as ammonium, anilinium, phosphonium or the like.
Examples of ammonium include trialkylammonium such as trimethylammonium, triethylammonium, tripropylammonium, tributylammonium, and tri (n-butyl) ammonium, and dialkylammonium such as di (n-propyl) ammonium and dicyclohexylammonium.

Examples of anilinium include N, N-dialkylanilinium such as N, N-dimethylanilinium, N, N-diethylanilinium, N, N-2,4,6-pentamethylanilinium.
Furthermore, examples of the phosphonium include triarylphosphonium, tributylphosphonium, triarylphosphonium such as tri (methylphenyl) phosphonium, tri (dimethylphenyl) phosphonium, and trialkylphosphonium.

In formula (4), R ⁶ and R ⁷ are the same or different aromatic or substituted aromatic hydrocarbon groups containing 6 to 20, preferably 6 to 16 carbon atoms, and are connected to each other by a bridging group. As the substituent of the substituted aromatic hydrocarbon group, an alkyl group typified by a methyl group, an ethyl group, a propyl group, an isopropyl group or the like, or a halogen such as fluorine, chlorine, bromine or iodine is preferable.
Further, X ⁴ and X ⁵ are a hydride group, a halide group, a hydrocarbon group containing 1 to 20 carbon atoms, a substituted carbon atom containing 1 to 20 carbon atoms in which one or more hydrogen atoms are replaced by halogen atoms. It is a hydrogen group.

  Specific examples of the compound represented by the general formula (4) include tributylammonium tetra (pentafluorophenyl) borate, tributylammonium tetra (2,6-ditrifluoromethylphenyl) borate, tributylammonium tetra (3,5- Ditrifluoromethylphenyl) borate, tributylammonium tetra (2,6-difluorophenyl) borate, tributylammonium tetra (perfluoronaphthyl) borate, dimethylanilinium tetra (pentafluorophenyl) borate, dimethylanilinium tetra (2,6- Ditrifluoromethylphenyl) borate, dimethylanilinium tetra (3,5-ditrifluoromethylphenyl) borate, dimethylanilinium tetra (2,6-difluoropheny) ) Borate, dimethylanilinium tetra (perfluoronaphthyl) borate, triphenylphosphonium tetra (pentafluorophenyl) borate, triphenylphosphonium tetra (2,6-ditrifluoromethylphenyl) borate, triphenylphosphonium tetra (3,5- Ditrifluoromethylphenyl) borate, triphenylphosphonium tetra (2,6-difluorophenyl) borate, triphenylphosphonium tetra (perfluoronaphthyl) borate, trimethylammonium tetra (2,6-ditrifluoromethylphenyl) borate, triethylammonium tetra (Pentafluorophenyl) borate, triethylammonium tetra (2,6-ditrifluoromethylphenyl) borate, triethyla Monium tetra (perfluoronaphthyl) borate, tripropylammonium tetra (pentafluorophenyl) borate, tripropylammonium tetra (2,6-ditrifluoromethylphenyl) borate, tripropylammonium tetra (perfluoronaphthyl) borate, di (1 -Propyl) ammonium tetra (pentafluorophenyl) borate, dicyclohexylammonium tetraphenylborate and the like.

  Among these, tributylammonium tetra (pentafluorophenyl) borate, tributylammonium tetra (2,6-ditrifluoromethylphenyl) borate, tributylammonium tetra (3,5-ditrifluoromethylphenyl) borate, tributylammonium tetra (perfluoro) Naphthyl) borate, dimethylaniliniumtetra (pentafluorophenyl) borate, dimethylaniliniumtetra (2,6-ditrifluoromethylphenyl) borate, dimethylaniliniumtetra (3,5-ditrifluoromethylphenyl) borate, dimethylanilinium Tetra (perfluoronaphthyl) borate is preferred.

Moreover, the 2nd example of a borate compound is represented by following Formula (5).
^{[L 2] + [BR 6} R 7 X 4 X 5] - ··· Equation (5)

In the formula (5), L ² is carbo cation, methyl cation, ethyl cation, propyl cation, isopropyl cation, butyl cation, isobutyl cation, tert-butyl cation, pentyl cation, tropinium cation, benzyl cation, trityl cation, sodium. A cation, a proton, etc. are mentioned. R ⁶ , R ⁷ , X ⁴ and X ⁵ are the same as defined in the general formula (4).

Specific examples of the compound include trityl tetraphenyl borate, trityl tetra (o-tolyl) borate, trityl tetra (p-tolyl) borate, trityl tetra (m-tolyl) borate, trityl tetra (o-fluorophenyl) borate, Trityltetra (p-fluorophenyl) borate, trityltetra (m-fluorophenyl) borate, trityltetra (3,5-difluorophenyl) borate, trityltetra (pentafluorophenyl) borate, trityltetra (2,6-ditrifluoro) Methylphenyl) borate, trityltetra (3,5-ditrifluoromethylphenyl) borate, trityltetra (perfluoronaphthyl) borate, tropiniumtetraphenylborate, tropiniumtetra (o-tolyl) Rate, tropinium tetra (p-tolyl) borate, tropinium tetra (m-tolyl) borate, tropinium tetra (o-fluorophenyl) borate, tropinium tetra (p-fluorophenyl) borate, tropinium tetra (m- Fluorophenyl) borate, tropinium tetra (3,5-difluorophenyl) borate, tropinium tetra (pentafluorophenyl) borate, tropinium tetra (2,6-ditrifluoromethylphenyl) borate, tropinium tetra (3,5 - ditrifluoromethylphenyl) borate, tropicity tetra (perfluoro-naphthyl) _{borate, NaBPh 4, NaB (o-} CH 3 -Ph) 4, NaB (p-CH 3 -Ph) 4, NaB (m-CH 3 - Ph) ₄ , Na _{B (o-F-Ph)} 4, NaB (p-F-Ph) 4, NaB (m-F-Ph) 4, NaB (3,5-F 2 -Ph) 4, NaB (C 6 F 5) _{4, NaB (2,6- (CF 3} ) 2 -Ph) 4, NaB (3,5- (CF 3) 2 -Ph) 4, NaB (C 10 F 7) 4, HBPh 4 · 2 diethyl ether, _{HB (3,5-F 2 -Ph)} 4 · 2 diethyl _{ether, HB (C 6 F 5)} 4 · 2 diethyl _{ether, HB (2,6- (CF 3)} 2 -Ph) 4 · 2 diethyl ether, HB (3,5- (CF ₃ ) ₂ -Ph) ₄ · 2 diethyl ether and HB (C ₁₀ H ₇ ) ₄ · 2 diethyl ether can be exemplified.

Among these, trityltetra (pentafluorophenyl) borate, trityltetra (2,6-ditrifluoromethylphenyl) borate, trityltetra (3,5-ditrifluoromethylphenyl) borate, trityltetra (perfluoronaphthyl) borate, Tropinium tetra (pentafluorophenyl) borate, tropinium tetra (2,6-ditrifluoromethylphenyl) borate, tropinium tetra (3,5-ditrifluoromethylphenyl) borate, tropinium tetra (perfluoronaphthyl) borate, _{NaB (C 6 F 5) 4} , NaB (2,6- (CF 3) 2 -Ph) 4, NaB (3,5- (CF 3) 2-Ph) 4, NaB (C 10 F 7) 4, _{HB (C 6 F 5) 4} · 2 diethyl ether, _{B (2,6- (CF 3) 2} -Ph) 4 · 2 diethyl _{ether, HB (3,5- (CF 3)} 2 -Ph) 4 · 2 diethyl _{ether, HB (C 10 H 7)} 4 · 2 Diethyl ether is preferred.

More preferably, among these, trityltetra (pentafluorophenyl) borate, trityltetra (2,6-ditrifluoromethylphenyl) borate, tropiniumtetra (pentafluorophenyl) borate, tropiniumtetra (2,6-ditrifluoro) Methylphenyl) borate, NaB (C ₆ F ₅ ) ₄ , NaB (2,6- (CF ₃ ) ₂ -Ph) ₄ , HB (C ₆ F ₅ ) ₄ · 2 diethyl ether, HB (2,6- ( _{CF 3) 2 -Ph) 4 ·} 2 diethyl _{ether, HB (3,5- (CF 3)} 2 -Ph) 4 · 2 diethyl _{ether, HB (C 10 H 7) 4} · 2 diethyl ether.

  In the present invention, the component (C), which is a compound that reacts with the component (B) to form a cationic complex, is preferably an organoaluminum compound, particularly an alumoxane. If the said compound is used, the effect of this invention can be exhibited in the more outstanding form.

4). Other ingredients: an organoaluminum compound as another component, the general formula organoaluminum compound represented by _{(AlR n X 3-n)} m is used. In formula, R represents a C1-C20 alkyl group, X represents a halogen, hydrogen, an alkoxy group, or an amino group, n represents 1-3, m represents the integer of 1-2, respectively. The organoaluminum compounds can be used alone or in combination.

  Specific examples of the organoaluminum compound include trimethylaluminum, triethylaluminum, trinormalpropylaluminum, trinormalbutylaluminum, triisobutylaluminum, trinormalhexylaluminum, trinormaloctylaluminum, trinormaldecylaluminum, diethylaluminum chloride, diethylaluminum. Examples thereof include sesquichloride, diethylaluminum hydride, diethylaluminum ethoxide, diethylaluminum dimethylamide, diisobutylaluminum hydride, and diisobutylaluminum chloride. Of these, trialkylaluminum and alkylaluminum hydride having m = 1 and n = 3 are preferable. More preferably, R is a trialkylaluminum having 1 to 8 carbon atoms.

5. Preparation of Olefin Polymerization Catalyst In the present invention, an olefin polymerization catalyst is subjected to a step of adding at least the component (B) dissolved or dispersed in a hydrocarbon or solvent to the component (A) slurried with a powder or a hydrocarbon solvent. The catalyst component is produced (hereinafter referred to as the first production method).
In the present invention, the olefin polymerization catalyst is subjected to a step of adding the component (C) together with the component (B) dissolved or dispersed in the hydrocarbon solvent to the component (A) that is powdered or slurried with a hydrocarbon solvent. Is manufactured (hereinafter referred to as the second manufacturing method). In the second production method, the contact order of each component can be exemplified by the following combinations.

(I) An inorganic oxide having a specific particle size (component A) and a transition metal compound of group 3-12 of the periodic table (component B) are contacted, and then reacted with component (B) to form a cationic complex. The compound to be formed (component C) is brought into contact.
(II) After contacting a compound (component C) that reacts with an inorganic oxide (component A) having a specific particle size and component (B) to form a cationic complex (component C), A transition metal compound (component B) is contacted.
(III) Compound that forms a cationic complex by reacting an inorganic oxide (component A) with a specific particle size with a transition metal compound (component B) of group 3 to 12 of the periodic table and component (B). Contact the mixture of component C).

  Of these, the contact method (III) is preferred. In any order of contact, it is preferable to add the component (B) and the component (C) to the component (A). Furthermore, the dried component (A) is dissolved or slurried with a hydrocarbon solvent. It is preferable to add the component (B), the component (C), or the mixture of the component (B) and the component (C).

In any contact method, usually in an inert gas atmosphere such as nitrogen or argon, aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene (usually having 6 to 12 carbon atoms), heptane, hexane, decane, A method of contacting each component with stirring or non-stirring in the presence of a liquid inert hydrocarbon such as aliphatic or alicyclic hydrocarbon (usually having 5 to 12 carbon atoms) such as dodecane or cyclohexane is employed.
As described above, an aromatic hydrocarbon solvent in which a certain component is soluble or hardly soluble and an aliphatic or alicyclic hydrocarbon solvent in which a certain component is insoluble or hardly soluble can be used. It is preferable to use a solvent that can dissolve the component (B) or the mixture of the component (B) and the component (C). For example, when component (A) is silica, component (B) is a cyclopentadienyl transition metal compound, and component (C) is an alumoxane compound, the solvent is an aromatic hydrocarbon, especially toluene, hexane, or heptane aliphatic. Hydrocarbons are preferred. Moreover, you may use the additive for improving melt | dissolution or dispersion | distribution of a component (A), a component (B) and / or a component (C), and a hydrocarbon.

  This contact is usually −100 ° C. to 200 ° C., preferably −50 ° C. to 100 ° C., more preferably 0 ° C. to 50 ° C., for 5 minutes to 50 hours, preferably 30 minutes to 24 hours, more preferably. It is desirable to carry out in 30 minutes to 12 hours.

  The amount of the liquid inert hydrocarbon used as the solvent needs to be 3 times or more the pore volume of the inorganic oxide used as the component (A). The amount of the solvent used is more preferably 3 to 30 times the volume of the pore volume of the component (A), more preferably 4 to 20 times the volume. The pore volume here is measured by the BET method. If it is out of the above range, the catalytic activity tends to decrease or the fluidity of the powder tends to decrease. When the amount of solvent used is less than 3 times the pore volume of the component (A), the particle size of the component (A) is small, resulting in poor dispersion of the component (B) and the component (C). On the other hand, when the amount of the solvent is too large, the concentration of each component becomes thin, so the amount of the component (B) and the component (C) supported on the component (A) decreases, and the load on the subsequent steps such as drying increases. Therefore, it is not preferable.

  In this invention, it reacts with the inorganic oxide (component (A)) of a specific particle size, the transition metal compound (component (B)) of periodic table group 3-12, and a component (B), and becomes cationic The use ratio of the compound forming the complex (component (C)) is not particularly limited, but the following range is preferable.

  When an organoaluminum oxy compound is used as a compound (component (C)) that reacts with a transition metal compound of group 3 to 12 of the periodic table (component (B)) to form a cationic complex, the transition metal compound (component The atomic ratio (Al / M) of the aluminum of the organoaluminum oxy compound to the transition metal (M) in (B)) is usually in the range of 1 to 100,000, preferably 5 to 1000, more preferably 50 to 200. In addition, when a borane compound or a borate compound is used, the atomic ratio (B / M) of boron to the transition metal (M) in the transition metal compound is usually 0.01 to 100, preferably 0.1. It is desirable to select in the range of -50, more preferably 0.2-10.

  The amount of the inorganic oxide having a specific particle size (component (A)) used is 1 g per 0.0001 to 5 mmol of transition metal in the transition metal compound (component (B)) of Groups 3 to 12 of the periodic table. Preferably, 1 g per 0.001 to 0.5 mmol, more preferably 1 g per 0.01 to 0.1 mmol.

  A cationic complex is formed by reacting with an inorganic oxide having a specific particle size (component (A)), a transition metal compound of Group 3-12 of the periodic table (component (B)), and component (B). After contacting the compound (component (C)) with any one of the contact methods (I) to (III), the compound (component (C)) may be used as it is as an olefin polymerization catalyst. It may be used after removing, or it may be used after removing the solvent and drying. In this, it is preferable to obtain an olefin polymerization catalyst as a solid catalyst by removing a solvent. The removal of the solvent is desirably performed under normal pressure or reduced pressure at 0 to 200 ° C., preferably 20 to 150 ° C. for 1 minute to 50 hours, preferably 10 minutes to 10 hours.

  The olefin polymerization catalyst obtained here may be contacted in the polymerization tank or outside the polymerization tank and preliminarily polymerized in the presence of the olefin. Olefin means a hydrocarbon containing at least one carbon-carbon double bond, and examples thereof include ethylene, propylene, 1-butene, 1-hexene, 3-methylbutene-1, styrene, divinylbenzene and the like. There is no restriction | limiting, You may use the mixture of these and another olefin. Ethylene and propylene are preferable.

  The olefin can be supplied by any method, such as a supply method for maintaining the olefin at a constant speed or in a constant pressure state, a combination thereof, or a stepwise change.

  The prepolymerization time is not particularly limited, but is preferably in the range of 5 minutes to 24 hours. The amount of prepolymerization is preferably 0.01 to 100, more preferably 0.1 to 50, based on 1 part of the component (A). After completion of the prepolymerization, the catalyst can be used as it is, depending on the usage form of the catalyst, but may be dried if necessary. The prepolymerization temperature is not particularly limited, but is preferably 0 ° C to 100 ° C, more preferably 10 to 70 ° C, particularly preferably 20 to 60 ° C, and further preferably 30 to 50 ° C. If it falls below this range, the reaction rate may decrease or the activation reaction may not proceed. There is a possibility that the active point may be deactivated due to a side reaction.

The preliminary polymerization can be carried out in a liquid such as an organic solvent, and this is preferable. The concentration of the solid catalyst during the prepolymerization is not particularly limited, but is preferably 50 g / L or more, more preferably 60 g / L or more, and particularly preferably 70 g / L or more. The higher the concentration, the more active the metallocene and the higher the activity of the catalyst.
Furthermore, a polymer such as polyethylene, polypropylene, or polystyrene, or an inorganic oxide solid such as silica or titania can be allowed to coexist during or after the contact of the above components.

  The catalyst may be dried after the prepolymerization. There are no particular restrictions on the drying method, but examples include vacuum drying, heat drying, and drying by circulating a drying gas. These methods may be used alone or in combination of two or more methods. Also good. In the drying step, the catalyst may be stirred, vibrated, fluidized, or allowed to stand.

6). Polymerization Method The polymerization performed using the above-mentioned catalyst for olefin polymerization is performed by bringing olefin alone or mixed contact with the olefin and another comonomer. In the case of copolymerization, the amount ratio of each monomer in the reaction system does not need to be constant over time, and it is convenient to supply each monomer at a constant mixing ratio. It is also possible to change with time. Also, any of the monomers can be added in portions in consideration of the copolymerization reaction ratio.

  As the olefin that can be polymerized, those having about 2 to 20 carbon atoms are preferred. Specifically, ethylene, propylene, 1-butene, 1-hexene, 1-octene, styrene, divinylbenzene, 7-methyl-1,7 -Octadiene, cyclopentene, norbornene, ethylidene norbornene and the like. Preferred is an α-olefin having 2 to 8 carbon atoms.

  In the case of copolymerization, the type of comonomer used can be selected from olefins other than the main component from those mentioned as the olefin. When ethylene is used as the olefin as the main component, it may be ethylene produced from crude oil derived from ordinary fossil raw materials, or may be ethylene derived from plants. Plant-derived ethylene and its polymers have the property of carbon neutral (does not use fossil raw materials and does not lead to an increase in carbon dioxide in the atmosphere), making it possible to provide environmentally friendly products.

  As the polymerization mode, any mode can be adopted as long as the catalyst component and each monomer come into contact efficiently. Specifically, a slurry method using an inert solvent, a method using propylene as a solvent without substantially using an inert solvent, a solution polymerization method, or a gas phase in which each monomer is kept in a gaseous state without substantially using a liquid solvent. Laws can be adopted. Further, a method of performing continuous polymerization, batch polymerization, or prepolymerization is also applied. Among these, the slurry method is preferable.

  In the case of slurry polymerization, a saturated aliphatic or aromatic hydrocarbon such as hexane, heptane, pentane, cyclohexane, benzene, toluene, or the like is used alone or as a polymerization solvent. The polymerization temperature is 0 to 150 ° C., and hydrogen can be used as an auxiliary molecular weight regulator. The polymerization pressure is 0 to 200 MPa, preferably 0 to 6 MPa.

7). Obtained polymer The polymer obtained by using the catalyst for olefin polymerization of the present invention improves the flowability and bulk density of powder, and suppresses the generation of fine powder polymer. Specifically, when compared under the same polymerization conditions, the catalyst efficiency is improved by 1.5 to 3 times, and a high-quality polyolefin can be obtained.

  EXAMPLES Next, although an Example demonstrates this invention concretely, this invention will not be restrict | limited by these Examples, unless it deviates from the summary.

-The inorganic oxide of the sample used was silica that was baked at 400 ° C for 7 hours in a nitrogen atmosphere and then stored in a nitrogen atmosphere.
-Specific surface area and pore volume were measured as follows.
Each sample of silica was sufficiently dried under heating and reduced pressure, and then an adsorption isotherm of nitrogen under liquid temperature was measured using an autosorb 3B type manufactured by Canterchrome. From the adsorption amount of the obtained adsorption isotherm at a relative pressure of 0.95, the pore volume was subjected to BET multipoint analysis to calculate the specific surface area. Furthermore, the average pore diameter was calculated according to the formula (i) by assuming that the pore structure is a cylinder. In this equation, Dave represents the average pore diameter, Vtotal represents the pore volume, and SBET represents the specific surface area according to the BET multipoint method.
Dave = 4Vtotal / SBET Formula (i)
Further, the mesopore distribution was determined by BJH method analysis, and the pore volume in the specified range was calculated.
-Silica particle size distribution: measured using a laser diffraction / scattering particle size distribution measuring apparatus LA-920 manufactured by HORIBA, Ltd. under conditions of ethanol, refractive index 1.0, and shape factor 1.0, and median The diameter value was defined as the average particle diameter.
The bulk density of silica was calculated by measuring the weight of silica when it was naturally dropped from a height of 5 cm and filled into a 20 ml container.

Polymer molecular weight distribution (Mw / Mn):
About the produced | generated ethylene polymer, gel permeation chromatograph (GPC) was performed on the following conditions, the number average molecular weight (Mn) and the weight average molecular weight (Mw) were calculated | required, and molecular weight distribution (Mw / Mn) was computed.
[Gel permeation chromatograph measurement conditions]
Equipment: Waters 150C model,
Column: Shodex-HT806M,
Solvent: 1,2,4-trichlorobenzene,
Temperature: 135 ° C
Universal rating using monodisperse polystyrene fraction.
・ Polymer density:
It measured according to JIS K-7112 (2004 edition).

Example 1
(A) Preparation of supported catalyst Into a flask equipped with an induction stirrer sufficiently substituted with nitrogen, silica having an average particle diameter of 12 μm (manufactured by Mizusawa Chemical Co., Ltd., P-78D, silica properties are listed in Table 1) was As A), 5 g was charged and heated to 40 ° C. by an oil bath. Into another flask, 8.1 ml of a toluene solution of methylalumoxane (manufactured by Albemarle, 3.0 molAl / L) was taken as component (C). As a component (B), a toluene solution (50 ml) of bis (n-butylcyclopentadienyl) zirconium dichloride (50.5 mg, 125 μmol) was added to a toluene solution of methylalumoxane at room temperature and stirred for 30 minutes. Next, this toluene solution was added to silica heated to 40 ° C. with stirring and held for 1 hour. At this time, the total amount of solvent (ml) / total pore volume (ml) was 6.8, and it was in a uniform slurry state. Thereafter, the solvent was distilled off under reduced pressure while being heated at 40 ° C. After the degree of vacuum became 0.8 mmHg or less, drying under reduced pressure was further continued for 15 minutes to obtain a supported catalyst.
A part of the obtained supported catalyst was diluted with n-heptane (10 mg-solid catalyst / ml) and used for olefin polymerization evaluation.
(B) Ethylene polymerization The inside of a 2 liter induction stirring stainless steel autoclave was replaced with purified nitrogen, and purified hexane (1000 mL) was introduced into the autoclave. After adding 1 ml of a heptane solution (0.1 mmol / ml) of triisobutylaluminum and 5 ml of 1-hexene, the temperature was raised to 80 ° C. After increasing the pressure to 0.7 MPa with ethylene, hydrogen was added to adjust the hydrogen concentration in the gas phase portion in the autoclave to 0.5%. Next, the polymerization was started by press-fitting the supported catalyst heptane slurry obtained in (a) above with 2.1 ml (21 mg catalyst) of the supported catalyst slurry.
After 1 hour, ethanol was injected to stop the polymerization reaction, and the polymer was recovered by filtration. The polymerization results are shown in Table 2.
In addition to the above, the component (A) is contacted with the component (B) to obtain a catalyst component, and then the component (C) is added thereto to prepare a supported catalyst, and ethylene polymerization is performed under the same conditions. Experiments were also conducted when performed. In this case, the ethylene polymerization activity slightly decreased, but the results were almost the same.

(Example 2)
(A) Preparation of supported catalyst The same procedure as in Example 1 (a) was conducted, except that 5 g of silica (manufactured by GRACE, Sypolpol 2212) shown in Table 1 was used.
(B) Ethylene polymerization Except that the heptane slurry of the supported catalyst prepared in the above (a) was added so as to have a catalyst amount described in Table 2, the polymerization was performed in the same manner as the polymerization in (b) of Example 1. The polymerization results are shown in Table 2.

(Example 3)
(A) Preparation of supported catalyst Into a flask equipped with an induction stirrer sufficiently substituted with nitrogen, silica having an average particle diameter of 11 μm (manufactured by GRACE, Sypolol 2212, silica properties are listed in Table 1) was used as component (A). 5 g was filled. Furthermore, after adding 30 ml of toluene, it heated at 40 degreeC with the oil bath. Into another flask, 8.1 ml of a toluene solution of methylalumoxane (manufactured by Albemarle, 3.0 molAl / L) was taken as component (C). As a component (B), a toluene solution (20 ml) of bis (n-butylcyclopentadienyl) zirconium dichloride (50.5 mg, 125 μmol) was added to a toluene solution of methylalumoxane at room temperature and stirred for 30 minutes. Next, this toluene solution was added to silica heated to 40 ° C. with stirring and held for 1 hour. At this time, the total amount of solvent (ml) / total pore volume (ml) was 12, and it was in a uniform slurry state. Thereafter, the solvent was distilled off under reduced pressure while being heated at 40 ° C. After the degree of vacuum became 0.8 mmHg or less, drying under reduced pressure was further continued for 15 minutes to obtain a supported catalyst.
A part of the obtained supported catalyst was diluted with n-heptane (10 mg-solid catalyst / ml) and used for olefin polymerization evaluation.
(B) Ethylene polymerization The polymerization was carried out in the same manner as in the polymerization of Example 1 (b) except that the supported catalyst heptane slurry prepared in Example 2 (a) was added so as to have the catalyst amount shown in Table 2. The polymerization results are shown in Table 2.

(Comparative Example 1)
(A) Preparation of supported catalyst Into a flask equipped with an induction stirrer sufficiently substituted with nitrogen, silica having an average particle diameter of 12 μm (manufactured by Mizusawa Chemical Co., Ltd., P-78D, silica properties are listed in Table 1) was As A), 5 g was charged and heated to 40 ° C. with an oil bath without adding toluene. In another flask, n-butylcyclopentadienylzirconium dichloride (50.5 mg, 125 μmol) was fractionated as component (B), and as a component (C), a toluene solution of methylalumoxane (manufactured by Albemarle, 3.0 mol Al / L) 8.1 ml was added at room temperature. After stirring at room temperature for 30 minutes, this toluene solution was added to silica heated to 40 ° C. with stirring and held for 1 hour. At this time, the total solvent amount (ml) / total pore volume (ml) is 1.0. At this time, since the fluidity of the silica powder was poor, the silica part impregnated with the toluene solution of the catalyst and the silica part where the catalyst component did not contact at all were separated. In addition, formation of silica aggregates was also observed.
From this, it was found that when silica having an average particle size of 12 μm is used, a solid catalyst in which the catalyst component is uniformly impregnated cannot be obtained when the amount of solvent is about 1 times the total pore volume.

Example 4
(A) Preparation of supported catalyst Instead of bis (n-butylcyclopentadienyl) zirconium dichloride (50.5 mg, 125 μmol) described in Example 1 (a), dimethylsilylene bis [1,1 ′-(2- Furylcyclopentadienyl)] zirconium dichloride (60.1 mg, 125 μmol) was used in the same manner as in Example 1 (a).
(B) Ethylene polymerization The polymerization was carried out in the same manner as in the polymerization of Example 1 (b) except that the supported catalyst heptane slurry prepared in Example (a) was added so as to have a catalyst amount described in Table 2. The polymerization results are shown in Table 2.

(Example 5)
(A) Preparation of supported catalyst Instead of bis (n-butylcyclopentadienyl) zirconium dichloride (50.5 mg, 125 μmol) in Example 3 (a), dimethylsilylene bis [1,1 ′-(2-furyl) was used. Cyclopentadienyl)] zirconium dichloride (60.1 mg, 125 μmol) was used in the same manner as in Example 3 (a) except that a toluene solution (50 ml) was used and 8.1 ml of a methylalumoxane toluene solution was used.
(B) Ethylene polymerization The polymerization was carried out in the same manner as in the polymerization of Example 1 (b) except that the supported catalyst heptane slurry prepared in Example (a) was added so as to have a catalyst amount described in Table 2. The polymerization results are shown in Table 2.

(Comparative Example 2)
(A) Preparation of supported catalyst The same procedure was performed except that 5 g of silica (manufactured by GRACE, Sylpol 948, average particle size 50 μm) was used instead of the silica used in Example 5 (a).
(B) Ethylene Polymerization Polymerization was carried out in the same manner as in the polymerization of Example 1 (b) except that the supported catalyst heptane slurry prepared in Comparative Example (a) was added so as to have the catalyst amount shown in Table 2. The polymerization results are shown in Table 2.
From the comparison between Example 5 and Comparative Example 2, it is found that when silica having an average particle diameter of 50 μm is used, the polymerization activity is lowered.

(Example 6)
(A) Preparation of supported catalyst Instead of bis (n-butylcyclopentadienyl) zirconium dichloride (50.5 mg, 125 μmol) in Example 3 (a), dimethylsilylene bis {1,1 ′-{2- [ 2- (5-trimethylsilyl) furyl] -4,5-dimethyl-cyclopentadienyl}} zirconium dichloride (88.6 mg, 125 μmol) in toluene (50 ml) and methylalumoxane in 8.1 ml The procedure was the same as in Example 3 (a) except that it was used.
(B) Ethylene polymerization The polymerization was carried out in the same manner as in the polymerization of Example 1 (b) except that the supported catalyst heptane slurry prepared in Example (a) was added so as to have a catalyst amount described in Table 2. The polymerization results are shown in Table 2.

(Comparative Example 3)
(A) Preparation of supported catalyst The same procedure was performed except that 5 g of silica (manufactured by GRACE, Sylpol 948, average particle size 50 μm) was used instead of the silica used in Example 6 (a).
(B) Ethylene Polymerization Polymerization was carried out in the same manner as in the polymerization of Example 1 (b) except that the supported catalyst heptane slurry prepared in Comparative Example (a) was added so as to have the catalyst amount shown in Table 2. The polymerization results are shown in Table 2.
From the comparison between Example 6 and Comparative Example 3, it can be seen that the polymerization activity is lowered when silica having an average particle diameter of 50 μm is used.

(Example 7)
(A) Preparation of supported catalyst Instead of bis (n-butylcyclopentadienyl) zirconium dichloride (50.5 mg, 125 μmol) in Example 1 (a), dimethylsilylene bis {1,1 ′-[2- ( 2-furyl) -4,5-dimethyl-cyclopentadienyl]} zirconium dichloride (67.1 mg, 125 μmol) and Example 1 (a) except that 8.1 ml of a toluene solution of methylalumoxane is used. The same was done.
(B) Ethylene polymerization The polymerization was carried out in the same manner as in the polymerization of Example 1 (b) except that the supported catalyst heptane slurry prepared in Example (a) was added so as to have a catalyst amount described in Table 2. The polymerization results are shown in Table 2.

(Example 8)
(A) Preparation of supported catalyst Instead of bis (n-butylcyclopentadienyl) zirconium dichloride (50.5 mg, 125 μmol) of Example 1 (a), diphenylmethylene (cyclopentadienyl) [9- (2 , 7-t-butyl) fluorenyl] zirconium dichloride (83.5 mg, 125 μmol) and 8.1 ml of toluene solution of methylalumoxane were used.
(B) Ethylene polymerization The polymerization was carried out in the same manner as in the polymerization of Example 1 (b) except that the supported catalyst heptane slurry prepared in Example (a) was added so as to have a catalyst amount described in Table 2. The polymerization results are shown in Table 2.

(Comparative Example 4)
(A) Preparation of supported catalyst The same procedure was followed except that 5 g of silica (manufactured by GRACE, Sypolol 948, average particle size 50 μm) was used instead of the silica used in Example 8 (a).
(B) Ethylene polymerization The polymerization was carried out in the same manner as in the polymerization of Example 8 (b) except that the supported catalyst heptane slurry prepared in Comparative Example (a) was added so as to have the catalyst amount shown in Table 2. The polymerization results are shown in Table 2.
From the comparison between Example 8 and Comparative Example 4, it can be seen that the polymerization activity is lowered when silica having an average particle diameter of 50 μm is used.

Example 9
(A) Preparation of supported catalyst Instead of bis (n-butylcyclopentadienyl) zirconium dichloride (50.5 mg, 125 μmol) in Example 1 (a), dimethylsilylene bis [1,1 ′-(2-methyl -4-phenyl-indenyl)] zirconium dichloride (78.5 mg, 125 μmol) and the same procedure as in Example 1 (a) except that 8.1 ml of a toluene solution of methylalumoxane was used.
(B) Ethylene polymerization The polymerization was carried out in the same manner as in the polymerization of Example 1 (b) except that the supported catalyst heptane slurry prepared in Example (a) was added so as to have a catalyst amount described in Table 2. The polymerization results are shown in Table 2.

(Example 10)
(A) Preparation of supported catalyst Instead of bis (n-butylcyclopentadienyl) zirconium dichloride (50.5 mg, 125 μmol) in Example 1 (a), dimethylsilylene bis {1,1 ′-[2- ( 2- (5-Methyl) furyl) -4-phenyl-indenyl]} zirconium dichloride (95.1 mg, 125 μmol) and Example 1 (a) except that 8.1 ml of a toluene solution of methylalumoxane is used. The same was done.
(B) Ethylene polymerization The polymerization was carried out in the same manner as in the polymerization of Example 1 (b) except that the supported catalyst heptane slurry prepared in Example (a) was added so as to have a catalyst amount described in Table 2. The polymerization results are shown in Table 2.

(Example 11)
(A) Preparation of supported catalyst In a flask equipped with an induction stirrer sufficiently substituted with nitrogen, silica having an average particle diameter of 11 μm (manufactured by GRACE, Sypolol 2212, silica properties are listed in Table 1) was used as component (A). 5 g was filled. Furthermore, after adding 90 ml of toluene, it heated at 40 degreeC with the oil bath. Into another flask, 8.1 ml of a toluene solution of methylalumoxane (manufactured by Albemarle, 3.0 molAl / L) was taken as component (C). As a component (B), a toluene solution (50 ml) of dimethylsilylenebis [1,1 ′-(2-furylcyclopentadienyl)] zirconium dichloride (60.1 mg, 125 μmol) was added to a toluene solution of methylalumoxane at room temperature. And stirred for 30 minutes. Next, this toluene solution was added to silica heated to 40 ° C. with stirring and held for 1 hour. At this time, the total amount of solvent (ml) / total pore volume (ml) was 19.1, and it was in a uniform slurry state. Thereafter, the solvent was distilled off under reduced pressure while being heated at 40 ° C. After the degree of vacuum became 0.8 mmHg or less, drying under reduced pressure was further continued for 15 minutes to obtain a supported catalyst.
(B) Ethylene polymerization The polymerization was carried out in the same manner as in the polymerization of Example 1 (b) except that the supported catalyst heptane slurry prepared in Example (a) was added so as to have a catalyst amount described in Table 2. The polymerization results are shown in Table 2.

(Example 12)
(A) Preparation of supported catalyst In a flask equipped with an induction stirrer sufficiently substituted with nitrogen, silica having an average particle diameter of 11 μm (manufactured by GRACE, Sypolol 2212, silica properties are listed in Table 1) was used as component (A). 5 g was filled. Further, 165 ml of toluene was added, and then heated to 40 ° C. with an oil bath. Into another flask, 8.1 ml of a toluene solution of methylalumoxane (manufactured by Albemarle, 3.0 molAl / L) was taken as component (C). As a component (B), a toluene solution (50 ml) of dimethylsilylenebis [1,1 ′-(2-furylcyclopentadienyl)] zirconium dichloride (60.1 mg, 125 μmol) was added to a toluene solution of methylalumoxane at room temperature. And stirred for 30 minutes. Next, this toluene solution was added to silica heated to 40 ° C. with stirring and held for 1 hour. At this time, the total amount of solvent (ml) / total pore volume (ml) was 28.8, which was a uniform slurry state. Thereafter, the solvent was distilled off under reduced pressure while being heated at 40 ° C. However, it took time to remove the solvent because of the large amount of the solvent. After the degree of vacuum became 0.8 mmHg or less, drying under reduced pressure was further continued for 15 minutes to obtain a supported catalyst.
(B) Ethylene polymerization The polymerization was carried out in the same manner as in the polymerization of Example 1 (b) except that the supported catalyst heptane slurry prepared in Example (a) was added so as to have a catalyst amount described in Table 2. The polymerization results are shown in Table 2.
Example 12 is a case where the amount of solvent used was further increased with respect to Example 11, but in comparison with Comparative Example 2, when silica having an average particle diameter of 11 μm was used, the polymerization activity was high. I understand.

"Evaluation"
As is apparent from the results of Table 2 above, in the examples, silica having an average particle diameter of 5 to 25 μm and a pore volume of 0.1 to 3.0 ml / g was used as the inorganic oxide, and a predetermined amount of hydrocarbon was used. Therefore, the catalyst efficiency is high and the desired polymer is obtained.
On the other hand, in Comparative Example 1, since the amount of solvent impregnated in silica was as small as about 1 time of the total pore volume, a solid catalyst uniformly impregnated with the catalyst component could not be obtained. In Nos. 2 and 3, since the silica having an average particle size exceeding 25 μm was used, the activity of the solid catalyst was lowered.

  The olefin polymerization catalyst having high activity and excellent storage stability of the present invention has a good polymerization activity, and polymers such as ethylene polymers obtained by using this have good particle properties. High availability.

Claims (12)

In the method for producing an olefin polymerization catalyst, a catalyst component is obtained by adding the following component (B) to the following component (A):
Component (B) is a method for producing an olefin polymerization catalyst, wherein the component (B) is dissolved or dispersed in a hydrocarbon in an amount of 3 or more times the pore volume measured by the BET method of component (A).
Component (A): Inorganic oxide component having an average particle diameter of 5 to 25 μm and a pore volume of 0.1 to 3.0 ml / g (B): Transition metal compound of Groups 3 to 12 of the periodic table In the method for producing an olefin polymerization catalyst in which the following component (B) and component (C) are added to the following component (A):
Component (B) is a method for producing an olefin polymerization catalyst, wherein the component (B) is dissolved or dispersed in a hydrocarbon in an amount of 3 or more times the pore volume measured by the BET method of component (A).
Component (A): Inorganic oxide component having an average particle diameter of 5 to 25 μm and a pore volume of 0.1 to 3.0 ml / g (B): Transition metal compound component of group 3 to 12 of the periodic table (C ): Compound that reacts with component (B) to form a cationic complex   The method for producing an olefin polymerization catalyst according to claim 1 or 2, wherein the component (A) is used as a powder.   The method for producing an olefin polymerization catalyst according to any one of claims 1 to 3, wherein the component (A) is used after being slurried with a hydrocarbon solvent.   The method for producing an olefin polymerization catalyst according to any one of claims 1 to 4, wherein the hydrocarbon is removed after adding the component (B) and / or the component (C) to the component (A). .   Component (A) is a silica, The manufacturing method of the olefin polymerization catalyst as described in any one of Claims 1-5 characterized by the above-mentioned.   Component (B) is a metallocene compound, The manufacturing method of the olefin polymerization catalyst as described in any one of Claims 1-6 characterized by the above-mentioned.   The method for producing an olefin polymerization catalyst according to any one of claims 1 to 7, wherein the component (B) is a metallocene compound having a heterocyclic aromatic group as a substituent.   Component (C) is alumoxane, The manufacturing method of the olefin polymerization catalyst as described in any one of Claims 2-7 characterized by the above-mentioned.   The olefin polymerization catalyst obtained by the manufacturing method as described in any one of Claims 1-9.   An olefin polymerization method comprising polymerizing an olefin using the olefin polymerization catalyst according to claim 10.   An olefin polymerization method comprising slurry-polymerizing an olefin using the olefin polymerization catalyst according to claim 10.