JP3941138B2 - Olefin polymerization catalyst carrier, olefin polymerization catalyst, and process for producing olefin polymer - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an olefin polymerization catalyst carrier, an olefin polymerization catalyst, and an olefin polymer production method using the same. More specifically, the present invention relates to a carrier for an olefin polymerization catalyst which gives an olefin polymer having excellent particle properties with high polymerization activity, and a method for producing an olefin polymer using the same.
[0002]
[Prior art]
Many reports have already been made on a method for producing an olefin polymer using a transition metal compound. For example, for metallocene transition metal compounds, Japanese Patent Application Laid-Open No. 58-19309 discloses a method for producing an olefin polymer using a metallocene complex and an aluminoxane. In Japanese National Publication No. 1-502036, a method for producing an olefin polymer using a metallocene complex and a boron compound is disclosed. However, the olefin polymers obtained from these proposed soluble metallocene catalyst systems are amorphous and have a low bulk specific gravity. When applied to slurry polymerization or gas phase polymerization, bulk polymer formation and polymer adhesion to the polymerization vessel wall There was a problem that it caused poor heat transfer and reduced productivity.
[0003]
In order to solve such a problem, a method of supporting a part or all of the catalyst component on an inorganic oxide carrier containing a surface hydroxyl group such as silica is disclosed in, for example, JP-A-61-108610 and JP-A-61. -276805 and JP-A 61-296008. By these methods, an olefin polymer having excellent particle properties can be obtained. However, there is a concern that the inorganic oxide remaining as an impurity in the produced polymer adversely affects the polymer physical properties.
[0004]
On the other hand, loading of catalyst components on an organic carrier has also been proposed. JP 63-92621 discloses loading on particulate polyethylene, and JP 6-25348 discloses a microporous polymer carrier. Support is disclosed. However, in the methods proposed in these methods, since the catalyst component and the carrier cannot have a chemical bonding point, there is a problem that the use of a solvent is restricted in catalyst preparation and polymerization so that the catalyst component does not leak from the carrier. ing. U.S. Pat. No. 5,362,824 and JP-A-7-53623 disclose support of a catalyst component on a polystyrene carrier functionalized with a group having an active hydrogen atom.
[0005]
As described above, when a catalyst component and a carrier are to be chemically supported, a polar functional group having an active hydrogen atom on the carrier has been indispensable. However, when supported by a polar functional group having an active hydrogen atom on the support, it is known that a side reaction product derived from the active hydrogen atom is generated in addition to the target solid catalyst component. The generation of this side reaction product cannot be completely controlled even after the carrying treatment is performed, and there is a concern that the catalyst component may be altered.
[0006]
[Problems to be solved by the invention]
Under such circumstances, the present invention, when applied to slurry polymerization or gas phase polymerization, provides an olefin polymerization catalyst that provides an excellent particle property olefin polymer with high polymerization activity, the catalyst carrier, and polymerization thereof. It is an object of the present invention to provide a method for producing an olefin polymer using a catalyst.
[0007]
[Means for Solving the Problems]
  As a result of intensive studies, the present inventors have found a specific carrier and have completed the present invention. That is, the present invention provides a pore volume at a pore radius of 10 nm to 500 nm.Is 0. 1ml / g or moreAverage particle diameter is 5 μm to 1,000 μmResponsible for olefin polymerization catalyst consisting of porous fine particle polymer which is a copolymer of vinylpyridines and divinylbenzenesBodyThe present invention relates to a solid catalyst component for olefin polymerization, a method for producing the solid catalyst component, an olefin polymerization catalyst containing the solid catalyst component, and a method for producing an olefin polymer using the catalyst.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
The carrier for an olefin polymerization catalyst of the present invention comprises a porous polymer having a non-proton donating Lewis basic functional group.
[0009]
The non-proton-donating Lewis basic functional group possessed by the carrier for olefin polymerization catalyst of the present invention is a functional group having a Lewis base moiety that does not have an active hydrogen atom, and is usually an organoaluminum compound or organoaluminum oxyoxygen that functions as a Lewis acid. It has a property capable of coordinating with a compound.
[0010]
  The non-proton-donating Lewis basic functional group possessed by the carrier for an olefin polymerization catalyst of the present invention is a functional group having a Lewis base moiety having no active hydrogen atom.AndSpecific examples include pyridyl group, imidazolyl group, indazolylBasicAnd so on. Particularly preferred are a pyridyl group and an indazolyl group, and most preferred is a pyridyl group. These groups may be substituted with a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
[0011]
The amount of the non-proton-donating Lewis basic functional group that the carrier for olefin polymerization catalyst of the present invention has is not particularly limited, but preferably 0.01 to 50 mmol / g as the molar amount of the functional group per unit gram of the carrier. More preferably, it is 0.1-20 mmol / g.
[0012]
  Pore radius of carrier for olefin polymerization catalyst of the present invention10nm~500nmThe pore volume in is preferably 0.1 ml / g or more, more preferably 0.2 ml / g or more, and preferably the pore radius10nm~500nmThe pore volume at is the pore radius3.5nm~7500nmIs 35% or more of the pore volume, more preferably 40% or more.
[0013]
The average particle diameter of the carrier for an olefin polymerization catalyst of the present invention is preferably 5 μm to 1,000 μm, more preferably 10 μm to 500 μm.
[0014]
  Such porous polymer having a non-proton donating Lewis basic functional group includes, for example, a monomer having a non-proton donating Lewis basic functional group having one or more unsaturated bonds and two or more unsaturated monomers. It can be obtained by copolymerizing with a crosslinkable monomer having a bond.
  Examples of the monomer having a non-proton-donating Lewis basic functional group having one or more unsaturated bonds include a functional group having a Lewis base part having no active hydrogen atom and one or more unsaturated functional groups. The monomer which has is mentioned. Such unsaturated sensationGroupThe vinyl groupIt is.Specific examples of the monomer having a non-proton-donating Lewis basic functional group having one or more unsaturated bonds are vinyl pyridine, vinyl indazo.LeCan be mentioned.
  Examples of the crosslinkable monomer having two or more unsaturated bonds include monomers having two or more unsaturated functional groups. Specific examples thereof include divinylbenzene.
[0015]
  The solid catalyst component for olefin polymerization of the present invention comprises (A)Group 4 metallocene seriesIt comprises a transition metal compound, (B) an organoaluminum compound and / or an organoaluminum oxy compound, and (C) the olefin polymerization catalyst carrier.
[0016]
  Used in the solid catalyst component for olefin polymerization of the present inventionGroup 4 metallocene seriesThe transition metal compound (A) has olefin polymerization activity.Group 4 metallocene seriesUse any transition metal compoundit can.
[0017]
  Usually, the metallocene transition metal compound has the general formula ML_a X_na It is represented by
  In the above formula, M is the fourth element of the periodic table of elements (1993, IUPAC).TribeIt is a transition metal atom. L is a group having a cyclopentadiene type anion skeleton or a group containing a hetero atom, and at least one is a group having a cyclopentadiene type anion skeleton. Several L may mutually bridge | crosslink. X is a halogen atom or an alkyl group having 1 to 20 carbon atoms. a is a number 0 <a ≦ n, and n is the valence of the transition metal atom M.
[0018]
  As a specific example of M, for example,Periodic tableGroup 4 transition metalsatomAs titanium atom, zirconium atom, hafnium sourceChildAnd so on. Preferably, they are a titanium atom, a zirconium atom, and a hafnium atom.
[0019]
L in the above general formula of the metallocene transition metal compound is a group having a cyclopentadiene type anion skeleton or a group containing a hetero atom, and at least one is a group having a cyclopentadiene type anion skeleton. Several L may mutually bridge | crosslink.
Examples of the group having a cyclopentadiene anion skeleton include a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a fluorenyl group, and a substituted fluorenyl group. Examples of the substituent include a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, and a substituted silyl group having 1 to 20 carbon atoms.
The hetero atom in the case of a group containing a hetero atom includes a nitrogen atom, an oxygen atom, a phosphorus atom, a sulfur atom and the like.
[0020]
Specific examples of the group having a cyclopentadiene type anion skeleton include, for example, a cyclopentadienyl group, a methylcyclopentadienyl group, an ethylcyclopentadienyl group, a normal propylcyclopentadienyl group, and a normal butylcyclopentadienyl group. Group, isopropylcyclopentadienyl group, isobutylcyclopentadienyl group, secondary butylcyclopentadienyl group, tertiary butylcyclopentadienyl group, 1,2-dimethylcyclopentadienyl group, 1,3 -Dimethylcyclopentadienyl group, 1,2,3-trimethylcyclopentadienyl group, 1,2,4-trimethylcyclopentadienyl group, tetramethylcyclopentadienyl group, pentamethylcyclopentadienyl group, Indenyl group, 4,5,6,7-tetrahydroindenyl Group, and a fluorenyl group.
Examples of the group containing a hetero atom include a methylamino group, a tertiary butylamino group, a benzylamino group, a methoxy group, a tertiary butoxy group, a phenoxy group, a pyrrolyl group, and a thiomethoxy group.
A group having a cyclopentadiene type anion skeleton or a group having a cyclopentadiene type anion skeleton and a hetero atom-containing group is an alkylene group such as ethylene or propylene, a substituted alkylene group such as isopropylidene or diphenylmethylene, or a silylene group. Further, it may be crosslinked with a substituted silylene group such as a dimethylsilylene group, a diphenylsilylene group or a methylsilylsilylene group.
[0021]
X in the above general formula of the metallocene transition metal compound is a halogen atom or an alkyl group having 1 to 20 carbon atoms. For example, the halogen atom may be a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a carbon atom number. Examples of the alkyl group having 1 to 20 include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, and a benzyl group.
[0022]
Above, ML_aX_naSpecific examples of the compound in which M is a zirconium atom among the metallocene transition metal compounds represented by the formula: bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dibromide, bis ( Cyclopentadienyl) zirconium dimethyl, bis (methylcyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dibromide, bis (methylcyclopentadienyl) zirconium dimethyl, bis (pentamethylcyclopentadienyl) ) Zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dibromide, bis (pentamethylcyclopentadienyl) zirconium dimethyl, bis (indenyl) zirconium dichloride Bis (indenyl) zirconium dibromide, bis (indenyl) zirconium dimethyl, bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, bis (4,5,6,7-tetrahydroindenyl) zirconium dibromide Bis (4,5,6,7-tetrahydroindenyl) zirconium dimethyl, bis (fluorenyl) zirconium dichloride, bis (fluorenyl) zirconium dibromide, bis (fluorenyl) zirconium dimethyl, ethylenebis (indenyl) zirconium dichloride, ethylenebis (Indenyl) zirconium dibromide, ethylenebis (indenyl) zirconium dimethyl, ethylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, Sopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilylenebis (cyclopentadienyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium dichloride, dimethylsilylenebis (4,5,6,7-tetrahydroindenyl) Zirconium dichloride, dimethylsilylene (cyclopentadienyl-fluorenyl) zirconium dichloride, diphenylsilylenebis (indenyl) zirconium dichloride, cyclopentadienyldimethylaminozirconium dichloride, cyclopentadienylphenoxyzirconium dichloride, dimethyl (tertiary butylamino) (Tetramethylcyclopentadienyl) silane zirconium dichloride The
[0023]
Moreover, the compound which replaced the zirconium atom with the titanium atom and the hafnium atom in said zirconium compound can be illustrated similarly.
[0024]
In the solid catalyst component for olefin polymerization of the present invention, an organoaluminum compound and / or an organoaluminum oxy compound (B) is used.
As the organoaluminum compound, a known organoaluminum compound can be used. Preferably, the general formula R¹ _aAlY_3-a(Wherein R¹Represents a hydrocarbon group having 1 to 8 carbon atoms, Y represents a hydrogen atom and / or a halogen atom, and a represents 0 to 3. ) Can be exemplified.
[0025]
General formula R¹ _aAlY_3-aSpecific examples of the organoaluminum compound represented by the formula are trialkylaluminum such as trimethylaluminum, triethylaluminum, trinormalpropylaluminum, triisobutylaluminum, trinormalhexylaluminum, dimethylaluminum chloride, diethylaluminum chloride, dinormalpropylaluminum. Dialkylaluminum chlorides such as chloride, diisobutylaluminum chloride and dinormalhexylaluminum chloride, alkylaluminum dichlorides such as methylaluminum dichloride, ethylaluminum dichloride, normalpropylaluminum dichloride, isobutylaluminum dichloride and normalhexylaluminum dichloride, dimethyl Le hydride, diethylaluminum hydride, di-n-propyl aluminum hydride, can be exemplified diisobutylaluminum hydride, dialkylaluminum hydride such as di-n-hexyl aluminum hydride. Of these, trimethylaluminum, triethylaluminum, and triisobutylaluminum are preferable.
[0026]
Known organoaluminum oxy compounds can be used as the organoaluminum oxy compounds. Preferably, the general formula {-Al (R²) -O-}_bA cyclic aluminoxane having a structure represented by the general formula R^Three(-Al (R^Three-O-)_cAlR^Three ₂A linear aluminoxane having a structure represented by the formula:²And R^ThreeIs a hydrocarbon group having 1 to 8 carbon atoms, and all R²And all R^ThreeMay be the same or different. Y is a hydrogen atom and / or a halogen atom, a is an integer of 0 to 3, b is an integer of 2 or more, and c is an integer of 1 or more. ).
[0027]
General formula {-Al (R²-O-}_bA cyclic aluminoxane having a structure represented by the general formula R^Three(-Al (R^Three-O-)_cAlR^Three ₂R in a linear aluminoxane having a structure represented by², R^ThreeSpecific examples thereof include alkyl groups such as methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, isobutyl group, normal pentyl group, and neopentyl group. A methyl group or an isobutyl group is preferable, and a methyl group is more preferable. Preferably, b is an integer of 2 to 40, c is an integer of 1 to 40, and more preferably, b and c are 3 to 20.
[0028]
The aluminoxane is produced by various methods. The method is not particularly limited and may be made according to a known method. For example, a solution in which at least one kind of trialkylaluminum (for example, trimethylaluminum) is dissolved in a suitable organic solvent (benzene, aliphatic hydrocarbon, etc.) is made by contacting with water. Alternatively, at least one trialkylaluminum (eg, trimethylaluminum) can be made by contacting a metal salt (eg, copper sulfate hydrate) containing water of crystallization.
[0029]
  The solid catalyst component for olefin polymerization of the present invention comprises:Group 4 metallocene seriesIt contains the transition metal compound (A), the organoaluminum compound and / or the organoaluminum oxy compound (B), and the olefin polymerization catalyst carrier (C). The order and combination of contacting them is arbitrary, but preferably, after contacting (C) with (B), contacting with (A), after contacting (A) and (B), It is a method of contacting with (C). More preferably, after contacting (C) with (B), contacting with (A).
[0030]
The contact operation is preferably performed in an inert gas atmosphere, and the temperature of the contact operation is usually −80 ° C. to 200 ° C., preferably 0 ° C. to 100 ° C. The time for the contact operation is usually 1 minute to 36 hours, preferably 10 minutes to 24 hours. The solvent used for the preparation of the solid catalyst component is preferably an aliphatic solvent or an aromatic solvent that is inert to transition metal compounds, organoaluminum compounds, and organoaluminum oxy compounds. Specific examples include normal butane, normal hexane, heptane, benzene, toluene and the like. The treatment operation after contacting (A) and / or (B) with respect to (C) includes a method of filtering the supernatant and washing with an inert solvent, and distilling the solvent under reduced pressure or an inert gas stream. Although the method to leave is mentioned, it is not necessary to perform these operations.
[0031]
  Included in the resulting solid catalyst componentGroup 4 metallocene seriesThe transition metal compound (A) is preferably 0.001 mmol to 10 mmol, more preferably 0.01 mmol to 5 mmol, in terms of the number of moles of transition metal atoms in 1 g of the solid catalyst component in a dry state. Moreover, the ratio (Al / M) of the aluminum atom by (B) to the transition metal atom by (A) in the obtained solid catalyst component is preferably 3 or more, more preferably 5 to 1,000. More preferably, it is 10-500. The obtained solid catalyst component may be used for polymerization in a fluid dry or semi-dry powder state, or may be used for polymerization in a state suspended in an inert solvent.
[0032]
The solid catalyst component (X) for olefin polymerization of the present invention can be used as it is as a polymerization catalyst, but is preferably used in combination with an organoaluminum compound and / or an organoaluminum oxy compound (Y). As the organoaluminum compound and organoaluminum oxy compound (Y) at that time, the same compounds as those exemplified as (B) can be mentioned, but an organoaluminum compound is preferred. More preferred is trialkylaluminum, and further preferred are trimethylaluminum, triethylaluminum, and triisobutylaluminum. The ratio (Al / M) of Al atoms by the compound to be added and transition metal atoms by the solid catalyst component is preferably 0.01 to 10,000, more preferably 0.1 to 1,000.
[0033]
In the present invention, the monomer used for the polymerization may be any of olefins and diolefins having 2 to 20 carbon atoms, and may be copolymerized using two or more types of monomers at the same time. Specific examples thereof include ethylene, propylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1, nonene-1, decene-1, hexadecene-1, eicosene-1, 4-methyl. Pentene-1,5-methyl-2-pentene-1, vinylcyclohexane, styrene, norbornene and the like are exemplified, but the present invention should not be limited to the above compounds. Specific examples of the monomer constituting the copolymer include ethylene and propylene, ethylene and butene-1, ethylene and hexene-1, propylene and butene-1, etc., but the present invention is limited to the above compounds. It shouldn't be.
[0034]
  The polymerization method is not particularly limited, and either a liquid phase polymerization method or a gas phase polymerization method is possible. Examples of the solvent used for liquid phase polymerization include aliphatic hydrocarbons such as butane, pentane, heptane, and octane, aromatic hydrocarbons such as benzene and toluene, and halogenated hydrocarbons such as methylene chloride. It can also be used as a solvent. The polymerization may be any of batch, semi-batch, and continuous, and the polymerization may be performed in two or more stages having different reaction conditions. The polymerization temperature is usually -50 ° C to 300 ° C, preferably -20 ° C to 200 ° C, more preferably 0 ° C to 100 ° C. The polymerization pressure is usually from normal pressure to100 MPa Preferably, normal pressure ~10 MPa More preferably, normal pressure to5 MPa It is. The polymerization time is appropriately determined depending on the kind of the target olefin polymer and the reaction apparatus, but can generally be in the range of 1 minute to 20 hours. In the present invention, a chain transfer agent such as hydrogen may be added during polymerization in order to adjust the molecular weight of the olefin polymer.
[0035]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these at all. The properties of the olefin polymer in the examples were measured by the following methods.
[0036]
(1) The pore volume and pore distribution of the carrier were measured by a mercury intrusion method using a porerizer 9310 manufactured by Micromeritics.
[0037]
(2) The average particle size of the carrier was measured using a laser diffraction particle size distribution measuring device manufactured by Sympatech.
[0038]
(3) The content of α-olefin in the ethylene-α-olefin copolymer is determined using a calibration curve from the characteristic absorption of ethylene and α-olefin using an infrared spectrophotometer (Perkin Elmer 1600 series). Calculated and expressed as the number of short chain branches per 1000 C (SCB).
[0039]
(4) MFR was measured at 190 ° C. according to the method defined in JIS K6760.
[0040]
Example 1
(1) Preparation of solid catalyst component
  A 200 ml flask equipped with a stirrer, a dropping funnel and a thermometer was purged with nitrogen, and then a vinylpyridine-divinylbenzene copolymer (divinylbenzene crosslinking degree 30 wt%, pore radius as an olefin polymerization catalyst carrier)10nm~500nmPore volume at 0.24 ml / g, pore radius3.5nm~5000nm6.35 g of a pore volume of 0.28 ml / g and an average particle diameter of 225 μm) was collected. 100 ml of toluene was added to make a slurry, and after cooling to 4 ° C., 23.5 ml of a toluene solution of methylaluminoxane (manufactured by Tosoh Akzo, 1.89 mmol / ml) was added dropwise. After stirring at 4 ° C. for 30 minutes and at 25 ° C. for 2 hours, the supernatant was removed by filtration, washed 4 times with 100 ml of toluene and once with 100 ml of hexane, and dried under reduced pressure. 1.11 g of the solid thus obtained was collected in a 100 ml flask equipped with a nitrogen-substituted stirrer. Next, 30 ml of toluene and 9.3 ml of a toluene solution of ethylenebisindenylzirconium dichloride (2.0 μmol / ml) were added and stirred at room temperature for 1 hour. The supernatant was removed by filtration, washed twice with 50 ml of toluene, once with 50 ml of hexane, and dried under reduced pressure to obtain a fluid solid catalyst component.
  Zirconium contained in 1 g of the solid catalyst component thus obtained was 8.8 μmol, and aluminum was 2.7 mmol.
[0041]
(2) Polymerization
  The inside of the autoclave equipped with a stirrer with an internal volume of 400 ml was evacuated and charged with 95 g of butane and 5 g of butene-1 and heated to 70 ° C. After heating, partial pressure of ethylene0.6 MPaAfter the system was stabilized, 1 ml of a heptane solution of triisobutylaluminum (1 mmol / ml) was added, and then 16.9 mg of the solid catalyst component prepared in (1) was added. Polymerization was carried out at 70 ° C. while feeding ethylene so as to keep the total pressure constant. After 60 minutes, the polymerization was stopped by adding 3 ml of ethanol. As a result, 8.34 g of an olefin copolymer was obtained, and no adhesion of the polymer to the inner wall of the autoclave was observed. Polymerization activity per transition metal is 5.6 × 10⁷ (G / mol).
  The obtained olefin polymer was SCB = 26.6 and MFR = 0.10.
[0042]
Example 2
Polymerization was conducted in the same manner as in Example 1 except that 26.6 mg of the solid catalyst component prepared in Example 1 was used and 1 ml of a heptane solution of trimethylaluminum (1 mmol / ml) was added instead of triisobutylaluminum. As a result, 2.04 g of a polymer was obtained, and no adhesion of the polymer to the inner wall of the autoclave was observed. Polymerization activity per transition metal is 8.7 × 10⁶(G / mol).
The obtained olefin polymer was SCB = 31.3 and MFR <0.1.
[0043]
Example 3
Polymerization was carried out in the same manner as in Example 1 except that 27.9 mg of the solid catalyst component prepared in Example 1 was used and 1 ml of a heptane solution of trinormal hexyl aluminum (1 mmol / ml) was added instead of triisobutylaluminum. As a result, 4.12 g of an olefin copolymer was obtained, and no adhesion of the polymer to the inner wall of the autoclave was observed. Polymerization activity per transition metal is 1.7 × 10⁷(G / mol).
The obtained olefin polymer was SCB = 25.3 and MFR = 3.43.
[0044]
Example 4
(1) Preparation of solid catalyst component
  A 200 ml flask equipped with a stirrer, a dropping funnel and a thermometer was purged with nitrogen, and then a vinylpyridine-divinylbenzene copolymer (Hayes Separations Co., Ltd., GC HayesS, pores as an olefin polymerization catalyst carrier) radius10nm~500nmPore volume at 0.70 ml / g, pore radius3.5nm~5000nm3.28 g of a pore volume of 0.75 ml / g and an average particle diameter of 135 μm was collected. 100 ml of toluene was added to form a slurry, and after cooling to 4 ° C., 12.0 ml of a toluene solution of methylaluminoxane (manufactured by Tosoh Akzo, 1.89 mmol / ml) was added dropwise. After stirring at 4 ° C. for 30 minutes and at 25 ° C. for 2 hours, the supernatant was removed by filtration, washed 4 times with 100 ml of toluene and once with 100 ml of hexane, and dried under reduced pressure. 0.88 g of the solid thus obtained was collected in a 100 ml flask equipped with a nitrogen-substituted stirrer. Next, 30 ml of toluene and 9.0 ml of a toluene solution of ethylenebisindenylzirconium dichloride (2.0 μmol / ml) were added and stirred at room temperature for 1 hour. The supernatant was removed by filtration, washed twice with 50 ml of toluene, once with 50 ml of hexane, and dried under reduced pressure to obtain a fluid solid catalyst component.
  Zirconium contained in 1 g of the solid catalyst component thus obtained was 17.5 μmol, and aluminum was 3.4 mmol.
[0045]
(2) Polymerization
Polymerization was conducted in the same manner as in Example 1 except that 15.8 mg of the solid catalyst component prepared in (1) was used. As a result, 20.86 g of an olefin copolymer was obtained, and adhesion of the polymer to the inner wall of the autoclave was not recognized. It was. Polymerization activity per transition metal is 7.5 × 10⁷(G / mol).
The obtained olefin polymer was SCB = 21.6 and MFR <0.1.
[0046]
【The invention's effect】
As described above in detail, by applying the olefin polymerization catalyst of the present invention and the method for producing an olefin polymer using the catalyst, it is possible to obtain an olefin polymer having excellent particle properties with high polymerization activity. .
[Brief description of the drawings]
FIG. 1 is a flowchart for helping understanding of the present invention. This flowchart is a representative example of the embodiment of the present invention, and the present invention is not limited to this.

Claims (6)

(A) Group 4 metallocene transition metal compound,
(B) an organoaluminum compound and / or an organoaluminum oxy compound, and (C) a vinyl having a pore volume at a pore radius of 10 nm to 500 nm of 0.1 ml / g or more and an average particle size of 5 μm to 1,000 μm A solid catalyst component for olefin polymerization comprising an olefin polymerization catalyst carrier comprising a porous fine particle polymer which is a copolymer of pyridines and divinylbenzenes. (C) The olefin polymerization catalyst carrier according to claim 1 is contacted with (B) an organoaluminum compound and / or an organoaluminum oxy compound, and then (A) a Group 4 metallocene transition metal compound is contacted. The olefin polymerization catalyst according to claim 1, wherein the catalyst is obtained or (A) a Group 4 metallocene transition metal compound and (B) an organoaluminum compound and / or an organoaluminum oxy compound are contacted. A solid catalyst component for olefin polymerization, which is obtained by contacting a carrier for olefin. (C) Whether the carrier for an olefin polymerization catalyst according to claim 1 is contacted with (B) an organoaluminum compound and / or an organoaluminum oxy compound, and then (A) a Group 4 metallocene transition metal compound is contacted Alternatively, (A) a Group 4 metallocene transition metal compound is contacted with (B) an organoaluminum compound and / or an organoaluminum oxy compound, and then (C) the olefin polymerization catalyst carrier according to claim 1 is used. A method for producing a solid catalyst component for olefin polymerization, which comprises contacting the olefin polymerization catalyst. (X) The solid catalyst component for olefin polymerization according to claim 1 or 2 , and (Y) an organoaluminum compound and / or an organoaluminum oxy compound. A method for producing an olefin polymer, wherein an olefin is polymerized or copolymerized using the olefin polymerization catalyst according to claim 4 . 6. The method for producing an olefin polymer according to claim 5 , wherein the olefin polymer is an ethylene- [alpha] -olefin copolymer.

Images