JPH06345808A - Production of solid catalyst component for polymerizing olefin and production of olefin using the same - Google Patents

Abstract

PURPOSE:To obtain a highly active catalyst, excellent in particle properties and capable of efficiently producing a polyolefin by bringing a specific silica get into contact with a mixture of a trialkylaluminum/aluminoxane under prescribed conditions. CONSTITUTION:This solid catalyst component for polymerizing an olefin is obtained by bringing (A) a silica gel having >=200m<2>/g specific surface area, 0.3-3.0ml/g pore diameter and 0.1-200mum average particle diameter into contact with (b) a mixture of a trialkylaluminum with an aluminoxane at 0.1-10 weight ratio of the aluminoxane/trialkylaluminum in an amount of the formula (c)X10<-7=[(a)+(b)/40]<=[-(c) X10<-5>+(d)/900]X2 [(a) is the number of mol of the trialkylaluminum; (b) is the number c mol W) of aluminum in the aluminoxane; (c) is the specific surface area (m<2>/g) of the silica gel in the component (A); (d) is the moisture content (wt.%) in the silica gell into contact with 1g silica gel. The contact is carried out at >=50 deg.C and the content of the aluminum component soluble in toluene at 20 deg.C in the resultant solid in an unwashed state to <=3wt.%.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a solid catalyst component for olefin polymerization and a method for producing a polyolefin using the same. Specifically, it is a method for efficiently producing a solid catalyst component for olefin polymerization, which comprises aluminoxane / silica gel. By using the solid catalyst component obtained in the present invention, a polyolefin having high activity and excellent particle properties can be produced.

[0002]

A transition metal compound having a cyclopentadienyl group, an indenyl group, a fluorenyl group, or a derivative thereof as a ligand, a so-called metallocene compound, is used together with a cocatalyst such as an aluminoxane to polymerize an α-olefin. It is known that a poly-α-olefin can be produced by JP 58-19309 A discloses (cyclopentadienyl) ₂ MeRHal (wherein R is cyclopentadienyl, C ₁ -C ₆ alkyl, halogen, Me is a transition metal, and Ha is
1 is a halogen) and a method of polymerizing or copolymerizing ethylene and / or α-olefin in the presence of a catalyst composed of a transition metal compound represented by the formula (1) and aluminoxane. JP-A-60-35008 describes that poly-α-olefin having a wide molecular weight distribution can be produced by using a catalyst composed of at least two kinds of metallocene compounds and aluminoxane.

Japanese Patent Application Laid-Open No. 61-130314 describes a method for producing a polyolefin using a catalyst composed of a sterically fixed zircon chelate compound and an aluminoxane. Further, the publication discloses a method for producing a polyolefin having a high degree of isotacticity by using ethylene-bis- (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride as a transition metal compound. Have been described. JP-A-64
JP-A-66124 discloses a catalyst for producing a stereoregular olefin polymer containing a transition metal compound having a silicon-crosslinked cyclopentadienyl compound as a ligand and an aluminoxane as an active ingredient. Japanese Patent Laid-Open No. 2-4130
No. 3, JP-A-2-274703, JP-A-2-
Japanese Patent No. 274704 describes that a syndiotactic polyolefin can be produced by using a catalyst composed of a metallocene compound having a crosslinkable ligand composed of asymmetrical ligands and aluminoxane.

On the other hand, the active species of the so-called Kaminsky type catalyst as described above is [Cp ' ₂ MR] ⁺ (where Cp' = cyclopentadienyl derivative, M = Ti, Zr, Hf, R
= Alkyl), some catalyst systems that do not use aluminoxanes as co-catalysts have been reported since they were suggested to be transition metal cations. Japanese Patent Laid-Open No. 3-18
Japanese Patent No. 8092 discloses a metallocene compound having a cyclopentadienyl ligand and a hetero atom-containing ligand as an olefin polymerization catalyst. Taube et al., J.O.
rganometall. Chem., 347 , C9 (1988) [Cp ₂ Ti
Me (THF)] ⁺ [BPh ₄ ] ^- (Me = methyl group,
Ethylene polymerization has been successful using a compound represented by Ph = phenyl group. Jordan et al., J. Am. Chem. Soc.,
109 , 4111 (1987), [Cp ₂ ZrR (L)] ⁺ (R
= Methyl group, benzyl group, L = Lewis base) shows that zirconium complexes polymerize ethylene.

Japanese Patent Publication No. 1-501950, Japanese Patent Publication No.
Japanese Patent Publication No. -502036 describes a method for polymerizing an olefin using a catalyst composed of a cyclopentadienyl metal compound and an ionic compound capable of stabilizing a cyclopentadienyl metal cation. Zambel
li et al. reported in Macromolecules, 22 , 2186 (1989) that isotactic polypropylene can be produced by a catalyst that combines a zirconium compound having a cyclopentadiene derivative as a ligand and trimethylaluminum and fluorodimethylaluminum. is doing.

Since the above-mentioned so-called Kaminsky type catalyst is generally a system soluble in a solvent, the bulk density of the produced polymer is low when the solvent polymerization or the gas phase polymerization is attempted, and the powdery property is obtained. However, there were problems such as poor adhesion to the polymerization machine and adhesion to the wall of the polymerization machine. To solve these problems,
JP-A-61-108610 and JP-A-63-662.
JP-A-06-173104 and JP-A-2-173104 describe a method of polymerizing an olefin using a solid catalyst in which a metallocene compound and an aluminoxane are supported on a fine particle carrier. However, the solid catalyst obtained by using these aluminoxanes has a drawback that the activity per solid catalyst is low.

[0007]

The so-called Kaminsky type catalyst composed of the metallocene compound / aluminoxane as described above requires the use of a large amount of aluminoxane in order to obtain high activity. Therefore, these catalyst systems have a very low activity per aluminoxane. According to the findings of the present inventors, the solid catalyst supporting the aluminoxane as described above has a relatively low aluminoxane loading rate, and thus has a problem that the activity per solid catalyst is low. On the other hand, as in JP-A-63-264606, it is possible to obtain a solid catalyst having a high aluminoxane-carrying rate by precipitating metallocene and aluminoxane on a carrier using a solvent in which aluminoxane is sparingly soluble. In the catalyst, when mainly applied to solution polymerization,
Aluminoxane was eluted during the polymerization, and problems such as generation of fine powder and adhesion to walls occurred. Prepolymerization and the like have been attempted as means for solving such problems. On the other hand, as a method of further activating a solid catalyst formed from an aluminoxane / support, a method of using an organoaluminum compound in combination as described in JP-A-4-7306 is known. However, even with the method disclosed in the publication, the supporting rate of aluminoxane in the solid catalyst was relatively low, and the polymerization activity was still insufficient. Further, as a method for improving the aluminoxane loading rate, Japanese Patent Application No.
In 298607, a catalyst in which an aluminoxane and a metallocene compound are supported on an inorganic oxide containing adsorbed water is described. However, when the catalyst is in contact with an organoaluminum compound used in combination for a long time, elution of the aluminoxane occurs. For example, when it is applied to continuous polymerization for a long time, there arises a problem that some fine powder is generated.

As described above, conventionally, as a method of supporting an aluminoxane / metallocene compound on a carrier, a method of depositing and supporting an aluminoxane on the carrier or a method capable of dissolving the aluminoxane after contacting the aluminoxane with the carrier is used. There has been known a method of removing only the solid catalyst firmly supported by washing. However, in the former method, when an organoaluminum compound is used in combination in order to exhibit high activity, problems such as wall adhesion of the polymer to the polymerization machine and generation of fine powder occur. Also,
In the latter method, high activity can be expressed by using an organoaluminum compound in combination, but the supporting rate of aluminoxane is still low and the activity is insufficient. Further, this method requires a large amount of aluminoxane for the production of the solid catalyst, resulting in a high cost.

[0009]

Means for Solving the Problems To solve the above problems, the present inventors have proposed a polyolefin having high activity per solid catalyst and excellent powder properties even when applied to solution polymerization. As a result of extensive studies on a method for producing a solid catalyst, it was found that the above-described object can be achieved by using a specific silica gel as a carrier and supporting an aluminoxane under specific conditions, and thus the present invention has been completed. It was. That is, the present invention provides (A) a surface area of 200 m ² / g or more and a pore size of 0.3 to
It is in the range of 3.0 ml / g and has an average particle size of 0.1 to 2
Silica gel in the range of 00 μm (B) A mixture of trialkylaluminum and aluminoxane such that the weight ratio of trialkylaluminum and aluminoxane satisfies the following formula (1) Formula (1) (aluminoxane) / (trialkylaluminum) =
0.1-10 In contacting the components (A) and (B) with each other in a hydrocarbon solvent to produce a solid catalyst component, 1 g of silica gel as the component (A) and trialkylaluminum as the component (B) are used. The amount of the mixture of aluminoxane and the following formula (2) is represented by the following formula (2) c × 10 ⁻⁷ ≦ (a + b / 40) ≦ (c × 10 ⁻⁵ + d / 8)
00) × 2 a: number of moles of trialkylaluminum (mol) b: number of moles of aluminum in aluminoxane (mo
l) c: surface area (m ² / g) of silica gel which is the component (A) d: solid catalyst component for olefin polymerization, which is contacted under conditions satisfying the water content (% by weight) in silica gel Is a manufacturing method.

The water content in the silica gel was determined by calculating the weight loss measured by heating the sample silica gel at 600 ° C. for a time until a constant weight was reached, and calculating the water content. Further, in the present invention, the components (A) and (B) are used so as to satisfy the formula (2), and at least 50 ° C.
3% by weight or less of the aluminum component dissolved in toluene at 20 ° C. of the solid component which is contacted at the above temperature without washing the solid obtained (even if the solid catalyst component is repeatedly washed at 20 ° C. with toluene) It means that the eluted aluminum component is 3% by weight or less with respect to the aluminum component supported in the solid catalyst component). Further, the present invention is a method for producing a polyolefin using the above catalyst component.

Used as the component (A) in the present invention
Silica gel has a surface area of 200 m ²/ G or more, pore size
Is in the range of 0.3 to 3.0 ml / g, and the average particle size is
Further add silica gel in the range of 0.1 to 200 μm.
Adsorbed water of 0 to 20% by weight, preferably 0 to 10% by weight
It is used after dehydration or addition of water. Preferred
Ku, surface area is 400m²/ G or more, pore size 0.4 to
It is in the range of 2.0 ml / g and the average particle size is 0.5 to 1
Silica gel having a water content of 0 to 7
It is used after being dehydrated or added with water so that the weight% becomes.
In addition, the silica gel used in the present invention contains
Al as long as it does not impair the performance as a solid catalyst
₂O₃, Na₂Metal oxides such as O and MgCl₂Such as
It does not matter if a little metal halide is mixed.
Alumina used as component (B) in the present invention
Sun is a general formula [Chemical formula 1]

[0012]

[Chemical 1] (Wherein R represents a hydrocarbon group having 1 to 10 carbon atoms and n represents an integer of 2 or more), and particularly methylaluminoxane in which R is a methyl group, n is 5 or more, preferably Ten or more are used. The aluminoxanes may be mixed with some alkylaluminum compounds. In addition, in addition to the above, JP-A-2-24
No. 701, JP-A-3-103407, and the like, aluminoxanes having two or more kinds of alkyl groups, and the fine-particle aluminoxane described in JP-A-63-198691, JP-A-2- 167
The aluminum oxy compound obtained by contacting aluminoxane with water or an active hydrogen compound described in JP-A No. 302, JP-A No. 2-167305 and the like can also be suitably used. These aluminoxanes can be produced by using a conventionally known method as described in the above publication.

The aluminoxane used in the present invention is a mixture containing trialkylaluminum as an essential component. Examples of the trialkylaluminum include trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-octylaluminum, etc., and among them, trimethylaluminum is preferable. The content of the trialkylaluminum satisfies the following formula (1) as a weight ratio with aluminoxane. Formula (1) (aluminoxane) / (trialkylaluminum) =
When the weight ratio of 0.1 to 10 (aluminoxane) / (trialkylaluminum) is smaller than 0.1, aluminoxane is not efficiently loaded even when contacted with silica gel, and the performance of the obtained solid catalyst becomes poor. If the (aluminoxane) / (trialkylaluminum) weight ratio is greater than 10, the performance may be significantly poor when the aluminoxane / trialkylaluminum mixture is used as a solid catalyst component. Since its performance varies depending on the manufacturing method of the aluminoxane as described above, it cannot necessarily be said in this way. However, according to the knowledge of the present inventors, it is better to mix a certain amount of trialkylaluminum. Often becomes better.

In producing the solid catalyst component for olefin polymerization in the present invention, what is important is that the amount of the aluminoxane as the component (B) to be used per 1 g of the silica gel as the component (A) is represented by the following formula (2), formula (2) c × 10. ^-7 ≤ (a + b / 40) ≤ (c × 10 ^-5 + d / 9
00) × 2 a: number of moles of trialkylaluminum (mol) b: number of moles of aluminum in aluminoxane (mo
l) c: Surface area (m ² / g) of silica gel which is the component (A) d: It is to be used so as to satisfy the water content (% by weight) in the silica gel. c × 10 ^-7 > (a
+ B / 40), the aluminoxane loading rate in the obtained solid catalyst component is low, and sufficient performance as a catalyst component cannot be obtained. (A + b / 40)> (c × 10 ⁻⁵ + d / 90
When it is 0) × 2, when the obtained solid catalyst component is used for the polymerization of olefin, adhesion of the polymer to the wall of the polymerization machine or generation of fine powder may occur, which is not preferable.

As the method of contacting the above-mentioned component (A) with the component (B), a method of contacting at least 50 ° C. in a hydrocarbon solvent is adopted. Preferably 9 in a solvent
A method of contacting in the range of 0 to 200 ° C. is used. The solvent used can be used without limitation as long as it is inert to aluminoxane, but preferred specific examples are pentane, hexane, heptane,
Examples thereof include aliphatic hydrocarbons such as octane and cyclohexane, and aromatic hydrocarbons such as benzene, toluene and xylene. The solid catalyst component thus obtained contains 5 to 30% by weight of aluminum atom,
It preferably contains 10 to 25% by weight. If the aluminum content is less than 5% by weight, the polymerization activity is low, which is not preferable. Further, if the aluminum content is more than 25% by weight, fine powder is generated during the polymerization and adhered to the wall of the polymerization machine, which is not preferable.

Further, what is important in the present invention is that almost all of the supplied aluminoxane can be supported on silica gel by controlling the amount of aluminoxane used. By doing so, it is possible to control the obtained solid catalyst component so that the aluminum component eluted in toluene at 20 ° C. is 3% by weight or less, preferably 1% by weight or less. If the amount of aluminum component eluted in toluene exceeds 3% by weight, adhesion of the polymer to the wall of the polymerization machine and generation of fine powder are not preferable. As a method of controlling the aluminum component eluted in toluene, there is a method of washing with an aromatic hydrocarbon solvent such as benzene, toluene, xylene, which can dissolve aluminoxane as conventionally known, but the method of the present invention is adopted. By doing so, the amount of aluminoxane used is small, and the manufacturing process such as the cleaning process is simplified, which is advantageous in terms of cost. Further, surprisingly, the solid catalyst component obtained by controlling the amount of aluminoxane used as in the present invention and without washing uses excess aluminoxane and removes unreacted aluminoxane by washing. It was found that it has a higher activity than the solid catalyst component thus obtained. The reason for this is not clear, but by using aluminoxane in excess, ineffective components (components that do not act as alkylaluminum and other cocatalyst components) in the aluminoxane preferentially crush the surface hydroxyl groups of silica gel, which is effective. It is considered that the supporting rate of the aluminoxane component decreased.

The solid catalyst component thus obtained is
It can be used in the presence of a transition metal compound of Groups 4 to 6 of the Periodic Table and an organoaluminum compound to be used as a catalyst for olefin polymerization. The transition metal compounds of Groups 4 to 6 of the Periodic Table used in the polymerization of olefins include transition metal halogen compounds of Group 4 to 6 of the Periodic Table, transition metal alkyl compounds, transition metal alkoxy compounds, non-crosslinkable or crosslinkable compounds. And metallocene compounds. Preferred are transition metal halogen compounds of Group 4 of the Periodic Table, transition metal alkyl compounds, non-crosslinkable or crosslinkable metallocene compounds, and the like. Specific examples thereof include transition metal halogen compounds, transition metal alkyl compounds, and transition metal alkoxy compounds such as titanium tetrachloride, dimethyltitanium dichloride, tetrabenzyl titanium, tetrabenzyl zirconium, and tetrabutoxy titanium, and non-crosslinking metallocenes. The compounds include cyclopentadienyl titanium trichloride, cyclopentadienyl zirconium trichloride, bis (cyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, (cyclopentadienyl) (pentamethyl Cyclopentadienyl) zirconium dichloride and the like, and as the crosslinkable metallocene compound, ethylenebis (1-indenyl) zirconium dichloride, ethylenebis (4,5) , 6,7-Tetrahydro-1-indenyl) zirconium dichloride, dimethylsilylenebis (methylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (dimethylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (9- Fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (9-fluorenyl) zirconium dichloride and the like can be mentioned. In addition to the similar hafnium compounds and the like, for example, JP-A-3-9913, JP-A-2-131488, JP-A-3-21607, JP-A-3-106907, and JP-A-3-188.
092, JP-A-4-69394, JP-A-4
Examples thereof include transition metal compounds described in Japanese Patent Publication No. 3008887. In some cases, two or more of the above transition metal compounds can be used simultaneously. Further, the above-mentioned transition metal compound may be used by supporting it on the solid catalyst obtained by the method of the present invention, or may be separately added and used in the polymerization system. The organoaluminum compound used in the polymerization of olefins has the general formula (Formula 2)

[0018]

Embedded image R ¹ _j Al (OR ² ) _k H _l X _m (wherein R ¹ and R ² represent a hydrocarbon group having 1 to 20 carbon atoms, R ¹ and R ² are the same as each other, and X is a halogen atom, O is an oxygen atom, H is a hydrogen atom, j is an integer from 1 to 3, k, l and m are integers from 0 to 2, and j + k + l + m = It is 3). Specific examples include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, diethyl aluminum chloride, ethyl aluminum dichloride, diisobutyl aluminum hydride, and the like. Among them, triethylaluminum and triisobutylaluminum are preferably used.

The ratio of the transition metal compound used to the solid catalyst component obtained in the present invention is 0.0001 to 100 mmol, preferably 0.001 to 10 mmol per 1 g of the solid catalyst component. The use ratio of the organoaluminum compound is 0.01 to 10000 mmol, preferably 0.1 to 1 with respect to 1 g of the solid catalyst component.
It is 000 mmol.

There are no particular restrictions on the polymerization method and the polymerization conditions, and known methods used in the polymerization of α-olefins can be used. For example, a solvent polymerization method using an inert hydrocarbon medium or a substantially inert hydrocarbon medium can be used. A bulk polymerization method or a gas phase polymerization method which does not exist can be used, and the polymerization temperature is -100.
~ 200 ° C, polymerization pressure is normal pressure ~ 100 kg / cm
It is common to do in ² . Preferably -50 to 100
C, normal pressure to 50 kg / cm ² .

The hydrocarbon medium used in the treatment or polymerization of the catalyst component includes, for example, butane, pentane, hexane, heptane, octane, nonane, decane, cyclopentane, cyclohexane, and other saturated hydrocarbons.
Aromatic hydrocarbons such as benzene, toluene, xylene can also be used. As the olefin used in the polymerization, ethylene, propylene, 1-butene, 4-
Methyl-1-pentene, 1-hexene, 1-octene,
Examples thereof include olefins having 2 to 25 carbon atoms such as 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene and 1-octadecene. The solid catalyst component obtained in the present invention can be used not only in the homopolymerization of olefins but also in the production of copolymers of olefins having about 2 to 25 carbon atoms such as propylene and ethylene, propylene and 1-butene. .

[0022]

EXAMPLES The present invention will be specifically described below with reference to examples. Example 1 Preparation of solid catalyst component Silica gel (manufactured by Fuji Devison Co., Ltd., calcined in a 100 cm ³ four-necked flask thoroughly replaced with nitrogen at room temperature for 3 hours.
A surface area of 485 m ² / g, a pore size of 0.72 ml / g, an average particle size of 32 μm, and a water content of 5.0% by weight (5 g) were suspended in 25 cm ³ of toluene. Methylaluminoxane (manufactured by Ethyl Corp., methylaluminoxane 9.
25 cm ^{3 of} a toluene solution containing 6% by weight of trimethylaluminum and 6.2% by weight of trimethylaluminum was added, and the mixture was reacted under reflux for 6 hours. The solvent was distilled off under reduced pressure to obtain 7 g of a white solid. Under this condition, a in the formula (2) is 0.0038.
8, b is 0.00928, c is 485, and d is 5.0. Therefore, when calculated from the above a, b, c, d, c ×
10 ⁻⁷ is 4.85 × 10 ⁻⁵ , (a + b / 40) is 4.1
12 × 10 ⁻³ , (c × 10 ⁻⁵ + d / 900) × 2 is 1.
It was 04 × 10 ^-2 . Analysis of this solid catalyst component revealed that it contained 23.7% by weight of aluminum. Further, a part of this solid catalyst component was taken and resuspended in toluene at 20 ° C., and the amount of aluminum dissolved in toluene in the solid catalyst component calculated from the aluminum content in the supernatant was 0% by weight. Polymerization Assay 1 1.5 dm ³ After autoclaving a stainless steel autoclave with nitrogen, liquid propylene 0.75 dm ³ and hydrogen 4
1 mmol was charged. Next, 20 mg of the above solid catalyst component
And diphenylmethylene (cyclopentadienyl) synthesized by the method described in JP-A-2-274703.
0.5 mg of fluorenyl zirconium dichloride and 71 mg of triisobutylaluminum were injected under pressure using nitrogen. Then, the temperature in the system was raised to 60 ° C., and polymerization was carried out at that temperature for 1 hour. Polymerization was stopped by adding a small amount of methanol, and propylene was purged and dried to obtain 144 g of syndiotactic polypropylene. No adhesion of polymer to the polymerizer wall was observed.
The polymerization activity per solid catalyst can be calculated as 7200 g · (polypropylene) / g · (solid catalyst) · (hour). The intrinsic viscosity (hereinafter abbreviated as [η]) of the obtained syndiotactic polypropylene in a tetralin solution at 135 ° C. was 1.52 dl / g, and the differential scanning calorimetry (DS
The melting point (Tm) measured by C) was 133 ° C., and the bulk density was 0.35 g / ml. Moreover, no fine powder passed through the 200-mesh screen. Polymerization Assay 2 15 mg of the solid catalyst prepared in Example 1 was suspended in 10 cm ³ of hexane in a 50 cm ³ three-necked flask that had been sufficiently replaced with nitrogen, and 0.5 mg of diphenylmethylene (cyclopentadienyl) fluorenylzirconium dichloride and A catalyst slurry was prepared by sequentially adding 71 mg of triisobutylaluminum. After sufficiently purging the autoclave made of 1.5 dm ³ stainless steel with nitrogen, the catalyst slurry prepared above was charged, and then liquid propylene was added to 0.2 wt.
75 dm ³ and 41 mmol hydrogen were added. The temperature was raised to 60 ° C., and polymerization was performed for 1 hour to obtain 141 g of syndiotactic polypropylene. Almost no polymer wall attachment was observed. The polymerization activity per solid catalyst can be calculated as 9400 g · (polypropylene) / g · (solid catalyst) · (hour). The [η] of the obtained syndiotactic polypropylene was 1.53 dl / g, the melting point (Tm) measured by differential scanning calorimetry (DSC) was 132 ° C., and the bulk density was 0.35 g / ml. Also,
No fines passed through the 200 mesh screen.

Example 2 Preparation of Solid Catalyst Component A solid catalyst component was prepared in the same manner as the solid catalyst component of Example 1 except that the amount of methylaluminoxane used was 35 cm ³ . (Enter the numerical value of the formula)
As a result, 7.9 g of a solid catalyst component was obtained. Under this condition, a is 0.00543, b is 0.0123, and c is 485.
And d is 5.0. The aluminum content in the solid catalyst component was 28.5% by weight, and the amount eluted in toluene at 20 ° C was 0.2% by weight. Therefore, the above a,
Calculating from b, c and d, c × 10 ^-7 is 4.85 × 1
0 ⁻⁵ , (a + b / 40) is 5.74 × 10 ⁻³ , (c × 1)
0 ⁻⁵ + d / 900) × 2 was 1.04 × 10 ⁻² . Polymerization Assay Polymerization was conducted in the same manner as in Polymerization Assay 2 of Example 2 except that the solid catalyst component prepared above was used as the solid catalyst component. As a result, 190 g of syndiotactic polypropylene was obtained. Almost no polymer wall attachment was observed. Polymerization activity per solid catalyst is 9500g
It can be calculated as (polypropylene) / g. (Solid catalyst). (Hour). [Η] of the obtained syndiotactic polypropylene was 1.54 dl / g, and differential scanning calorimetry (DS
The melting point (Tm) measured by C) was 133 ° C., and the bulk density was 0.38 g / ml.

Comparative Example 1 Preparation of Solid Catalyst Component The amount of methylaluminoxane used was 150 cm ^3.
The solid catalyst component was prepared in the same manner as the preparation of the solid catalyst component of Example 1 except that As a result, 16 g of a solid catalyst component was obtained. Under this condition, a is 0.0233, b
Is 0.0557, c is 485, and d is 5.0. Therefore, when calculated from the above a, b, c, d, c ×
10 ⁻⁷ is 4.85 × 10 ⁻⁵ , (a + b / 40) is 2.4
7 × 10 ^-2 , (c × 10 ^-5 + d / 900) × 2 is 1.0
It was 4 × 10 ^-2 . The aluminum content in the solid catalyst component was 51.1% by weight, and the amount eluted into toluene at 20 ° C was 39% by weight. Polymerization Assay Polymerization was performed in the same manner as in Polymerization Assay 2 of Example 1 except that the solid catalyst component prepared above was used as the solid catalyst component. As a result, 210 g of syndiotactic polypropylene was obtained, but severe polymer wall adhesion was observed.

Comparative Example 2 Preparation of Solid Catalyst Component The solid catalyst component prepared in Comparative Example 1 was thoroughly washed with toluene and dried to obtain 5.1 g.
The solid catalyst component of was obtained. Analysis of this solid catalyst component revealed that it contained 11.2% by weight of aluminum. The amount of aluminum dissolved in toluene in this solid catalyst component was 0% by weight. Polymerization was carried out in the same manner as in Polymerization Assay 2 of Example 1 except that the solid catalyst component prepared above was used as the assay polymerization solid catalyst component, but almost no polymer was obtained. It is considered that this is because methylaluminoxane is hardly supported on the carrier.

Example 3 Preparation of solid catalyst component In a 100 cm ³ 4-necked flask which had been sufficiently replaced with nitrogen, 20
Silica gel calcined at 0 ° C. for 3 hours (Fuji Davison, surface area 485 m ² / g, pore size 0.72 ml / g,
5 g of an average particle diameter of 32 μm and a water content of 0.3% by weight) was suspended in 25 cm ³ of toluene. 25 cm ³ of methylaluminoxane (a toluene solution containing 9.6% by weight of methylaluminoxane and 6.2% by weight of trimethylaluminum, manufactured by Ethyl Corp.) was added to this suspension, and the mixture was reacted under reflux for 6 hours. The solvent was distilled off under reduced pressure to obtain 7 g of a white solid. Under this condition, a in the formula (2) is 0.003.
88, b is 0.00928, c is 485, and d is 0.3. Therefore, when calculated from the above a, b, c, d, c
× 10 ⁻⁷ is 4.85 × 10 ⁻⁵ , and (a + b / 40) is 4.
112 × 10 ⁻³ and (c × 10 ⁻⁵ + d / 900) × 2 were 5.18 × 10 ⁻³ . Analysis of this solid catalyst component revealed that it contained 23.4% by weight of aluminum.
Further, a portion of this solid catalyst component was taken and resuspended in toluene at 20 ° C., and the amount of aluminum dissolved in toluene in the solid catalyst component calculated from the aluminum content in the supernatant was 0.1% by weight. It was Polymerization Assay Polymerization was conducted in the same manner as in Polymerization Assay 2 of Example 1 except that the above-prepared solid catalyst component was used. As a result, 141 g of syndiotactic polypropylene was obtained. Almost no polymer wall attachment was observed. The polymerization activity per solid catalyst can be calculated as 9400 g · (polypropylene) / g · (solid catalyst) · (hour). [Η] of the obtained syndiotactic polypropylene was 1.53 dl / g, and differential scanning calorimetry (DS
The melting point (Tm) measured by C) was 132 ° C., and the bulk density was 0.35 g / ml. Moreover, no fine powder passed through the 200-mesh screen.

Example 4 Preparation of Solid Catalyst Component A solid catalyst component was prepared in the same manner as the solid catalyst component of Example 3 except that the amount of methylaluminoxane used was 15 cm ³ . As a result, 6.2 g of a solid catalyst component was obtained. Under this condition, a is 0.00233,
b is 0.00557, c is 485, and d is 0.3.
Therefore, when calculated from the above a, b, c, d, c × 10
^-7 is 4.85 × 10 ^-5 , (a + b / 40) is 2.47 ×
10 ⁻³ , (c × 10 ⁻⁵ + d / 900) × 2 is 5.18 ×
It was 10 ^-3 . The aluminum content in the solid catalyst component was 16.3% by weight, and the amount eluted into toluene at 20 ° C was 0% by weight. Polymerization Assay Polymerization was performed in the same manner as in Polymerization Assay 2 of Example 1 except that the solid catalyst component prepared above was used as the solid catalyst component. As a result, 77 g of syndiotactic polypropylene was obtained. Almost no polymer wall attachment was observed. Polymerization activity per solid catalyst is 5130g
It can be calculated as (polypropylene) / g. (Solid catalyst). (Hour). [Η] of the obtained syndiotactic polypropylene was 1.49 dl / g, and differential scanning calorimetry (DS
The melting point (Tm) measured by C) was 132 ° C., and the bulk density was 0.30 g / ml.

Comparative Example 3 Preparation of Solid Catalyst Component A solid catalyst component was prepared in the same manner as the solid catalyst component of Example 3 except that the amount of methylaluminoxane used was 75 cm ³ . As a result, 11 g of a solid catalyst component was obtained. Under these conditions, a is 0.0116, b is 0.0279, c is 485, and d is 0.3. Therefore, when calculated from the above a, b, c, d, c × 10 ⁻⁷ is 4.85 × 10 ⁻⁵ , and (a + b / 40) is 1.23 × 10
^-2 , (c × 10 ^-5 + d / 900) × 2 is 5.18 × 10
It was ^-3 . Aluminum content in the solid catalyst component is 4
4.8% by weight, and the elution amount in toluene at 20 ° C. is 3
It was 2% by weight. Polymerization Assay Polymerization was performed in the same manner as in Polymerization Assay 2 of Example 1 except that the solid catalyst component prepared above was used as the solid catalyst component. As a result, 160 g of syndiotactic polypropylene was obtained, but severe polymer wall adhesion was observed.

Comparative Example 4 Preparation of Solid Catalyst Component The solid catalyst component prepared in Comparative Example 1 was thoroughly washed with toluene and then dried to give 5.1 g.
The solid catalyst component of was obtained. Analysis of this solid catalyst component revealed that it contained 12.1% by weight of aluminum. The amount of aluminum dissolved in toluene in this solid catalyst component was 0% by weight. Polymerization Assay Polymerization was carried out in the same manner as in Polymerization Assay 2 of Example 1 except that the above-prepared solid catalyst component was used, but almost no polymer was obtained. It is considered that this is because methylaluminoxane is hardly supported on the carrier.

[0030]

By carrying out the method of the present invention, a solid catalyst component for olefin polymerization having excellent performance can be produced. By using the solid catalyst component obtained by the method of the present invention, a polyolefin having excellent powder properties can be produced, which is extremely industrially valuable.

[Brief description of drawings]

FIG. 1 is a flow chart diagram of catalyst production for helping understanding of a catalyst production process.

Claims (5)

[Claims] 1. A silica gel having a surface area of (A) 200 m ² / g or more, a pore diameter of 0.3 to 3.0 ml / g, and an average particle diameter of 0.1 to 200 μm (B) trialkyl. Mixture of trialkylaluminum and aluminoxane such that the weight ratio of aluminum and aluminoxane satisfies the following formula (1) Formula (1) (aluminoxane) / (trialkylaluminum) =
0.1-10 A method for producing a solid catalyst component for olefin polymerization, which comprises contacting 1 g of silica gel as the component (A) with the component (B) under conditions satisfying the following formula (2). Formula (2) c × 10 ⁻⁷ ≦ (a + b / 40) ≦ (c × 10 ⁻⁵ + d / 9
00) × 2 a: number of moles of trialkylaluminum (mol) b: number of moles of aluminum in aluminoxane (mo
l) c: surface area of silica gel as component (A) (m ² / g) d: water content in silica gel (% by weight) 2. (A) Silica gel having a surface area of 200 m ² / g or more, a pore size of 0.3 to 3.0 ml / g, and an average particle size of 0.1 to 200 μm (B). Mixture of trialkylaluminum and aluminoxane such that the weight ratio of trialkylaluminum and aluminoxane satisfies the following formula (1) Formula (1) (aluminoxane) / (trialkylaluminum) =
0.1-10 In contacting the components (A) and (B) with each other in a hydrocarbon solvent to produce a solid catalyst component, 1 g of silica gel as the component (A) and trialkylaluminum as the component (B) are used. and usage of a mixture of aluminoxane formula (2) ^{(2) c × 10 -7 ≦} (a + b / 40) ≦ (c × 10 -5 + d / 9
00) × 2 a: number of moles of trialkylaluminum (mol) b: number of moles of aluminum in aluminoxane (mo
l) c: Surface area (m ² / g) of silica gel which is the component (A) d: Used so that the water content (wt%) in silica gel is satisfied, and it is obtained by contacting at a temperature of at least 50 ° C. or higher. A method for producing a solid catalyst component for olefin polymerization, characterized in that the solid component contains 3% by weight or less of an aluminum component dissolved in toluene at 20 ° C. without washing. 3. The method for producing a solid catalyst component for olefin polymerization according to claim 1, wherein the trialkylaluminum is trimethylaluminum and the aluminoxane is methylaluminoxane. 4. The method for producing a solid catalyst component for olefin polymerization according to claim 2, wherein the trialkylaluminum is trimethylaluminum and the aluminoxane is methylaluminoxane. 5. A method for producing a polyolefin, which comprises polymerizing an olefin in the presence of a catalyst formed from the solid catalyst component obtained by the method according to claim 1 or 2, a transition metal compound and an organoaluminum compound. .