JPS6412286B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel method for producing polyolefins. More specifically, the present invention provides (i) a reaction product of silicon oxide and/or aluminum oxide with one or more compounds selected from ethers, esters and ketones, and (ii) magnesium dihalide and/or Alternatively, a material obtained by supporting a titanium compound or a titanium compound and a vanadium compound on a manganese halide is used as a solid component, and an olefin is polymerized or co-polymerized using a catalyst system obtained by combining this with an organoaluminum compound. The present invention relates to a method for producing polyolefin by polymerization. According to the method of the present invention, the polymer yield per solid and the polymer yield per transition metal are significantly increased, thereby eliminating the need for the step of removing catalyst residues in the polymer, and at the same time reducing the amount of polymer produced. It is possible to increase the bulk specific gravity of the polyolefin and reduce the fine powder portion of the produced polymer, thereby making it possible to suitably produce a polyolefin. Conventionally, in this type of technical field, many catalysts are known in which a transition metal compound such as titanium or vanadium is supported on an inorganic magnesium solid such as magnesium halide, magnesium oxide, or magnesium hydroxide.
However, in these known techniques, the particle shape of the obtained polymer is amorphous, the bulk specific gravity is generally small, and the particle size distribution is generally wide, so there are many fine particulate powder parts, which makes productivity and slurry handling difficult. Improvements were strongly desired from this perspective. Furthermore, when molding these polymers, problems such as generation of dust and reduction in efficiency during molding occur, so it has been strongly desired to increase the bulk specific gravity and reduce the particulate powder portion as described above. The present invention has been made through intensive research aimed at improving the above-mentioned drawbacks and obtaining a polymer having good shape, high bulk specific gravity, narrow particle size distribution, and significantly less fine particulate portions. As a result, we have arrived at the present invention. That is, the present invention provides a method for polymerizing or copolymerizing an olefin using a solid component and an organoaluminum compound (hereinafter referred to as an organometallic compound) as a catalyst, in which the solid component contains (i) a silicon oxide and/or an aluminum oxide; a reaction product with one or more compounds selected from ethers, esters, and ketones; and (ii) magnesium dihalide (hereinafter referred to as magnesium halide) and/or manganese halide with a titanium compound or a titanium compound and a vanadium compound. This is a method for producing polyolefin, characterized in that the material is obtained by contacting a supported material. By using the method of the present invention, it is possible to obtain a highly active polyolefin in which the shape of the polymer particles is extremely good, the particle size distribution is narrow, and there are few fine particulate parts, and the bulk specific gravity of the produced polyolefin is high. This is extremely advantageous, and there are also fewer troubles during molding, making it possible to produce polyolefins extremely advantageously. Here, the term "polymer particles having good shape" means that the polymer particles have a spherical or nearly spherical shape and have a smooth particle surface. The silicon oxide used in the present invention is silica or a double oxide of silicon and at least one other metal of groups 1 to 10 of the periodic table. The aluminum oxide used in the present invention is alumina or aluminum and the periodic table ~
It is a double oxide with at least one other metal of the group. Typical double oxides of silicon or aluminum and at least one other metal from Groups ~ of the periodic table include Al ₂ O ₃ · MgO, Al ₂ O ₃ · CaO,
Al ₂ O ₃・SiO ₂ , Al ₂ O ₃・MgO・CaO, Al ₂ O ₃・
MgO・SiO ₂ , Al ₂ O ₃・CuO, Al ₂ O ₃・Fe ₂ O ₃ ,
Various natural or synthetic complex oxides such as Al ₂ O ₃ ·NiO and SiO ₂ ·MgO can be exemplified. Here, the above formula is not a molecular formula but represents only the composition, and the structure and component ratio of the multiple oxide used in the present invention are not particularly limited. It goes without saying that the silicon oxide and/or aluminum oxide used in the present invention may adsorb a small amount of water without any problem, and can be used without any problem even if it contains a small amount of impurities. The ether used in the present invention has the general formula R-O-R' (where R and R' represent hydrocarbon residues such as alkyl groups, alkenyl groups, aryl groups, and aralkyl groups having 1 to 20 carbon atoms, They may be the same or different.These include oxygen, nitrogen, sulfur,
It may also be an organic residue containing chlorine or other elements. Also, R and R' may form a ring)
Compounds represented by are preferably used, and specific examples thereof include dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, diamyl ether, tetrahydrofuran, dioxane, anisole, and the like. Moreover, these may be used as a mixture. The ester used in the present invention has the general formula
Saturated or unsaturated fatty acid ester or aromatic carboxylic acid ester represented by RCOOR', dibasic carboxylic acid ester represented by the general formula R'OOC-(CH ₂ ) _o -COOR', general formula R'OOC-CH =
Maleic acid ester represented by CH−COOR′,
and general formula

A phthalate ester represented by the formula is preferably used (in the above formula, R is hydrogen or an alkyl group having 1 to 20 carbon atoms,
It represents an alkenyl group, an aryl group, or an aralkyl group, and R' represents an alkyl group, an alkenyl group, an aryl group, or an aralkyl group having 1 to 20 carbon atoms. n is an integer from 0 to 8). Preferred specific examples of these esters include methyl formate, ethyl formate, methyl acetate, ethyl acetate, butyl acetate, vinyl acetate, methyl acrylate, methyl methacrylate, octyl butyrate, ethyl laurate, octyl laurate, methyl benzoate, Examples include ethyl benzoate, octyl paraoxybenzoate, dibutyl phthalate, dioctyl phthalate, dimethyl malonate, dimethyl maleate, diethyl maleate, and the like. Moreover, these may be used as a mixture. The ketone used in the present invention has the general formula

[Formula] (where R and R' are alkyl groups having 1 to 20 carbon atoms,
It represents a hydrocarbon residue such as an alkenyl group, an aryl group, an aralkyl group, and may be the same or different. These may be organic residues containing oxygen, nitrogen, sulfur, chlorine, and other elements. In addition, compounds represented by R and R' may form a ring are preferably used, and specific examples thereof include acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl butyl ketone, dihexyl ketone, Examples include acetophenone, diphenyl ketone, and cyclohexane. Moreover, these may be used as a mixture. The magnesium halide used in the present invention is substantially anhydrous and includes magnesium fluoride, magnesium chloride, magnesium bromide, and magnesium iodide, with magnesium chloride being particularly preferred. Manganese chloride is particularly preferred as the manganese halide used in the present invention. In the present invention, solids containing magnesium halide and/or manganese halide as one component can also be used as the magnesium halide and/or manganese halide. treated with electron donors such as alcohols, esters, ketones, carboxylic acids, ethers, amines, and phosphines, magnesium halides and/or manganese halides with the general formula Me(OR) _n X _ln (where Me Elements in groups ~ groups of the periodic table, l is the element
The valence of Me, m, represents a number satisfying 0<m≦l. However, Ti and V of Me are excluded. In addition, X represents a halogen atom, and R represents a hydrocarbon residue having 1 to 20 carbon atoms, each of which may be the same or different), magnesium halide and/or manganese halide. A co-pulverized product of magnesium halide and/or manganese halide with a polycyclic aromatic compound, anhydrous compounds of groups of the periodic table, and magnesium halide and/or manganese halide are pretreated with alcohol and then tetrachlorinated. It includes all known carriers made from magnesium halide and/or manganese halide, such as those reacted with silicon or organic aluminum compounds. Examples of these include magnesium chloride treated with methanol, ethanol, ethyl benzoate, diethyl ether, etc., magnesium chloride and Mg(OC ₂ H ₅ ) ₂ , Mg(OC ₂ H ₅ )Cl, Al
( _{OCH3 ) 3} , Al( _OC2H5 ) ₃ , Al( _OnC3H7 ) _{3 ,} Al
(OiC ₃ H ₇ ) ₃ , Al (OnC ₄ H ₉ ) ₃ , Al (OsecC ₄ H ₉ ) ₃ ,
_Al ( _OtC4H9 ) ₃ , Al( _OCH3 ) _2Cl , Al _{( OC2H5} ) _2Cl ,
Al(OC ₂ H ₅ ) Cl ₂ , Al(OiC ₃ H ₇ ) ₂ Ci, Al(OiC ₃ H ₇ )
_Cl2 , Si( _OC2H5 ) ₄ , _{Si ( OC2H5} ) _3Cl , Si
(OC ₂ H ₅ ) ₂ Cl ₂ , Si(OC ₂ H ₅ ) ₃ Cl, P(OC ₂ H ₅ ) ₃ , P
(OC ₆ H ₅ ) ₃ , Ca (OC ₂ H ₅ ) ₂ , Mn (OC ₂ H ₅ ) ₂ , Fe
Complexes with ( _{OC2H5 ) 3} , Zn( _OC2H5 ) ₂ , etc., co _- pulverized products of magnesium chloride and naphthalene, anthracene, phenanthrene, pyrene, fluorene, etc., magnesium chloride and aluminum chloride, alumina, silica , boria, etc., and those obtained by treating magnesium chloride with ethanol and then reacting it with silicon tetrachloride or diethylaluminum monochloride. A known method can be used to support a titanium compound and/or a vanadium compound on a magnesium halide, a manganese halide, or a solid compound containing these as one component. For example, this can be carried out by bringing a magnesium halide and/or a manganese halide into contact with a transition metal compound under heating in the presence or absence of an inert solvent, preferably by bringing both in the absence of a solvent at 50%
This is conveniently carried out by heating to ~300°C, preferably 100-150°C. Although the reaction time is not particularly limited, it is usually 5 minutes or more, and long-term contact may be allowed, although it is not necessary. For example, processing times can range from 5 minutes to 10 hours. Other supporting methods include a method of co-pulverizing a magnesium halide and/or a manganese halide with a titanium compound and/or a vanadium compound. Of course, these operations should be carried out in an inert gas atmosphere, and moisture should be avoided as much as possible. The equipment used for co-grinding is not particularly limited, but a ball mill, a vibration mill, a rod mill, an impact mill, etc. are used, and those skilled in the art can easily determine the conditions such as the grinding temperature and grinding time depending on the grinding method. It is determined. Generally, the grinding temperature is 0°C to 200°C, preferably 20°C to 100°C,
The grinding time is 0.5 to 50 hours, preferably 1 to 30 hours. Titanium compound and/or used in the present invention
Or the amount of vanadium compound may be used in excess, but it is usually 0.001 to 0.001 to magnesium halide and/or manganese halide.
Can be used at 50 times the weight. Preferably, excess titanium compound and/or vanadium compound is removed by washing with a solvent after the mixing and heating treatment. After the completion of the reaction, the means for removing unreacted titanium compounds and/or vanadium compounds is not particularly limited, and the Ziegler catalyst is washed several times with an inert solvent and the washings are evaporated under reduced pressure to obtain a solid powder. This is usually done. In addition, the amount of the titanium compound or titanium compound and vanadium compound to be supported is such that the titanium and vanadium content contained in the produced solid is 0.5 to 20% by weight.
It is most preferable to adjust it so that it falls within the range of
Well-balanced activity per titanium and vanadium,
A range of 1 to 10% by weight is particularly desirable to obtain activity on a solid basis. Examples of the titanium compound or the titanium compound and vanadium compound used in the present invention include halides, alkoxy halides, alkoxides, and halogenated oxides of these metals. Preferred titanium compounds are tetravalent titanium compounds and trivalent titanium compounds, and specific examples of tetravalent titanium compounds include the general formula Ti(OR) _o X _4-o
(Here, R represents an alkyl group, aryl group, or aralkyl group having 1 to 20 carbon atoms, and X represents a halogen atom. n is 0≦n≦4.) Titanium tetrachloride is preferable. , titanium tetrabromide,
Titanium tetraiodide, monomethoxytrichlorotitanium, dimethoxydichlorotitanium, trimethoxymonochlorotitanium, tetramethoxytitanium, monoethoxytrichlorotane, diethoxydichlorotitanium, triethoxymonochlorotitanium, tetraethoxytitanium, monoisopropoxytrichlorotitanium, diiso Propoxydichlorotitanium, triisopropoxymonochlorotitanium, tetraisopropoxytitanium, monobutoxytrichlorotitanium, dibutoxydichlorotitanium, monopentoxytrichlorotitanium, monophenoxytrichlorotitanium,
Examples include diphenoxydichlorotitanium, triphenoxymonochlorotitanium, and tetraphenoxytitanium. Examples of trivalent titanium compounds include titanium trihalides obtained by reducing titanium tetrahalides such as titanium tetrachloride and titanium tetrabromide with hydrogen, aluminum, titanium, or organometallic compounds of group metals of the periodic table. It will be done.
Also, the general formula Ti(OR) _n X _4-n (where R is 1 to
20 alkyl group, aryl group or aralkyl group, X represents a halogen atom, m is 0<m<
It is 4. ) A trivalent titanium compound obtained by reducing a tetravalent alkoxy titanium halide represented by the following formula with an organometallic compound of a group metal of the periodic table is exemplified. Examples of vanadium compounds include tetravalent vanadium compounds such as vanadium tetrachloride, vanadium tetrabromide, vanadium tetraiodide, and tetraethoxyvanadium; Examples include trivalent vanadium compounds such as trivalent vanadium compounds, vanadium trichloride, and vanadium triethoxide. In order to make the present invention even more effective, when a titanium compound and a vanadium compound are used together, V/
The Ti molar ratio is preferably in the range of 2/1 to 0.01/1. In the present invention, the reaction between silicon oxide and/or aluminum oxide and one or more compounds selected from ethers, esters and ketones is preferably carried out in the presence or absence of an inert solvent. The reaction temperature at 0
-300℃, preferably 10-100℃, and reaction time is 1 minute to 48 hours, preferably 2 minutes to 10 minutes.
It is a minute. As for the reaction ratio, per 1 g of silicon oxide and/or aluminum oxide,
1 selected from ether, ester and ketone
0.01-5 g of more than one species, preferably 0.1-2
Use g. Component (i) a reaction product of silicon oxide and/or aluminum oxide with one or more compounds selected from ethers, esters and ketones, and component (ii) titanium on magnesium halide and/or manganese halide. The method of contacting the compound or titanium compound with the substance obtained by supporting the vanadium compound is preferably in the presence of an inert solvent, and the contact temperature at this time is 0 to 300°C, preferably 10 to 300°C. 100℃
The contact time is 1 minute to 48 hours, preferably 2 minutes to 10 hours. The contact ratio between component (i) and component (ii) is as follows:
(ii) A range of 0.001 to 500 g is used. The inert solvent used is not particularly limited, and hydrocarbon compounds and/or derivatives thereof that do not normally inactivate the Ziegler type catalyst can be used. Specific examples of these include propane, butane, pentane, hexane, heptane, octane, benzene, toluene, xylene,
Examples include various aliphatic saturated hydrocarbons such as cyclohexane, aromatic hydrocarbons, and alicyclic hydrocarbons. Examples of organometallic compounds used in the present invention include general formulas R ₃ Al, R ₂ AlX, RAlX ₂ , R ₂ AlOR, RAl
(OR) Organoaluminum compounds of X and R ₃ Al ₂ X ₃ (R is an alkyl group or aryl group having 1 to 20 carbon atoms, Examples include triethylaluminum, triisopropylaluminum, triisobutylaluminum, and triethylaluminum.
Examples include sec-butylaluminum, tri-tert-butylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminium chloride, diisopropylaluminum chloride, ethylaluminum sesquichloride, and mixtures thereof. There is no particular limit to the amount of organometallic compound used, but it is usually 0.1 to 0.1 to titanium compound or titanium compound and vanadium compound.
Can be used 1000mol times. Olefin polymerization using the catalyst of the present invention can be carried out by slurry polymerization, solution polymerization or gas phase polymerization, and the polymerization reaction is carried out in the same manner as the olefin polymerization reaction using a conventional Ziegler type catalyst. That is, all reactions are carried out in the presence or absence of inert hydrocarbons, substantially deprived of oxygen, water, and the like. The polymerization conditions for olefin are a temperature of 20 to 120°C, preferably 50 to 100°C, and a pressure of normal pressure to 70 kg/cm ² , preferably 2
to 60Kg/ ^cm2 . Although the molecular weight can be adjusted to some extent by changing polymerization conditions such as polymerization temperature and catalyst molar ratio, it is effectively carried out by adding hydrogen to the polymerization system. Of course, using the catalyst of the present invention, a two-step or more multi-step polymerization reaction with different polymerization conditions such as hydrogen concentration and polymerization temperature can be carried out without any problem. The method of the present invention is applicable to the polymerization of all olefins that can be polymerized with Ziegler's catalyst, and α-olefins having 2 to 12 carbon atoms are particularly preferred, such as ethylene, propylene, 1-butene, hexene-1,4-methyl Homopolymerization of α-olefins such as pentene-1 and octene-1, and ethylene and propylene, ethylene and 1-butene, ethylene and hexene-1, ethylene and 4-methylpentene-1, ethylene and octene-1, propylene and 1
- Suitable for use in copolymerization of butene, etc. Copolymerization with dienes is also preferably carried out for the purpose of modifying polyolefins. Examples of diene compounds used at this time include butadiene, 1,4-hexadiene, ethylidenenorbornene, dicyclopentadiene, and the like. Examples will be described below, but these are for illustrative purposes to carry out the present invention, and the present invention is not limited thereto. Example 1 (a) Production of solid component 2 g of silica (100-200 mesh, vacuum dried at 150°C for 3 hours) and 1 ml of tetrahydrofuran were placed in 50 ml of hexane and stirred at room temperature for 30 minutes. After that, magnesium chloride 10
and 1.9 g of titanium tetrachloride in a ball mill under nitrogen at room temperature for 16 hours. 2 g of a solid substance obtained was added thereto and stirred for an additional 10 minutes to obtain a slurry liquid. The solid component concentration of this slurry liquid was 80 g/100 ml. (b) Polymerization The stainless steel autoclave equipped with an induction stirrer from step 2 was purged with nitrogen, and 1000 ml of hexane was added, followed by 1 mmol of triethylaluminum and 1 ml of the above slurry liquid (containing 80 mg of solid components).
was added and the temperature was raised to 85°C while stirring. The vapor pressure of hexane brings the system to 1.7Kg/cm ²・G, but hydrogen is added until the total pressure becomes 6Kg/cm ²・G, and then ethylene is added until the total pressure becomes 10Kg/cm ²・G. Polymerization was started. Total pressure is 10Kg/cm ²・G
Polymerization was carried out for 1.5 hours by continuously introducing ethylene such that After the polymerization was completed, the polymer slurry was transferred to a beaker, and hexane was removed under reduced pressure to obtain 190 g of white polyethylene having a melt index of 8.0 and a bulk density of 0.31. Catalyst activity is 118000g
It was polyethylene/gTi. In addition, the average particle size of the polymer powder is 900μ, the part smaller than 44μ is 0%, and the part larger than 710μ is 0%.
57.9%, less fine particles and larger average particle size.
It was found that polymers with high bulk density and high activity can be obtained. Comparative Example 1 When polymerization was carried out in the same manner as in Example 1 using 10 mg of the substance obtained by co-pulverizing the magnesium chloride and titanium tetrachloride used in Example 1 as a solid component, the melt index was 4.5 63 g of white polyethylene with a bulk density of 0.18 was obtained. The catalytic activity was 158,000g polyethylene/gTi, and the average particle size of the polymer powder was 340μ, which was smaller than in Example 1, with 0.5% of the particles being 44μ or less and 22.0% of the particles being 710μ or more. Moreover, the bulk density was also extremely small. Comparative Example 2 Polymerization was carried out in the same manner as in Example 1 except that tetrahydrofuran was not used, and 60 g of white polyethylene with a melt index of 7.6 and a bulk density of 0.20 was obtained. The catalyst activity was 150000g polyethylene/gTi, and the average particle size of the polymer powder was as small as 340μ, with 1.0% of the particles being 44μ or less and 22.8% of the particles being 710μ or more.
It is clear that the obtained polymer powder has a small average particle size and a small bulk density. Comparative Example 3 In Example 1, polymerization was carried out in the same manner as in Example 1 except that silica was not used, and 60 g of white polyethylene with a melt index of 14.0 and a bulk density of 0.25 was obtained. Catalytic activity is
148,000g polyethylene/gTi, the average particle size of the polymer powder is as small as 480μ, and the parts smaller than 44μ are
1.0%, and 38.7% of the parts were 710μ or more. Although the average particle size was relatively large, only a polymer powder with a low bulk density could be obtained. Example 2 Polymerization was carried out in the same manner as in Example 1, except that alumina (100 to 200 mesh, vacuum dried at 150°C for 3 hours) was used instead of silica. It turns out that white polyethylene 195 has a melt index of 7.5 and a bulk density of 0.32.
g was obtained. Catalytic activity is 121000g polyethylene/
It was gTi. The average particle size of the polymer is 750μ, with 0% of the particles smaller than 44μ and 0% of the particles larger than 710μ.
A highly active polymer with a large average particle size and high bulk density was obtained with a small amount of fine particles (51.0%). Example 3 Example 1 except that acetone was used instead of tetrahydrofuran in Example 1.
When polymerization was carried out in the same manner as above, white polyethylene with a melt index of 11.0 and a bulk density of 0.31 was obtained.
I got 200g. The catalyst activity was 125,000 g polyethylene/g Ti. In addition, the average particle size of the polymer powder was 1400μ, with 0% of the particles below 44μ and 70.0% of the particles larger than 710μ, making it possible to obtain a highly active polymer with a large average particle size and high bulk density. . Example 4 Polymerization was carried out in the same manner as in Example 2, except that 0.5 ml of di-n-butyl ether was used instead of tetrahydrofuran, and the result was a melt index of 6.8 and a bulk density.
236 g of 0.30 white polyethylene were obtained. The catalyst activity was 147,000 g polyethylene/g Ti. In addition, the average particle size of the polymer powder is 690μ, and the portion below 44μ is 0.1%, and the portion over 710μ is 47.8%, making it possible to obtain a highly active polymer with a large average particle size and high bulk density. Ta. Example 5 In Example 1, ethyl acetate was used instead of tetrahydrofuran, and magnesium chloride was used instead of the co-pulverized product of magnesium chloride and titanium tetrachloride.
9.3 g of aluminum chloride and 1.9 g of titanium tetrachloride in a ball mill under nitrogen at room temperature for 16 hours. As a result of polymerization, 180 g of polyethylene having a melt index of 7.0 and a bulk density of 0.33 was obtained. Catalytic activity is
It was 112,000g polyethylene/gTi. The average particle size of the polyethylene produced was 1500μ, with 0% of the particles smaller than 44μ and 80.0% of the particles larger than 710μ, resulting in a highly active polymer with a large average particle size and high bulk density. . Example 6 In Example 1, 0.5 ml of ethyl ether was used instead of tetrahydrofuran, and 40 g of magnesium oxide and 133 g of aluminum chloride were used instead of the co-pulverized product of magnesium chloride and titanium tetrachloride.
The procedure was carried out except that a solid material obtained by ball milling 9.5 g of the reactant obtained by reacting at ℃ for 4 hours and 1.7 g of titanium tetrachloride at room temperature for 16 hours under nitrogen in a ball mill was used. When polymerization was carried out in the same manner as in Example 1, the melt index was
10.0, and 160 g of polyethylene with a bulk density of 0.31 was obtained.
Catalytic activity was 100,000 g polyethylene/g Ti. The average particle size of the produced polyethylene is 600μ,
0% for parts below 44μ, 50.0% for parts above 710μ
A highly active polymer with a small particulate fraction, a large average particle size, and a high bulk density was obtained. Example 7 A catalyst component was synthesized in the same manner as in Example 1, except that 2.2 g of monobutoxytrichlorotitanium was used instead of 1.9 g of titanium tetrachloride, and the solid component of the slurry liquid was Concentration is 80g/
10 ml of slurry liquid was obtained. Using 1 ml of the above slurry liquid, polymerization was carried out for 1.5 hours in the same manner as in Example 1, resulting in 180 g of white polyethylene with a melt index of 8.5 and a bulk density of 0.33.
I got it. Catalytic activity is 112000g polyethylene/gTi
It was hot. In addition, the average particle size of the polymer powder is 920μ,
0% for parts below 44μ, 60.1% for parts above 710μ
Polyethylene particles with good particle properties, having a small number of fine particles, a large average particle size, and a high bulk density were obtained with high activity. Example 8 A slurry liquid was synthesized in the same manner as in Example 1, except that 1.9 g of titanium tetrachloride and 0.5 g of triethoxyvanadyl were used in place of 1.9 g of titanium tetrachloride. Using 1 ml of the above slurry liquid, polymerization was carried out for 1.5 hours in the same manner as in Example 1, resulting in 158 g of white polyethylene with a melt index of 8.7 and a bulk density of 0.34.
I got it. Catalytic activity is 98000g polyethylene/gTi
It was hot. In addition, the average particle size of the polymer powder is 930μ,
0% for parts below 44μ, 61.0% for parts above 710μ
Polyethylene particles with very high activity and good particle properties were obtained, with few fine particles, a large average particle size, and high bulk density. The stainless steel autoclave equipped with an induction stirrer from Example 9 2 was purged with nitrogen, 1000 ml of hexane was added thereto, 5 mmol of triethylaluminum and 3 ml of the slurry obtained in the same manner as in Example 1 were added, and the temperature was raised to 60°C with stirring. It was warm. Then, propylene was continuously introduced so that the total pressure was 10 kg/cm ² G, and polymerization was carried out for 1 hour. After the polymerization was completed, the polymer slurry was transferred to a beaker, and hexane was removed under reduced pressure to obtain 178 g of white polypropylene. The catalyst activity was 37,000 g polypropylene/g Ti, and the bulk density was 0.40, indicating good particle properties. In addition, the melt index measured at 230℃ is
It was 3.6.

[Brief explanation of drawings]

FIG. 1 is a flow chart showing an example of catalyst preparation in olefin polymerization of the present invention.

Claims (1)

[Scope of Claims] 1. A method of polymerizing or copolymerizing olefin using a solid component and an organoaluminum compound as a catalyst, in which the solid component comprises (i) a silicon oxide and/or an aluminum oxide, and an ether, ester, or ketone. A substance obtained by contacting a reaction product with one or more selected compounds, and (ii) a substance obtained by supporting a titanium compound or a titanium compound and a vanadium compound on magnesium dihalide and/or manganese halide. A method for producing polyolefin, characterized by the following.