JPS6410527B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing polyolefin using a novel polymerization catalyst. Conventionally, in this type of technical field, the
A catalyst in which a transition metal compound such as a titanium compound is supported on magnesium halide is known from Publication No. 12105, and a catalyst in which magnesium halide and titanium tetrachloride are co-pulverized is known from Belgian Patent No. 742112. . However, in the production of polyolefins, it is desirable for the catalyst activity to be as high as possible, and from this point of view, the method described in Japanese Patent Publication No. 39-12105 has a still low polymerization activity, while the method described in Belgian Patent No. 742112 has a considerably high polymerization activity. Although it is getting better, improvements are still desired. Furthermore, in German Patent No. 2137872, the amount of magnesium halide used is substantially reduced by co-pulverizing magnesium halide, titanium tetrachloride, alumina, etc., but the activity per solid, which is a measure of productivity, is significantly increased. was not observed, and a catalyst with even higher activity is desired. Further, in the production of polyolefin, it is desirable that the bulk specific gravity of the polymer produced be as high as possible from the viewpoint of productivity and slurry handling. From this point of view, the method described in Japanese Patent Publication No. 39-12105 has a low bulk specific gravity and an unsatisfactory polymerization activity, and the Belgian patent
Although the method of No. 742112 has a high polymerization activity, the bulk specific gravity of the resulting polymer is low, and improvements are desired. The present invention improves the above-mentioned drawbacks, provides a method for producing a novel polymerization catalyst that can obtain a polymer with high polymerization activity and high bulk specific gravity in high yield, and allows continuous polymerization to be carried out extremely easily, as well as a method for producing the polymerization catalyst. This method relates to the polymerization or copolymerization method of olefins, and because the polymerization activity is extremely high, the monomer partial pressure during polymerization is low, and the bulk specific gravity of the resulting polymer is high, making it possible to improve productivity. The amount of catalyst residue in the produced polymer after completion is extremely small, and therefore the catalyst removal step can be omitted in the polyolefin production process, simplifying the polymer treatment process and providing an extremely economical polyolefin production method as a whole. It is something. In the method of the present invention, since the bulk specific gravity of the obtained polymer is large, the amount of polymer produced per unit solvent is large. A further advantage of the present invention is that although the bulk specific gravity of the produced polymer is high in terms of particle size, there are few coarse particles and fine particles of 50μ or less, which facilitates continuous polymerization reactions and facilitates polymer processing. The handling of polymer particles, such as centrifugation and powder transport, is facilitated. Another advantage of the present invention is that the polyethylene obtained using the catalyst of the present invention has a large bulk specific gravity as described above, and in order to obtain a polymer with a desired melt index, it requires a lower hydrogen concentration than conventional methods. Therefore, the total pressure during polymerization can be made relatively small, and the effects on economy and productivity are also large. In addition, when ethylene is polymerized using the catalyst of the present invention, an advantage is that the ethylene absorption rate decreases little with time, so that the polymerization can be carried out for a long time with a small amount of catalyst. Another advantage of the present invention is that when ethylene and other α-olefins are copolymerized using the catalyst of the present invention, the copolymerizability is extremely good and the density of the polyolefin produced is low. It's easy. The present invention provides a novel catalyst system that has many of these features and improves on the drawbacks of the prior art described above, and the fact that these points can be easily achieved by using the solvent of the present invention is that I must say it's surprising. The present invention will be specifically explained below. That is,
The present invention comprises (1) magnesium dihalide (hereinafter abbreviated as magnesium halide), (2) general formula Al(OR) _o X _3-o (where R has 1 to 1 carbon atoms).
24 alkyl, aryl and/or aralkyl groups, and X represents a halogen atom. (n is 0<n≦3) and (3) a substance obtained by reacting an organic carboxylic acid anhydride as a solid carrier, and a titanium compound or a titanium compound and a vanadium compound are added to the solid carrier. The present invention relates to a method for producing a polyolefin by polymerizing or copolymerizing an olefin using a supported component and an organoaluminum compound as a catalyst. The magnesium halide used in the present invention is substantially anhydrous and includes magnesium fluoride, magnesium chloride, magnesium bromide, magnesium iodide, and mixtures thereof, with magnesium chloride being particularly preferred. The general formula _Al (OR) _o group, X represents a halogen atom, n is 0<n≦3), examples include aluminum trimethoxide, aluminum triethoxide, aluminum tri-n-propoxide, aluminum triisopropoxide,
Aluminum tri-n-butoxide, aluminum tri-sec-butoxide, aluminum tri-tert-
Butoxide, aluminum tri-n-pentoxide, aluminum triphenoxide, aluminum dimethoxy monochloride, aluminum monomethoxy dichloride, aluminum diethoxy monochloride, aluminum diethoxy monobromide, aluminum monoethoxy dichloride, aluminum diisopropoxy monochloride, aluminum di-n -Butoxy monochloride, aluminum di-sec-butoxy monochloride, aluminum di-sec-butoxy monobromide, aluminum di-t-butoxy monochloride, aluminum diphenoxy monochloride, aluminum monoethoxy monoisopropoxy monochloride, aluminum monoethoxy monosec- Butoxy monochloride and the like can be mentioned. As the organic carboxylic acid anhydride used in the present invention, a compound selected from the compounds represented by the following general formula is preferably used.

【formula】

【formula】

【formula】

[Formula] (In the above formulas () to (), R ₁ , R ₂ , R ₃ ,
R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are hydrogen and have a carbon number of 1 to 24
represents an alkyl group, alkenyl group or aryl group, and Y represents hydrogen, halogen, or an alkyl group or alkenyl group having 1 to 24 carbon atoms. Further, the 6-membered ring in formula () may include a benzene nucleus, a 6-membered ring consisting of a saturated carbon bond, or a partially unsaturated carbon-carbon bond. ) Examples of such organic carboxylic anhydrides include acetic anhydride, propionic anhydride, n-butyric anhydride, isobutyric anhydride, caproic anhydride, isocaproic anhydride, caprylic anhydride, and lauric acid. Anhydride, palmitic anhydride, stearic anhydride, crotonic anhydride, phenyl acetic anhydride, succinic anhydride, dimethylsuccinic anhydride, glutaric anhydride, maleic anhydride, diphenylmaleic anhydride , benzoic anhydride, toluic anhydride, phthalic anhydride, naphthalic anhydride, pyromellitic dianhydride, and the like. Among these, benzoic anhydride and toluic anhydride are particularly preferred. 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 titanium or a titanium compound and vanadium. 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 (where R is 1 carbon number) ~20 alkyl group, aryl group or aralkyl group, X represents a halogen atom, n is 0≦
n≦4. ) are preferred, and titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, monomethoxytrichlorotitanium, dimethoxydichlorotitanium, trimethoxymonochlorotitanium, tetramethoxytitanium, monoethoxytrichlorotitanium, diethoxydichlorotitanium, Triethoxymonochlorotitanium, tetraethoxytitanium, monoisopropoxytrichlorotitanium, diisopropoxymonochlorotitanium, triisopropoxymonochlorotitanium, tetraisopropoxytitanium, monobutoxytrichlorotitanium, dibutoxydichlorotitanium, monobentoxytrichlorotitanium, monophenol Citrichlorotitanium, diphenoxydichlorotitanium, triphenoxymonochlorotitanium,
Examples include tetraphenoxy titanium. As trivalent titanium compounds, titanium tetrahalides such as titanium tetrachloride and titanium tetrabromide are combined with hydrogen, aluminum, titanium, or periodic titanium.
Examples include titanium trihalides obtained by reduction with organometallic compounds of group metals. Also general formula
Ti(OR _{) n}
indicates a halogen atom. m is 0<m<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, pentavalent vanadium compounds such as vanadium oxytrichloride and orthoalkylvanadate, vanadium trichloride, and vanadium triethoxy. Examples include trivalent vanadium compounds such as . In the present invention, a combination system of a titanium compound and a vanadium compound often gives more preferable results than a titanium compound alone, but in this case, the V/Ti molar ratio is 2/1 to
A range of 0.01/1 is preferred. Examples of organoaluminum compounds used in the present invention include general formulas R ₃ Al, R ₂ AlX, RAlX ₂ , R ₂ AlOR,
Organoaluminum compounds of RAl( _{OR)X and R 3 Al 2} Specific examples include triethylaluminum, triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-
Examples include butylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum chloride, diisopropylaluminum chloride, ethylaluminum sesquichloride, and mixtures thereof. Moreover, it is also preferable to use an organic aluminum compound in combination with an organic carboxylic acid ester. The proportion of the organic carboxylic acid ester used at this time is preferably 1 mol or less per 1 mol of the organoaluminum compound. The organic carboxylic acid ester used at this time is preferably an alkyl ester of an organic carboxylic acid having 1 to 20 carbon atoms, such as ethyl formate, ethyl acetate, ethyl propionate, ethyl valerate, ethyl succinate, methyl benzoate, and benzoic acid. Ethyl, i-propyl benzoate, t-butyl benzoate, p-
Examples include ethyl toluate, i-propyl p-toluate, ethyl p-ethylbenzoate, ethyl p-ethoxybenzoate, and ethyl terephthalate. In the present invention, the amount of the organoaluminum compound to be used is not particularly limited, but it can usually be used in an amount of 0.1 to 1000 times the amount of the transition metal compound. In the present invention, (1) magnesium halide,
The reaction mode of (2) the compound represented by the general formula Al(OR _{) o} Performed in the presence or absence. At this time, the reaction should be carried out in an inert gas atmosphere, and moisture should be avoided as much as possible. In the present invention, as a method for supporting a titanium compound or a titanium compound and a vanadium compound on a solid support, the solid support is heated to a titanium compound or a titanium compound and a vanadium compound in the presence or absence of an inert solvent. This can be carried out by bringing the two into contact with each other, preferably in the presence of a solvent at a temperature of 50 to 300°C, preferably 100 to 300°C.
This is conveniently carried out by heating to 150°C. The reaction time is not particularly limited, but is usually 5
Although it is not necessary, there is no problem with contacting for a long time. For example, processing times can range from 5 minutes to 10 hours. Of course, this treatment should be carried out under an inert gas atmosphere free of oxygen and moisture. The means for removing unreacted transition metal compounds after completion of the reaction is not particularly limited, and a solid powder can be obtained by washing the Ziegler catalyst several times with an inert solvent and evaporating the washings under reduced pressure. However, a more desirable method is to combine the necessary amounts of a titanium compound or a titanium compound and a vanadium compound with (1) magnesium halide, (2) a compound represented by the general formula Al(OR) _o X _3-o ,
and (3) co-pulverized simultaneously in the coexistence with an organic carboxylic acid anhydride, or (1) magnesium halide, (2) a compound represented by the general formula Al(OR) _o X _3-o , and (3 ) co-pulverizing organic carboxylic acid anhydride;
Thereafter, a titanium compound or a titanium compound and a vanadium compound are added and further co-pulverized, so that the titanium compound or a titanium compound and a vanadium compound are supported on the solid carrier. Of course, the co-grinding operation should be carried out in an inert gas atmosphere and moisture should be avoided as much as possible. Magnesium halide with the general formula Al(OR) _o
Regarding the mixing ratio with the aluminum compound represented by X3 _-o , if the amount of the aluminum compound is too small or too large, the polymerization activity tends to decrease.
The Al(OR) _o X _3-o molar ratio is in the range of 1/0.01 to 1/1, preferably in the range of 1/0.05 to 1/0.5 for producing a highly active catalyst. In the present invention, if the amount of organic carboxylic acid anhydride used is too large or too small, no effect can be expected, and it is usually within the range of 0.1 to 5.0 g, preferably 0.5 to 20 g, per 100 g of magnesium halide. It is. In addition, the amount of titanium compound or titanium compound and vanadium compound to be supported is 0.5.
It is most preferable to adjust it within the range of ~10% by weight, and the range of 1~8% by weight is particularly desirable in order to obtain a well-balanced titanium or titanium compound, activity per vanadium, and activity per solid. . When co-pulverization is used as a reaction means, the equipment used for co-pulverization is not particularly limited, but ball mills, vibration mills, rod mills, impact mills, etc. are usually used, and the mixing order, grinding time, grinding etc. Conditions such as temperature are not particularly limited and can be easily determined by those skilled in the art. Usually 0℃~200℃ Preferably 20℃
The catalyst of the present invention can be produced by co-milling at a temperature of 0.5 to 30 hours at a temperature of 100°C to 100°C. 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. Polymerization conditions for olefin include temperature of 20 to 120°C, preferably 50 to 100°C.
The pressure is normal pressure to 70 kg/cm ² , preferably 2 to 60 kg/cm ² . 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 catalysts, such as ethylene, propylene, 1-butene, hexene-
It is suitably used for the homopolymerization of α-olefins such as 1,4-methylpentene-1, and the copolymerization of ethylene and propylene, ethylene and 1-butene, and propylene and 1-butene. Copolymerization with dienes is also preferably carried out for the purpose of modifying polyolefins. Examples of these include copolymerization of ethylene and butadiene, ethylene and 1,4-hexadiene, 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) Preparation of catalyst components 11 g of commercially available anhydrous magnesium chloride and 1.9 g of aluminum triethoxide were placed in a 400 ml stainless steel pot containing 25 1/2 inch diameter stainless steel balls.
g and 0.9 g of benzoic anhydride were added thereto, and ball milling was performed at room temperature for 16 hours under a nitrogen atmosphere. Next, add 2.6g of titanium tetrachloride and further
Ball milling was carried out for 16 hours. 1 g of solid powder obtained after ball milling contained 40 mg of titanium. (b) Polymerization The stainless steel autoclave equipped with an induction stirrer from step 2 was purged with nitrogen, 1000 ml of hexane was added thereto, 1 mmol of triethylaluminum and 20 mg of the above solid powder were added, and the temperature was heated at 80°C with stirring.
The temperature rose to . At the vapor pressure of hexane, the system is 1.5Kg/
cm ²・G, but hydrogen is pumped in until the total pressure is 4.0Kg/cm ²・G, then 6g of butene-1 is injected under ethylene pressure, and ethylene is added until the total pressure is 6.5Kg/cm 2・G.
Polymerization was started by filling the solution until the temperature reached cm ² ·G.
Ethylene was continuously introduced so that the total pressure was 6.5 Kg/cm ² ·G, and polymerization was carried out for 52 minutes. After the polymerization was completed, the polymer slurry was transferred to a beaker, and hexane was removed under reduced pressure to obtain 123 g of white polyethylene having a melt index of 4.8 and a bulk specific gravity of 0.40.
Catalyst activity is 70800g polyethylene/gTi.hr.
C ₂ H ₄ pressure, 2830g polyethylene/g solids. hr.
Polyethylene with high bulk specific gravity and C ₂ H ₄ pressure was obtained with extremely high activity. In addition, the density of the produced polymer was measured using ASTM D1505-67 method.
0.9394, indicating excellent copolymerizability. Comparative Example 1 10 g of anhydrous magnesium chloride and aluminum triethoxide were placed in the ball mill pot described in Example 1.
1.9 g of titanium tetrachloride and 2.5 g of titanium tetrachloride were added, and ball milling was performed at room temperature for 16 hours under a nitrogen atmosphere. 1 g of solid powder obtained after ball milling contained 43 mg of titanium. Using 20 mg of the above solid powder, polymerization was carried out for 50 minutes in the same manner as in Example 1 to obtain a melt index.
4.5, and 121 g of white polyethylene with a bulk specific gravity of 0.32 was obtained. Catalytic activity is 67700g polyethylene/gTi.hr.
C ₂ H ₄ pressure, 2910g polyethylene/g solids. hr.C ₂ H ₄
It was hot under pressure. The density of the produced polymer is 0.9447,
Compared to Example 1, copolymerizability was inferior. Comparative Example 2 0 g of anhydrous magnesium chloride, 0.9 g of benzoic anhydride and titanium tetrachloride were placed in the ball mill pot described in Example 1, and ball milling was carried out at room temperature under a nitrogen atmosphere for 16 hours. 1 g of solid powder obtained after ball milling contained 45 mg of titanium. Using 20 mg of the above solid powder, polymerization was carried out for 169 minutes in the same manner as in Example 1, and the melt index was
121 g of white polyethylene with a bulk specific gravity of 4.1 and 0.18 was obtained. Catalyst activity is 19100g polyethylene/gTi.hr.
C ₂ H ₄ pressure, 860g polyethylene/g solids. hr.C ₂ H ₄
It was hot under pressure. The density of the produced polymer is 0.9453,
Compared to Example 1, copolymerizability was inferior. Example 2 10 g of anhydrous magnesium chloride, 1.9 g of aluminum diethoxy monochloride, and 1.2 g of benzoic anhydride were placed in the ball mill pot described in Example 1, and ball milling was carried out at room temperature under a nitrogen atmosphere for 16 hours. Next, 2.5 g of titanium tetrachloride was added, and ball milling was further carried out at room temperature for 16 hours under a nitrogen atmosphere. 1 g of solid powder obtained after ball milling contained 42 mg of titanium. Using 20 mg of the above solid powder, polymerization was carried out for 44 minutes in the same manner as in Example 1, and the melt index was
4.9, and 122 g of white polyethylene with a bulk specific gravity of 0.38 was obtained. Catalytic activity is 79800g polyethylene/gTi.hr.
C ₂ H ₄ pressure, 3350g polyethylene/g solids. hr.C ₂ H ₄
It was hot under pressure. The density of the produced polymer was 0.9405. Example 3 10 g of anhydrous magnesium chloride and aluminum triethoxide were placed in the ball mill pot described in Example 1.
1.9 g of toluic anhydride and 1.5 g of toluic anhydride were added, and ball milling was performed at room temperature for 16 hours under a nitrogen atmosphere. Next, 2.5 g of titanium tetrachloride was added and ball milling was carried out for an additional 16 hours. 1 g of solid powder obtained after ball milling contained 42 mg of titanium. Using 20 mg of the above solid powder, polymerization was carried out for 47 minutes in the same manner as in Example 1 to obtain a melt index.
5.1, and 122 g of white polyethylene with a bulk specific gravity of 0.35 was obtained. Catalyst activity is 74500g polyethylene/gTi.hr.
C ₂ H ₄ pressure, 3130g polyethylene/g solids. hr.C ₂ H ₄
It was hot under pressure. The density of the produced polymer was 0.9402. Example 4 10 g of anhydrous magnesium chloride and aluminum triethoxide were placed in the ball mill pot described in Example 1.
1.9 g of acetic anhydride and 0.8 g of acetic anhydride were added, and ball milling was performed at room temperature for 16 hours under a nitrogen atmosphere. Next, 2.5 g of titanium tetrachloride was added, and ball milling was further carried out at room temperature for 16 hours under a nitrogen atmosphere. For 1 g of solid powder obtained after ball milling,
Contains 41mg of titanium. Using 20 mg of the above solid powder, polymerization was carried out for 57 minutes in the same manner as in Example 1, and the melt index was
6.1, and 121 g of white polyethylene with a bulk specific gravity of 0.36 was obtained. Catalytic activity 61700g polyethylene/gTi.hr.
C ₂ H ₄ pressure, 2530g polyethylene/g solids. hr.C ₂ H ₄
It was hot under pressure. The density of the produced polymer was 0.9422. Example 5 10 g of anhydrous magnesium chloride and aluminum triethoxide were placed in the ball mill pot described in Example 1.
1.9 g of maleic anhydride and 0.8 g of maleic anhydride were added, and ball milling was performed at room temperature for 16 hours under a nitrogen atmosphere. Next, 2.5 g of titanium tetrachloride was added and ball milling was carried out for 16 hours. 1 g of solid powder obtained after ball milling contained 39 mg of titanium. Using 20 mg of the above solid powder, polymerization was carried out for 60 minutes in the same manner as in Example 1 to obtain a melt index.
5.2, and 120 g of white polyethylene having a bulk specific gravity of 0.38 was obtained. Catalyst activity is 62100g polyethylene/gTi.hr.
C ₂ H ₄ pressure, 2420g polyethylene/g solids. hr.C ₂ H ₄
It was hot under pressure. The density of the produced polymer was 0.9408. Example 6 10 g of anhydrous magnesium chloride and aluminum triethoxide were placed in the ball mill pot described in Example 1.
1.9 g of benzoic anhydride and 1.3 g of benzoic anhydride were added, and ball milling was performed at room temperature for 16 hours under a nitrogen atmosphere.
Next, 3.2 g of titanium trichloride (TiCl ₃ .1/3 AlCl ₃ ) was added and after further ball milling for 16 hours, 1 g of the solid powder obtained contained 47 mg of titanium. Using 20 mg of the above solid powder, polymerization was carried out for 53 minutes in the same manner as in Example 1, and the melt index was
4.5, and 123 g of white polyethylene with a bulk specific gravity of 0.33 was obtained. Catalytic activity is 59100g polyethylene/gSi.hr.
C ₂ H ₄ pressure, 2780g polyethylene/g solids. hr.C ₂ H ₄
It was hot under pressure. The density of the produced polymer was 0.9391. The stainless steel autoclave equipped with an induction stirrer from Example 7 2 was purged with nitrogen, 1000 ml of hexane was added thereto, 2 mmol of triethylaluminum, 0.7 mmol of ethyl benzoate, and 30 mg of the solid powder obtained in Example 1 were added thereto at 60°C with stirring. The temperature rose to . Next, propylene was charged until the total pressure reached 5 kg/cm ² ·G to initiate polymerization. Total pressure is 5Kg/
Propylene was continuously introduced to give a concentration of 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 83 g of white polypropylene with a bulk specific gravity of 0.42. The n-heptane extraction residue of the produced polypropylene is 93.2
It was %. Example 8 A catalyst component was synthesized in the same manner as in Example 1, except that 3.0 g of monobutoxytrichlorotitanium was used in place of 2.6 g of titanium tetrachloride, and 39 mg per 1 g of solid powder was used. A solid powder containing titanium was obtained. Using 20 mg of the above solid powder, polymerization was carried out for 1 hour in the same manner as in Example 1, and the melt index was
5.1, and 108 g of white polyethylene with a bulk specific gravity of 0.41 was obtained. Catalytic activity is 63,700g polyethylene/gTi・
hr・C ₂ H ₄ pressure, 2480g polyethylene/g solids・
hr・C ₂ H ₄ pressure, and polyethylene with high bulk specific gravity was obtained with extremely high activity. Furthermore, the density of the produced polymer was 0.9398 g/cm ² , indicating excellent copolymerizability. Example 9 A catalyst component was synthesized in the same manner as in Example 1, except that 2.6 g of titanium tetrachloride and 0.5 g of triethoxyvanadyl were used in place of 2.6 g of titanium tetrachloride. 40 per gram
A solid powder containing mg of titanium and 7 mg of vanadium was obtained. Using 20 mg of the above solid powder, polymerization was carried out for 1 hour in the same manner as in Example 1, and the melt index was
5.3, and 102 g of white polyethylene with a bulk specific gravity of 0.42 was obtained. Catalytic activity is 58,700g polyethylene/gTi・
V・hr・C ₂ H ₄ pressure, 2350 g polyethylene/g solid・hr・C ₂ H ₄ pressure, and polyethylene with high bulk specific gravity was obtained with extremely high activity. Further, the density of the produced polymer was 0.9400 g/cm ³ and the copolymerizability was excellent.

[Brief explanation of drawings]

FIG. 1 is a flowchart showing one example of the preparation of a catalyst for olefin polymerization of the present invention.

Claims (1)

[Scope of Claims] 1. A method of polymerizing or copolymerizing an olefin using a component in which a titanium compound or a titanium compound and a vanadium compound are supported on a solid carrier and an organoaluminum compound as a catalyst, wherein the solid carrier is (1) dihalogenated. Magnesium, (2) General formula Al (OR) _o X _3-o (where R is 1 to 1 carbon number
24 alkyl, aryl and/or aralkyl groups, and X represents a halogen atom. 1. A method for producing a polyolefin, comprising: a compound represented by (n is 0<n≦3); and (3) a substance obtained by reacting an organic carboxylic acid anhydride.