JPS648644B2 - - 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 further Belgian Patent No. 742112
A catalyst made by co-pulverizing magnesium halide and titanium tetrachloride is known. However, in the production of polyolefins, it is desirable that the catalyst activity be as high as possible, and from this point of view, the polymerization activity of the method described in Japanese Patent Publication No. 39-12105 is still low, while the polymerization activity of the method of Belgian Patent No. 742112 is quite high. Although the cost has increased, 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, No significant increase was 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 bulk specific gravity of the polymer produced by the method described in Japanese Patent Publication No. 39-12105 is low and the polymerization activity is not satisfactory.
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 novel polymerization catalyst that can obtain polymers 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 an olefin polymer produced using the polymerization catalyst. This method provides a polymerization or copolymerization method, 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, so productivity can be improved.
In addition, the amount of catalyst residue in the resulting polymer after polymerization is extremely small, so the catalyst removal step can be omitted in the polyolefin manufacturing process, simplifying the polymer processing process and making polyolefins extremely economical overall. be able to. 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 polymerization reactor is large. Furthermore, the advantages of the present invention are 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, so continuous polymerization reaction is facilitated, and polymer processing is possible. This facilitates the handling of polymer particles, such as centrifugation and powder transportation in the process. Another advantage of the present invention is that the polyolefin obtained using the catalyst of the present invention has a large bulk specific gravity as described above, and the hydrogen concentration is required to obtain a polymer with a desired melt index compared to conventional methods. Therefore, the total pressure during polymerization can be made relatively small, which has a large effect on economic efficiency and productivity. In addition, when olefin is polymerized using the catalyst of the present invention, there is little decrease in the olefin absorption rate over time, so another advantage is that polymerization can be carried out for a long time with a small amount of catalyst. Furthermore, the polymer obtained using the catalyst of the present invention has an extremely narrow molecular weight distribution and is characterized by extremely low by-products of low polymers, such as a small amount of hexane extraction. Therefore, it is possible to obtain a product of good quality, such as film grade, which has excellent blocking resistance. The catalyst of the present invention has many of these characteristics,
Moreover, the present invention provides a novel catalyst system that improves the drawbacks of the prior art described above, and it must be said that it is surprising that these points can be easily achieved by using the catalyst of the present invention. The present invention will be specifically explained below. That is,
The present invention provides a method for polymerizing or copolymerizing an olefin using a solid catalyst component and an organic aminium compound (hereinafter referred to as an organic metal compound) as a catalyst, in which the solid catalyst component has at least the following three components (1) with the general formula R ¹ _n (OR ² ) _o MgX _2-no (here R ¹ , R ²
represents a hydrocarbon residue having 1 to 24 carbon atoms, and X represents a halogen atom. m and n are 0≦m≦2, 0<n≦
2,0<m+n≦2), (2) General formula

[Formula] (where R ³ , R ⁴ , and R ⁵ represent a hydrocarbon residue having 1 to 24 carbon atoms, an alkoxy group, hydrogen, or a halogen, and R ⁶ represents a hydrocarbon residue having 1 to 24 carbon atoms. .q is 1≦q≦
30) and (3) a substance obtained by reacting a halogen-containing titanium compound. Examples of the compound represented by R ¹ _n (OR ² ) _o MgX _2-no used in the present invention include methoxymagnesium chloride, ethoxymagnesium chloride, isopropoxymagnesium chloride, n-butoxymagnesium chloride, and n-octoxymagnesium chloride. , methylmagnesium methoxide,
Ethylmagnesium methoxide, n-butylmagnesium ethoxide, sec-butylmagnesium ethoxide, decylmagnesium ethoxide, diethoxymagnesium, diisopropoxymagnesium, di-n-butoxymagnesium, di-sec-
Examples include butoxymagnesium, di-t-butoxymagnesium, di-n-octoxymagnesium, and the like. General formula used in the present invention

Compounds represented by the formula include monomethyltrimethoxysilane, monomethyltriethoxysilane, monomethyltri-n-butoxysilane, monomethyltrisec-butoxysilane,
Monomethyltriisopropoxysilane, monomethyltripentoxysilane, monomethyltrioctoxysilane, monomethyltristearoxysilane, monomethyltriphenoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane,
Dimethyldiisopropoxysilane, dimethyldiphenoxysilane, trimethylmonomethoxysilane, trimethylmonoethoxysilane, trimethylmonoisopropoxysilane, trimethylmonophenoxysilane, monomethyldimethoxymonochlorosilane, monomethyldiethoxymonochlorosilane, monomethylmonoethoxydichlorosilane , monomethyldiethoxymonochlorosilane, monomethyldiethoxymonobromosilane, monomethyldiphenoxymonochlorosilane, dimethylmonoethoxymonochlorosilane, monoethyltrimethoxysilane, monoethyltriethoxysilane, monoethyltriisopropoxysilane, monoethyltriphenoxy Silane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldiphenoxysilane, triethylmonomethoxysilane, triethylmonoethoxysilane, triethylmonophenoxysilane, monoethyldimethoxymonochlorosilane, monoethyldiethoxymonochlorosilane,
Monoethyldiphenoxymonochlorosilane, monoisopropyltrimethoxysilane, mono-n-butyltrimethoxysilane, mono-n-butyltriethoxysilane, mono-sec-butyltriethoxysilane, monophenyltriethoxysilane, diphenyldiethoxysilane, diphenyltriethoxysilane enylmonoethoxymonochlorosilane, monomethoxytrichlorosilane, monoethoxytrichlorosilane, monoisopropoxytrichlorosilane, mono n-butoxytrichlorosilane, monopentoxytrichlorosilane, monooctoxytrichlorosilane, monostearoxytrichlorosilane, monophenoxytrichlorosilane Chlorosilane, mono p-methylphenoxytrichlorosilane, dimethoxydichlorosilane, diethoxydichlorosilane, diisopropoxydichlorosilane, di-n-butoxydichlorosilane, dioctoxydichlorosilane, trimethoxymonochlorosilane, triethoxymonochlorosilane, triiso Propoxymonochlorosilane, tri-n-butoxymonochlorosilane, trisec-butoxymonochlorosilane, tetraethoxysilane, tetraisopropoxysilane, and repeating units obtained by condensing the above compounds.

Chain or cyclic polysiloxanes represented by the formula can be mentioned. Examples of the halogen-containing titanium compound used in the present invention include titanium halides, alkoxy halides, and the like. As the titanium compound, a tetravalent titanium compound and a trivalent titanium compound are suitable. Specifically, the tetravalent titanium compound has the general formula Ti(OR) _r X _4-r (where R
represents an alkyl group, aryl group or aralkyl group having 1 to 24 carbon atoms, and X represents a halogen atom.
r is 0≦r<4. ) are preferred, and titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, monomethoxytrichlorotitanium, dimethoxydichlorotitanium, trimethoxymonochlorotitanium, monoethoxytrichlorotitanium, diethoxydichlorotitanium, triethoxymonochlorotitanium , monoisopropoxytrichlorotitanium, diisopropoxydichlorotitanium, triisopropoxymonochlorotitanium, monobutoxytrichlorotitanium, dibutoxydichlorotitanium, monopentoxytrichlorotitanium, monophenoxytrichlorotitanium, diphenoxydichlorotitanium, triphenoxy Examples include monochlorotitanium. As trivalent titanium compounds, titanium tetrahalides such as titanium tetrachloride and titanium tetrabromide are combined with hydrogen, aluminum, titanium, or the periodic table ~
Examples include titanium trihalides obtained by reduction with organometallic compounds of group metals. Also general formula
Ti(OR _{) s}
indicates a halogen atom. s is 0<s<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. In the present invention, tetravalent titanium compounds are most preferred. (1) General formula R ¹ _n (OR ² ) _o MgX _2-no in the present invention
A compound represented by (2) general formula

There is no particular restriction on the method of reacting the compound represented by the formula and (3) the halogen-containing titanium compound to obtain the solid catalyst component of the present invention.
The reaction can be carried out by contacting under heating at 20 to 400°C, preferably 50 to 300°C, for usually 5 minutes to 20 hours, by co-pulverization, or by a suitable combination of these methods. You can. There is no particular restriction on the reaction order of components (1) to (3), and the three components may be reacted at the same time, or two components may be reacted and then another component may be reacted. The inert solvent used at this time 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, various aliphatic saturated hydrocarbons such as cyclohexane, aromatic hydrocarbons, alicyclic hydrocarbons, and ethanol and diethyl. Examples include alcohols, ethers, and esters such as ether, tetrahydrofuran, ethyl acetate, and ethyl benzoate. The equipment used for co-pulverization is not particularly limited, but ball mills, vibration mills, rod mills, impact mills, etc. are usually used, and those skilled in the art can easily determine conditions such as grinding temperature and grinding time depending on the grinding method. It is something that can be done. 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. Of course, these operations should be carried out in an inert gas atmosphere, and moisture should be avoided as much as possible. In the present invention, a method of reacting components (1) to (3) in a solution or a method of co-pulverizing a material obtained by reacting components (1) and (2) in a solution with component (3) is particularly preferred. In addition to the above components (1) to (3), the present invention also includes a component (4) selected from organic halogen compounds, halogenating agents, phosphoric acid esters, electron donors, and polycyclic aromatic compounds. It is also preferably employed to use one or more kinds of compounds.
The reaction method when using component (4) is not particularly limited, but methods include a method of reacting components (1) to (4) in a solution, and a method of reacting components (1), (2), and (4) in a solution. A method of co-pulverizing the substance obtained by the above method and component (3) is preferably used. The organic halogen compound used at this time is a compound in which a portion of a saturated or unsaturated aliphatic hydrocarbon, aromatic hydrocarbon, etc. is substituted with a halogen, and includes mono-substituted compounds, di-substituted compounds, tri-substituted compounds, and the like. Further, the halogen may be any of fluorine, chlorine, bromine and iodine. Specifically, these organic halogen compounds include methylene chloride, chloroform, carbon tetrachloride,
Bromochloromethane, dichlorodifluoromethane, 1-bromo-2-chloroethane, chloroethane, 1,2-dibromo-1,1-dichloroethane, 1,1-dichloroethane, 1,2-dichloroethane, 1,2-dichloro-1, 1,2,2-tetrafluoroethane, hexachloroethane, pentachloroethane, 1,1,2,2-tetrachloroethane, 1,1,2,2-tetrachloroethane,
1,1,1-trichloroethane, 1,1,2-trichloroethane, 1-chloropropane, 2-chloropropane, 1,2-dichloropropane, 1,3
-dichloropropane, 2,2-dichloropropane, 1,1,1,2,2,3,3-heptachloropropane, 1,1,2,2,3,3-hexachloropropane, octachloropropane, 1,1, 2
-Trichloropropane, 1-chlorobutane, 2-
Chlorobutane, 1-chloro-2-methylpropane, 2-chloro-2-methylpropane, 1,2-
dichlorobutane, 1,3-dichlorobutane, 1,
4-dichlorobutane, 2,2-dichlorobutane,
1-chloropentane, 1-chlorohexane, 1-
Chloroheptane, 1-chlorooctane, 1-chlorononane, 1-chlorodecane, vinyl chloride,
1,1-dichloroethylene, 1,2-dichloroethylene, tetrachlorethylene, 3-chloro-1
-propene, 1,3-dichloropropene, chloroprene, oleyl chloride, chlorobenzene, chloronaphthalene, benzyl chloride, benzylidene chloride, chloroethylbenzene, styrene dichloride, α-chlorocumene and the like. Examples of halogenating agents include sulfur chloride, PCl ₃ ,
Nonmetal halides such as PCl ₅ and SiCl ₄ ,
Examples include nonmetallic oxyhalides such as POCl ₃ , COCl ₂ , NOCl ₂ , SOCl ₂ , and SO ₂ Cl ₂ . As phosphoric acid esters, the general formula

[Formula] (where R represents a hydrocarbon residue having 1 to 24 carbon atoms,
(which may be the same or different), specifically triethyl phosphate, tri-n-butyl phosphate, triphenyl phosphate, tribenzyl phosphate, trioctyl phosphate, tri- Examples include cresyl phosphate, tritolyl phosphate, tricylyl phosphate, diphenylxylenyl phosphate, and the like. As electron donors, alcohol, ether,
Ketones, aldehydes, organic acids, organic acid esters,
Examples include acid halides, acid amides, amines, nitriles, and the like. Examples of alcohol include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, allyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, t-butyl alcohol, n-amyl alcohol, n-hexyl alcohol, and cyclohexyl. Alcohol, decyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, benzyl alcohol, naphthyl alcohol, phenol, cresol, etc. with 1 to 18 carbon atoms
of alcohol. Examples of the ether include ethers having 2 to 20 carbon atoms, such as dimethyl ether, diethyl ether, dibutyl ether, isoamyl ether, anisole, phenethole, diphenyl ether, phenyl allyl ether, and benzofuran. Examples of the ketone include ketones having 3 to 18 carbon atoms, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl phenyl ketone, ethyl phenyl ketone, and diphenyl ketone. Examples of aldehydes include acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, naphthaldehyde, etc. having 2 to 2 carbon atoms.
I can name 15 aldehydes. Organic acids include formic acid, acetic acid, propionic acid,
Butyric acid, valeric acid, pivalic acid, caproic acid, caprylic acid, stearic acid, oxalic acid, malonic acid, succinic acid, adipic acid, methacrylic acid, benzoic acid, toluic acid, anisic acid, oleic acid, linoleic acid,
Examples include organic acids having 1 to 24 carbon atoms such as linolenic acid. Examples of organic acid esters include methyl formate, methyl acetate, ethyl acetate, propyl acetate, octyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl methacrylate, methyl benzoate, ethyl benzoate, propyl benzoate, and benzoic acid. octyl, phenyl benzoate, benzyl benzoate, o
-Ethyl methoxybenzoate, ethyl p-methoxybenzoate, butyl p-ethoxybenzoate, methyl p-toluate, ethyl p-toluate, ethyl p-ethylbenzoate, methyl salicylate, phenyl salicylate, methyl naphthoate, naphthoate Examples include organic acid esters having 2 to 30 carbon atoms such as ethyl acid and ethyl anisate. Examples of the acid halide include acid halides having 2 to 15 carbon atoms, such as acetyl chloride, benzyl chloride, toluyl chloride, and anisyl chloride. Examples of acid amides include acetic acid amide, benzoic acid amide, and toluic acid amide. Examples of the amine include amines such as methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline, and tetramethylenediamine. Examples of the nitrile include nitriles such as acetonitrile, benzonitrile, and trinitrile. Specific examples of polycyclic aromatic compounds include naphthalene, phenanthrene, triphenylene, chrysene, 3,4-benzophenanthrene, 1,2-benzochrysene, picene, anthracene, tetraphene, 1,2,3,4-di benzanthracene,
Pentaphene, 3,4-benzopentaphene, tetracene, 1,2-benzotetracene, hexaphene, hepetaphene, diphenyl, fluorene,
Examples include biphenylene, perylene, coronene, bisanthene, obalene, pyrene, perinaphthene, and halogen-substituted and alkyl-substituted products thereof. The usage ratio of components (1) to (3) in the present invention is as follows:
Component (2) is used in an amount of 0.1 to 300 g, preferably 0.5 to 200 g, per 100 g of (1). In addition, it is most preferable to adjust the amount of the titanium compound as component (3) so that the titanium contained in the catalyst component is within the range of 0.5 to 20% by weight. In order to obtain activity, a range of 1 to 10% by weight is particularly desirable. In addition, when using component (4), the amount used is
Component (4) is present in an amount of 0.01 to 5 mol, preferably 0.05 to 2 mol, per 1 mol of (1). In the present invention, it is also preferable to use the thus obtained solid catalyst component supported on an oxide of a metal of Groups 1 to 10 of the periodic table. The oxides of groups 1 to 2 of the periodic table to be used may be not only oxides of individual metals of groups 1 to 1 of the periodic table, but also compounds of plural of these metals, and, of course, mixtures thereof. Specific examples of these metal oxides include MgO, CaO, ZnO, BaO,
SiO ₂ , SnO ₂ , Al ₂ O ₃ , MgO・Al ₂ O ₃ , SiO ₂・
Al ₂ O ₃ , MgO・SiO ₂ , MgO・CaO・Al ₂ O ₃ ,
Examples include Al ₂ O ₃ ·CaO, and particularly preferred are SiO ₂ , Al ₂ O ₃ , SiO ₂ ·Al ₂ O ₃ , and MgO·Al ₂ O ₃ . The method of supporting a solid catalyst component on an oxide of a metal of Groups 1 to 3 of the periodic table is not particularly limited, but for example, component (1), component (3), if necessary, are supported in an ether compound as a solvent and in the presence of the metal oxide. A method in which component (4) is also added and reacted, the liquid phase is removed by washing, dry-up, etc., and then component (2) is added and reacted with a hydrocarbon such as hexane to obtain a solid catalyst component. can be mentioned as a preferable example. 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) Organic aminium compound of X and _{R 3 Al 2} Examples include triethylaluminum, triisopropylaluminum, triisobutylaluminum, trisec-
butylaluminum, tri-tert-butylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum chloride,
Specific examples include diisopropylaluminum chloride, ethylaluminum sesquichloride, and mixtures thereof. In addition, organic carboxylic acid esters such as ethyl benzoate, o- or p-ethyl toluate, and p-ethyl anisate can also be used in combination with these organometallic compounds. There is no particular limit to the amount of organometallic compound used, but it is usually 0.1 to 0.1 to the amount of titanium 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 it can be particularly preferably used for gas phase polymerization. The polymerization reaction is carried out in the same manner as an ordinary olefin polymerization reaction using a 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 as follows: temperature is 20 to 120°C, preferably 50 to 100°C, and 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-stage or more multi-stage 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, ethylene and propylene, ethylene and 1-butene, ethylene and hexene-1, ethylene and 4-methylpentene-1, ethylene and octene-1, propylene and 1
- It is suitably used for copolymerization of butene, copolymerization of ethylene and two or more other α-olefins, 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 catalyst component Ethanol was added to a 50 c.c. three-necked flask equipped with a stirrer.
200 ml, 20 g of ethoxymagnesium chloride (Mg/Cl molar ratio = 0.81) obtained by treating magnesium diethoxide with HCl, 10 g of triethyl phosphate, and 20 g of tetraethoxysilane were added, and the mixture was reacted for 3 hours under ethanol reflux. . After the reaction is complete, remove the supernatant and add 200 ml of hexane.
Washed 3 times with ml. Then, 200 ml of hexane and 5 ml of titanium tetrachloride were added and reacted for 2 hours under hexane reflux. After the reaction was completed, the supernatant liquid was removed and washed five times with hexane to obtain a solid catalyst component containing 21 mg of titanium per gram. (b) Polymerization A stainless steel autoclave was used as the gas phase polymerization apparatus, a loop was created with a blower, a flow controller, and a dry cyclone, and the temperature of the autoclave was adjusted by flowing hot water through the jacket. The above solid catalyst component [] was fed at a rate of 50 mg/hr and triethylaluminum was fed at a rate of 5 mmol/hr to an autoclave adjusted to 80°C, and the butene-1/ethylene ratio (molar ratio) in the gas phase of the autoclave was set to 0.27. Furthermore, each gas was supplied while adjusting the hydrogen to 15% of the total pressure, and the gases in the system were circulated using a blower to maintain the total pressure.
Polymerization was carried out while maintaining the pressure at 10 kg/cm ² ·G.
The produced ethylene copolymer had a bulk specific gravity of 0.29, a melt index (MI) of 1.1, and a density of 0.9208. The catalyst activity was 238,000 g copolymer/g Ti. After 10 hours of continuous operation, the autoclave was opened and the interior was inspected, but the inner walls and stirrer were clean with no polymer attached at all. _This copolymer has _an FB value (FR
=MI ₁₀ /MI _2.16 ) was 7.3, and the molecular weight distribution was extremely narrow. Furthermore, when a film of this copolymer was extracted in boiling hexane for 10 hours, the amount of hexane extracted was
It was 1.5wt%, and the extractable content was extremely small. Comparative Example 1 A solid catalyst component was synthesized in the same manner as in Example 1 except that tetraethoxysilane was not added. In 1 g of solid catalyst component,
Contains 22mg of titanium. Ethylene and butene-1 were prepared in the same manner as in Example 1 except that the above solid catalyst component was fed at 50 mg/hr.
Continuous gas phase polymerization was carried out. The produced ethylene copolymer had a bulk specific gravity of 0.23, a density of 0.9203, and a melt index of 1.4. Also, the catalyst activity is 1640000
g copolymer/g Ti. Further, the FR value of this copolymer was 8.1, and when the film was extracted in boiling hexane for 10 hours, the amount of hexane extracted was 4.4 wt%. Example 2 Hexane 200 in a 50 c.c. 3-necked flask with a stirrer
ml, 30 g of ethoxymagnesium chloride (Mg/Cl molar ratio = 0.81) obtained by treating magnesium ethoxide with HCl, and 18 g of t-butyl chloride were reacted for 2 hours under hexane reflux, and then 10 g of titanium tetrachloride was added. The mixture was added and reacted for an additional 2 hours. After the reaction is complete, remove the supernatant and add hexane.
Washed three times with 200 ml. Next, 200 ml of hexane and 20 g of tetraethoxysilane were added, and the mixture was reacted for 2 hours under hexane reflux. After the reaction was completed, the supernatant liquid was removed and washed five times with hexane to obtain a solid catalyst component containing 18 mg of titanium per gram. Ethylene and butene
1 continuous gas phase polymerization was carried out. The produced ethylene copolymer had a bulk specific gravity of 0.34, a density of 0.9211, and a melt index of 1.2. Also, the catalytic activity is
The activity was extremely high at 294,000g copolymer/gTi. After 10 hours of continuous operation, the autoclave was opened and the interior was inspected, but the inner walls and stirrer were clean with no polymer attached at all. Furthermore, the FR value of this copolymer was 7.2, and when the film was extracted in boiling hexane for 10 hours, the hexane extraction amount was 1.4 wt%, which was an extremely small amount. Example 3 The stainless steel autoclave equipped with an induction stirrer from 2 was purged with nitrogen, 1000 ml of hexane was added thereto, 1 mmol of triethylene aluminum and 20 mg of the solid powder obtained in Example 1 were added, and the temperature was raised to 90° C. with stirring. At the vapor pressure of hexane, the system is 2
Kg/cm ²・G, but the total pressure of hydrogen is 4.8Kg/cm ²・G
, then add ethylene until the total pressure is 10
The polymerization was carried out for 1 hour by supplying the polymer so as to keep it at kg/cm ² ·G. After the polymerization was completed, the polymer slurry was transferred to a beaker, and hexane was removed under reduced pressure to obtain 175 g of a white polymer having a melt index of 1.2 and a bulk specific gravity of 0.32. Catalytic activity is 80100g polyethylene/gTi, hr.
G ₂ H ₄ pressure, 1680g polyethylene/g solids, hr.C ₂ H ₄
It was hot under pressure. The FR value of the obtained polyethylene was 8.1, the molecular weight distribution was extremely narrow, and the hexane extraction amount was 0.17 wt%. Example 4 A catalyst was synthesized in the same manner as in Example 1, except that 8 ml of monobutoxytrichlorotitanium was used instead of 5 ml of titanium tetrachloride.
A solid catalyst component containing 24 mg of titanium per gram of solid powder was obtained. Continuous gas phase polymerization of ethylene and butene-1 was carried out in the same manner as in Example 1 using the above solid catalyst component. The produced ethylene copolymer has a bulk specific gravity
0.30, density 0.9212, and melt index 1.4. Furthermore, the catalyst activity was extremely high at 209,000 g copolymer/g Ti. After 10 hours of continuous operation, the autoclave was opened and the interior was inspected, but the inner walls and stirrer were clean with no polymer attached at all. Furthermore, the FR value of this copolymer was 7.2, and when the film was extracted in boiling hexane for 10 hours, the hexane extraction amount was 1.4 wt%, which was an extremely small amount. Example 5 In place of 5 ml of titanium tetrachloride in Example 1,
5 ml of titanium tetrachloride and 3 ml of triethoxyvanadyl
Synthesis was carried out in the same manner as in Example 1 except that 21 mg of titanium and 6 ml were used in 1 g of solid powder.
A solid powder containing mg of vanadium was obtained. Continuous gas phase polymerization of ethylene and butene-1 was carried out in the same manner as in Example 1 using the above solid catalyst component.
The produced ethylene copolymer had a bulk specific gravity of 0.31, a density of 0.9213, and a melt index of 1.5. Moreover, the catalyst activity was extremely high at 196,000 g copolymer/g Ti. After 10 hours of continuous operation, the autoclave was opened and the interior was inspected, but the inner walls and stirrer were clean with no polymer attached at all. Furthermore, the FR value of this copolymer was 7.1, and when the film was extracted in boiling hexane for 10 hours, the hexane extraction amount was 1.3 wt%, which was an extremely small amount. Example 6 (a) Production of solid catalyst Ethanol in a 50 c.c. three-necked flask equipped with a stirrer
200 ml, 20 g of ethoxymagnesium chloride (Mg/Cl molar ratio = 0.81) obtained by treating magnesium diethoxide with HCl, 10 g of triethyl phosphate, and 20 g of tetraethoxysilane were added, and the mixture was reacted for 3 hours under ethanol reflux. . After the reaction was completed, the supernatant liquid was removed and dry-up was performed to obtain a white solid substance. Next, 10 g of the above solid substance and 1/2 titanium trichloride were placed in a stainless steel pot with an internal volume of 400 ml containing 25 stainless steel balls each having a diameter of 1/2 inch.
Add 1.3g of aluminum trichloride and under nitrogen atmosphere.
Ball milling was performed at room temperature for 16 hours. 1 g of the solid catalyst component obtained after ball milling contained 28 mg of titanium. Continuous gas phase polymerization of ethylene and butene-1 was carried out in the same manner as in Example 1 using the above solid catalyst component. The produced ethylene copolymer has a bulk specific gravity
0.38, density 0.9200, and melt index 2.0. The catalyst activity was extremely high at 245,000 g copolymer/g Ti. After 10 hours of continuous operation, the autoclave was opened and the interior of the autoclave was inspected. No polymer was attached to the inner wall and the stirrer, and the autoclave was clean. Furthermore, the FR value of this copolymer was 7.5, and when the film was extracted in boiling hexane for 10 hours, the hexane extraction amount was 1.7 wt%, which was an extremely small amount. Example 7 The following gas phase polymerization was carried out using the apparatus described in Example 1. The solid powder (A) obtained in Example 1 was fed into an autoclave prepared at 60°C at a rate of 80 mg/hr and triethylaluminum at a rate of 5 mmol/hr. Propylene was also fed into the autoclave, and the gas in the system was removed using a blower. is circulated to a total pressure of 7Kg/
Polymerization was carried out in cm ² . The polypropylene produced had a bulk specific gravity of 0.35. In addition, the catalyst activity is 81000g
It was polypropylene/gTi. After 10 hours of continuous operation, the autoclave was opened and the interior was inspected, but the inner walls and stirrer were clean with no polymer attached at all.

[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 for polymerizing or copolymerizing olefin using a solid catalyst component and an organoaluminum compound as a catalyst, wherein the solid catalyst component has at least the following three components (1) having the general formula R ¹ _n (OR ² ) _o MgX _2-no (here R ¹ , R ²
represents a hydrocarbon residue having 1 to 24 carbon atoms, and X represents a halogen atom. m, n are 0m2, 0<n
2, 0<m+n2), (2) a compound represented by the general formula [Formula] (where R ³ , R ⁴ , R ⁵ are a hydrocarbon residue having 1 to 24 carbon atoms, an alkoxy group, hydrogen or a halogen and R ⁶ represents a hydrocarbon residue having 1 to 24 carbon atoms. q is 1q
30) and (3) a substance obtained by reacting a halogen-containing titanium compound.