JPS647605B2 - - 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 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 fairly high polymerization activity. 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 method described in Japanese Patent Publication No. 39-12105 has a low bulk specific gravity and unsatisfactory polymerization activity, while the method described in Belgian Patent No. 742112 has a high polymerization activity but does not produce a polymer. There is a drawback that the bulk specific gravity of the polymer is low, and improvement is 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 treatment process and making polyolefins extremely economical overall. I can do it. 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, it is 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 has the following features: 1 [] At least the following two components (i) General formula R ¹ _n (OR ² ) _o MgX _2-no (where 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)
and (ii) a solid substance obtained by reacting a titanium compound or a titanium compound and a vanadium compound, [] General formula

[Formula] (where R ³ , R ⁴ , R ⁵ represent a hydrocarbon residue having 1 to 24 carbon atoms, an alkoxy group, hydrogen or halogen,
R ⁶ represents a hydrocarbon residue having 1 to 24 carbon atoms.
q is 1≦q≦30) and [] A method for producing a polyolefin, characterized by polymerizing or copolymerizing an olefin using a catalyst system formed by combining an organoaluminum compound, or 2 [ ] At least the following two components (i) General formula R ¹ _n (OR ² ) _o MgX _2-no (where 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)
and (ii) a solid substance obtained by reacting a titanium compound or a titanium compound with a vanadium compound; and [] (iii) general formula

[Formula] (where R ³ , R ⁴ , and R ⁵ represent a hydrocarbon group having 1 to 24 carbon atoms, an alkoxy group, hydrogen, or a halogen, and R ⁶ represents a hydrocarbon group having 1 to 24 carbon atoms. (q is 1≦q≦30) and (iv) an organometallic compound. The present invention relates to a method for producing polyolefin. The compounds represented by R ¹ _n (OR ² ) _o MgX _2-no used in the present invention include diethylmagnesium, diisopropylmagnesium, di-n-butylmagnesium, disec-butylmagnesium, methylmagnesium chloride, ethylmagnesium chloride. , ethylmagnesium bromide, ethylmagnesium iodide, n-propylmagnesium chloride, n-butylmagnesium chloride, n-butylmagnesium bromide, sec-butylmagnesium chloride, phenylmagnesium chloride, decylmagnesium chloride, methoxymagnesium chloride, ethoxymagnesium chloride , isopropoxymagnesium chloride, n-butoxymagnesium chloride, n-octoxymagnesium chloride, methylmagnesium methoxide, ethylmagnesium methoxide, n-butylmagnesium ethoxide, sec-
Butylmagnesium ethoxide, decylmagnesium ethoxide, diethoxymagnesium, diisopropoxymagnesium, di-n-butoxymagnesium, di-sec-butoxymagnesium, di-t
-butoxymagnesium, di-n-octoxymagnesium, and the like. Also, Jin n-
It can also be used as a complex with trialkylaluminium, such as a complex of butylmagnesium and triethylaluminum. 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) _r X _4-r
(Here, 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.) Titanium tetrachloride is preferable. , titanium tetrabromide,
Titanium tetraiodide, monomethoxytrichlorotitanium, dimethoxydichlorotitanium, trimethoxymonochlorotitanium, tetramethoxytitanium, monoethoxytrichlorotitanium, diethoxydichlorotitanium, triethoxymonochlorotitanium, tetraethoxytitanium, monoisopropoxytrichlorotitanium, diiso Propoxydichlorotitanium, triisopropoxymonochlorotitanium, tetraisopropoxytitanium, monobutoxytrichlorotitanium,
Examples include dibutoxydichlorotitanium, monopentoxytrichlorotitanium, monophenoxytrichlorotitanium, 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. Can be mentioned. In addition, the general formula Ti(OR _{) s}
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. As a vanadium compound,
4 such as vanadium tetrachloride, vanadium tetrabromide, vanadium tetraiodide, and tetraethoxyvanadium.
vanadium compounds such as oxyvanadium trichloride, pentavalent vanadium compounds such as ethoxydichlorovanadyl, triethoxyvanadyl, and tributoxyvanadyl, and trivalent vanadium compounds such as vanadium trichloride and vanadium triethoxide. In the present invention, tetravalent titanium compounds are most preferred. 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, (i) general formula R ¹ m (OR ² ) _o
There is no particular restriction on the method of reacting the compound represented by MgX _2-no with (ii) a titanium compound and/or a vanadium compound to obtain the catalyst component of the present invention. A method can be used in which the reaction is carried out by contacting in the presence of the compound under heating at a temperature of 20 to 400° C., preferably 50 to 300° C., usually for 5 minutes to 20 hours, or a method in which the reaction is carried out by co-pulverization. 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,
Various aliphatic saturated hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons such as heptane, octane, benzene, toluene, xylene, and cyclohexane, and alcohols such as ethanol, diethyl ether, tetrahydrofuran, ethyl acetate, and ethyl benzoate; Examples include ethers and esters. 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. The reaction ratio between the compound represented by the general formula R ¹ _n (OR ² ) _o MgX _2-no and the titanium compound or the titanium compound and the vanadium compound is 0.5 to 20% by weight of titanium and vanadium contained in the catalyst component []. It is most preferable to adjust the amount within the range of 1 to 10% by weight in order to obtain a well-balanced activity per titanium and vanadium and activity per solid. In the present invention, (i) general formula R ¹ _n (OR ² ) _o
Compounds represented by MgX _2-no and (ii) titanium compounds In addition to these metal vanadium compounds, other components, namely component α, include organic halogen compounds, halogenating agents, phosphate esters, electron donors, and polycyclic compounds. It is also preferably employed to prepare the catalyst component using one or more compounds selected from aromatic compounds. When using the above component α, the amount used is component (i)
R ¹ _n (OR ² ) _o For 1 mole of MgX _2-no , component α is
The amount is 0.01 to 5 mol, preferably 0.05 to 2 mol. 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, 1,1,1,2-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- Examples include chlorocumene. 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 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 tolnitrile. 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, and specifically include triethyl phosphate, tri-n-butyl phosphate, triphenyl phosphate, tribenzyl phosphate, trioctyl phosphate, Examples include tricresyl phosphate, tritolyl phosphate, tricylyl phosphate, diphenylxylenyl phosphate, and the like. 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. In the present invention, it is also preferable to use the catalyst component [] thus obtained as supported on an oxide of a metal of Groups 1 to 10 of the periodic table. The oxides of Groups 1 to 1 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 double oxides 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 the catalyst component [ ] on the oxide of a metal of group ~ of the periodic table is not particularly limited, but for example, component (i), component (ii), A preferred example is a method in which component α is added if necessary, the reaction is carried out under heating, and then the liquid phase is removed. General formula used in the present invention

Compounds represented by the formula include monomethyltrimethoxysilane, monomethyltriethoxysilane, monomethyltri-n-butoxysilane, monomethyltrisec-butoxysilane, monomethyltriisopropoxysilane, monomethyltripentoxysilane, and monomethyltrioctoxysilane. , monomethyltristearoxysilane, monomethyltriphenoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiisopropoxysilane, dimethyldiphenoxysilane, trimethylmonomethoxysilane, trimethylmonoethoxysilane, trimethylmonoisopropoxysilane, trimethyl Monophenoxysilane, monomethyldimethoxymonochlorosilane,
Monomethyldiethoxymonochlorosilane, monomethylmonoethoxydichlorosilane, monomethyldiethoxymonochlorosilane, monomethyldiethoxymonobromosilane, monomethyldiphenoxymonochlorosilane, dimethylmonoethoxymonochlorosilane, monoethyltrimethoxysilane, monoethyltriethoxysilane, mono Ethyltriisopropoxysilane, monoethyltriphenoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldiphenoxysilane, triethylmonomethoxysilane, triethylmonoethoxysilane, triethylmonophenoxysilane, monoethyldimethoxymonochlorosilane, Monoethyldiethoxymonochlorosilane, monoethyldiphenoxymonochlorosilane, monoisopropyltrimethoxysilane, mono-n-butyltrimethoxysilane, mono-n-butyltriethoxysilane, mono-sec-butyltriethoxysilane, monophenyltriethoxysilane, Diphenyldiethoxysilane, diphenylmonoethoxymonochlorosilane, monomethoxytrichlorosilane, monoethoxytrichlorosilane, monoisopropoxytrichlorosilane, mono n-butoxytrichlorosilane, monopentoxytrichlorosilane, monooctoxytrichlorosilane, monostair Roxytrichlorosilane, monophenoxytrichlorosilane, mono p-methylphenoxytrichlorosilane, dimethoxydichlorosilane, diethoxydichlorosilane, diisopropoxydichlorosilane,
di-n-butoxydichlorosilane, dioctoxydichlorosilane, trimethoxymonochlorosilane,
Repeating units obtained by condensing triethoxymonochlorosilane, triisopropoxymonochlorosilane, tri-n-butoxymonochlorosilane, trisec-butoxymonochlorosilane, tetraethoxysilane, tetraisopropoxysilane and the above compounds are

Chain or cyclic polysiloxanes represented by the formula can be mentioned. In the present invention, the general formula

The amount of the compound represented by [Formula] is usually 0.1 to 1 mole of the titanium compound and/or vanadium compound in the catalyst component []. 100 mol, preferably within the range of 0.3 to 20 mol. 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, As an example,
Triethylaluminum, triisopropylaluminium, triisobutylaluminum, tri-
Specific examples include sec-butylaluminum, tri-tert-butylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum chloride, diisopropylaluminum chloride, ethylaluminum sesquichloride, and mixtures thereof. Additionally, along with these organometallic compounds, ethyl benzoate, o
-Or organic carboxylic acid esters such as ethyl p-toluate and ethyl p-anisate can also be used in combination. There is no particular restriction on 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. In addition, in the present invention, the general formula

The compound represented by the formula may be used by reacting with the organometallic compound described above. The reaction rate at this time is the general formula

The molar ratio of the compound represented by the formula: organometallic compound is in the range of 1:500 to 1:1, more preferably in the range of 1:100 to 1:2. general formula

The amount of the product obtained by reacting the compound represented by [Formula] with the organometallic compound is Si:
The molar ratio of Ti to V is preferably in the range of 0.1:1 to 100:1, more preferably in the range of 0.3:1 to 20:1. 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 Tegler 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 60 kg/cm ² . Molecular weight can be adjusted by polymerization temperature,
Although it can be controlled to some extent by changing polymerization conditions such as the molar ratio of catalysts, it is effectively achieved by adding hydrogen to the polymerization system. of course,
Using the catalyst of the present invention, two-stage or more multi-stage polymerization reactions with different polymerization conditions such as hydrogen concentration and polymerization temperature can be carried out without any problems. 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, 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 Ethoxymagnesium chloride (Mg/Cl molar ratio = 0.81) obtained by adding 200 ml of ethanol to a 500 c.c. three-necked flask equipped with a stirrer and treating magnesium diethoxide with HCl. 20 g of aluminum trisec-butoxide and 15 g of aluminum trisec-butoxide were added thereto, and the mixture was reacted for 3 hours under ethanol reflux. After the reaction was completed, the supernatant was removed and washed with hexane, then 200 ml of hexane and 5 ml of titanium tetrachloride were added, and the mixture was reacted for 2 hours under hexane reflux. After the reaction was completed, the supernatant liquid was removed, and the obtained solid catalyst component was washed three times with hexane. 22 mg of titanium was contained in 1 g of the solid catalyst component. (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, monomethyltriethoxysilane 0.22 mmol/hr, and triethylaluminum at a rate of 5 mmol/hr to an autoclave adjusted to 80°C.
Each gas was supplied while adjusting the 1/ethylene ratio (molar ratio) to 0.27 and hydrogen to 15% of the total pressure, and the gases in the system were circulated using a blower to reduce the total pressure to 10 kg/ Polymerization was carried out while maintaining the temperature at cm ² ·G. The produced ethylene copolymer has a bulk specific gravity of 0.37 and a melt index (MI)
0.9, and the density was 0.9203. The catalyst activity was 314,000 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. The FR of this copolymer is expressed as the ratio of the melt index MI _2.16 measured at 190°C under a load of 2.16 kg and the melt index MI ₁₀ measured under a load of 10 kg using the method of ASTM-D1238-65T.
The value (FR=MI ₁₀ /MI _2.16 ) was 7.4, 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 1.8 wt%, which was an extremely small amount. Comparative Example 1 Example 1 except that 2.5 g of monomethyltriethoxysilane was not added.
Continuous gas phase polymerization of ethylene and butene-1 was carried out in the same manner as above. The produced ethylene copolymer has a bulk specific gravity of 0.31, a density of 0.9208, and a melt index of 1.5.
It was hot. The catalyst activity was 248,000 g copolymer/g Ti. After 10 hours of continuous operation, the autoclave was opened and the interior was inspected, but some polymer was found adhering to the inner walls and the stirrer. The FR value of this copolymer was 8.5, and when the film was extracted in boiling hexane for 10 hours, the amount of hexane extracted was 5.1 wt%. Example 2 (a) Production of solid catalyst component Ethoxymagnesium chloride obtained by treating magnesium diethoxide with HCl (Mg/Cl molar ratio = 1/ 1) 20 g and 10 g of triethyl phosphate were added and reacted for 3 hours under ethanol reflux. After the reaction was completed, the supernatant was removed and washed three times with 200 ml of hexane. Then, 200 ml of hexane and 5 ml of titanium tetrachloride were added, and the mixture was reacted for 2 hours under hexane reflux. After the reaction is complete, remove the supernatant and
After washing with hexane five times, a solid catalyst component containing 23 mg of titanium per gram was obtained. (b) Polymerization Continuous gas phase polymerization of butene-1 from ethylene was carried out in the same manner as in Example 1, except that the above solid catalyst component was fed at a rate of 50 mg/hr. The produced ethylene copolymer has a bulk specific gravity of 0.34, a density of 0.9203,
The melt index was 1.1. The catalyst activity was extremely high at 318,000 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. In addition, the FR value of this copolymer is 7.5,
When the film was extracted in boiling hexane for 10 hours, the amount of hexane extracted was 1.7wt%, which was an extremely small amount. Example 3 (a) Production of solid catalyst component 200 ml of n-hexane and n-butylmagnesium chloride were placed in a 500 c.c. three-necked flask equipped with a stirrer.
20 g of aluminum triethoxide and 15 g of aluminum triethoxide were added thereto and reacted for 3 hours under hexane reflux. After the reaction was completed, the supernatant liquid was removed and the mixture was dried to obtain a white solid substance. Next, 10 g of the above solid substance and titanium tetrachloride 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.
1.2 g was added and ball milling was performed at room temperature under a nitrogen atmosphere for 16 hours. 1 g of the solid catalyst component obtained after ball milling contained 25 mg of titanium. (b) Polymerization Continuous gas phase polymerization of ethylene and butene-1 was carried out in the same manner as in Example 1 except that the above solid catalyst component was fed at a rate of 50 mg/hr. The produced ethylene copolymer has a bulk specific gravity of 0.35, a density of 0.9210,
The melt index was 1.2. Moreover, the catalyst activity was extremely high at 251,000 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. In addition, the FR value of this copolymer is 7.3,
When the film was extracted in boiling hexane for 10 hours, the amount of hexane extracted was 1.3 wt%, which was an extremely small amount. The stainless steel autoclave equipped with an induction stirrer from Example 4 2 was purged with nitrogen and 1000 ml of hexane was added thereto, and 1 mmol of triethylaluminum, 0.05 mmol of tetraethoxysilane and 10 mg of the solid catalyst component obtained in Example 1 were added to the autoclave with stirring. ℃
The temperature rose to . The vapor pressure of hexane is 2Kg/ ^cm2 .
Hydrogen is added until the total pressure is 4.8Kg/cm ²・G, and then ethylene is added until the total pressure is 10Kg/cm ²・G.
The pressure of the autoclave was maintained at 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 85 g of white polyethylene having a melt index of 1.3, a density of 0.9628, and a bulk specific gravity of 0.35. Catalytic activity is 74300
g polyethylene/g Ti・hr・C ₂ H ₄ pressure, 1630 g polyethylene/g solid・hr・C ₂ H ₄ pressure. The FR value of the obtained polyethylene was 7.9, the molecular weight distribution was extremely narrow compared to Comparative Example 2, and the amount of hexane extracted was extremely small at 0.15 wt%. Comparative Example 2 Polymerization was performed for 1 hour in the same manner as in Example 4 except that tetraethoxysilane was not added, and the melt index was 1.5 and the density was
81 g of white polyethylene having a bulk specific gravity of 0.9631 and a bulk specific gravity of 0.31 was obtained. Catalytic activity is 70800g polyethylene/gTi・
hr・C ₂ H ₄ pressure, 1560g polyethylene/g solid・
It was hr・C ₂ H ₄ pressure. The FR value of the obtained polyethylene was 9.3, and the hexane extraction amount was 1.2 wt%. Example 5 A product obtained by feeding the solid catalyst component obtained in Example 1 at a rate of 50 mg/hr and reacting triethylaluminum and monomethyltriethoxysilane at a composition (molar ratio) of 5:0.22 at room temperature for 2 hours. The material was fed at a rate of 5 mmol/hr in terms of aluminum, and ethylene and butene were added in the same manner as in Example 1.
1 continuous gas phase polymerization was carried out. The produced ethylene copolymer had a bulk specific gravity of 0.35, a density of 0.9208, and a melt index of 1.1. The catalyst activity was extremely high at 294,000 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. The FR value of this copolymer was 7.3, and when the film was extracted in boiling hexane for 10 hours, the amount of hexane extracted was 1.7 wt%, which was extremely small. Example 6 A catalyst component 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, and 26 mg of titanium was added to 1 g of solid powder. A solid catalyst component 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
0.39, density 0.9210, and melt index 1.0. Furthermore, the catalyst activity was extremely high at 281,000 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. The FR value of this copolymer was 7.3, and when the film was extracted in boiling hexane for 10 hours, the hexane extraction amount was 1.6 wt%, which was an extremely small amount. Example 7 Synthesis was performed in the same manner as in Example 1, except that 5 ml of titanium tetrachloride and 3 ml of triethoxyvanadyl were used in place of 5 ml of titanium tetrachloride, and 22 mg was added to 1 g of solid powder. A solid powder was obtained containing 50 mg of titanium and 6 mg of vanadium. 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
0.39, density 0.9209, and melt index 1.1. Moreover, the catalyst activity was extremely high at 283,000 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. The FR value of this copolymer was 7.3, and when the film was extracted in boiling hexane for 10 hours, the hexane extraction amount was 1.6 wt%, which was an extremely small amount. Example 8 (a) Production of solid catalyst component Ethoxymagnesium chloride (Mg/Cl molar ratio = 0.81) obtained by adding 200 ml of ethanol to a 500 c.c. three-necked flask equipped with a stirrer and treating magnesium diethoxide with HCl. 20 g of aluminum trisec-butoxide and 15 g of aluminum trisec-butoxide were added thereto, and the mixture was reacted for 3 hours under ethanol reflux. After the reaction is complete,
The supernatant was removed and dry-up to obtain a white solid material. Next, 10 g of the above solid substance and 1.3 g of titanium trichloride and 1/3 aluminum chloride were placed in a stainless steel pot with an internal volume of 400 ml containing 25 stainless steel balls with a diameter of 1/2 inch, and the mixture was heated at room temperature under a nitrogen atmosphere. Ball milling took place for 16 hours. Solid catalyst component 1 obtained after ball milling
g contained 26 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 had a bulk specific gravity of 0.39, a density of 0.9208, and a melt index of 1.1. In addition, the catalyst activity is 320000g copolymer/
It had extremely high activity as 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. In addition, the FR value of this copolymer is 7.5,
When the film was extracted in boiling hexane for 10 hours, the amount of hexane extracted was 1.9 wt%, which was an extremely small amount. Example 9 The following gas phase polymerization was carried out using the apparatus described in the example. Example 1 was placed in an autoclave adjusted to 60℃.
The solid powder (A) obtained above was supplied at a rate of 80 mg/hr and triethylaluminum at a rate of 5 mmol/hr. Propylene was also supplied into the autoclave, and the gas in the system was circulated using a blower to maintain a total pressure of 7 kg/hr.
Polymerization was carried out in cm ² . The polypropylene produced had a bulk specific gravity of 0.42. In addition, the catalyst activity is 108000g
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)

[Claims] 1 [] At least the following two components (i) General formula R ¹ m (OR ² ) _o MgX _2-no (where 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) and (ii) a solid substance obtained by reacting a titanium compound or a titanium compound and a vanadium compound [] General formula (Here, 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 A method for producing a polyolefin, which comprises polymerizing or copolymerizing an olefin using a catalyst system comprising a combination of a compound represented by 1≦q≦30 and an organoaluminum compound. 2 [] At least the following two components (i) General formula R ¹ m (OR ² ) _o MgX _2-no (where 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); (ii) a solid substance obtained by reacting a titanium compound or a titanium compound with a vanadium compound; and [] (iii) a general formula (Here, 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 (iv) an organoaluminum compound. Production method.