JPS5896609A - Manufacture of polyolefin - Google Patents

Abstract

PURPOSE:To obtain in high productivity a high-bulk density polyolefin with uniform granular size, without any catalyst-eliminating process, by the use of a catalyst consisting of a specific silane compound, an organometallic compound and a solid component comprising a reaction product derived from a specific magnesium compound and a titanium compound. CONSTITUTION:An olefin is (co)polymerized by the use of a catalyst consisting of (A) a solid component comprising a reaction product derived from (i) a compound of formulaI(R<1> and R<2> are each 1-24C hydrocarbon; X is halogen; 0<= m<=2; 0<=n<=2; 0<m+n<=2) (e.g., diethylmagnesium) and (ii) a titanium and/or vanadium compound(s) (e.g., titanium tetrachloride), (B) a third compound of formula II (R<3>-R<5> are each 1-24C hydrocarbon, alkoxy, H, etc.; R<6> is 1-24C hydrocarbon; 1<=q<=30) (e.g., monomethyl trimethoxy silane) and (C) an organometallic compound.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing polyolefins 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. 05, and a catalyst in which magnesium halide and titanium tetrachloride are co-pulverized is known from Belgian Patent No. 742,112. It is being

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 still has a low polymerization activity, while the method described in Belgian Patent No. 742,112 has a low polymerization activity. Although it has become quite high, improvements are still desired.

In addition, in German Patent No. 2157872, the amount of magnesium halide used is substantially reduced by co-pulverizing magnesium halide, titanium tetrachloride base, alumina, etc., but the amount of magnesium halide used is substantially reduced. No significant increase in the activity of tl 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. 39-1210'5 has a low bulk specific gravity and unsatisfactory polymerization activity, and the method of Belgian Patent No. 742,112 has a low polymerization activity. However, there is a drawback that the bulk specific gravity of the produced polymer is low, and improvements are desired.

The present invention aims to improve the above-mentioned drawbacks, to provide a novel polymerization catalyst that can obtain polymers with high polymerization activity and high bulk specific gravity in high yields, and that allows continuous polymerization to be carried out extremely easily. It 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 it is possible to improve productivity. Since the amount of catalyst residue in the produced polymer is extremely small, the catalyst removal step can be omitted in the polyolefin production process, simplifying the polymer treatment process and making it possible to produce polyolefins very economically as a whole.

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 This facilitates the handling of polymer particles in processes such as centrifugal separation and powder transportation.

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 in addition, 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 effect on economy and productivity is also large.

In addition, when olefin polymerization is carried out using the catalyst of the present invention, it is also advantageous that the olefin absorption rate decreases little with time, so 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 formation 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 % fines and improves the drawbacks of the prior art described above. It is a new catalyst system that
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 t(1) at least the following two components (1) general formula R-(OR'')nMgX, ---n (where R1, R1 is a hydrocarbon residue having 1 to 24 carbon atoms, X is)
・Indicates a rogen atom. m, n are 0, m≦2.0≦n
≦2.0 (m+n≦2) and (11) a solid substance obtained by reacting a titanium compound and/or a vanadium compound, 3 R is a hydrocarbon residue having 1 to 24 carbon atoms, alkoxy group,
Indicates hydrogen or nitrogen L/% R4 has 1 to 2 carbon atoms
The hydrocarbon residue of No. 4 is shown. A method for producing a polyolefin, characterized by polymerizing or copolymerizing an olefin using a catalyst system consisting of a compound represented by (q is 1≦q≦30) and a CHD organic gold compound, or λ [■] At least the following two components (i) General formula R-(oR”)nMgX, -m-n
(Here, 81, R2 is a hydrocarbon residue having 1 to 24 carbon atoms,
X represents a )・rogen atom. mX n is 0 m≦2.0
≦n≦2.0 (m-1-n≦2) and (11) a solid substance obtained by reacting a titanium compound and/or a vanadium compound, and a 1g is a compound having 1 to 24 carbon atoms. Hydrocarbon residue, alkoxy group,
It represents hydrogen or nitrogen, and number 8 represents a hydrocarbon group having 1 to 24 carbon atoms. It is characterized in that olefins are polymerized or copolymerized using a catalyst system consisting of a combination of a compound represented by n (where q is 1≦q≦30) and a product obtained by reacting a 0φ organometallic compound. The present invention relates to a method for producing a polyolefin.

nBg(OBm)nMgX2-m-n used in the present invention
Compounds represented by include diethylmagnesium, diisopropylmagnesium, dibutylmagnesium, di5ee-butylmagnesium, methylmagnesium chloride, ethylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium iodide, n-probylmagnesium chloride, n- Butylmagnesium chloride, n-butylmagnesium bromide,
1le-butylmagnesium chloride, phenylmagnesium chloride, decylmagnesium chloride, methoxymagnesium chloride, ethoxymacnesium chloride, iso-1oboxymagnesium chloride, n-butoxymagnesium chloride, n-octoxymagnesium chloride, methylmagnesium methoxide, ethyl Magnesium methoxide, n-butylmagnesium ethoxide, 1ee-butylmagnesium ethoxide, decylmagnesium ethoxide, jetoxymagnesium,
Examples include diisopropoxymagnesium, di-n-butoxymagnesium, di-ec-butoxymagnesium, di-t-butoxymagnesium, di-n-octoxymagnesium, and the like. It can also be used as a complex with trialkylaluminium, such as a complex with di-n-butylmagnesium triethylaluminum.

Examples of the titanium compound and/or vanadium compound used in the present invention include titanium and/or vanadium halides, alkoxy halides, alkoxides, halogenated solutions, and the like. Preferred titanium compounds are tetravalent titanium compounds and trivalent titanium compounds, and specific examples of tetravalent titanium compounds include the general formula TI(OR)rX4- (where R is 1 to 24 carbon atoms). LAX represents an alkyl group, an aralkyl group, or an aralkyl group, and LAX represents a rogen atom. r is preferably represented by 0) where 0≦r≦4, titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, monomethoxytrichlorotitanium, dimethoxydichlorotitanium, trimethoxymonochlorotitanium, tetramethoxytitanium, Monoethoxytrichlorotitanium, jetoxydichlorotitanium, triethoxymonochlorotitanium, tetraethoxytitanium, monoiso10poxytrichlorotitanium, diiso10poxydichlorotitanium, triisoproboxymonochlorotitanium, tetraisoproboxytitanium, monobutoxytrichlorotitanium, di Examples include butoxydichlorotitanium, monopentoxytrichlorotitanium, monophenoxytrichlorotitanium, diphenoxydichlorotitanium, triphenoxymonochlorotitanium, tetraphenoxytitanium, and the like. As trivalent titanium compounds, titanium tetrahalides such as titanium tetrachloride and titanium tetrabromide can be combined with hydrogen, aluminum,
Examples include titanium trihalide obtained by reduction with titanium or an organometallic compound of a metal of groups 1 to 2 of the periodic table.

In addition, the general formula TI (OR), Examples of the vanadium compound include vanadium compounds such as vanadium tetrachloride, Tetravalent vanadium compounds such as vanadium tetrabromide, vanadium tetraiodide, tetraethoxyvanadium, vanadium oxytrichloride, ethoxydichlorvanadyl, triethoxyvanadyl,
pentavalent vanadium compounds such as tributoxyvanadyl,
3 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, titanium compounds and vanadium compounds are often used in combination.

The V/Ti molar ratio at this time is preferably in the range of 2/1 to αo1/1.

In the present invention, (i) general formula R'fn (OR")
A compound represented by HMg X2- m -n and (i
i) The method for obtaining the catalyst component (1) of the present invention by reacting with a titanium compound and/or a vanadium compound is not limited to the percentage, and the method may be mixed at 20 to 400°C in the presence or absence of an inert solvent. , a method of reacting by contacting the components under heating, preferably 50 to 300° C., usually for 5 minutes to 20 hours, or a method of reacting by co-pulverization treatment can be used.

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-grinding is not particularly limited, but ball mills, vibration mills, rod mills, swing mills, etc. are usually used, and those skilled in the art can easily determine the conditions such as grinding gAt and grinding time depending on the grinding method. It is something that

Generally, the grinding temperature is 0°C to 200°C, preferably 20°C.
C to 100 C, and the grinding time is α5 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 of the compound represented by the general formula R-(OR)nMgX, -, -1 with the titanium compound and/or vanadium compound is 0.5% of the titanium and/or vanadium contained in the catalyst component [I]. It is most preferable to adjust the amount to be within the range of ~20% by weight, and particularly preferably from 1 to 10% by weight in order to obtain a well-balanced activity per titanium and/or vanadium and activity per solid.

In the present invention, (i) general formula Rt, (□H2)nM
g It is also preferably employed to prepare catalyst component CI) using one or more compounds selected from aromatic compounds and polycyclic aromatic compounds.

When using the component (ii), the amount used is the component (i)
)R%, (OR'')nMgX, -, n With respect to 1 mole, the component (-) is
It is 2 moles.

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, tetracarbohydrate, bromochloromethane, dichlorodifluoromethane, 1-bromo-2-chloroethane, chloroethane, 1,2-dibromo-1,1 -dichloroethane, 1.1-dichloroethane, 1.2-dichloroethane, 'L2-dichloroethane, 1.2.2-tetrafluoroethane, hexachloroethane, pentachloroethane, 1. tl, 2-tetrachloroethane, 1,1
．． λ2-Tetrachloroethane, 1,1.1-)chloroethane, 1,1.2-4+7chloroethane, 1-chloropropane, 2-chlorogloba/, 1.2-dichloropropane, 1.3-dichloropropane, 2.2 -dichloropropane, 1,1°1, 2.2. Heptachloroproban, 1.1.2, 2. to 3-hexachloro 10 pans,
Octachloropropane, tl, 2-1 chloro10pan,
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, tetrachloroethylene, 3-chloro-1-10 Pen, 1,3-dichloropropane, chloroprene, oleyl chloride, chlorobenzene, chloronaphthalene, benzyl chloride, benzylizo/chloride, chloroethylbenzene, styrene dichloride, a
-Chlorocumene and the like can be mentioned.

As a halogenating agent, sulfur chloride, Pet, Pets
.

Non-metallic halides such as Si C14, POCIs
, C0C1t, N0CI Tomi, 5OC1! ,SO 鵞σi
Examples include nonmetallic oxyhalides such as.

As electron donors, alcohol, ether, ketone,
Examples include aldehydes, organic acids, organic acid esters, acid halides, acid amides, amines, and nitriles.

Alcohol toshiteha, methyl alcohol, ethyl alcohol, n-7' propyl alcohol, isopropyl alcohol, allyl alcohol, n-butyl alcohol, imbutyl alcohol, 5ee-butyl alcohol, t-7
Chyl alcohol, n-amyl alcohol, n-hexyl alcohol, cyclohexyl alcohol, allyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, benzyl alcohol, naphthyl alcohol, phenol, cresol, etc. having 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 ketones include ketones having 5 to 18 carbon atoms, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl phenyl ketone, ethylphenyl ketone, and diphenyl ketone.

Examples of the aldehyde include aldehydes having 2 to 15 carbon atoms, such as acetaldehyde, probionaldehyde, octylaldehyde, benzaldehyde, and nathaldehyde.

Examples of organic acids include formic acid, acetic acid, probionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, glycolic acid, stearic acid, oxalic acid, malonic acid, succinic acid, adipic acid, methacrylic acid, benzoic acid, and toluic acid. , anisic acid, oleic acid, linoleic acid, linolic acid, and other organic acids having 1 to 24 carbon atoms.

Examples of organic acid esters include methyl formate, methyl acetate, ethyl acetate, propyl acetate, octyl acetate, ethyl 10pionate, methyl butyrate, ethyl valerate, methyl methacrylate, methyl benzoate, ethyl benzoate, filobil benzoate, and benzoate. octyl acid, phenyl benzoate, benzyl benzoate, ethyl O-methoxybenzoate, ethyl p-methoxybenzoate, butyl p-ethoxybenzoate, p-)
Examples include organic acid esters with carbon atoms of 2 to 3°, such as methyl rulyate, ethyl p-)ruylate, ethyl p-ethylbenzoate, methyl salicylate, phenyl salicylate, methyl naphthoate, ethyl naphthoate, and ethyl anisate. .

Examples of the acid halide include acid halides having 2 to 15 carbon atoms, such as acetyl chloride, benzyl chloride, tolyl chloride, anisyl chloride, and the like.

Acid amides include acetic acid amide, benzoic acid amide, toluic acid amide, etc.

Examples of the amine include amines such as methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline, and tetramethylenediamine.

Nitriles include acetonitrile, benzonitrile,
Examples include nitriles such as tolnitrile.

R represents a hydrocarbon residue having 1 to 24 carbon atoms, each of which may be the same or different), specifically triethyl phosphate, tri-n-butyl phosphate, triphenyl phosphate, tri-n-butyl phosphate, Examples include benzyl phosphate, trioctyl phosphate, tricresyl phosphate, tritolyl phosphate, tricylyl phosphate, diphenylxylenyl phosphate, and the like.

Specific examples of polynomial aromatic compounds include naphthalene, phenanthrene, triphenylene, chrysene, he4-benzo7enanthrene, 1,2-benzochrysene, bicene,
Anthracene, tetraphene, 1,2,44-dibenzanthracene, pentaphene, 3V4-benzopentaphene, tetracene, 1,2-benzotetracene, hexaphene, hepetafene, diphenyl, fluorene, biphenylene, perylene, coronene, bisanthene, obalene, Examples include pyrene, berinaphthene, and halogen-substituted and alkyl-substituted products thereof.

In the present invention, it is also preferable to use the catalyst component (1) thus obtained as supported on an oxide of a metal of Groups 1 to 2 of the periodic table.

The oxides of Groups ■ to ■ of the periodic table to be used are those of Groups ■ to ■ of the periodic table.
~■ Not only oxides of group metals alone but also 11 of these metals
It may be an oxide or, of course, a mixture thereof. Specific examples of these gold lA oxides include M
g0XCab.

ZnO1Ba02, Bag 03, Sin, 5n03
, Alx Os, Mg0eAl Snow 03, Sin, ・At
,O,,MgO*SiO,,MgO-CaO*Al 0
3, A1103-CaO, etc., but especially 5i01, AI! 03, stow-A1. o.

MgOsd-03 is preferred.

The method of supporting the catalyst component (1) on the oxide of metal of Groups 1 to 1 of the periodic table is not particularly limited, but for example, the method of supporting the catalyst component (1) on the oxide of the metal of Groups 1 to 1 of the periodic table is supported, but for example, the catalyst component (1) may be supported in the presence of the metal oxide using an ether compound as a solvent.
, component (-) If necessary, add component (i), react under heating, and then remove the liquid phase. O 3 General formula used in the present invention R' 4 S i
Examples of the compound represented by -OX R'4 include monomethyltrimethoxysilane, monomethyltriethoxysilane, monomethyltributoxysilane, monomethyltri5tee-butoxysilane, monomethyltriiso10poxysilane, monomethyltriindoxysilane, and monomethyltrioctoxysilane. Xysilane, monomethyltristearoxysilane, monomethyltriphenoxysilane, dimethyldimethoxysilane, dimethyljethoxysilane, dimethyldiisoproboxysilane, dimethyldiphenoxysilane, trimethylmonomethoxysilane, trimethylmonoethoxysilane, trimethylmonoiso10boxysilane , trimethylmonophenoxysilane, monomethyldimethoxymonochlorosilane/, monomethyljethoxymonochlorosilane, monomethylmonoethoxydichlorosilane, monomethyljethoxymonochlorosilane, monomethyljethoxymonobromosilane, monomethyldiphenoxymonochlorosilane, dimethylmonoethoxymonochlorosilane, mono Ethyltrimethoxysilane, monoethyltriethoxysilane, monoethyltriisoproboxysilane, monoethyltriphenoxysilane, diethyldimethoxysilane, diethyljethoxysilane, diethyldiphenoxysilane, triethylmonomethoxysilane, triethylmonoethoxysilane, Triethylmonophenoxysilane, monoethyldimethoxymonochlorosilane, monoethyljethoxymonochlorosilane, monoethyldiphenoxymonochlorosilane,
Mono-impropyltrimethoxysilane, mono-n-butyltrimethoxysilane, mono-n-butyltriethoxysilane, mono-butyltriethoxysilane, monophenyltriethoxysilane, diphenyljethoxysilane, diphenylmonoethoxymonochlorosilane, mono- Methoxytrichlorosilane, monoethoxytrichlorosilane, monoiso 10-Φ citrichlorosilane, mono n-butoxytrichlorosilane, monopentoxytrichlorosilane, monooctoxytrichlorosilane, monostearoxytrichlorosilane, monophenoxytrichlorosilane, mono p-methyl Phenoxytrichlorosilane, dimethoxydichlorosilane, jetoxydichlorosilane, diimpropoxydichlorosilane, moro-butoxydichlorosilane, dioctoxydichlorosilane, trimethoxymonochlorosilane, triethoxymonochlorosilane, triisoproboxymonochlorosilane, tri-n-butoxy Monochlorosilane, triH1e-butoxymonochlorosilane, tetraethoxysilane, tetraisoproboxysilane and repeating R polysiloxanes obtained by condensation of the above compounds can be mentioned.

If the amount of the compound used is too large or too small, no effect can be expected.
It is within the range of 11 to 100 moles, preferably α3 to 20 moles.

As the organometallic compound used in the present invention, organometallic compounds belonging to groups 1 to 2 of the periodic table, which are known as components of Ziegler's catalyst, can be used, but organoaluminum compounds and organozinc compounds are particularly preferred. Specific examples include the general formula Rs Al, Rz AI X, RAI,
R4A1OR%RA1 (OR)X and R,A1.
x, an organoaluminum compound (where R has 1 to 1 carbon atoms)
20 alkyl or aryl groups, X represents a halogen atom, μR may be the same or different) or the general formula RIZn (however, R is an alkyl group having 1 to 20 carbon atoms, and the two are the same or different) There are organozinc compounds represented by triethylaluminum, triisobutylaluminum, triisobutylaluminum,
bird! 1ee-butylaluminum, tri-tert-butylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum chloride,
Specific examples include diimpropylaluminum chloride, ethylaluminum sesquichloride, diethylzinc, and mixtures thereof. - An organic carboxylic acid ester such as ethyl anisate can also be used in combination. There is no particular limit to the amount of organometallic compound used. Normally α1 to 1001 for the titanium compound and/or vanadium compound.
It can be used 000 times.

The compound represented by 3 is reacted with the organometallic compound described above, so that the compound represented by 3:organometallic compound (molar ratio) is 1
:500 to 1:1, more preferably 1:
The ratio is in the range of 100 to 1:2.

3 The amount of the product obtained by reacting the metal compound is such that the Si:Ti and/or V (molar ratio) is 11:1 to 100 with respect to the titanium compound and/or vanadium compound in the catalyst component (1). : The range of 1 is preferable, α3
The range of :1 to 20:1 is more preferable.

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. In other words, all reactions involve substantially oxygen,
It is carried out in the absence or presence of an inert hydrocarbon in the absence of water or the like. Olefin polymerization conditions Fi hot water temperature 20 to 120°C, preferably 50 to 100°C
℃, and the pressure is normal pressure to 70 Kg/-, preferably 2 to 60 Kg/-. Although the molecular weight can be controlled 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 hindrance.

The method of the present invention is applicable to the polymerization of all olefins that can be polymerized with Ziegler's catalyst, and direct 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,
Suitable for copolymerization of ethylene and hexene-1, ethylene and 4-methylpentene-1, ethylene and octene-1, propylene and 1-butene, and copolymerization of ethylene and two or more other α-olefins. be done.

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 t (a) Production of solid catalyst component 20 ml of ethanol in a 500 cc three flask equipped with a stirrer
〇-, Ethoxymagnesium chloride obtained by HCI treatment of magnesium jetoxide (Mg/Cl molar ratio = α81) 2(1,) Add ethyl phosphate 1 (l) and tetraethoxysilane 209, and ethanol reflux. The reaction was continued for 3 hours. After the reaction was completed, the supernatant was removed and washed 3 times with 200ml of hexane. Then, 200ml of hexane and 5ml of titanium tetrachloride were added, and the reaction was performed for 2 hours under hexane reflux. The reaction was completed. Afterwards, the supernatant was removed, washed 5 times with hexane, and washed with 21
A solid catalyst component containing 19 titanium was obtained.

(b) Polymerization A stainless steel autoclave was used as the gas phase polymerization apparatus, a loop was created with a blower-1 flow controller and a dry cyclone, and the temperature of the autoclave was adjusted by flowing water through the jacket.

The above solid catalyst component C was placed in an autoclave adjusted to 80°C.
I) is supplied at a rate of 5019/hr and triethylaluminum is supplied at a rate of 5 mmol/hr.
In step 27, each gas was supplied while adjusting hydrogen to 15% of the total pressure, and the gases in the system were circulated using a blower to maintain the total pressure at 1aKg/cd-G for polymerization. I did this. The produced ethylene copolymer had a bulk specific gravity α29, a melt index (MI) 1.1, and a density α9208.

Further, the catalyst activity was 258,00Of copolymer/fTl.

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 melt index M I of this copolymer was measured by the method of ASTM-01258-65T at 190°C and a load of 2.16111. 1. ．． F expressed as the ratio of the melt index M11o measured at a load of 10~,
R, value (F, R, = MIl.

/MIus) was 7.3, and the molecular weight distribution was extremely narrow.

In addition, a film of this copolymer was prepared in boiling hexane for 10
When time-extracted, the amount of hexane extracted was 1.5 vt.
%, and the number of extraction valves was extremely small.0 Comparative Example 1 A solid catalyst component was synthesized in the same manner as in Example 1, except that tetraethoxysilane was not added. Solid catalyst component 1f contained 221q of titanium.

Continuous gas phase polymerization of ethylene and butene-1 was carried out in the same manner as in Example 1 except that the solid catalyst component was fed at 5019/hT. The produced ethylene copolymer has a bulk specific gravity of 0.23, a density of α9203, and a melt index of 1.
．． It was 4. The catalyst activity was 164,000 copolymer/fTi.

Further, the F, R, values of this copolymer were al, and when the film was extracted in boiling hexane for 10 hours, the amount of hexane extracted was 44vt.

Example 2 Ethoxymagnesium chloride (Mg/Cl molar ratio = α
81) 50F and t-butyl chloride 18F were added and reacted for 2 hours under hexane reflux, then titanium tetrachloride 10F was added and reacted for an additional 2 hours. After the reaction is complete,
The supernatant was removed and washed three times with 200-hexane. Next, 200 m of hexane and 20 f of tetraethoxysilane were added, and the mixture was reacted for 2 hours under hexane reflux. After the reaction, the supernatant liquid was removed and washed five times with lehexane. A solid catalyst component containing 18'Mg of titanium in LA If was obtained. Same as Example 1 except that the above solid catalyst component was fed at 50ap/hr. The operation involved continuous gas phase polymerization of ethylene and butene-1. The produced ethylene copolymer had a bulk specific gravity of α54, '13 and α9211, and a melt index of 1.2. Further, the catalyst activity was extremely high at 294,0009 copolymer/7Ti.

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 F, R, values of this copolymer were z2, and when extracted in film la boiling hexane for 10 hours, the hexane extraction amount was 1.4 wt%, which was extremely small. .

Example 2 n-hexane in 3 500cc flasks with stirrers
00ss/, n-butylmagnesium chloride 2 Of
Then, 7.59 g of ethyl benzoate and 20 g of triethoxymonochlorosilane were added and reacted for 3 hours under hexane reflux.

After the reaction was completed, the supernatant was removed and dried to obtain a white solid substance.

10 f of the above solid substance and 71.2 f of titanium tetrachloride were placed in a stainless steel pot with an internal volume of 400 mm containing 25 stainless steel balls having a diameter of 1/2 inch, and the mixture was heated at room temperature under a nitrogen atmosphere for 16 hours. Ball milling was performed. One ton of solid catalyst component obtained after ball milling contained 27 m9 of titanium.

Continuous gas phase polymerization of ethylene and butene-1 was carried out in the same manner as in Example 1 except that the solid catalyst component was fed at a rate of 5019/hr. The produced ethylene copolymer has a bulk specific gravity α36, a discharge α9198, and a melt index α9.
Met. Furthermore, the catalyst had an extremely high activity of Fi239,0009 copolymer/fTi.

After 10 hours of continuous operation, the autoclave was opened and the interior was inspected, but the interior walls and stirrer were clean and free of any polymer sticks.

1. The F, R, value of this copolymer is 7.4, and when the film was extracted in boiling hexane for 10 hours, the amount of hexane extracted was 1.6 vt, which was an extremely small amount. Ta.

Example 4 A 2-ton stainless steel autoclave equipped with an induction stirrer was vented with nitrogen, and 1. OOO- was added, 1 mmol of triethylaluminum and 20 μm of the solid powder obtained in Example 1 were added, and the temperature was raised to 90° C. with stirring. The system becomes 2iQ/cd-G with the vapor pressure of hexa/, but hydrogen is charged until the total pressure becomes 4.8 g/d-G, and then ethylene is added until the total pressure is l Q Kf/ed-G K is maintained. Polymerization was carried out for 1 hour. After polymerization, transfer the polymer slurry to a beaker and remove hexane under reduced pressure.
A white polymer 175f with a melt index of 1.2 and a bulk specific gravity of [L52] was obtained. Catalyst activity is 8 (1,10Of polyethylene/t Ti, hr, C1Hn pressure, 1.68
0 f polyethylene/solid, hr, CtL pressure.

Furthermore, the F, R, values of the obtained polyethylene are &1, the molecular weight distribution is extremely narrow, and the hexane extraction amount is α17.
It was wtjG.

Patent Applicant Nippon Oil Co., Ltd., x+'-', Agent Patent Attorney Ryoji Kawase 2゛1 Procedural Amendment January 6, 1980 Commissioner of the Patent Office Shima 1) Hibiki Judono 1, Indication of Case 1982 Patent Application No. 193687 2, Name of the invention Process for producing polyolefin 3, Relationship with the case of the person making the amendment t Name of the patent applicant (444) Nippon Oil Co., Ltd. 6, Contents of the amendment (1) Mei Mill (hereinafter the same) page 15 Correct with 8-line orm and Jt-rail.

(2) Page 17, lines 10 and 13; Page 18, line 1: Correct the "component (lit) J t r component ← month" on page 26, line 7.

Claims (1)

[Claims] t C1) At least the following two components (:) General formula R-(OR”)nMgXx-m-n(
Here, paper R represents a hydrocarbon residue having 1 to 24 carbon atoms, and X represents a halogen atom. m, n are 0, m≦2.0≦n≦
2.0 (m 10m≦2) and (11) a solid substance obtained by reacting a titanium compound and/or a vanadium compound, 3 a hydrocarbon residue having 1 to 24 carbon atoms, Represents an alkoxy group, hydrogen or halogen. L% R' represents a hydrocarbon residue having 1 to 24 carbon atoms. A method for producing a polyethylene resin, which comprises polymerizing or copolymerizing an olefin using a catalyst system comprising a combination of a compound represented by the formula (q is 1≦q≦30) and an organic metal compound. 2, CI) At least the following two components (i) General formula a4(ou3)IIMgX, -m-n
(Here, R1 and R town are hydrocarbon residues having 1 to 24 carbon atoms,
≦n≦2, o<m+n≦2) and (i) a solid substance obtained by reacting a titanium compound and/or a vanadium compound, and 1? R11 represents a hydrocarbon residue having 1 to 24 carbon atoms, an alkoxy group, hydrogen or a halogen, and R- represents a hydrocarbon residue having 1 to 24 carbon atoms. q is 1≦q≦30) and (iv) a product obtained by reacting an organometallic compound.
Alternatively, a method for producing a polyolefin characterized by copolymerization.