JPS5896607A - Manufacture of polyolefin - Google Patents

Abstract

PURPOSE:To obtain in high poroductivity a high-bulk density polyolefin with uniform granular size, by the use of a catalyst consisting of an organometallic compound and a solid component comprising a reaction product derived from each specific magnesium, another metallic and silane compound and a halogen-contg. 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), (ii) a second compound of formula II (Me is an element found in theI-VII groups of the periodic table; R<3> is 1-24C hydrocarbon; 0<=p<=z) (e.g., sodium ethoxide), (iii) a third compound of formula III (R<4>-R<6> are each 1-24C hydrocarbon, alkoxy, H, etc.; R<7> is 1- 24C hydrocarbon; 1<=q<=30) (e.g., monomethyl triethoxysilane) and (iv) a halogen- contg. titanium compound and (B) an organometallic compound.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing polyolefins using a novel polymerization catalyst.

Traditionally, in the technical field of this cypress,
No. 05 discloses a catalyst in which a transition metal compound such as a titanium compound is supported on magnesium halide.
A catalyst in which magnesium halogenide and titanium tetrachloride are co-pulverized 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 still has a low polymerization activity, while the method described in Belgian Patent No. 742,112 has a low polymerization activity. Although the cost is quite high, improvements are still desired.

In addition, in Doik 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 can be said to be a measure of productivity. No significant increase was observed, and a highly active catalyst 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. 59-12105 has a low bulk specific gravity and an unsatisfactory polymerization activity, and the method described in Belgian Patent No. 7,42,112 has a low polymerization activity. However, there is a drawback that the bulk specific gravity of the produced polymer is low, so improvement in papermaking 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 produced by 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 remaining in the resulting polymer after polymerization is extremely small, so the catalyst removal step can be omitted in the polyolefin production process, simplifying the polymer treatment process and making it possible to produce polyolefins extremely economically as a whole. can.

In the method of the present invention, since the bulk specific gravity of the obtained polymer is large, the amount of polymer produced in the 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 makes it easier to handle the polymer particles in processes such as centrifugation 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, since there is little decrease in olefin absorption rate over time when olefins are polymerized using the catalyst of the present invention, 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 anti-blocking properties.

The catalyst of the present invention provides a novel catalyst system that has many of these features and improves the drawbacks of the prior art described above, and these points can be easily overcome by using the catalyst of the present invention. What we can achieve in the future is something to be admired.

The present invention will be specifically explained below. That is, the present invention provides a method for polymerizing or copolymerizing olefins using a solid catalyst component and an organometallic compound as a catalyst, in which the solid catalyst component has at least the following four components (1) having the general formula R'm(σR'' )nMgX, -1Tl-,
A compound represented by (2) general formula Me (o R”) p x z −p
(3) A compound S represented by the general formula R'+5i-0 R7 and (4) a substance obtained by reacting a halogen-containing titanium compound (in the above formula, R1, R2, R
@.

R1 is a hydrocarbon residue having 1 to 24 carbon atoms, R', R'
, R% represents a hydrocarbon residue having 1 to 24 carbon atoms, an alkoxy group, hydrogen or halogen. X represents a halogen atom. M. indicates the origin of groups f to ■ of the periodic table. However, Sf and TI are excluded.

2 represents the valence of Me. "s"s ps q is 0
Form m≦2.0≦n (2,0(m+n≦2, O(p≦z
, 1≦q≦30).

Rlm (OR”)nMgX l used in the present invention
Examples of the compound represented by -m-n include diethylmagnesium, diisopropylmagnesium, di-n-butylmagnesium, di@eC-butylmagnesium, methylmagnesium chloride, ethylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium iodide, n- Probylmagnesium chloride, n-butylmagnesium chloride, n-butylmagnesium bromide, 5ed-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, 5ee-butylmagnesium ethoxide, decylmagnesium ethoxide, and the like. It can also be used as a complex with trialkylaluminium, such as a complex of di-n-butylmagnesium and triethylaluminum.

'General formula M e (o R'') used in the present invention
Examples of compounds represented by pX, -p include:
NaOR, Mg(ORh, Mg (OR)X, Ca
(OR)z, Zn(OR)*, Zn(OR)\Ca(O
Rh, AI(OR)s, AI(OR)*ycSB(O
R)s, B(OR)! X, Ga(OR)s, Ge(OR
)4.5n(OR)4, P(OR)s, Cr(ORh,
Mn(OR)g, Fe(OR)z, F@(OR)3, c
Various compounds such as o(OR)z, N1(OR), etc. can be mentioned, and more preferable specific examples include Na0
CzHs, Na0CiHs, Mg (0CHs
)*, Mg(OCzHsh, Mg(OCsHI)z,
Ca(OCgHiz, Zn(OCaHs)z, Zn (
OCsHs ) CI, k l (OCHs )s, A
I(OCaHs)m, AI(OCzHs)C'1SA
l (OCsHth, ^1 (QC4kb )s, A
I (0CsHs)s, B(OCtHs)s, B(O
CzHs)zcl.

P (QC!H5)! ,P(0CsHs)s,Fe
Examples include compounds such as (QC4Is).

In the present invention, in particular, the general formula Mg(OR), X, -p
.

Preferred are p compounds represented by AI(OR)Xs- and B(OR)pX3-p. Moreover, as R, an alkyl group having 1 to 4 carbon atoms and a phenyl group are particularly preferable.

4 General formula R'+ S i -0 used in the present invention
)-R? Compounds represented by S include 1. Monomethyltrimethoxysilane, monomethyltriethoxysilane, monomethyltri-n-butoxysilane, monomethyltri5ee-butoxysilane, monomethyltriisopropoxysilane, monomethyltripentoxysilane, monomethyltrioctoxysilane, monomethyltristearoxysilane, monomethyltriphenoxysilane Sisilane, dimethyldimethoxysilane, dimethyljethoxy7rane, dimethyldiisopropoxysilane, dimethyldiphenoxysilane, trimethylmonomethoxysilane, trimethylmonoethoxysilane,
Trimethylmonoisopropoxinerane, trimethylmonophenoxysilane, monomethyldimethoxymonochlorosilane, monomethyljethoxymonochlorosilane, monomethylmonoethoxydichlorosilane, monomethyljethoxymonochlorosilane, monomethyljethoxymonobromocrane, monomethyldiphenoxymonochlorosilane, dimethylmonoethoxy Monochlorosilane, monoethyltrimethoxysilane, monoethyltriethoxysilane, monoethyl isopropoxysilane, monoethyltriphenoxysilane, diethyldimethoxysilane, diethyljethoxysilane, diethyldiphenoxysilane, triethylmonomethoxysilane, triethylmonoethoxy Silane, triethyl monophenoxysilane, monoethyldimethoxymonochlorosilane, monoethyljethoxymonochlorosilane, monoethyldiphenoxymonochlorosilane, monoisopropyltrimethoxysilane, mono-n-butyltrimethoxysilane, mono-n-butyltriethoxysilane, Mono5ee-butyltriethoxysilane, monophenyltriethoxysilane, diphenyljethoxysilane, diphenylmonoethoxymonochlorosilane, monomethoxytrichloro7rane, monoethoxytrichlorosilane, monoinpropoxytrichloro7rane, mono n-butoxytrichlorosilane, Monopentoxytrichlorosilane, monooctoxytrichlorosilane, monostearoxytrichlorosilane, monophenokiditrichlorosilane, monop-methylphenokiditrichlorosilane, dimethoxydichlorosilane, jetoxydichlorosilane, diisopropoxydichlorosilane, dibutoxydichlorosilane , dioctoxydichlorosilane, trimethoxymonochlorosilane, triethoxymonochlorosilane/, triinpropoxymonochlorosilane, tri-n-butoxymonochlorosilane, tri5ec-butoxymonochlorosilane, tetraethoxysilane, tetraisopropoxysilane and the above compounds Examples include chain or cyclic polyB and siloxanes whose repeating positions are +5i-0 and which are obtained by condensation.

Examples of the halogen-containing titanium compound used in the present invention include titanium halides, alkoxyhalogenides, and the like. Preferred titanium compounds are tetravalent ≠tanium compounds and trivalent titanium compounds.
Specifically, the titanium compound having the general formula Ti (O
R) rX4-r (where R represents an alkyl group, aryl group, or aralkyl group having 1 to 24 carbon atoms; Preferred are titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, monomethoxytrichlorotitanium, dimethoxydichlorotitanium, trimethoxymonochlorotitanium, monoethoxy 1-lichlorotitanium, jetoxydichlorotitanium, triethoxymonochlorotitanium, monoisopropoxytrichlorotitanium. , diisopropoxydichlorotitanium,
Examples include triisopropoxymonochlorotitanium, monobutoxytrichlorotitanium, dibutoxydichlorotitanium, monopentoxytrichlorotitanium, monophenoxytrichlorotitanium, diphenoxydichlorotitanium, triphenoxymonochlorotitanium, and the like. 3i1fli
Examples of 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 metals from groups 1 to m of the periodic table. Can be mentioned. In addition, the general formula T i (OR) s
■〈4. ) is added to the organometallic compound of groups ■~■ of the periodic table.
Examples include trivalent titanium compounds obtained by be-forming.

In the present invention, tetravalent titanium compounds are most preferred.

(1) General formula R” m (OR” ) n in the present invention
X 2-m-, e) a compound represented by the general formula Me (
OR''), There are no particular restrictions on the method for obtaining the solid catalyst component of the invention, and the method is not particularly limited.
Under heating at 00°C, preferably 50 to 300°C, usually
A method of reacting by contacting for 5 minutes to 20 hours,
The reaction may be carried out by co-pulverization, or by a suitable combination of these methods. There is no particular restriction on the reaction order of components (1) to (4), and the four components may be reacted at the same time, the three components may be reacted and then one other component may be reacted, or the two components may be reacted. After reacting, the other two components may be reacted, or after reacting the two components, the next one component may be reacted, and then the remaining one component may be reacted.

The inert solvent used at this time is not particularly controlled, 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, photographic 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. Generally the grinding temperature is 0℃~200℃, preferably 20℃
~100°C, and the grinding time is [15 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 in which components (1) to (4) are reacted in a solution, or a substance obtained by reacting components (1) to (3) in a solution and a component (4) are co-pulverized. A method of reacting is particularly preferred.

The usage ratio of component (1) and component (2) is determined by the general formula M e
(OR) If the amount of the compound represented by pXz is too small or, conversely, too large, the polymerization activity tends to decrease, and if the Mg/Ma molar ratio is 1/[L
o 01 ” 1/20, preferably 1/α01~
The range is 1/1, most preferably 1/α05 to 1/α05.
A range of IIL5 is desirable for the production of highly active catalysts.

The usage ratio of component (1) and component (3) is 10% of component (1)
0f, component (5) is in the range of (11-500F, preferably (L5-20Of).

Moreover, it is most preferable to adjust the amount of the halogen-containing titanium compound so that the titanium contained in the solid catalyst component is within the range of 15 to 20% by weight. A range of 1 to 10% by weight is particularly desirable in order to obtain a solid level of activity.

Further, in the present invention, in addition to the above-mentioned components (1) to (4), component (5) is selected from organic halogen compounds, halogenating agents, phosphoric acid esters, electron donors, and polycyclic aromatic compounds. It is also preferably employed to use a compound having one or more layers. The reaction method when using component (5) tl- is not particularly limited, but includes a method of reacting components (1) to (5) in a solution, component (1), ←)
, (3) and (5) in a solution to co-pulverize the substance obtained and component (4).

When using component 1 e (5), the amount used is component (1
) per 1 mole of the component (R) is 101 to 5 moles, preferably 005 to 2 moles.

The organic halogen compound used at this time is a compound in which a portion of a saturated or unsaturated aliphatic hydrocarbon, an aromatic hydrocarbon, etc. is substituted with a halogen, and includes monofill substituted compounds, disubstituted compounds, trisubstituted compounds, and the like. Further, the halogen may be any of fluorine, salt, bromine, and iodine.

Specifically, these organic halogen compounds include methylene chloride, chloro, form, carbon tetrachloride, bromochloromethane, dichlorodifluoromethane, 1-bromo-2-chloroethane, chloroethane, 1,2-sifuromor 1.1
-dichloroethane, 1.1--)chloroethane, 1.2
-dichloroethane, 1,2-dichloro-1,1,2,2
-tetrachloroethane, hexachloroethane, pentachloroethane, 1,1,1.2-tetrachloroethane, 1
．． 1.2.2-tetrachloroethane, 1.1.1-trichloroethane, 41. z-) 9 chloroethane, 1-chloropropane, 2-chloropropane, 1,2-dichloropropane, 1,3-dichloropropane, 2,2-dichloropropane 7.1,1°1, 2.2.43-heptachloropropane , 1.1.2.2. to 5-hexachloropropane, octachloropropane, 1,1.2-)! J Dichloropropane 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 1-7'lopene, 1,3-dichloropropane, chloroprene, oleyl chloride, chlorobenzene, chloronaphthalene, benzyl chloride, benzyritine chloride, chloroethylbenzene, styrene dichloride, a-chlorocumene and the like can be mentioned.

As a halogenating agent, sulfur chloride, PCl5, PCl5
Non-metallic halides such as ゜5il14, POCI
Examples include non-metallic oxyhalides such as COCl, NOCIs, 800 h, and 80 C1.

As electron donors, alcohol, ether, ketone,
aldehydes, organic acids, organic acid esters, acid nolides,
Acid amides, amines, di[lyl, etc.] can be mentioned.

Examples of alcohol include methyl alcohol, ethyl alcohol, n-propyl alcohol, in-propyl alcohol, allyl alcohol, n-butyl alcohol, isobutyl alcohol, 5ee-7'yl alcohol, t-butyl alcohol, n-amyl alcohol, n-hexyl alcohol, cyclohexyl alcohol, Examples include alcohols having 1 to 18 carbon atoms such as tacyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, sulfur alcohol, oleyl alcohol, benzyl alcohol, naphthyl alcohol, phenol, and cresol.

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.

Ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl phenyl ketone, ethyl phenyl ketone, diphenyl ketone, etc. having 3 to 180 carbon atoms.
I can give you ketones.

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

Examples of 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, Examples include organic acids having 1 to 24 carbon atoms, such as anisic acid, oleic acid, linoleic acid, and lylunic 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, ethyl 0-methoxybenzoate, ethyl p-methoxybenzoate, butyl p-ethoxybenzoate, methyl p-)toluate, ethyl p-toluate, p-ethylbenzoic acid Ethyl, methyl salicylate, phenyl salicylate,
Organic acid esters having carbon atoms of 2 to 5 degrees, such as methyl naphthoate, ethyl naphthoate, and ethyl anisate, can be mentioned.

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.

Nitriles include acetonitrile, pen/dinitrile,
Examples include nitriles such as tolnitrile.

represents a hydrocarbon residue having 1 to 24 carbon atoms, each of which may be the same or different), specifically triethyl phosphate, triethyl phosphate (butyl phosphate), 1) phenyl Phosphe-),)IJ
Examples include behenyl phosphate, trioctyl phosphate, tricresyl phosphate, tritolyl phosphate, tricylyl phosphate, diphenylxylenyl phosphate, and the like.

Specific examples of polycyclic aromatic compounds include naphthalene, phenanthrene, triphenylene, chrysene, 4-benzophenanthrene, 1,2-benzochrysene, picene,
An-1-hracene, tetraphene, 1,2,3,4-dibenzanthracene, pentaphene, he4-benzopentaphene, tetracene, 1,2-benzotetracene, hexaphene, hepetaphene, diphenyl, fluorene, biphenylene, perylene, coronene , bisanthene, obalene, pyrene, perinaphthene and the like, as well as norogen-substituted products and alkyl-substituted products thereof.

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 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.
-W group metals Not only oxides of individual metals but also double oxides of these metals may be used, and of course, mixtures thereof may be used. A specific example of these gold 114ell compounds is MgO1Cab.

ZnO, BaO1, BazOl, Si02, 5
nOs, A 1.0. , MgO-^1tOs , S 1
o1AlsOs , MgO・S i(h, MgO・Ca
O"Al2O3, Al201*CaO, etc. can be exemplified, but sometimes S i 02, Al2O3, StO
! 1IA1203, MgO・^lYuki03 are preferable.

The method of supporting a solid catalyst component on an oxide of a metal of Groups ① to ② of the Dark Periodic Table is not particularly limited, but for example, components (1) and (2
), (5), if necessary, component (5) is added and reacted, then the liquid phase is removed by washing, drying, etc., and then component (5) is added together with ashing hydrogen such as hexane.
A preferred example is a method in which a supported solid catalyst component is obtained by adding and reacting 4).

As the organometallic compound used in the present invention, organometallic compounds of Groups 1 to 1 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 R3Al, R*AIX, RAIXz,
R2^10R, RAI (OR)X well R, A I,
X, an organoaluminum compound (the beginning R has 1 to 1 carbon atoms
24 alkyl group, aryl group or aralkyl group, X
represents a halogen atom, and R may be the same or different.
There are organozinc compounds represented by a noalkyl group (which may be the same or different), including triethylaluminum, triisopropylaluminium, triisobutylaluminum, tri1ee-butylaluminum,
Specific examples include tri-tert-butylaluminum, trihexylaluminum, triophnalaluminum, diethylaluminum chloride, diisopropylaluminum chloride, stylaluminium sesquichloride, diethyl sacrificial lead, and mixtures thereof. In addition, along with these organometallic compounds, ethyl benzoate, 0
-Or organic carboxylic acid esters such as ethyl p-toluate and ethyl p-anisate can also be used in combination. The amount of the organic zinc compound to be used is not particularly limited, but it can usually be used in an amount of 11 to 100,100 times the amount of the titanium compound and/or vanadium compound.

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 an inert hydrocarbon, with the #R element, water, etc. being substantially excluded. The polymerization conditions for the olefin include a temperature of 20 to 120°C, preferably 50 to 100°C.
℃, the rolling pressure is normal pressure to 70 degrees/ad, preferably 2
Or bobloi. Molecular weight can be adjusted by polymerization temperature,
This can be controlled to some extent by changing polymerization conditions such as the molar ratio of catalysts, but it can be effectively controlled 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 degree of polymerization 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 a-olefins having 2 to 12 carbon atoms are particularly preferred, such as ethylene, propylene, 1-butene, hexene-1,4-methyl Homopolymerization of a-olefins such as pentene-1 and octene-1, ethylene tofuropyrene, 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 a-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 1 (a) Production of solid catalyst component 20 ml of ethanol was placed in a 5000C three-bottle flask equipped with a stirrer.
〇-, ethoxymagnesium chloride obtained by MCI treatment of magnesium jetoxide (Mg/Cl molar ratio = [LSI) 20t1 aluminum tri1ee-butoxide 1st and tetraethoxysilane 20F were added,
Ethanol reflux reaction was carried out for 2115 hours. After the reaction was completed, the ethanol was dried up, 200d of hexane and 5-titanium tetrachloride were added, and the mixture was heated under hexane reflux for 2 hours.
Allowed time to react. After the reaction was completed, the supernatant liquid was removed, and the obtained solid catalyst component was washed five times with hexane. Solid catalyst component 1 contained 25 capes of electric tan.

(b) Polymerization A stainless steel autoclave was used as the gas phase polymerization apparatus, and the autoclave was looped with a blower 1 flow rate regulator and a dry cyclone.The temperature of the autoclave was regulated by flowing hot water through the jacket.

The above solid catalyst component was fed to an autoclave adjusted to 80° C. at a rate of 504/hr and triethylaluminum at a rate of 5 mmol/hr, and the butene-17 ethylene ratio (mole ratio) in the gas phase of the autoclave was set to 127. Furthermore, each gas was supplied while adjusting the hydrogen to 15% of the total pressure, and the gas in the side system was circulated using a blower to maintain the total pressure of 10 Kg/cd -GK. I did this. The produced ethylene copolymer has a bulk specific gravity [128, melt index (MI) 1.2, density 1α
It was 9203.

The catalyst activity was 254,000f copolymer/fTi.

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 M1 of this copolymer was measured by the method of ASTM-D1258-65T at 190°C and a load of 2.1614, 1. and melt index MI measured under a load of 10 Kf. The value of F, R, expressed as the ratio of (F, R, = MI, , /M111@) is z2,
The molecular weight distribution was extremely narrow.

In addition, a film of this copolymer was prepared in boiling hexane for 10
When extracted for a time, the amount of hexane extracted was 1. S v
was -, and the amount extracted 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. The solid catalyst component 1f contained 21N9 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 described above was fed at 5019/hr. The produced ethylene copolymer had a bulk specific gravity of 125, a density of 0.9215, and a melt index of 1.2. In addition, the catalytic activity is 18400 (l
It was copolymer/fTi.

Further, the F, R, values of this copolymer were &2, and when the film was extracted in boiling hexane for 1θ hour, the amount of hexane extracted was 4.2 Wt.

Example 2 (IL) Production of solid catalyst component A solid catalyst component was synthesized in the same manner as in Example 1 except that boron ethoxide 15f was used instead of aluminum tri-1lee-butoxide 15f. Solid catalyst component 1 contained 2719 titanium.

(b) Polymerization Ethylene and butene-1 were prepared in the same manner as in Example 1 except that the above solid catalyst component was fed at a rate of 5019/hr.
Continuous gas phase polymerization was carried out. The produced ethylene copolymer had a bulk specific gravity of a27, a density of α9195, and a melt index of 1.1. Also, the catalytic activity is 22 o a o
It had an extremely high activity of t:x*combination/fT1.

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 extracted at 1S, and when the film was extracted in boiling hexane for 10 hours, the amount of hexane extracted was t 5 w t 9, which was extremely small. .

Example 3 (1) Production of solid catalyst component In Example 1, substitute 9 for tetraethoxysilane 209
A solid catalyst component was synthesized in the same manner as in Example 1 except that tetraethoxysilane 5-201 was used. Solid catalyst component 1 contained 21 capes of titanium.

(b) Polymerization '4i! except that the above solid catalyst component was fed at 5019/hr! Continuous gas phase polymerization of ethylene and butene-1 was carried out in the same manner as in Example 1. The produced ethylene copolymer has a bulk specific gravity [154 and a density α9200. The melt index was 1.0. Also, catalyst activity i; sS2.
It had extremely high activity as ooor 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.

In addition, the F and R values of this copolymer are '1.2,
The film was extracted in boiling hexane for 10 hours.
The hexane extraction amount was t 3 wt%, and the extraction amount was extremely small.

Example 4 (a) Production of solid catalyst component 72 n-hexa
00d, 20 tons of n-butylmagnesium chloride, 1st of aluminum triethoxide, and 2Of of triethoxymonochlorosilane were added and reacted for 3 hours under hexane reflux. After the reaction was completed, the supernatant was removed and dried up to obtain a white solid substance.

Next, a stainless steel ball with a diameter of h inches is 25
The solid substance tof and 1.2 f of titanium tetrachloride were placed in a stainless steel pot with an internal volume of 400 wt, and ball milling was performed at room temperature under a nitrogen atmosphere for 16 hours. After ball milling, the obtained solid catalyst component 12 contains 2
Contains 719 titanium.

Polymerization Continuous gas phase electrolysis of ethylene and Puden-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 5019/hr. The produced ethylene copolymer has a bulk specific gravity α51 and a density Q of 9205. The melt index was 1.1. Also, the catalytic activity is 248,000
It had an extremely high activity of f copolymer/lTk.

After 10 hours of continuous TFJ rotation, the autoclave was opened,
The interior was inspected and was found to be clean with no polymer attached to the inner walls or the stirrer.

Further, the F, R, values of this copolymer were Z5, and when the film was extracted in boiling hexane for 10 hours, the amount of hexane extracted was 1.4 wt %, which was extremely small.

Example 5 A 2 t stainless steel autoclave equipped with an induction stirrer was replaced with 1 l of nitrogen, 1,000 m of hexane was added, 1 mmol of triethylaluminum and the solid powder 2019 superior in Example 1 was added, and the temperature was raised to 90°C while stirring. did. The vapor pressure of hexane is 2 Kg/cj, G, but the total pressure of hydrogen is 4.8111/aI1. Pump in until the pressure reaches G, then add ethylene to a total pressure of 10 Kf/csi.
, G and polymerization was carried out for 1 hour. After the award, the polymer slurry was transferred to a beaker, the hexane was removed under reduced pressure, and the melt index was 1.3 and the bulk specific gravity was α33.
White polyethylene 1831 was obtained. Catalytic activity is 711
1.40 Of polyethylene/fTi-hr, CaH2
pressure, 1.76Of poly-=r-/f solid, hr-C
The pressure was zL.

Furthermore, the F, R, values of the obtained polyethylene were a2, the molecular weight distribution was extremely narrow, and the hexane extraction amount was α15!
There were very few.

Patent Applicant Nippon Oil Co., Ltd., 4π Fee, Patent Procedural Amendment January 6, 1939, Commissioner of the Japan Patent Office Shima 1) Haru II R 1, Indication of the Case, Showa S6 Patent No. 198685 2, Title of the Invention Polyolefin manufacturing method 3, amendment [relationship with the case] Patent applicant name (444) Nippon Oil Co., Ltd. 6, self-answer of amendment (2) rBG, O, JYt on page 27, line 9 of the specification are deleted.

Claims (1)

[Claims] A method for polymerizing or copolymerizing an olefin using a solid catalyst component and an organometallic compound as a catalyst, in which the solid catalyst component comprises at least the following four components (1) having the general formula R' m (OR") 1 Mg X2
A compound represented by -m-n, (2) a compound represented by the general formula ye (o a'')p xt, -p, 4 (3) a compound represented by the general formula R'-4-, S i -0←R A product obtained by reacting the represented compound sq and (4) a halogen-containing titanium compound* (in the above formula, "%",
"s・it'+jjJ element a 1~24)m hydrogen hydride'
Ats, R' s R', R' t-j carbon number 1~
24 hydrocarbon residues, alkoxy groups, hydrogen or halogens. X represents a halogen atom. Me represents an element in groups 1 to 2 of the synchronous table. However, Si and Ti are excluded. 2 represents the valence of M. "s", P, q are O≦
m≦2, O≦n (2,0< m + n≦2.0(p
≦z, 1≦q≦30).