JPS5958009A - Preparation of polyolefin - Google Patents

Abstract

PURPOSE:To obtain the titled polymer having high stereoregularity without removal of ash, by using a catalyst prepared by blending a solid consisting of a Mg halide, a specific Si compound, an organoaluminum compound, and an organic acid ester with a specified Si compound and an organometallic compound. CONSTITUTION:An olefin is (co)polymerized by using a catalyst system prepared by blending (A) a solid catalyst component obtained by bringing a magnesium halide and a silicon compound shown by the formula (R<1> and R<2> are 1-24C hydrocarbon residue, alkoxy, H, or halogen; R<3> and R<4> are 1-24C hydrocarbon residue; 1<=q<=30) into contact with a compound shown by the formula II (R<9> is 1-24C hydrocarbon residue; 0<=n<=3; X is halogen) to give a soild substance, followed by supporting a titanium compound and/or an adduct compound of the titanium compound with an organic acid ester on the solid substance with (B) a compound shown by the formula III (R<5>-R<7> are 1-24C hydrocarbon residue, alkoxy, H, or halogen; R<8> is 1-24C hydrocarbon residue; 1<=q<=30) or the organic acid ester, and (C) an organometallic compound.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for polymerizing or copolymerizing α-olefins with high activity and good stereoregularity using a novel catalyst.

As highly stereoregular polymerization catalysts for α-olefins, catalysts made of cytitanium halides or organoaluminum compounds have been known. However, in polymerization using this catalyst system, although a highly stereoregular polymer can be obtained, the catalyst activity is low, so it is necessary to remove residual catalyst from the resulting polymer.

In recent years, many proposals have been made to improve the activity of catalysts. According to these proposals, it has been shown that a highly active catalyst can be obtained when a catalyst component in which titanium tetrachloride is supported on an inorganic solid carrier such as MgClx is used.

However, in the production of polyolefins, it is preferable that the catalyst activity be as high as possible, and catalysts with even higher activity have been desired. It is also important that the amount of atactic moieties formed in the polymer be as small as possible.

As a result of intensive research on these points, the present inventors found that
Here, a new catalyst was discovered. That is,
The present invention relates to a method for producing polyolefins with extremely high activity and high stereoregularity using a novel catalyst. By using the catalyst of the present invention, the monomer partial pressure during polymerization is low and the polymerization time is short. The amount of catalyst residue in the resulting polymer is extremely small due to the polymerization over a long period of time, so the catalyst removal step can be omitted in the polyolefin manufacturing process, and the amount of atactic moieties produced in the resulting polymer is also extremely small. It will be done. The present invention will be explained in detail below.

The present invention relates to CI Xl,) magnesium halide,
(2) General formula I represents a hydrocarbon residue of the number 1 to 24, where q is 1≦q≦30), and (8) a compound represented by the general formula R”nAlX3-n (where R9 is a carbonized group having 1 to 24 carbon atoms represents a hydrogen residue, where n is 0≦n≦8, and X represents ). A solid catalyst component obtained by supporting an addition compound with 5 (Il) (4) General formula R'<vS i-〇±7R
'(Here, 11", R6, 1 pyro R7 is a hydrocarbon residue having 1 to 24 carbon atoms, an alkoxy group,
Frozen confectionery size or halogen is represented, and R8 represents a hydrocarbon residue having 1 to 24 carbon atoms. q is 1≦q≦80), or (5) an organic acid ester, and (I
II] This invention relates to a method for producing polyolefins with extremely high activity and stereoregularity by polymerizing or copolymerizing olefins using a catalyst system comprising a combination of organometallic compounds.

In the invention, (1) magisium halide, (2
)-R' A compound represented by the general formula R''+S Z-OiR' and a compound represented by the general formula R8LA I There is no limit, and the temperature is 20 to 4.00°C, preferably 50 to 80°C, in the presence or absence of an inert solvent.
The reaction may be carried out by contacting the mixture under heating at 0°C for 5 minutes to 20 hours, by co-pulverization, or by appropriately combining these methods. .

There is still no particular restriction on the reaction order of components (1) to (8).

The inert solvent 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, tetrahedron, hexane, heptane, octane, benzene, lluene, xylene, cyclohexane, and other low-fat hydrocarbons, aromatic hydrocarbons, and alicyclic hydrocarbons. , and alcohols, ethers, and esters such as ethanol, diethyl ether, tetrahydrofuran, ethyl acetate, and ethyl benzoate. In the case of co-pulverization, it is usually a ball mill, a vibration mill,
Using equipment such as a rod mill or impact mill, usually 0 to 20
At a temperature of 0°C, preferably 20-100°C, 0.5-3
It is desirable to do this for 0 hours.

In the present invention, a method of obtaining a solid carrier by co-pulverizing components (1) to (3) is particularly preferably employed.

In the present invention, the molar ratio of component (1) magnesium chloride to component 1 (2) compound represented by the general formula R''+S j -0+7.R' is component (1):component. (2) is 1:Q
O01-10, preferably 1:0.01-1. The usage ratio of the compound represented by component (3) R% A I Xs -7L is component (1):component (3) in molar ratio.
is 1:0.001 to 10, preferably 1: A solid catalyst component is obtained by supporting a titanium compound and/or an addition compound of a titanium compound and an organic acid ester on the thus obtained solid carrier.

A known method can be used to support the titanium compound and/-P, the additive compound of the bamboo titanium compound and the organic acid ester on the carrier. For example, this can be carried out by bringing a solid support into contact with an excess of a titanium compound and an adduct of a titanium compound and an organic acid ester under heating in the presence or absence of an inert solvent. Preferably, both are heated at 50 to 300°C, preferably at 1°C in the presence of an inert solvent such as n-hexane.
It is convenient to heat it to 00 to 150°C. Although the reaction time is not particularly limited, it is usually 5 minutes or more, and although it is not necessary, there is no problem in contacting for an extended period of time. For example, processing times can range from 5 minutes to 10 hours. Of course, this treatment should be carried out under an inert gas atmosphere free of oxygen and moisture. After the completion of the reaction, the method for removing unreacted titanium compounds and/or adducts of titanium compounds and organic acid esters is not particularly limited. A solid powder can be obtained by evaporation under reduced pressure conditions. Another preferred method includes a method of co-pulverizing a solid support and a required amount of a titanium compound and/or an addition compound of a titanium compound and an organic acid ester.

Co-pulverization is usually carried out at a temperature of 0°C to 200°C, preferably 20°C to 10°C.
The catalyst component of the present invention can be produced by co-milling at a temperature of 0° C. for 0.5 to 30 hours. Of course, the co-grinding operation should be carried out in an inert gas atmosphere.
Moisture should also be avoided as much as possible.

The magnesium chloride used in the present invention is substantially anhydrous and includes magnesium fluoride, magnesium chloride, magnesium bromide, magnesium iodide, and mixtures thereof, with magnesium chloride being particularly preferred. .

/-71 1 to 12 hydrocarbon residues, q is l≦q≦30), monomethyltrimethoxysilane, monomethyltriethoxysilane, monomethyltri-n-butoxysilane, monomethyltri5eC-butoxysilane,
Monomethyltriisopropoxysilane, monomethyltriisopropoxysilane, monomethyltrioctoxysilane,
Monomethyltristearoxysilane, monomethyltriphenoxysilane, dimethyldimethoxysilane, dimethyljethoxysilane, dimethyldiisopropoxysilane,
Diethyljethoxysilane, trimethylmonomethoxysilane, trimethylmonoethoxysilane, trimethylmonoisopropoxysilane, trimethylmonophenoxysilane, monomethyldimethoxymonochlorosilane, monomethyljethoxymonochlorosilane, monomethylmonoethoxydichlorosilane, monomethyljethoxymonochlorosilane, monomethyl Jetoxymonobromosilane, monomethyldiphenoxymonochlorosilane, dimethylmonoethoxymonochlorosilane, monoethyltrimethoxysilane, monoethyltriethoxysilane, monoethyltriisopropoxysilane, monoethyltriphenoxysilane,
Diethyldimethoxysilane, diethyljethoxysilane, diethyldiphenoxysilane, triethylmonoethoxysilane, triethylmonoethoxysilane, triethylmonophenoxysilane, monoethyldimethoxymonochlorosilane, monoethyljethoxymonochlorosilane, monoethyldiphenoxymonochlorosilane, mono Isopropyltrimethoxysilane, mono-n-butyltrimethoxysilane, mono-n-butyltriethoxysilane, mono-5e
Examples include c-butyltriethoxysilane, monophenyltriethoxysilane, diphenyljethoxysilane, diphenylmonoethoxymonochlorosilane, and repeating units obtained by condensing the above compounds. General formula R7(-8s
O+qR"6 (here, R5, R6, R? represents a hydrocarbon residue having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, an alkoxy group, hydrogen, or a halogen, and RII represents a carbon number of 1 to 24, preferably 1
~12 hydrocarbon residues are shown. 71:+ where q is l≦q≦30) In addition to the compounds described in 71:+, monomethoxytrichlorosilane, monoethoxytrichlorosilane, monoisopropoxytrichlorosilane, mono n-butoxytrichlorosilane, monooctoxytrichlorosilane, monooctoxytrichlorosilane, monostearoxytrichlorosilane, monophenoxytrichlorosilane, mono p-
Methylphenokiditrichlorosilane, dimethoxydichlorosilane, jetoxydichlorosilane, diisopropoxydichlorosilane, mole-butoxydichlorosilane, dioctogydichlorosilane, trimethoxymonochlorosilane, triethoxymonochlorosilane, triisopropoxymonochlorosilane, trin -Butoxymonochlorosilane, tos5ec-butoxymonochlorosilane, tetraethoxysilane, tetraisopropoxysilane, and the repeating unit obtained by condensing the above compound is +5i-0
Examples include linear or cyclic poly/<' siloxanes represented by +.

The organic acid ester used in the present invention has 1 to 1 carbon atoms.
It is an ester of 24 saturated or unsaturated monobasic or dibasic organic carboxylic acids and an alcohol having 1 to 80 carbon atoms. Specifically, methyl formate, ethyl acetate, amyl acetate, phenyl acetate, octyl acetate, methyl methacrylate, ethyl stearate, methyl benzoate, ethyl benzoate, n-propyl benzoate, iso-propyl benzoate, benzoic acid. Butyl, hexyl benzoate, cyclohytyl benzoate, cyclohexyl benzoate, phenyl benzoate, 4-tolyl benzoate, methyl salicylate, ethyl salicylate, methyl p-oxybenzoate, ethyl p-oxybenzoate, phenyl salicylate, p- Cyclohexyl oxybenzoate, benzyl salicylate, ethyl α-resorcylate, methyl anisate, ethyl anisate, phenyl anisate, benzyl anisate, ethyl 0-methoxybenzoate, methyl p-ethoxybenzoate, methyl p-)ruylate , p-)ethyl toluate, p-phenyl toluate, O-)ethyl toluate, m-ethyl toluate,
Examples include methyl p-aminobenzoate, ethyl p-aminobenzoate, vinyl benzoate, allyl benzoate, benzyl benzoate, methyl naphthoate, and ethyl naphthoate.

Among these, particularly preferred are alkyl esters of benzoic acid, 0- or p-)ruyl acid, or p-anisic acid, and particularly preferred are methyl esters and ethyl esters thereof.

General formula R9nAlX3-n (where R9
represents a hydrocarbon residue having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms.

Specifically, the compound represented by n is 0≦n≦8, preferably 0≦n<8, and X represents a halogen),
Trimethylaluminum, triethylaluminum, triimpropylaluminum, triimbutylaluminum, tridecylaluminum, dimethylaluminum chloride, diethylaluminum chloride, diisobutylaluminum chloride, dioctylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride, hexylaluminum Examples include dichloride, ethylaluminum sesquichloride, aluminum chloride, aluminum bromide, and aluminum iodide, with aluminum chloride being particularly preferred.

As the titanium compound used in the present invention, a 41-valent titanium compound and a trivalent titanium compound are suitable. Specifically, the tetravalent titanium compound has the general formula 'I'i (O
R) nX, -FL (where R represents an alkyl group, aryl group, or aralkyl group having 1 to 20 carbon atoms, and X represents a halogen atom. n is 0≦n≦4.) Titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, monomethoxytrichlorotitanium, dimethoxydichlorotitanium, tritoxymonochlorotitanium, tetramethoxytitanium, monobutoxytrichlorotitanium,
Jetoxydichlorotitanium, Trie) xymonochlorotitanium, tetraethoxytitanium, monoisopropoquine trichlorotitanium/, diisopropoxydichlorotitanium, triisopropoxymonochlorotitanium, tetraisopropoxytitanium, monobutoxytrichlorotitanium, jetoxydichlorotitanium, monobentotrichlorotitanium,
Monophenoxytri, chlorotitanium, diphenoxydi>
Examples include lorotitanium, triphenoxymonochlorotitanium, and tetraphenoxytitanium. Trivalent titanium compounds include trihalides obtained by reducing titanium tetrahalides such as titanium tetrachloride and titanium tetrabromide with hydrogen, aluminum, titanium, or organometallic compounds of Group I-III metals of the periodic table. Titanium is mentioned. Also, the general formula Ti(OR)mX, -m (where R is 1 carbon number
~20 alkyl, aryl, or aralkyl groups, and X represents a halogen atom. m is O<771. <4
It is. ) is a trivalent titanium compound obtained by reducing a tetravalent alkoxy titanium halide with an organometallic compound of a metal of Groups 1 to 1 of the Periodic Table.

As an addition compound of a titanium compound and an organic acid ester, titanium (IZ compound:organic acid ester molar ratio is 2=1
The one with ~1:2 is t・return+1~. These additional compounds include TiCl4 ・C, Ply, Co0C2, Ff
, , TiCl4 ・2C,FmuC(,)OC,
Its,Ticl,・p-CH30CeH
s C00C2PI,, TiCl3 ・C0H,C00
C, H, etc. can be exemplified.

In the present invention, titanium compounds and/! f. The amount of the addition compound of the bamboo titanium compound and the organic acid ester is not particularly limited ('・However, the amount of the titanium compound contained in the solid product is usually 0.5 to 20 kg, preferably 1~
It is preferable to adjust the amount to 10% by weight.

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 general formulas R, Al, I? 2AIX, RAIX, ,
R2AlOR,R,Al(OR)X and R,AI,
X, an organoaluminum compound (where R has 1 carbon number)
~20 alkyl group or aryl group, (but may also be different) organozinc isopropylaluminum, triisobutylaluminum, tri5ec-butylaluminum, trit
Examples include ert-butylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum chloride, diisopropylaluminum chloride, ethylaluminum sesquichloride, diethylzinc, and mixtures thereof.

In the present invention, the ratio of the total organic compound component to the organometallated compound (5) or the organic acid ester (component (5)) is usually 0.00%.
It is used in an amount of 1 to 5 mol, preferably 0.01 to 2 mol.

In the present invention, the organometallic compound component can also be used as a reactant with the organic gold pI+ or component (5) organic acid ester.

5. The amount of the compound represented by the general formula R'+Si-i→nR8 or the component (5) organic acid ester is the same as that of the titanium compound in the catalyst component [I]. Ester:Ti ratio of 0.1 to 100:l, preferably 0.8
~20:l.

Tei.

When a compound represented by the following formula is used as a reactant, the molar ratio of the compound to be reacted is in the range of 1:0.001 to 5, preferably 1:0.01 to 2.

When used as a reaction product between an organometallic compound and an organic acid ester (component (5)), it is preferable that the molar ratio of organometallic compound to organic acid ester is 1:0.1 to 2.

There are no particular limitations on the organometallic compound and organic acid ester, or the -jIk method, and the reaction is carried out at -50°C to 300°C, preferably from 50°C to 200°C, in the presence or absence of an inert solvent.
There is also a method of carrying out the reaction by contacting at a temperature of 50°C for 5 minutes to 20 hours.

In the present invention, the amount of the organometallic compound to be used is not particularly limited, but it can usually be used in an amount of 0.1 to 1000 times the amount of the titanium compound.

The olefin polymerization reaction using the composition of the present invention is carried out in the same manner as the olefin polymerization reaction using a conventional Ziegler type catalyst. That is, all reactions are carried out substantially in the absence of oxygen, water, etc., in the gas phase, or in the presence of an inert solvent or with the monomer itself as the solvent. The polymerization conditions for olefins are a temperature of 20 to 300°C, preferably 40 to 180°C, and a pressure of normal pressure to 70°C.
kg/cm”・G1 preferably 2 to 60 kg/
cm''・G. Although the molecular weight can be adjusted to some extent by changing polymerization conditions such as polymerization temperature and catalyst molar ratio, it is effectively carried out by adding hydrogen to the polymerization system. Of course, Using the catalyst of the present invention, a two-step or more multi-step polymerization reaction with different polymerization conditions such as hydrogen concentration and polymerization temperature can be carried out without any trouble.

The method of the present invention is applicable to the polymerization of all olefins that can be polymerized with Ziegler's catalyst, such as homopolymerization of α-olefins such as ethylene, propylene, butene-11-methylpentene-1, and ethylene and propylene, ethylene and butene-11 propylene and butene-1 random and block co-tops etc. In addition, copolymerization with dienes for the purpose of modifying polyolefins, such as ethylene and butadiene,
Copolymerization of ethylene and 1,4-hexadiene is also preferably carried out.

In the present invention, it can be particularly effectively used to polymerize or copolymerize α-olefins having 8 to 8 carbon atoms with good stereoregularity.

Examples will be described below, but these are for illustrative purposes in carrying out the present invention, and the present invention is not limited thereto.

Example 1 (a) Synthesis of catalyst components 10 g of hot water magnesium chloride and 5.5 ml of monomethyltriethoxysilane 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 inch, and placed in a nitrogen atmosphere. After performing ball milling for 16 hours at room temperature, 6 g of anhydrous aluminum trichloride was added and ball milling was performed at room temperature for 16 hours under a nitrogen atmosphere. Furthermore, 72 ml of titanium tetrachloride was added and ball milling was performed for 16 hours at room temperature under a nitrogen atmosphere. Milling was done. One gram of the solid powder obtained after ball milling contained 881n';I of titanium. -1(b) Autoclave with stainless steel induction stirrer for polymerization 21
Add 1000ml of hexane and add 5 mmol of triethylaluminum, 1.4 mmol of tetraethoxysilane and 100ml of precursor solid powder, and add hydrogen until the gas phase partial pressure reaches 0.025 kg/an"G. After insertion, the temperature was raised to 50°C while pressing 4W.The vapor pressure of hexane brought the system to 0.5 kg/lyn"G, but then propylene was added to the system at a total pressure of 7 kg/cm"G.
Polymerization was carried out for 1 hour by continuously introducing propylene so as to achieve the following.

After the polymerization was completed, excess propylene was discharged, cooled, and the contents were taken out and dried for 1-IL to obtain 221 g of white polypropylene.

This is the total amount of the product, including the amorphous material.

Catalytic activity is 340g polypropylene/g solids・hr・
C5H, pressure, 8950.9 polypropyref/9Ti
-h, r -C3 pressure, melt flow index is 4
1.0, including -power solvent soluble polymers, the boiling point n
-The total extraction residual rate with hebutane was 94.5.

Comparative Example 1 A catalyst component was synthesized and polymerized in the same manner as in Example 1 except that anhydrous aluminum trichloride was not used, and 89 g of polypropylene was obtained. Catalytic activity is 60g polypropylene/g solid.
hr・C3Im pressure, ], 600 g polypropylene/
1 Ti-hr-CJI, pressure, solvent acceptable, 'i 1 polymer included, total extraction residue with boiling n-hebutane,
I was in charge of 94.

The catalyst components were synthesized and polymerized in the same manner as in Example 1, except that methyltriethoxysilane was not used, and 111 g of polypropylene was obtained.

Catalytic activity is 170.9 Polypropylene #solid・nr・C
, Impressure, 4500g polypropy L'7/! 97'1
-hr -C3J pressure, and the total extraction residue with boiling n-hebutane including the solvent-soluble polymer was 88.1.

Comparative Example 3 A catalyst component was synthesized in the same manner as in Example 1, except that tetraethoxysilane was used instead of methyltriethoxysilane. When polymerizing using the 2F+ej9:l+ medium, the same 1K1r reaction as in Example 1 was carried out using ethyl benzoate in place of tetraethoxysilane in Example I, and 168 g of polypropylene was obtained.

Catalytic activity is 25.0. ! i'Polypropylene/ ,! /
Solid・hr・C, II, pressure, 7100g polypropylene/M'l'i・ノL7''C,If, pressure, and the total extraction residue with boiling and 5?L-hebutane including the solvent-soluble polymer is It was 90.2%.

Examples 2 to 8 Catalyst components were synthesized in the same manner as in Example 1, and propylene was polymerized in the same manner as in Example 1. The results are summarized in the table below.

Example 9 ♀ Monomethyltriethoxysilane 5.5d (
28 mmol) and n-hebutane 10 (1 ml to 800 mmol)
m / in a round bottom flask, add 93 m / of n-hebutane solution containing 2 mmol / ml of ethylaluminum dichloride to the dropping funnel, and add 1 l of male blade over 30 minutes with stirring.
Thereafter, the thread was stirred at 100° C. for 3 hours to cause tetraethoxysilane and ethylaluminum dichloride to react.

5 g of reaction product and anhydrous salt; L magnesium 10! After ball milling was carried out at room temperature under a nitrogen atmosphere for 5 hours in a stainless steel pot with an internal volume of 400 m containing 25 stainless steel SZ-rules having a diameter of 1 inch, the obtained milled product 1.0, '? , 100 ml of n-heptane and 20 rnl of titanium tetrachloride were placed in a round bottom flask and stirred for 2 hours at 100°C under a nitrogen atmosphere. Then washed 9 times with 1(B) m/n-hexane. After removing unreacted titanium tetrachloride, it was vacuum dried to obtain a solid powder.The obtained solid powder 1.9 contained 23 mg of titanium.

Using the obtained solid powder, polymerization was carried out in the same manner as in Example 2, and polypropylene 161 was obtained.

Touch 1■Activity is 2509 polypropylene/g solid・hr・
Cs H6 pressure, 10900g polypropyref/gTi-
hr-C8H,l pressure, including solvent-soluble polymers,
The total extraction residual rate was 93.0chi.

Example 10 The catalyst components were synthesized in the same manner as in Example 9, except that diethylaluminum chloride was used instead of ethylaluminum dichloride in Example 9, and propylene was polymerized in the same manner as in Example 9. As a result, white polypropylene was
56I was obtained.

Catalytic activity is 240g polypropylene/g solids・hr・C
3B, pressure, 10400g polypropyref/9Ti-hr
-CsH6 pressure, boiling n including solvent-soluble polymers
-The residual rate after extraction with hebutane was 93.8%.

Example 11 Solid powder log obtained in Example 1, n of 100 l/
-heptane, and titanium tetrachloride'; 200 lOme
ml round bottom flask and heated at 100°C for 2 hours in an atmosphere of 9 elements 1! I stirred it up. Next, unreacted titanium tetrachloride was removed by washing with n-hex/100 ml nine times, followed by vacuum drying to obtain a solid powder. The obtained solid powder 1.9 contains 22
Contains 7n9 titanium.

When carrying out polymerization in the same manner as in Example 1 using the obtained solid powder, 1 ethyl benzoate was used instead of tetraethoxysilane.
．． Other beams using 4 mm IJ moles? When polymerization was carried out in the same manner as in Example 1, 215 g of polypropylene was obtained.

Catalytic activity is 8809 polypropylene/& solid/h
r・C3H, pressure, 15000g polypropylene/J? T
i-hr·C, Il, and the pressure, and the total extraction residue including the solvent-soluble polymer was 92.1.

Example 12 When polymerizing the solid powder obtained in Example 9 in the same manner as in Example 1, the polymerization was performed using 1.4 mmol of ethyl benzoate instead of tetraethoxysilane, resulting in white polypropylene. 117g was obtained.

Catalytic activity is 180.9 polypropylene/,! IQ, i-body/hr/C, H0 pressure, 7800g polypropyref/g
The pressure was Ti-hr-C,H, and the total extraction residue including the solvent-soluble polymer was 92.8 Ti.

Example 8 Polymerization was carried out using the same solid powder as in Example 1, but
During polymerization, the tetraethoxysilane used in Example 1 was
Polymerization was carried out in the same manner as in Example 1, except that 0.59 of the reaction product of triethylaluminum and tetraethoxysilane (mole ratio) was used in place of mmol, and 215 g of white polypropylene was obtained. Ta.

Catalytic activity is 880 & polypropylene/y solid/hr/
C3I-1, pressure, 8'700g polypropylene/jJT
The pressure was i-hγ·C,if, and the total extraction residue including the solvent-soluble polymer was 94.5.

Patent applicant: Nippon Oil Co., Ltd.

[゛・Representative Patent Attorney Ryoji Kawa ・4
11. Procedural amendment dated April 1, 1980 Kazuo Wakasugi, Commissioner of the Patent Office 1. Indication of the case Patent Application No. 168665 of 1988 2. Name of the invention Process for producing polyolefin 3. Person making the amendment 6. Column 7 for claims and detailed description of the invention in the specification subject to amendment
, Contents of amendment (1) The entire scope of the claims shall be amended as shown in the appendix.

(2) "Various fats" in the bottom three lines of page 6 of the specification will be corrected to "various aliphatics."

(3) On page 10, line 10 of the same book, the “Fund Showing” meeting “Showing the Fund,
” he corrected.

(4) All "n-butoxy" and "r 5ec-butoxy" in lines 12 and 13 of page 10 of the same book are corrected to "n-butoxy" and "5ec-butoxy," respectively.

(5) Delete "ethyl 0-methoxybenzoate" from line 2 on page 15 of the same book.

(6) 3 lines from the bottom of page 18 of the same book [・2C5H5~J
kr・2C6H5~".

(7) 1-0-3-, R8J in the general formula on the bottom line of page 20 and the third line of page 21 of the same Ministry, respectively f-0+qR
Correct to 8J.

(3) "-chloride" in lines 4 and 8 on page 30 of the same book is corrected to "chloride."

(4) “Chloride” on page 31, lines 10 and 11 of the same book
All are corrected as "chloride".

Claims CI) (1) Magnesium halide, (2) General formula R3 + starting -〇+qR4 (where R1 and R2 represent a 2 hydrocarbon residue having 1 to 24 carbon atoms, an alkoxy group, hydrogen or a halogen) , R3, and R4 represent hydrocarbon residues having 1 to 24 carbon atoms; q is 1≦q≦30); and (3) compounds represented by the general formula R7LA1X3-n (where R9 is The addition of a titanium compound and/or a titanium compound and an organic acid ester to a solid material obtained by contacting a hydrocarbon residue of 24, where n is O≦n≦3, and X is a halogen. A solid catalyst component obtained by supporting a compound, 7?5 or halogen, and R8 represents a hydrocarbon residue having 1 to 24 carbon atoms. q is 1≦q≦30); and l) an organometallic compound.

Claims (1)

[Claims] (1) (1) Magnesium halide, (2)
It represents a hydrocarbon residue, an alkoxy group, hydrogen or a halogen of the general formula %, and R and 'R' represent a hydrocarbon residue having 1 to 24 carbon atoms. q is 1≦q≦80), and (3) a compound represented by the general formula R9nA I X3-7L (where RQ represents a hydrocarbon residue having 1 to 24 carbon atoms; n is 0≦
(II) (4) General formula R5 (Here R5
, R6, R7-C-8i-O-)-Rδ q 6 R7 is a hydrocarbon residue having 1 to 24 carbon atoms, an alkoxy group,
It represents hydrogen or halogen, and R6 represents a hydrocarbon residue having 1 to 24 carbon atoms. q is l≦q≦80), the dimensions are (5) organic acid ester, and
A method for producing a polyolefin, which comprises polymerizing or copolymerizing an olefin using a catalyst system comprising a combination of organometallic compounds.