JPS6067505A - Production of polyolefin - Google Patents

Abstract

PURPOSE:A catalyst which is composed of a halogenated magnesium, a specific organosilicon compound, a phosphoric ester, an acetic ester, a solid component containing a titanium compound supported, an organometallic compound and an organosilicon compound is used to produce the titled polymer of high stereoregularity. CONSTITUTION:A catalyst as a combination of (A) the solid component that has been prepared by allowing a solid to bring into contact with a halogenated magnesium, at least one of silicon compounds of the formula (R<1>, R<2>, R<3> are 1-24C hydrocarbon, alkoxy, H, halogen; R<4> is 1-24C hydrocarbon; 1<=n<=30), a phosphate ester of the formula: OP(OR<5>)3 (R<5> is 1-24C hydrocarbon), an acetic ester of the formula: CH3COOR<6> (R<6> is 1-24C hydrocarbon) or an ether of the formula: R<7>OR<7> (R<7> is 1-24C hydrocarbon) and to support a titanium compound, (B) an organometallic compound and (C) a compound of the formula is used to effect polymerization or copolymerization of alpha olefins to give the objective polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for highly active polymerization or copolymerization of a-olefins with good stereoregularity using a novel catalyst.

As a highly stereoregular polymerization catalyst for Q-olefin, a catalyst comprising a titanium halide and an organoaluminum compound has 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 catalyst residues from the produced 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 tetravalent titanium is supported on an inorganic solid carrier such as MgC1 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 produced in the polymer be as small as possible.

As a result of intensive research on these points, the present inventors found that
This is where we found a new catalyst. That is, the present invention relates to a method for producing extremely highly active and highly stereoregular polyolefins using a novel catalyst. By using the catalyst of the present invention, the monomer partial pressure during polymerization is low and Due to the short polymerization time, the amount of catalyst residue in the resulting polymer is extremely small, so the catalyst removal step can be omitted in the polyolefin production process.
In addition, many effects can be obtained, such as the amount of atactic moieties produced in the produced polymer is extremely small.

The present invention will be explained in detail below.

The present invention is 0) (1) Magnesium halide, (2)
At least 1 E' R3 is a hydrocarbon residue having 1 to 24 carbon atoms, an alkoxy group,
Represents hydrogen or halogen atom, R4 has 1 to 24 carbon atoms
The hydrocarbon residue of n is 1≦n≦30. ), and (3) general formula 〇P(OR')
a (here, R5 represents a hydrocarbon residue having 1 to 24 carbon atoms, and R5 may be the same or different) and (4) a compound represented by the general formula CHsCOOR' (here, R6 is a hydrocarbon residue having 1 to 24 carbon atoms); ) or the general formula R'OR' (where R7 represents a hydrocarbon residue having 1 to 24 carbon atoms, and R7 may be the same or different). (5) a solid catalyst component obtained by supporting a titanium compound on a solid substance obtained by contacting the represented compound; (II) an organometallic compound;
(6) represents a hydrocarbon residue of the general formula % formula % 24, an alkoxy group, hydrogen or a halogen atom, and R4 represents a hydrocarbon residue having 1 to 24 carbon atoms.

n is 1≦n≦60. This invention relates to a method for producing polyolefins with extremely high activity and stereoregularity by polymerizing or copolymerizing a-olefins using a catalyst formed by combining the compounds represented by the following formulas.

In the present invention, (1) magnesium halide, (2
) A compound represented by the general formula R''+5l-0sR4, (
3) a compound represented by the general formula op2 (OR'), and (4) a compound represented by the general formula C
There is no particular restriction on the method of contacting the compound represented by I(gcOOR' or the general formula R'OR' to obtain the solid material of the present invention, and the method is not particularly limited. ℃〜400
℃, preferably 50℃ to 500℃ under heating, usually 5
The reaction may be carried out by contacting for minutes to 20 hours, by co-pulverization, or by a suitable combination of these methods.

Moreover, 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, or the three components may be reacted and then the remaining one component may be reacted.

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, pentane, hexane, heptane, octane, benzene, toluene, xylene, various aliphatic saturated hydrocarbons such as cyclohexane, aromatic hydrocarbons, alicyclic hydrocarbons, and methanol and ethanol. Examples include alcohols such as

The co-pulverization process is usually carried out using equipment such as a ball mill, vibration mill, rod mill, or impact mill, and is usually carried out at 0°C to 200°C.
Preferably, the wetting is carried out at a temperature of 20°C to 100°C for 0.5 to 30 hours.

In the present invention, a method of obtaining a solid substance by co-pulverizing components (1) to (4) is particularly preferably employed.

In the present invention, the ratio of component (1) magnesium halide to component (2) compound represented by the general formula R3+5j-0+oR' is such that the molar ratio of component (1) to component (2) is 1. :0.
001-1o, preferably 1:001-1. Component (3) The usage ratio of the compound represented by the general formula 〇P (OR')s is such that the molar ratio of component (1) to component (3) is 0.
001-10, preferably 1:0.01-1. Component (4) General formula CH3CO0R' or general formula R' O
The molar ratio of component (1) to component (4) of the compound represented by R7 is 1:[LOOl~10, preferably 1:0.01~1.

A solid catalyst component 0) is obtained by supporting a titanium compound on the solid material thus obtained.

A known method can be used to support the titanium compound on the carrier. For example, this can be carried out by bringing the solid support into contact with an excess of the titanium compound under heating in the presence or absence of a solvent, and preferably,
50°C to 300°C, more preferably 80°C to 150°C
It is convenient to do this by heating. Although the reaction time is not particularly limited, it is usually 5 minutes or more, and long-term contact may be allowed, although it is not necessary. For example, treatment times can range from 5 minutes to 10 hours, preferably from 1 to 4 hours. Of course, this process requires oxygen,
and should be carried out under a moisture-free inert gas atmosphere. After completion of the reaction 9- The method for removing unreacted titanium compounds is not particularly limited, and a solid powder can be obtained by washing the Ziegler catalyst several times with a solvent inert to the catalyst and evaporating the washing liquid under reduced pressure conditions. .

Another method is to co-pulverize the solid support and the required amount of the titanium compound.

In the present invention, the solid catalyst component of the present invention can be produced by co-pulverizing normally at a temperature of 0°C to 200°C, preferably 20°C to 100°C for 0.5 to 30 hours.

Of course, the co-grinding operation should be carried out in an inert gas atmosphere and moisture should be avoided as much as possible.

The magnesium halide 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.

10-H' (Here, R1, R2, R8 represent a hydrocarbon residue having 1 to 24 carbon atoms, preferably 1 to 18 carbon atoms, an alkoxy group, hydrogen or a halogen atom. 1. R4 represents a carbon number of 1 to 24, Preferably represents a hydrocarbon residue of 1 to 18, where n is 1≦n≦3
It is 0. ) Examples include monomethyltrimethoxysilane, monomethyltriethoxysilane,
Monomethyltri n-butoxysilane, monomethyltri5
ec-butoxysilane, monomethyltriisopropoxysilane, monomethyltripentoxysilane, monomethyltrioctoxysilane, monomethyltristearoxysilane, monomethyltriphenoxysilane, dimethyldimethoxysilane, diethyljethoxysilane, dimethyldiisopropoxysilane, dimethyl diphenoxysilane,
Trimethylmonomethoxysilane, trimethylmonoethoxysilane, trimethylmonoisopropoxysilane, trimethylmonophenoxysilane, monomethyldimethoxymonochlorosilane, -monomethylmonoethoxydichlorosilane, monomethyljethoxymonochlorosilane, monomethyljethoxymonobromosilane, monomethyldiphenoxymono Chlorosilane, dimethylmonoethoxymonochlorosilane, monoethyltrimethoxysilane, monoethyltriethoxysilane, monoethyltriynepropoxysilane, monoethyltriphenoxysilane, diethyldimethoxysilane, diethyljethoxysilane, diethyldiphenoxysilane, triethylmono Methoxysilane, triethylmonoethoxysilane, triethylmonophenoxysilane, monoethyldimethoxymonochlorosilane, monoethyljethoxymonochlorosilane, monomethyldiphenoxymonochlorosilane, monoisopropyltrimethoxysilane, mono n-butyltrimethoxysilane, mono n-butyl Triethoxysilane, monosee-7'tiltriethoxysilane, monophenyltrimethoxy7rane, monophenyltriethoxysilane, monophenyltriphenoxysilane, diphenyljethoxysilane, diphenylmonoethoxymonochlorosilane, monomethoxytrichlorosilane, Monoethoxytrichlorosilane, monopropoxytrichlorosilane, monooctoxytrichlorosilane, monopentoxytrichlorosilane, monooctoxytrichlorosilane, monostearoxytrichlorosilane, monophenoxytrichlorosilane, mono p-methylphenoxytrichlorosilane, dimethoxytrichlorosilane Chlorosilane, jetoxydichlorosilane, diisopropoxydichlorosilane, dibutoxydichlorosilane, dioctoxydichlorosilane, trimethoxymonochlorosilane, triethoxymonochlorosilane, triisoprophoki-13-cyomonochlorosilane, tri-n-butoxymonochlorosilane, tri5eC-butoxy Monochlorosilane, tetraethoxysilane, tetraisopropoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyldimethoxymonochlorosilane, vinyljethoxymonochlorosilane, vinylmethoxydichlorosilane, vinylethoxydichlorosilane, allyltrimethoxysilane, allyltri Ethoxysilane, allyldimethoxymonochlorosilane, allyljethoxymonochlorosilane, allylmethoxydichlorosilane, allylethoxydichlorosilane, vinyltriphenoxysilane, vinylethoxydiphenoxysilane, allyltriphenoxysilane, allylethoxydiphenoxysilane, and the above. Examples include chain or cyclic polysiloxanes in which the repeating unit obtained by condensing compounds is represented by 〒''+5i-0+. It can also be used as a mixture of these.

Among these compounds, component (2) is preferably one in which at least one substituent has an olefinic hydrocarbon group or an aromatic hydrocarbon group, and examples include vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltriphenoxysilane. , allyltrimethoxysilane, allyltriethoxysilane, allyltriphenoxysilane, monophenyltrimethoxysilane, and monophenyltriethoxysilane are particularly preferred.

In addition, as component (6), it is preferable that at least the substituent group has an aromatic hydrocarbon group, and monophenyltrimethoxysilane and monophenyltriethoxysilane are particularly preferable.

General formula 〇P(OR')s used in the present invention (
Here, R5 represents a hydrocarbon residue having 1 to 24 carbon atoms, preferably 1 to 18 carbon atoms, and R5 may be the same or different. ) Examples of the compounds represented by trimethyl phosphate, triethyl phosphate, tripropyl phosphate, triisopropyl phosphate, tri n-butyl phosphate, triisobutyl phosphate, trivinyl phosphate, triallyl phosphate, triisodecyl phosphate, triphenyl phosphate, tri- Cyclohexyl phosphate, tris(tert-amylphenyl) phosphate, tris(nonyl-phenyl)
phosphate, tri(3,5-diethylphenyl) phosphate, tri-o-tolyl phosphate, tri-1-naphthyl phosphate, )IJs(2-ethylhexyl)
Phosphate, diphenyl-ethyl phosphate, diphenyl-isopropyl phosphate, diphenyl-imbutyl phosphate, diphenyl-nonylphenyl phosphate, diphenyl-isodecyl phosphate, phenyl-diisooctyl phosphate, phenyl-diisodecyl phosphate, phenyl-diisobutyl phosphate, etc. I can do it.

Among these compounds, the hydrocarbon residue preferably has an aromatic hydrocarbon group, such as triphenyl phosphate, )! J-0-toluyl phosphate and tri-1-naphthyl phosphate are particularly preferred.

The general formula used in the present invention is CHaCOOR' (
Here, R6 represents a hydrocarbon residue having 1 to 24 carbon atoms, preferably 1 to 6 carbon atoms. ) Examples of compounds represented by methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, aisec-butyl acetate, te acetate
r-butyl, n-amyl acetate, isooryl acetate, n-hexyl acetate, n-heptyl acetate, octyl acetate, nonyl acetate, dodecyl acetate, stearyl acetate, phenyl acetate, cyclohexyl acetate, 17-rufutul acetate, lauryl acetate, 0-tolyl acetate, m-acetate
Examples include toluyl, p-toluyl acetate, α-naphthyl acetate, and β-naphthyl acetate.

Among these compounds, methyl acetate, ethyl acetate, acetic acid n
-propyl and isopropyl acetate are particularly preferred.

The general formula R'OR7 (where R
7 represents a hydrocarbon residue having 1 to 24 carbon atoms, and R7 may be the same or different. ) Compounds represented by: dimethyl ether, diethyl ether, cyclobyl ether, dibutyl ether, diisobutyl ether, di-n-amyl ether, diisoamyl ether, methyl ethyl ether, methyl ethyl ether, methyl isopropyl ether, methyl butyl ether, methyl isobutyl Ether, methyl n-amyl ether, methyl isobutyl ether, ethylpropyl ether, ethyl isopropyl ether, ethyl 18-butyl ether, ethyl isobutyl ether, ethyl n-amyl ether, ethyl isoamyl ether, divinyl ether, diallyl ether, methyl vinyl ether, methyl Examples include allyl ether, ethyl vinyl ether, ethyl vinyl ether, anisole, phenethole, diphenyl ether, dibenzyl ether, phenylbenzyl ether, a-naphthyl ether, and β-naphthyl ether.

At least one substituent among these compounds preferably has an aromatic hydrocarbon group, such as anisole, phenethole, diphenyl ether, dibenzyl ether, phenylbenzyl ether, α-naphthyl ether,
Particularly preferred is β,-naphthyl ether. “ As the titanium compound used in the present invention, a tetravalent titanium compound and a trivalent titanium compound are suitable. Specifically, the tetravalent titanium compound has the general formula T+(OFt)n
Those represented by X4-n (where R represents an alkyl group, aryl group, or aralkyl group having 1 to 20 carbon atoms; Titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, monomethoxytrichlorotitanium, dimethoxydichlorotitanium, trimethoxymonochlorotitanium, tetramethoxytitanium, monoethoxytrichlorotitanium, jetoxydichlorotitanium, trinidoxymonochlorotitanium, tetraethoxy Titanium, monoisopropoxytrichlorotitanium, diisopropoxydichlorotitanium, triisopropoxymonochlorotitanium, tetraisopropoxytitanium,
Examples include monobutoxytrichlorotitanium, dibutoxydichlorotitanium, monopentoxytrichlorotitanium, monophenoxytrichlorotitanium, diphenoxydichlorotitanium, 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 metals from groups I to II of the periodic table. Titanium can be given. In addition, the general formula Ti(OR)m
It is. Examples include trivalent titanium compounds obtained by reducing a tetravalent alkoxy titanium halide represented by ) with an organometallic compound of a metal of Groups 1 to 2 of the Periodic Table.

In the present invention, the amount of the titanium compound used is not particularly limited, but it is usually adjusted so that the amount of the titanium compound contained in the solid product is 0.5 to 20% by weight, preferably 1 to 10% by weight. preferable.

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 organoaluminum compounds of the general formula %) and R3A12X3 (where R is an alkyl group or aryl group having 1 to 20 carbon atoms,
represents a halogen atom, R may be the same or different) or the general formula R, Zn (where R represents a carbon number of 1
~20 alkyl groups, which may be the same or different), such as triethylaluminum, triisopropylaluminum, triisobutylaluminum, tri5ec-butylaluminum, tritert-butyl Examples include aluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, diethylaluminium 22-muchloride, diisopropylaluminum chloride, diethylaluminum ethoxide, ethylaluminum sesquichloride, diethylzinc, and mixtures thereof.

In the present invention, the organometallic compound and the component (6) general formula R
The usage ratio of the compound represented by 3+ SiO+n R' is 2. Component (6) general formula R is used per 1 mole of the organometallic compound.
+st -0-)-nR' is usually 0
．． 0012 to 5 mol, preferably 0.01 to 1 mol.

In the present invention, an organometallic compound component can also be used as a reactant with the organometallic compound.

Organometallic compound and component (6) General formula R” + S t
When used by reacting the compound represented by 2 with O+n R', the reaction ratio of the compound represented by I 6 is usually 0.001 to 2 mol, preferably 0.01 to 1 mol.

1 The amount of the product obtained by reacting the compound represented by the general formula R"+5t-0+-11R' with the organic 2 metal compound is such that Si:Ti is 0.1% relative to the titanium compound in the catalyst component (1).
It ranges from 1 to 100:1, preferably from 0.3 to 20:1.

There are no particular restrictions on the method of obtaining the reaction product with the compound represented by 1 to 4, and the reaction product is obtained by reacting with the compound shown in 4 at a temperature of -50°C to 400°C, preferably 50°C to 250°C, in the presence or absence of an inert solvent. There is also a method of reacting by contacting for 20 minutes to 20 hours.

In the present invention, the amount of the organometallic compound used is not particularly limited, but usually α1 to 10
00 moles can be used.

The olefin polymerization reaction using the catalyst 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 in a gas phase, in the presence of an inert solvent, or in the presence of a heptamer itself as a solvent in the absence of oxygen, water, etc. The polymerization conditions for olefin are: temperature is 20°C to 300°C, preferably 40°C to 180°C, and pressure is normal pressure to 70 kg/c.
m"・G, preferably 2 K17cm"・G or 6
0 Kg/c11?・It is 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 hindrance.

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

In the present invention, it can be particularly effectively used to polymerize or copolymerize a-olefins having 3 to 8 carbon atoms with good stereoregularity.

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) Synthesis of solid catalyst component [■] Anhydrous magnesium chloride 1 (In (105 mmol), vinyltriethoxysilane 1.68d (8 mmol) and triphenylphosphate) 1.3 t (4 mmol) I.J.
The diphenyl ether 0.68 ft (0.68 ft) was placed in a stainless steel pot with an internal volume of 400 mm containing 25 stainless steel balls with a diameter of mol > 1 inch (mol) and milled for 6 hours in a room source under a nitrogen atmosphere.
4 mmol) was added thereto, and ball milling was performed for an additional 16 hours under a nitrogen atmosphere. The obtained solid powder 51 and titanium tetrachloride 20m/200m7! The mixture was placed in a round bottom flask and stirred at 100° C. for 2 hours under a nitrogen atmosphere. Then, in order to remove excess titanium tetrachloride, it was washed with hexane until no titanium tetrachloride was observed in the washing solution. Thereafter, it was dried under reduced pressure to obtain a solid catalyst component [■]. 1v of the obtained solid catalyst component [l] contained 24q of titanium.

Φ) Polymerization A 3-ton stainless steel autoclave equipped with an induction stirrer was purged with nitrogen, and 1500 ml of hexane was added, and 2.5 mmol of triethylaluminum, 1.4 mmol of phenyltriethoxysilane, and the above solid catalyst component [I
] 20■ was added, and the hydrogen was 0.05 Kg/gas phase partial pressure.
After charging so that the temperature was 1-, the temperature was raised to 50° C. while stirring. At the vapor pressure of hexane, the system is 0.5 Kylo-・G
Then, propylene was added to the reactor until the total pressure reached 7 g/2 G to start polymerization. Total pressure is 7 edges/cwt'
-a, propylene was continuously introduced and polymerization was carried out for 2 hours.

After polymerization, excess propylene is discharged, cooled, and the contents are taken out and dried to obtain white polypropylene 192f.
Ta.

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

Catalyst activity is 740f polypropylene/f solid/hr-C
3H6 pressure, 3a8Kg polypropyref/? Tie
hr *cs) 1 g pressure, and the total extraction residue (total II) with boiling n-hebutane, including the solvent-soluble polymer, was 9
7.7 and the melt flow index (MFI)
was a5. Compared with Comparative Examples 1 to 5, both the catalyst activity and the total extraction residue were higher.

Example 2 (a) Preparation of solid catalyst component (1) Anhydrous magnesium chloride 1 (1 (105 mmol), vinyltriethoxysilane 1.68*j (8 mmol), and triphenyl phosphate)1. 3f (4 mmol) was placed in a stainless steel pot with an internal volume of 400 mm containing 25 stainless steel balls with a diameter of % inch, and ball milling was carried out for 3 hours in a room source under a nitrogen atmosphere. After adding 0.7 F (3 mmol) of phenyltriethoxysilane, ball milling was carried out for 16 hours at room temperature under a nitrogen atmosphere. 5 tons of the obtained solid powder and 20 ml of titanium tetrachloride were placed in a 200-mm round bottom flask and heated under a nitrogen atmosphere.
The mixture was stirred at 00°C for 2 hours. Then, in order to remove excess titanium tetrachloride, it was washed with hexane until no titanium tetrachloride was observed in the washing solution. Thereafter, it was dried under reduced pressure to obtain a solid catalyst component CI). Obtained solid catalyst component (T) 1
t contained 51 ■ titanium.

Φ) Polymerization 30- Polymerization was carried out in the same manner as in Example 1. The results are shown in Table 2.

Comparative Example 1 A solid catalyst component was synthesized in the same manner as in Example 1, except that diphenyl ether was not used, and propylene was polymerized in the same manner as in Example 1. The results are shown in Table 1.

Comparative Examples 2 to 3 A solid catalyst component was synthesized in the same manner as in Example 1, except that the upstream phenyl phosphate was not used, and propylene was polymerized in the same manner as in Example 1. The results are shown in Table 1.

Comparative Examples 4 to 5 A solid catalyst component was synthesized in the same manner as in Example 1, except that vinyltriethoxysilane was not used, and propylene was polymerized in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 6 A solid catalyst component was synthesized in the same manner as in Example 2, except that ethyl acetate was not used, and propylene was polymerized in the same manner as in Example 1. The results are shown in Table 1.

Examples 3 to 8 A solid catalyst component was synthesized in the same manner as in Example 2, except that the various compounds shown in Table 2 were used, and propylene was polymerized in the same manner as in Example 1. The results are shown in Table 2.

Examples 9 to 16 A solid catalyst component was synthesized in the same manner as in Example 1, except that the various compounds shown in Table 2 were used, and propylene was polymerized in the same manner as in Example 1. The results are shown in Table 2.

Example 17 Using the solid catalyst component of Example 1, polymerization of propylene was carried out using a reaction product of triethylaluminum and tetraethoxysilane (AI) instead of phenyltriethoxysilane.
((4Hs)a/S i (0CIIH5)4 =
(molar ratio) ) 0.5 Polymerization was carried out in the same manner as in Example 1 except that r was used. The results are shown in Table 2.

33-

Claims (1)

[Scope of Claims] [I] (1) Magnesium halide 1 (2) At least one compound of the general formula R''(-8i-0+
nR42 (where R1, RR, R3 represent a hydrocarbon residue having 1 to 24 carbon atoms, an alkoxy group, hydrogen or a hydrogen atom,
V represents a hydrocarbon residue having 1 to 24 carbon atoms. n is 1≦n
≦30. ), (3) general formula 0
A compound represented by R(OR')s (where R'Gt represents a hydrocarbon residue having 1 to 24 carbon atoms, and 111 may be the same or different) and (4) a compound represented by the general formula CHICOOR' (wherein R6 represents a hydrocarbon residue having 1 to 24 carbon atoms) or the compound represented by the general formula R'OR' (where R7 represents a hydrocarbon residue having 1 to 24 carbon atoms)
4 hydrocarbon residues, and R7 may be the same or different. ) A solid catalyst component obtained by supporting (5) a titanium compound on a solid substance obtained by contacting a compound represented by the formula (■)] an organometallic compound, and 1 Q[l) (6) a general formula R''4- 8i-0+-nR'
(Here, Hl, R2, 2 Wu represents a hydrocarbon residue having 1 to 24 carbon atoms, an alkoxy group, hydrogen or a halogen atom; R4 represents a hydrocarbon residue having 1 to 24 carbon atoms; n is 1≦n≦ A method for producing a polyolefin, which comprises polymerizing or copolymerizing an a-olefin using a catalyst comprising a combination of compounds represented by (60).