JPH0134448B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for highly active polymerization or copolymerization of α-olefins with good stereoregularity using a novel catalyst. Catalysts consisting of titanium halides and organoaluminum compounds have been known as highly stereoregular polymerization catalysts for α-olefins. 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 by using a catalyst component in which titanium tetrachloride is supported on an inorganic solid support such as MgCl ₂ . 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 have discovered a novel catalyst here. That is, the present invention relates to a method for producing extremely highly active and highly stereoregular polyolefin 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 produced polymer is extremely small, so the catalyst removal step can be omitted in the polyolefin manufacturing process, and the amount of attic moieties produced in the produced polymer is also extremely small. Effects can be obtained. The present invention will be explained in detail below. The present invention [] (1) Magnesium dihalide (hereinafter abbreviated as magnesium halide) (2) General formula Si
(OR ¹ ) _n X _4-n (where R ¹ is a hydrocarbon residue having 1 to 24 carbon atoms,
m≦4), and (3)
A compound represented by the general formula R ² _o AlX _3-o (where R ² is a hydrocarbon residue having 1 to 24 carbon atoms, X is a halogen atom, and n is 0≦n≦3), and ( 4) A solid material obtained by contacting an organic carboxylic acid halide and/or an organic carboxylic acid anhydride with the general formula Ti(OR _{) o} group or aralkyl group, and X represents a halogen atom.n
is 0≦n≦4. ) (hereinafter abbreviated as titanium compound) and /
Or a solid catalyst component obtained by supporting an addition compound of the titanium compound and an organic acid ester, [] General formula

[Formula] (where R ³ , R ⁴ , R ⁵ represent a hydrocarbon residue having 1 to 24 carbon atoms or an alkoxy group, and R ⁶ represents a hydrocarbon residue having 1 to 24 carbon atoms. q is 1 ≦q≦30), and []organoaluminum compounds (hereinafter abbreviated as organometallic compounds).
This invention relates to a method for producing polyolefins with extremely high activity and stereoregularity by polymerizing or copolymerizing α-olefins using a catalyst comprising a combination of the following. In the present invention, (1) magnesium halide,
(2) A compound represented by the general formula Si(OR ¹ ) _n X _4-n , (3)
A compound represented by the general formula R ² _o AlX _3-o , and (4)
There are no particular limitations on the method of contacting organic carboxylic acid halides or organic carboxylic acid anhydrides to obtain the solid material of the present invention, and the method may be carried out at a temperature of 20 to 400°C, preferably 50 to 400°C, in the presence or absence of an inert solvent.
The reaction may be carried out by contacting under heating at 300°C for usually 5 minutes to 20 hours, by co-pulverization, or by an appropriate combination of these methods. Furthermore, there is no particular restriction on the reaction order of components (1) to (4). 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,
Various aliphatic saturated hydrocarbons such as butane, pentane, hexane, heptane, octane, benzene, toluene, xylene, cyclohexane, aromatic hydrocarbons, alicyclic hydrocarbons, and ethanol, diethyl ether, tetrahydrofuran, ethyl acetate,
Alcohols such as ethyl benzoate, ethers,
Examples include esters. In the case of co-pulverization, it is desirable to carry out the co-pulverization using a device such as a ball mill, vibration mill, rod mill, or impact mill, usually at a temperature of 0 to 200°C, preferably 20 to 100°C, for 0.5 to 30 hours. In the present invention, a method of obtaining a solid carrier 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 Si(OR ² ) _n is 1:0.001-10, preferably 1:0.01-1.
The ratio of component (3) used is a compound represented by the general formula R ² _o AlX _3-o in a molar ratio of component (1) to component (3) of 1:0.001.
~10, preferably 1:0.01~1. The usage ratio of component (4) organic carboxylic acid halide and/or organic carboxylic acid anhydride is component (1):component in molar ratio.
(4) is 1:0.001-10, preferably 1:0.01-1. A solid catalyst component is obtained by supporting a titanium compound and/or an addition compound of a titanium compound with an organic acid ester on the thus obtained solid support. A known method can be used to support the titanium compound and/or the addition compound of the titanium compound and the organic acid ester on the carrier.
For example, this can be carried out by bringing the solid support into contact with an excess of a titanium compound and/or an addition compound of a titanium compound and an organic acid ester under heating in the presence or absence of an inert solvent. , both in the presence of an inert solvent such as n-hexane at 50-300°C, preferably 100-300°C.
This is conveniently carried out by heating to 150°C. The reaction time is not particularly limited, but is usually 5
Although it is not necessary, there is no problem with contacting for a long 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 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. In the present invention, the 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. General formula Si(OR ¹ ) _n used in the present invention
X _4-n (where R ¹ has 1 to 24 carbon atoms, preferably 1 to 24 carbon atoms)
12 hydrocarbon residues, X represents a halogen atom,
m is 0≦m≦4), silicon tetrachloride, monomethoxytrichlorosilane, monoethoxytrichlorosilane, monoisopropoxytrichlorosilane, mono n-butoxytrichlorosilane, monopentoxytrichlorosilane, Monooctoxytrichlorosilane, monostearoxytrichlorosilane, monophenoxytrichlorosilane, mono p-methylphenoxytrichlorosilane, dimethoxydichlorosilane, diethoxydichlorosilane, diisopropoxydichlorosilane, di-n-butoxydichlorosilane, dioctochlorosilane cydichlorosilane, trimethoxymonochlorosilane, triethoxymonochlorosilane, triisopropoxymonochlorosilane, tri-n-butoxymonochlorosilane, trisec-butoxymonochlorosilane, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, Examples include tetraphenoxysilane. General formula R ² _o AlX _3-o used in the present invention (where R ² is a hydrocarbon residue having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, X is a halogen atom, and n is 0≦n≦3 Examples of compounds represented by aluminum chloride, aluminum bromide, aluminum iodide,
Methylaluminum dichloride, ethylaluminum dichloride, isobutylaluminum dichloride, phenylaluminum dichloride, octylaluminum dichloride, dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, dihexylaluminum chloride, diphenylaluminum chloride,
trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n
-butylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, triphenylaluminum and the like, with aluminum chloride being particularly preferred. As the organic carboxylic acid anhydride used in the present invention, a compound selected from the compounds represented by the following general formula is preferably used. (In the above formulas () to (), R ⁷ , R ⁸ ,
R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ have 1 carbon number
to 24, preferably 1 to 12 alkyl groups, alkenyl groups, aryl groups, or hydrogen, and Y represents an alkyl group, alkenyl group, hydrogen, or halogen atom having 1 to 24 carbon atoms. Also, 6 in the formula ()
The membered ring may include a benzene nucleus, a 6-membered ring consisting of a saturated carbon bond, or a partially unsaturated carbon-carbon bond. ) Examples of such organic carboxylic anhydrides include acetic anhydride, propionic anhydride, n-butyric anhydride, isobutyric anhydride, caproic anhydride, isocaproic anhydride, caprylic anhydride, and lauric acid. Anhydride, palmitylic anhydride, stearic anhydride, crotonic anhydride, phenylacetic anhydride, succinic anhydride, dimethylsuccinic anhydride, glutaric anhydride, maleic anhydride, diphenylmaleic anhydride , benzoic anhydride, toluic anhydride, phthalic anhydride, naphthalic anhydride, pyromellitic dianhydride, etc., with benzoic anhydride and toluic anhydride being particularly preferred. The organic carboxylic acid halide used in the present invention is
general formula

[Formula] (where R ¹⁵ is a hydrocarbon residue having 1 to 24 carbon atoms, preferably 1 to 28 carbon atoms, and X represents a halogen atom), and specific examples include acetyl fluoride and acetyl chloride. Acetyl bromide, acetyl iodide, propionyl chloride, propionyl bromide, n-butyryl chloride, sec-butyryl chloride, t-
Butyryl chloride, n-valeryl chloride, isovaleryl chloride, n-caproyl chloride, capryl chloride, stearoyl chloride, benzoyl chloride, benzoyl fluoride, benzoyl bromide, benzoyl iodide, toluoyl chloride, toluoyl fluoride, Examples include toluoyl bromide and naphthoyl chloride, with benzoyl chloride and toluoyl chloride being particularly preferred. General formula used in the present invention

Compounds represented by [Formula] include monomethyltrimethoxysilane, monomethyltrimethoxysilane, in addition to those listed as compounds represented by the general formula Si(OR ¹ ) _n X _4-n , excluding silicon tetrachloride. Ethoxysilane, monomethyltri-n-butoxysilane, monomethyltrisec-butoxysilane, monomethyltriisopropoxysilane, monomethyltripentoxysilane, monomethyltrioctoxysilane, monomethyltristearoxysilane, monomethyltriphenoxysilane, dimethyldimethoxysilane, Dimethyldiethoxysilane, dimethyldiisopropoxysilane, dimethyldiphenoxysilane, trimethylmonomethoxysilane, trimethylmonoethoxysilane, trimethylmonoisopropoxysilane, trimethylmonophenoxysilane, monoethyltrimethoxysilane, monoethylethoxysilane, Monoethyltriisopropoxysilane, monoethyltriphenoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldiphenoxysilane, triethylmonomethoxysilane, triethylmonoethoxysilane, triethylmonophenoxysilane, monoisopropyltrimethoxysilane ,
Mono-n-butyltrimethoxysilane, mono-n-butyltriethoxysilane, mono-sec-butyltriethoxysilane, monophenyltriethoxysilane, diphenyldiethoxysilane, and repeating units obtained by condensing the above compounds.

Chain or cyclic polysiloxanes represented by the formula can be mentioned. The titanium compound used in the present invention has the general formula _Ti (OR) _o n is 0≦n≦4), titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, monomethoxytrichlorotitanium, dimethoxydichlorotitanium, trimethoxymonochlorotitanium, tetramethoxy Titanium, monoethoxytrichlorotitanium, diethoxydichlorotitanium, triethoxymonochlorotitanium, tetraethoxytitanium, monoisopropoxytrichlorotitanium, diisopropoxychlorotitanium, triisopropoxymonochlorotitanium, tetraisopropoxytitanium, monobutoxytrichlorotitanium, di butoxydichlorotitanium,
Examples include monopentoxytrichlorotitanium, monophenoxytrichlorotitanium, diphenoxydichlorotitanium, triphenoxymonochlorotitanium, and tetraphenoxytitanium. When using an addition compound of a titanium compound and an organic acid ester as the titanium compound, as the organic acid ester, a saturated or unsaturated monobasic or dibasic organic carboxylic acid having 1 to 24 carbon atoms and a carbon number 1 is an ester with ~30 alcohols,
Specifically, methyl formate, ethyl acetate, amyl acetate, phenyl acetate, octyl acetate, methyl methacrylate, ethyl stearate, methyl benzoate,
Ethyl benzoate, n-propyl benzoate, isopropyl benzoate, butyl benzoate, hexyl benzoate, cyclopentyl benzoate, cyclohexyl benzoate, phenyl benzoate, 4-tolyl benzoate, methyl salicylate, ethyl salicylate, p
-Methyl oxybenzoate, ethyl p-oxybenzoate, phenyl salicylate, cyclohexyl p-oxybenzoate, benzyl salicylate, ethyl α-resorcylate, methyl anisate, ethyl anisate, phenyl anisate, benzyl anisate, p-
Methyl ethoxybenzoate, methyl p-toluate, ethyl p-toluate, phenyl p-toluate, ethyl o-toluate, ethyl m-toluate, methyl p-aminobenzoate, ethyl p-aminobenzoate, benzoin Examples include vinyl acid, allyl benzoate, benzyl benzoate, methyl naphthoate, and ethyl naphthoate. Among these, benzoic acid, o
- or alkyl esters of p-toluic acid or p-anisic acid, and methyl esters and ethyl esters thereof are particularly preferred. As an addition compound of a titanium compound and an organic acid ester, one having a molar ratio of titanium compound:organic acid ester of 2:1 to 1:2 is preferable, and examples of these addition compounds include TiCl ₄ .C ₆ H ₅ COOC _{2 H5} ,
TiCl ₄・2C ₆ H ₅ COOC ₂ H ₅ , TiCl ₄・p—
Examples include CH ₃ OC ₆ H ₄ COOC ₂ H ₅ , TiCl ₃ .C ₆ H ₅ COOC ₂ H ₅ and the like. In the present invention, the amount of the titanium compound and/or the addition compound of the titanium compound and the organic acid ester used is not particularly limited, but usually the amount of the titanium compound contained in the solid product is 0.5 to 20% by weight,
It is preferable to adjust the amount to preferably 1 to 10% by weight. As the organometallic compound used in the present invention, an organoaluminum compound known as a component of Ziegler's catalyst is used. Specific examples include the general formulas R ₃ Al, R ₂ AlX, RAlX ₂ , R ₂ AlOR, RAl
(OR) _{An organoaluminum compound of X and R 3 Al 2} , triethylaluminum, triisopropylaluminium, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum chloride, diisopropylaluminum chloride, ethylaluminum sesquichloride, and mixtures thereof, etc. can be given. In the present invention, an organometallic compound and a general formula

The usage ratio of the compound represented by [Formula] is as follows:

The compound represented by the formula is usually used in an amount of 0.001 to 5 moles, preferably 0.01 to 2 moles. In addition, in the present invention, the organometallic compound component has the general formula

Reaction with the compound represented by [Formula] It can also be used as an object. general formula

The amount of the compound represented by [Formula] to be used is preferably such that the Si:Ti ratio is in the range of 0.1 to 100:1 with respect to the titanium compound in the catalyst component [],
A range of 0.3 to 20:1 is more preferred. general formula

When using the compound represented by [Formula] by reacting with the organometallic compound described above, the reaction ratio is determined by the general formula

Compound represented by [Formula]: Organometallic compound (molar ratio)
It is in the range of 0.001 to 5:1, more preferably
It is in the range of 0.01 to 2:1. general formula

The amount of the product obtained by reacting the compound represented by [Formula] with an organometallic compound is preferably such that the Si:Ti ratio is in the range of 0.1 to 100:1 with respect to the titanium compound in the catalyst component [].
A range of 0.3 to 20:1 is more preferred. general formula

There are no particular restrictions on the method for obtaining the reaction product of the compound represented by the formula and the organometallic compound, and the temperature is 0 to 300°C, preferably 50 to 200°C, in the presence or absence of an inert solvent. There is also a method in which the reaction is carried out by contacting for 5 minutes to 2 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 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 substantially in the absence of oxygen, water, etc., in the gas phase, in the presence of an inert solvent, or using the monomer itself as a solvent. The polymerization conditions for olefins include a temperature of 20 to 300°C, preferably 40 to 300°C.
The temperature is 180℃, the pressure is normal pressure to 70Kg/ ^cm2・G,
Preferably it is 2 to 60 kg/cm ² ·G. Molecular weight can be adjusted to some extent by changing polymerization conditions such as polymerization temperature and catalyst molar ratio.
This is effectively carried out by adding hydrogen into 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 problem. 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 1-butene, propylene and 1-butene, 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 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 catalyst components 10 g of anhydrous magnesium chloride, 6 ml of tetraethoxysilane and 1.5 ml of benzoyl chloride were placed in a stainless steel pot with an internal volume of 400 ml containing 25 stainless steel balls each having a diameter of 1/2 inch. After performing ball milling at room temperature under a nitrogen atmosphere for 16 hours, 6 g of anhydrous aluminum trichloride was added and ball milling was performed at room temperature under a nitrogen atmosphere for 16 hours, and further 1.3 ml of titanium tetrachloride was added and the mixture was heated at room temperature under a nitrogen atmosphere. Ball milling was carried out for 16 hours. 1 g of the catalyst component obtained after ball milling contained 22 mg of titanium. (b) Polymerization The stainless steel autoclave equipped with an induction stirrer from step 2 was purged with nitrogen, and 1000 ml of hexane was added, followed by 1 mmol of triethylaluminum, 0.28 mmol of methyltriethoxysilane, and 25 mg of the above catalyst components.
and further hydrogen at a gas phase partial pressure of 0.025Kg/cm ² G
After inserting the tube until the temperature reached 50°C, the temperature was raised to 50°C while stirring. The vapor pressure of hexane was 0.5 kg/cm ² G in the system, and then propylene was continuously introduced so that the total pressure was 7 kg/cm ² G, and polymerization was carried out for 2 hours. After the polymerization was completed, excess propylene was discharged, cooled, and the contents were taken out and dried to obtain 195 g of white polypropylene. This is the total amount of the product, including the amorphous material. Catalytic activity is 600g polypropylene/g solid.
hr・C ₃ H ₆ pressure, 27.3Kg polypropylene/gTihr・
The C ₃ H ₆ pressure and melt flow index were 4.3, while the total extraction residue with boiling n-heptane, including the solvent-soluble polymer, was 96.0%. Comparative Example 1 In Example 1, a catalyst component was synthesized and polymerized in the same manner as in Example 1 except that benzoyl chloride was not used, and 110 g of polypropylene was obtained. The catalyst activity is 340 g polypropylene/g solid・hr・C ₃ H ₆ pressure, 9700 g polypropylene/g Ti・hr・C ₃ H ₆ pressure, and the total extraction residue with boiling n-heptane including solvent-soluble polymer is It was 93%. Comparative Example 2 Catalyst components were synthesized and polymerized in the same manner as in Example 1, except that anhydrous aluminum chloride was not used. 36 g of polypropylene was obtained. The catalyst activity was 110 g of polypropylene/ g solid・hr・C ₃ H ₆ pressure, 2800 g polypropylene/g Ti・hr・C ₃ H ₆ pressure, and the total extraction residue with boiling n-heptane including the solvent-soluble polymer was 90.0%. Comparative Example 3 A catalyst component was synthesized and polymerized in the same manner as in Example 1, except that tetraethoxysilane was not used, and 55 g of polypropyl was obtained. Catalytic activity is 170g polypropylene/g solid.
hr・C ₃ H ₆ pressure, 4300g polypropylene/gTi・
hr·C ₃ H ₆ pressure, and the total extraction residue with boiling n-heptane, including the solvent-soluble polymer, was 88%. Example 2 A catalyst component was synthesized in the same manner as in Example 1, except that 4.5 g of benzoic anhydride was used instead of benzoyl chloride. 1 g of solid powder obtained
contained 20mg of titanium. Catalyst component 20mg
Polymerization was carried out in the same manner as in Example 1 except that 158 g of polypropylene was obtained. Catalytic activity is 610 polypropylene/g solids・hr・
C ₃ H ₆ pressure, 30.4Kg polypropylene/gTi・hr・
_The pressure was _C3H6 , and the total extraction residue with boiling n-heptane, including the solvent-soluble polymer, was 96.5%. Comparative Example 4 A catalyst component was synthesized in the same manner as in Example 2, except that anhydrous aluminum chloride was not used in Example 2, and polymerization was carried out in the same manner as in Example 1. As a result, 23 g of polypropylene was obtained. It was done. Catalytic activity is 70g polypropylene/g solids・hr・
C ₃ H ₆ pressure, 1900g polypropylene/gTi・hr・
_The pressure was _C3H6 , and the total extraction residue with boiling n-heptane, including the solvent-soluble polymer, was 89.5%. Comparative Example 5 A catalyst component was synthesized in the same manner as in Example 2, except that tetraethoxysilane was not used in Example 2, and polymerization was carried out in the same manner as in Example 1, yielding 50 g of polypropylene. . Catalytic activity is 150g polypropylene/g solid.
hr・C ₃ H ₆ pressure, 4200g polypropylene/gTi・
hr·C ₃ H ₆ pressure, and the total extraction residue with boiling n-heptane, including the solvent-soluble polymer, was 85%. Examples 3 to 13 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 Table 1.

【table】

【table】

[Table] Example 14 300ml of 10g of anhydrous magnesium chloride, 6ml of tetraethoxysilane, and 6g of anhydrous aluminum trichloride
After adding 100 ml of n-heptane to a round bottom flask and stirring at 100°C for 2 hours, the n-heptane was removed, and the obtained solid 10
Inner volume containing 25 stainless steel balls with a diameter of 1/2 inch containing 1.5 ml of benzoyl chloride and g
After ball milling in a 400 ml stainless steel pot at room temperature under a nitrogen atmosphere for 16 hours, 10 g of the above milled material, 100 ml of n-heptane, and 20 titanium tetrachloride were placed in a 200 ml round bottom flask under a nitrogen atmosphere.
ml was added and stirred at 100°C for 2 hours. Next, it was washed nine times with 100 ml of n-hexane to remove unreacted titanium tetrachloride, and then dried in vacuum to obtain a catalyst component. 1 g of the obtained catalyst component contained 19 mg of titanium. When propylene was polymerized in the same manner as in Example 1 using the above catalyst components, 169 g of white polypropylene was obtained. Catalyst activity is 520g polypropylene/g solid.
hr・C ₃ H ₆ pressure, 27.4Kg polypropylene/gTi・
hr・C ₃ H ₆ pressure, including solvent-soluble polymers,
The residual rate after extraction with boiling n-heptane was 94.5%. Example 15 Example 14 except that 4.5 g of benzoic anhydride was used instead of benzoyl chloride.
A catalyst component was synthesized in the same manner as in Example 1, and propylene was polymerized in the same manner as in Example 1, yielding 121 g of white polypropylene. Catalytic activity is 370g polypropylene/g solid.
hr・C ₃ H ₆ pressure, 16.1Kg polypropylene/gTi・
hr・C ₃ H ₆ pressure, including solvent-soluble polymers,
The residual rate after extraction with boiling n-heptane was 95%. Example 16 Under a nitrogen atmosphere, 6 ml (28 mmol) of tetraethoxysilane and 100 ml of n-heptane were placed in a 300 ml round bottom flask, and 23 ml of n-heptane solution containing 2 mmol/ml of ethylaluminum dichloride was placed in a dropping funnel for 30 minutes with stirring. Add it over a period of time and then
The mixture was stirred at 100°C for 3 hours to react tetraethoxysilane and ethylaluminum dichloride. 5 g of the reaction product, 1.5 ml of benzoyl chloride, and 10 g of anhydrous magnesium chloride were placed in a stainless steel pot with an internal volume of 400 ml containing 25 stainless steel balls each having a diameter of 1/2 inch, and heated under a nitrogen atmosphere at room temperature for 5 minutes.
After ball milling for an hour, 10 g of co-ground material obtained under nitrogen atmosphere, 100 ml of n-heptane,
Add 20ml of titanium tetrachloride to a 200ml round bottom flask,
The mixture was stirred at 100°C for 2 hours. Next, 100ml of n-hexane
The catalyst was washed nine times to remove unreacted titanium tetrachloride, and then dried under vacuum to obtain a catalyst component. 1 g of the obtained catalyst component contained 23 mg of titanium. Polymerization was carried out in the same manner as in Example 1, except that 1.4 mmol of phenylethoxysilane was used instead of methyltriethoxysilane, and 176 g of polypropylene was obtained.
Catalytic activity is 540g polypropylene/g solids・hr・
C ₃ H ₆ pressure, 23.5Kg polypropylene/gTi・hr・
The pressure was _C3H6 , and the total extraction residue with boiling n _- heptane, including the solvent-soluble polymer, was 95.5%. Example 17 A catalyst component was synthesized in the same manner as in Example 16, except that 4.5 g of benzoic anhydride was used instead of benzoyl 70lide in Example 16, and propylene was polymerized in the same manner as in Example 1. However, 111 g of white polypropylene was obtained. Catalytic activity is 340g polypropylene/g solid.
hr・C ₃ H ₆ pressure, 14.2Kg polypropylene/gTi・
hr・C ₃ H ₆ pressure, including solvent-soluble polymers,
The residual rate after extraction with boiling n-heptane was 95.8%. Example 18 Polymerization was carried out using the same catalyst components as in Example 1, but instead of 1.4 mmol of methyltriethoxysilane used in Example 1, triethylaluminum and tetraethoxysilane in a ratio of 1:1 were used.
Polymerization was carried out in the same manner as in Example 1 except that 0.5 g of the reaction product (molar ratio) was used, and 185 g of polypropylene was obtained. Catalytic activity is 570g polypropylene/g solid.
hr・C ₃ H ₆ pressure, 25.8Kg polypropylene/gTi・
hr·C ₃ H ₆ pressure, and the total extraction residue with boiling n-heptane, including the solvent-soluble polymer, was 96.1%. Example 19 Polymerization was carried out using the same catalyst components as in Example 2, but instead of 1.4 mmol of methyltriethoxysilane used in Example 1, triethylaluminum and tetraethoxysilane were used in a 1:1 molar ratio.
Polymerization was carried out in the same manner as in Example 1, except that 0.5 g of the reaction product was used, and 150 g of polypropylene was obtained. Catalytic activity is 460g polypropylene/g solid.
hr・C ₃ H ₆ pressure, 23Kg polypropylene/gTi・hr・
_The pressure was _C3H6 , and the total extraction residue with boiling n-heptane, including the solvent-soluble polymer, was 96.3%.

[Brief explanation of drawings]

FIG. 1 is a flowchart showing the steps for preparing a catalyst used in the method of the present invention.

Claims (1)

[Claims] 1 [] (1) Magnesium dihalide, (2) General formula Si (OR ¹ ) _n X _4-n (where R ¹ has 1 to 24 carbon atoms)
hydrocarbon residue, X represents a halogen atom, m
is 0≦m≦4), (3)
A compound represented by the general formula R ² _o AlX _3-o (where R ² is a hydrocarbon residue having 1 to 24 carbon atoms, X is a halogen atom, and n is 0≦n≦3), and ( 4) A solid material obtained by contacting an organic carboxylic acid halide and/or an organic carboxylic acid anhydride with the general formula Ti(OR _{) o} group or aralkyl group, and X represents a halogen atom.n
is 0≦n≦4) and/or a solid catalyst component obtained by supporting a titanium compound and/or an addition compound of the titanium compound and an organic acid ester, [] General formula (Here, R ³ , R ⁴ , R ⁵ represent a hydrocarbon residue having 1 to 24 carbon atoms or an alkoxy group, and R ⁶ represents a hydrocarbon residue having 1 to 24 carbon atoms. q is 1≦q
≦30) and an organoaluminum compound.