JPS5956405A - Production of polyolefin - Google Patents

Abstract

PURPOSE:To obtain a highly stereoregular polyolefin in high activity, by using a catalyst comprising a specified catalyst component, an organometallic compound and a specified silane compound or a ketone compound. CONSTITUTION:An alpha-olefin is polymerized or copolymerized by using a catalyst prepared by combining [ I ] a solid catalyst component obtained by allowing a solid substance obtained by contacting (a) a magnesium halide with (b) a compound of the formula, wherein R<1>, R<2>, and R<3> are each a 1-24C hydrocarbon residue, an alkoxy, H or a halogen, R<4> is a 1-24C hydrocarbon residue, and 1<=n<=30, and (c) a ketone compound to support a titanium compound and/or a titanium compound/electron doneor adduct, with [II] an organometallic compound, a compound of the formula and/or a ketone 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.

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 when a catalyst component in which titanium tetrachloride is supported on an inorganic solid assembly such as 1Mg012 is used, a highly active catalyst can be obtained.

However, in the production of polyolefins, it is preferable to have as high a catalyst activity as possible, right? -・Uji A highly active catalyst was desired. It is also important that the amount of atactic portion of the carapace formed is as small as possible.

As a result of intensive research on these points, the present inventors found that
Here, a new catalyst was discovered. Ding, that is,
The present invention relates to a method for producing an extremely highly active erect irregular polyolefin using a novel catalyst. By using the catalyst of the present invention, the monomer partial pressure during synthesis is low and The amount of catalyst residue in the produced polymer is extremely small after a short time on the stand, so the catalyst removal step can be omitted in the polyolefin manufacturing process, and the amount of atactic moiety 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 provides [I:N1) magnesium halide, (2)
1 represents a hydrocarbon residue having 1 to 24 carbon atoms, an alkoxy group, hydrogen or a halogen, and R4 represents a hydrocarbon residue having 1 to 24 carbon atoms. n is 1≦n≦3o. ), X, and (3) a solid catalyst component obtained by supporting a solid substance obtained by contacting a ketone compound with (4) a titanium compound and/or an addition compound of a titanium compound and an electron donor. , []T) an organometallic compound, and ['N) (5) a hydrocarbon residue of general formulas 1 to 24,
It represents an alkoxy group, hydrogen or halogen, and R4 represents a hydrocarbon residue having 1 to 24 carbon atoms. n is 1≦n≦3'0
It is. ) and/or (6) A method for producing polyolefins with extremely high activity and high stereoregularity by polymerizing or copolymerizing α-olefins using a catalyst comprising a combination of the compound represented by (6) and (6) a ketone compound. .

The present invention includes (1) magnesium halide, (2)
) There are no restrictions on the load as a method for obtaining the solid WI contribution of the general formula invention,
In the presence or absence of an inert solvent at a temperature of 20 to 40 F.
Under heating at 0°C, preferably 50 to 300°C, usually 5
The reaction may be carried out by contacting for 1 to 20 hours, by co-pulverization, or by appropriately combining these methods.

Furthermore, there is no particular restriction on the reaction order of components (1) to (3), and the three components may be reacted at the same time, or the two components may be reacted and then the remaining one component may be reacted. .

The inert solvent is not limited to specific solvents, and it is possible to use hydrocarbon compounds or derivatives thereof that do not normally inactivate the Tegler type catalyst. 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, S and ethanol, Examples include alcohols, ethers, and esters such as diethyl ether, tetrahydrofuran, ethyl acetate, and ether benzoate.

For co-pulverization, ball mills, vibration mills,
Using equipment such as rod mills and +tu palm mills, the
2() at a temperature of 0°C, preferably 20-100'C, 0
．． 5~! It is recommended to do this for 10 hours.

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

In the present invention, the components (1) are magnesium halide and the component (2) has the general formula %1. The molar ratio of component (3) to component (3) is 1:0.001 to 10.
, preferably 1:0.01-1.

A titanium compound, vlJ and/or an addition compound of a titanium compound and an electron donor are added to the solid support thus obtained. By making it 4, lI! ! 11 As a method for supporting the titanium compound 2 and/or the dissociation compound W of the titanium compound and the electron donor on all the catalyst components, Koyo's method can be used. For example, by bringing the solid support into contact with a titanium compound and/or an addition compound of a titanium compound and an electron donor with heating F in the presence or absence of an inert bath medium. Preferably, both are heated at 50 to 300°C, preferably 100 to 15°C, in the presence of an inert solvent such as n-hexitine.
This is conveniently carried out by heating to 0°C. The reaction time is not particularly limited, but is usually 5 minutes or more,
Although it is not necessary, there is no problem in contacting II5 for a long time. For example, the processing time can be 5 minutes to 10:11. Of course, this process requires oxygen,? The test should be carried out under an inert gas atmosphere and free of moisture.

After the completion of the reaction, the method for removing the unreacted titanium compound Σ and/or the addition compound of the titanium compound and the electron donor is not particularly limited, and the method includes washing the Tegler catalyst several times with a solvent inert to the catalyst and reducing the pressure of the washing solution. It can be evaporated under conditions to obtain a solid powder. Another preferred method is a method of co-pulverizing a solid support and a required amount of titanium compound S and/or a 9-addition compound of a titanium compound and an electron donor.

In the present invention, co-grinding is usually carried out at a temperature of 0'C to 20[]''C, preferably 20C to 100C, to obtain the catalyst batch of the present invention. The grinding operation should be carried out in an inert atmosphere and should be free of moisture.

The magnesium halide used in the present invention is practically anhydrous and includes magnesium fluoride, magnesium chloride, magnesium bromide, magnesium iodide B, and mixtures thereof, but magnesium chloride is particularly preferred. preferable.

Hydrocarbon groups of general formulas 1 to 24, preferably 1 to 18, used in the present invention, Ar 1
〇 - Represents a lukoxy group, hydrogen or herogen, R4 is carbon #
! i1 to 24, preferably 1 to 18 hydrocarbon residues. n is 1≦n≦30. ) Examples of the compounds represented by are monomethyltrimethoxysilane, monomethyltriethoxysilane, monomethyltri-n-butoxysilane, monomethyltri8ec-butoxysilane, monomethyltriinoproboxysilane, monomethyltripentoxysilane, and monomethyltrioctoxysilane. Silane, monome fl
l/tristearoxysilane, monomethyltriphenoxysilane, dimethyldimethoxysilane, dimethyljethoxysilane, dimethyldiisobroboxysilane, dimethyldiphenoxysilane, trimethylmonomethoxysilane, trimethylmonoethoxysilane, trimethylmonoisopropoxysilane, trimethyl monophenoxysilane,
Monomethyldimethoxymonochlorosilane, monomethyljethoxymonochlorosilane, monomethylmonoethoxydichlorosilane, monomethyljethoxymonochlorosilane, monomethyljethoxymonobromosilane, monomethyldiphenoxymonochlorosilane, dimethylmonoethoxymonochlorosilane, monoethertrimethoxysilane, monoether Trimethoxysilane, monoethyltriynepropoxy 7rane, monoethyltriphenoxysilane, diethyldimethoxysilane, diethyldimethoxysilane, diethyldiphenoxysilane, triethylmonomethoxysilane, triethylmonoethoxysilane, triethylmonophenoxysilane, monoethyldimethoxy Monochlorosilane, monoethyljethoxymonochlorosilane, monoetherdiphenoxymonochlorosilane, monoisopropyltrimethoxysilane, mono-n-butyltrimethoxysilane, mono-n-butyltriethoxysilane, mono-5eC-
Butyltriethoxysilane, monophenyltriethoxysilane, diphenyljethoxysilane, diphenylmonoethoxymonochlorosilane, monomethoxytrichlorosilane, monoethoxytrichlorosilane, mono n-butoxytrichlorosilane, mono n-butoxytrichlorosilane, monopentoxytrichlorosilane Chlorosilane, monooctoxytrichlorosilane, monostearoxytrichlorosilane, monophenokiditrichlorosilane, mono p-methylphenokiditrichlorosilane, dimethoxydichlorosilane, jetoxydichlorosilane, diimpropoxydichlorosilane, di-n-butoxydichlorosilane, dioctochlorosilane Cydichlorosilane, trimethoxymonochlorosilane, triethoxymonochlorosilane, triisopropoxymonochlorosilane, tri-n-butoxymonochlorosilane, tri8ee-butoxymonochlorosilane, tetraethoxysilane, tetraisopropoxysilane and the above compounds are condensed together , or cyclic polysilxanes. It can also be used as a mixture of these.

(a) represents a hydrocarbon residue such as an alkyl group, alkenyl group, aryl group, or aralkyl group having 1 to 24 carbon atoms, and may be the same or different. These may be organic residues including nitrogen, nitrogen, sulfur, chlorine, and other radicals.

Further, R and R' may form a ring. 2 is +C
H2+ represents an aromatic hydrocarbon group or an alicyclic hydrocarbon group, and n is 0≦n≦10. ) and (ii)
Examples include quinones. Moreover, these may be used as a mixture.

(Compounds represented by the general formula R-convex-R' include acetone, methyl ethyl ketone, methyl n-propyl ketone, diethyl ketone, 2-hexanone, 3-
Hexanone, methyl t-butyl ketone, syllabary ketone, diisobutyl ketone, moro-amyl ketone, distearyl ketone, ethylbenzyl ketone, 2.5-dimethyl-3-hexanone% 2-methyl-3-heptanone, 2-methyl-4- Heptanone, 5-methyl-3-heptanone, 2-octanone, 3-octanone, holon, 2
．． 6-Simethyl-4-heptanone, 2-nonanone, benzalacetone, benzyl acetone, 3-decanone, benzyl isopropyl ketone, 2-undecanone, benzyl n-butyl ketone, 3-dodecanone, 2-methyl-4-
Undecanone, isobutylstyryl ketone, 2-tridecanone, α-ionone, β・-ionone, 1.1-diphenylacetone, 1.5-diphenyl-2-propanone, 8
-Pentadecanone, 3-hexadecamene, dicinnamalacetone, heneicosanone, 12-) liconanone, 1
6-hentriacontanone, 18-pentatriacontanone, 1,5-diphenyl-1,4-pentadiene-3
-one, 9-heptadecanone, β-methylionone, γ-
Methylionone, benzophenone, acetophenone, gropiofenone, p-methylacetophenone, m-methylacetophenone, phenylpropenyl t-ton, benzalacetophenone, 1-phenyl-1,6-butadione,
0-ethylacetophenone, inglobylphenylketone, isoparelophenone, valerophenone, 2-acetonaphthone, 1-acetonaphthone, cyclopentylphenylketone III'-"-butylacetophenone, n-hegisanophenone, n-heptanophenone, benzyl phenyl ketone , n-octanophenone, chalcone, 4.4
-dimethylbenzophenone, n-decanophenone, β-
naphthylphenylketone.

Rau tetraphenone, n-tetrazocaffenone, cyclohexanone, 3-methylcyclohexanone.

2-Methylcyclohexanone, cyclopentanone, Schiftetraheptanone, 1-indanone, 2.6-Cifthylcyclohexanone, 3.5-dimethylschiftetrahexanone, 5
, 3.5-trimethylcyclohexanone, α-tetralone, 2-adamantane, camphor, 2-cyclopentylcyclopentanone, 4-1-butylcyclohexanone, menthone, 2-n-hexylcyclopentanone, 4
-n-pentylcyclohexanone, 2-cyclohexylcyclohexanone, cyclodecanone, 2-n-hebutylcyclopentanone, 9-fluorenone, 2-benzylidenecyclohexanone, anthrine, 5-schif-17-lohexadecen-1-one, cyclooctanone, 2- Acetylcyclopentanone, 2-acetylcy(ii) Compounds represented by the general formula R-C-Z-CR' include diacetyl, acetylacetone, 2.3-pentadione, acetonylacetone, 2.3-hexadione, 2
, 3-hebutadione, 6-methyl-2,4--butadione, dibenzoylmethane, dibenzoyl, 1-phenyl-i, 2-7'lobandione, p-cya-7tylbenzene, and the like.

θil) Quinones include benzoquinone, duroquinone, α-naphthoquinone, β-naphthoquinone, p-torquinone, p-xyquinone, triquinonyl, acenaphthenequinone, anthraquinone, 9.10-7 enanthrenequinone, 2,5-di- t-butyl-p-quinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-t
-butylanthraquinone, 1,2-benzanthraquinone, 2.5-diphenyl-p-benzoquinone, 1.2-
Examples include cyclohexanedione and 1,4-cyclohexanedione.

As the titanium compound used in the present invention, tetravalent titanium compounds and trivalent titanium compounds are suitable. Specifically, the tetravalent titanium compound has the general formula Ti(OR)n
Preferably, those represented by Titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, monomethoxytrichlorotitanium, dimethoxydichlorotitanium, trimethoxymonochlorotitanium, tetramethoxytitanium, monoethoxytrichlorotitanium, jetoxydichlorotitanium, triethoxymonochlorotitanium, tetraethoxytitanium , monoisopropoxytrichlorotitanium, diisopropoxydichlorotitanium, triisopropoxymonochlorotitanium, tetraisopropoxytitanium,
Monobutoxytrichlorotitanium, dibutoxydichlorotitanium, monopentoxytrichlorotitanium, monophenoxytrichlorotitanium, diphenoxydichlorotitanium, triphenoxymonochlorotitanium.

Examples include tetraphenoxy titanium.

Examples of trivalent titanium compounds include trihalides obtained by reducing titanium tetrahalides such as titanium tetrachloride and titanium tetrabromide with tree leaves, aluminum, titanium, or organometallic compounds of metals from groups I to Groups of the Periodic Table. Titanium is mentioned. Also, the general formula TI(OR)mX4-m (where R represents an alkyl group, aryl group, or aralkyl group of carbon'I & 1 to 2°, and X represents a halogen atom. m is 0 <
m<4. Examples include hexavalent titanium compounds obtained by reducing a tetravalent alkoxyhalide represented by ) with an organometallic compound belonging to groups I to II of the periodic table.

Further, when an addition compound of a titanium compound and an electron donor is used as the titanium compound, an oxygen-containing compound is preferable as the electron donor. Examples include ether, phenol, aldehyde, ketone, and polyester. Specifically, examples of the ether compound include dimethyl ether, dimethyl ether, methyl ethyl ether, diisoamyl ether, diallyl ether, and tetrahydrofuran.

Examples include dioxane, anisole, diphenyl ether, and the like. Phenol compounds include phenol, 0-
Cresol, m-cresol, p-cresol, β-naphthol, eugenol, isoeugenol, 0-cyclohexylphenol, m-cyclohexylphenol, p-cyclohexylphenol, catechol, resorcinol, hydroquinone, 1,3.5 -trihydroxybenzene and the like. Examples of aldehyde compounds include formaldehyde, acetaldehyde, glyoxal, isobutyraldehyde, stearylaldehyde, acrolein, crotonaldehyde, benzaldehyde so-tolylaldehyde, m-)lylaldehyde, p-tolylaldehyde,
Examples include anisaldehyde and 9-anthraaldehyde. As the ketone compound, the above-mentioned compounds can be mentioned. Examples of organic acid ester compounds include methyl formate, ethyl formate, methyl acetate, ethyl acetate, butyl acetate, methyl acrylate, methyl methacrylate, octyl butyrate, ethyl laurate, octyl laurate, methyl benzoate, ethyl benzoate, p -Octyl oxybenzoate, diisobutyl phthalate, dioctyl phthalate, dimethyl malonate, dimethyl maleate, diethyl maleate, and the like.

In the present invention, the amount of the titanium compound and/or the addition compound of the titanium compound and the electron donor used is not particularly limited, but the amount of the titanium compound contained in the solid product is usually 05 to 20% by weight, preferably /dj It is preferable to adjust the amount to 10% by weight.

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. A specific example is the general formula R3Al.

R2AIX, RAIXz, R2AlOR, RAJ(OR
)X and R3Al2X3 organoaluminum compounds (
However, R is an alkyl group or an aryl group having 1 to 20 carbon atoms; (the two groups may be the same or different); triethylaluminum, triisobutylaluminum, triisobutylaluminum, tri5ec-butylaluminumtritcrt-butylaluminum, trihexylaluminum , trioctylaluminum, diethylaluminium chloride, diisopropylaluminum chloride chloride, diethylzinc, and mixtures thereof.

In the present invention, the proportion of the organometallic compound and the compound represented by the formula RL+S i - 0+rlR'2 and/or the ketone compound (component (6)) is the same as the component ((6)) relative to 1 mole of the organometallic compound. 5) Compound represented by general formula 1 and/or component (6) ketone compound.Usually 0,001 to 5 mol, preferably 0,01 to 2 mol are used.

In the present invention, a specific metal compound or component can also be used as a reaction product of the organometallic compound and component (5) a compound represented by the general formula and/or component (6) a ketone compound.

The amount of component (5) the compound represented by the general formula and/or component (6) the ketone compound used is preferably such that the 3i:Ti ratio is in the range of 01 to 100:1 relative to the titanium compound in the catalyst component [1].
More preferred is a slope of 0.03 to 20:1.

In addition, when using an organometallic compound and component (5) a compound represented by the general formula and/or component (6) a ketone compound, the reaction ratio is 1 mole of the organometallic compound to 1 mole of component (5). R"(-Si-0-)- R number n 1 2 6- and/or component (6) ketone compound! is usually 0.001 to 1 mol, preferably 0.01
~2 moles are used.

The amount of the product obtained by reacting the specific metal compound with component (5) the compound represented by the general formula and/or component (6) the ketone compound is 3i based on the titanium compound in catalyst component CI). :'['i ratio is 0.1 to 1oo:1. Preferably it is in the range of 0.3 to 20:1.

There is no particular limit to the method for obtaining a reaction product between an organometallic compound and component (5) a compound represented by the general formula % formula % and/or a ketone compound.
- -50° to 40° in the presence or absence of an inert solvent
There is also a method in which the reaction is carried out by one contact at a temperature of 0°C, preferably 50 to 300°C, for 5 minutes to 20:11.

In the present invention, the amount of the metal compound used is not particularly limited, but it is usually 0.1 to 1
000 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. In other words, all reactions take place virtually in the gas phase, without water, etc.

Alternatively, it is carried out in the presence of an inert solvent or using the monomer itself as a solvent. The polymerization conditions for the olefin are as follows: the temperature is 20 to 600°C, preferably l-1:40 to 180°C, and the pressure is normal pressure to 70 to 97 cm''·G, preferably 2 to 6Q K4/am2·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, there is no problem with a two-step or more multi-step polymerization reaction with different polymerization conditions such as hydrogen concentration and polymerization temperature. It is applicable to the polymerization of α-olefins such as ethylene, propylene, and butene-1,4-methylpentene-1, and the random polymerization of ethylene and propylene, ethylene and butene-1, and propylene and butene-1. and block copolymerization. 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.

291 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 101/(105 mmol) of anhydrous magnesium chloride and 6 ml (27 mmol) of tetraethoxysilane were contained in 25 stainless steel balls each having a diameter of 1 inch, with an internal volume of 400 tons! ! After ball milling at room temperature under a nitrogen atmosphere for 16 hours, 123 g (55 mmol) of dibenzoylmethane was added and ball milling was performed at room temperature under a phonetic atmosphere for 16 hours to give a rough texture. Add titanium tetrachloride 2-16 at room temperature under nitrogen atmosphere.
Time=30- Ball milling was performed to obtain a catalyst component. 1 g of the obtained catalyst component contained 28 m9 of titanium. (b) Polymerization The autoclave made of stainless steel with an induction stirrer of 31 was purged with nitrogen, and 1500 m9 of n-hexane was added. 10 mmol of triethylaluminum, 30 mmol of tetraethoxysilane 03-9 were added, and 0.05 kg of hydrogen was added at a gas phase partial pressure.
/ cv2, and then stirred at 50
The temperature was raised to ℃. The vapor pressure of n-hexane is 0,5
Kg/cm2 o, but then propylene for metalwork is 7
Polymerization was started by charging the reactor until the pressure reached Ky/cm"G. Propylene was continuously introduced so that the total pressure was 7 Kp/cm2G, 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 white polypropylene 215I. This is the total amount of the product, including the amorphous material.

Catalytic activity: 551g polypropylene/g solids・h
Cs H6sho, 20 to 2 polypropylene/1l Ti-h
r-C3H6 pressure, and the total extraction residue (total II) with boiling n-hebutane, including solvent-soluble polymers, is 945%.
The melt flow index was 86.

Comparative Examples 1 to 6 Same as Example 1 except that the catalyst component was synthesized by a method similar to Example 1 and LRA, and the aromatic carbon limited ester listed in Table 1 was used instead of tetraethoxysilane. The polymerization was carried out by the method. The results are shown in Table 1.

Comparative Example 4 A catalyst component was synthesized in the same manner as in Example 1, except that dibenzoylmethane was not used, and polymerization was carried out in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 5 A catalyst component was synthesized in the same manner as in Example 1, except that tetraethoxysilane was not used, and polymerization was carried out in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 6 A catalyst component was synthesized in the same manner as in Example 1, except that ethyl benzoate was used instead of dibenzoylmethane in Example 1, and polymerization was carried out in the same manner as in Example 1. .

The results are shown in Table 1.

Examples 2 to 17 Catalyst components were synthesized in the same manner as in Example 1, except that the ketone compounds listed in Table 2 were used instead of dibenzoylmethane in Example 1. Polymerization was carried out using the following method. The results are shown in Table 2.

Examples 18 to 22 The catalyst components were prepared in the same manner as in Example 1, except that the various compounds listed in Table 2 were used instead of tetraethoxysilane in the synthesis of the catalyst components in Example 1. It was synthesized and polymerized in the same manner as in Example 1. The results are shown in Table 2.

Examples 26 to 27 In the synthesis of the catalyst component of Example 1, adducts of titanium tetrachloride and electron donors listed in Table 2 were used instead of titanium tetrachloride, and adducts of titanium tetrachloride and an electron donor listed in Table 2 were used instead of dibenzoylmethane. A catalyst component was synthesized in the same manner as in Example 1, except that a ketone compound was used, and polymerization was carried out in the same manner as in Example 1. I showed the results to 2.

Example 28 3 4- (a) Synthesis of catalyst components 10 g of anhydrous magnesium chloride and 6 tetraethoxysilane
A stainless steel bowl with a diameter of 1 inch contains 2 ml
After ball milling was performed at room temperature under nitrogen atmosphere for 16 hours in a stainless steel pot containing 5 pieces with an internal volume of 400, dibenzoylmethane 123I was added and ball milling was performed at room temperature under nitrogen atmosphere for 16 hours. . The obtained co-pulverized product was placed in a 300-mm round bottom flask under a nitrogen atmosphere.
50 ml of titanium tetrachloride and 100 ml of n-hebutane were added, and the mixture was stirred at 100° C. for 2 hours to react. Then n
- Washing with 100 ml of hexane 9 times to remove unreacted titanium tetrachloride was followed by vacuum drying to obtain a catalyst component. 1 g of the obtained catalyst component contained 29 μg of titanium.

(b) Polymerization It was carried out in the same manner as in Example 1, and the results are shown in Table 2.

Example 29.30 The catalyst components were synthesized in the same manner as in Example 28, except that the ketone compounds listed in Table 2 were used instead of dibenzoylmethane in the synthesis of the solid catalyst in Example 28. Polymerization was carried out in the same manner as in Example 1. The results are shown in Table 2.

Example 31 Polymerization was carried out using the catalyst components of Example 1 in the same manner as in Example 1, except that the amount of tetraethoxysilane used in the compounding was 0.5 mmol. The results are shown in Table 2.

Example 32 The stainless steel autoclave equipped with induction stirrer No. 31 was purged with nitrogen, 1500 yffl of n-hexane was added, 1.0 mmol of triethylaluminum and 0.3 mmol of tetraethoxysilane were added, and the temperature was raised to 50°C while stirring. , and allowed to react for 30 minutes. Thereafter, it was cooled to room temperature, 30 ~ of the catalyst of Example 1 was added, and the water pressure was further increased to 0.0 at a gas phase partial pressure.
The system was charged to a pressure of 5 Ky/cm" and then heated to 50°C while stirring. The vapor pressure of n-hexane gave the system a pressure of 0.5 Kg/cm", but propylene was then increased to a total pressure of 7 Ky/cm. The pressure was increased to cm2G and polymerization was started. The following steps were carried out in the same manner as in Example 1. The results are shown in Table 2.

Examples 33 to 35 In the same manner as in Example 1, except that the catalyst components of Example 1 were used and the silicon compounds shown in Table 2 were used instead of tetraethoxysilane in the polymerization of Example 1. Polymerization was performed. The results are shown in Table 2.

Examples 36-38 Similar to Example 1 and 37, except that the catalyst components of Example 1 were used and the ketone compounds shown in Table 2 were used in place of tetraethoxysilane in the polymerization of Example 1. The polymerization was carried out by the method. The results are shown in Table 2.

Example 39 Example 3 except that 4 mmol of dibenzoyl was used instead of 03 mmol of tetraethoxysilane in Example 32.
I made 1 cup using the method of 2 and L.

The results are shown in Table 2.

Example 40.41 Example 1 except that in the polymerization of Example 1, 04 mmol of the silicon compound listed in Table 2 and 0.1 mmol of the ketone compound were used instead of 03 mmol of tetraethoxysilane. Polymerization was carried out in the same manner as. The results are shown in Table 2.

Example 42 Polymerization was carried out in the same manner as in Example 4 using the catalyst components of Example 23. The results are shown in Table 2.

Example 43 38--04 mmol of tetraethoxysilane, 0.1 mmol of dibenzoyl instead of 0.6 mmol of tetraethoxysilane in the polymerization of Example 32 using the catalyst components of Example 25
(2) 1 cup was carried out in the same manner as in Example 32, except that mmol was used. The results are shown in Table 2.

Example 44 Triethylaluminum and tetraethoxysilane (AI(CzHs)3/S) were substituted for tetraethoxysilane in the polymerization of Example 1 using the catalyst of Example 1.
i (OC2Hs)4 (molar ratio) = 3.371)
Polymerization was carried out in the same manner as in Example 1, except that 0.4 g of the reactant was used. The results are shown in Table 2.

Procedural amendment February 22, 1980 Kazuo Wakasugi, Commissioner of the Japan Patent Office1, Indication of the case, Patent Application No. 165002 of 19822, Name of the invention Process for producing polyolefin 3, Person making the amendment Relationship with the case Poetry permit Applicant name (444) Nippon Oil Co., Ltd. 5, Detailed explanation of the invention column 6 of the specification subject to amendment, Contents of the amendment (1) “0.5 hour stopper” in line 4 on page 10 of the specification, all “ 0.
Corrects color powder for 5 to 30 hours.

(2) "Hydrocarbon group" at the end of page 10 of the same book is corrected to "hydrocarbon residue."

(3) Two lines from the bottom of page 12 of the same book: “Mono nJ2r Mono n
- Correct as J.

(4) In the same book, p. 24, line 1, the entire sentence "may be different" is amended to "may be different."

(5) In the second line from the bottom of page 27 of the same book, "or ketone" is corrected to read "or ingredient 6) ketone" in its entirety.

(6) In the upper right column of Table 1 on page 40 of the same book, the unit of titanium activity is "~/Ti・hr・pressure" k r Ky/ gT
i-hr・pressure”.

(7) “α5iCOC2H5)4 J to rQ)-
Correct as si (oc2n5) 3J.

Claims (1)

[Claims] CI: Hl) Magnesicium halide, R,1 几2, R3 represents a hydrocarbon residue having 1 to 24 carbon atoms, an alkoxy group, hydrogen or a halogen, R4 represents a carbon number of 1 to 2
The hydrocarbon residue of No. 4 is shown. n is 1≦n≦30. )
A solid catalyst component obtained by carrying (4) a titanium compound and/or an addition compound of a titanium compound and an electron donor on a solid substance obtained by contacting a compound represented by (6) a ketone compound. , [■] Organic position compound proboscis, Z and R' R1, R'' represent a hydrocarbon residue having 1 to 24 carbon atoms, an alkoxy group, hydrogen or halogen, and R4 represents a carbon number of 1 to 2
The hydrocarbon residue of No. 4 is shown. n is 1≦n≦30. )
A method for producing a polyolefin comprising polymerizing or copolymerizing an α-olefin using a catalyst formed by combining the compound represented by (8) and/or (6) a ketone compound.