JPH02242804A - Polymerization of olefin - Google Patents

Abstract

PURPOSE:To obtain a highly stereoregular olefin polymer in high yield at low cost by using a catalyst made up of a solid catalytic cmoponent containing Ti, Mg and halogen, an organoaluminum compound and an acetal compound of specific structure. CONSTITUTION:An olefin is polymerized in the presence of a catalyst made up of (A) a solid catalytic component containing Ti, Mg and halogen, (B) an organoaluminum compound (pref. triethylaluminum) and (C) an acetal compound of the formula (R<1> and R<6> are each hydrocarbon residue; R<2> - R<5> are H, or hydrocarbon, etc.) (e.g. 5,5-dimethoxy-1,3-cyclopentadiene). It is preferable that the Mg compound, Ti compound and halogen each constituting the component A to be magnesium chloride, TiCl4 etc. and chlorine, respectively. The polymerization temperature is pref. at 20 - 130 deg.C.

Description

Detailed Description of the Invention (1) Industrial Application Field The present invention relates to a method for producing olefins using a catalyst that exhibits high performance when used in the polymerization of olefins.
In particular, the present invention relates to a method for producing olefins that can produce highly stereoregular polymers in high yield during the polymerization of α-olefins having 3 or more carbon atoms.

(2) Prior art Conventionally, esters (for example, JP-A-48-16986) and organic silicon compounds (JP-A-54-94590, JP-A-54-55) have been used as promoter components of supported Ziegler catalysts.
-36203, 57-63312) or acetal compounds (JP-A-61-145206, JP-A-61-271304, JP-A-62-54705, JP-A-62-54706). well known.

However, according to our knowledge, when the above-mentioned compounds are used as co-catalyst components of supported Ziegler catalysts, each of them has serious drawbacks as shown below.

That is, regarding esters, (a) It is necessary to add a large amount.

(b) brings about a significant decrease in polymerization activity;

(c) Insufficient stereoregularity.

(d) Offensive odor due to ester remaining in the produced polymer.

Regarding organic silicon compounds, (a) Polymerization activity is insufficient for practical use.

(b) The price is high.

As for the conventional acetal type.

(a) It is necessary to add a large amount.

(b) brings about a significant decrease in polymerization activity;

(c) Insufficient stereoregularity.

Therefore, there is a strong demand to develop a catalyst that solves all of the above problems.

(3) Problems to be Solved by the Invention It is an object of the present invention to provide a cocatalyst which solves the above-mentioned drawbacks, has high polymerization activity and stereogenic support, is free from bad odor, and is relatively inexpensive.

(4) Means for Solving the Problems The present inventors have made extensive studies to obtain a cocatalyst system that solves these problems.

In the method of producing an olefin polymer by polymerizing olefins in the presence of a catalyst, the catalyst used is (A) a solid catalyst component containing titanium, magnesium, and halogen as essential components, (B) an organoaluminum compound, and (C) The following general formula (1), RI R8 (wherein R1 and R6 are hydrocarbon residues, R2-R5 are hydrogen, hydrocarbons, halogenated hydrocarbons, or residues of a compound containing a heteroatom, and R2+ R6 may be wholly or partially the same or different, and RI
Re may form a ring in whole or in part.

) The present invention has been achieved by discovering a method for polymerizing olefins characterized in that they are formed from acetal compounds represented by:

The gist of the present invention is to use an acetal compound having a specific structure as a cocatalyst component, especially a component called an external donor, and it is believed that the acetal compound having this specific structure has such an effect. This was unexpected.

The present invention will be specifically explained below.

Magnesium compounds used in the present invention include magnesium halides such as magnesium chloride and magnesium bromide, alkoxymagnesiums such as ethoxymagnesium and isopropoxymagnesium, and magnesium carboxyl compounds such as magnesium laurate and magnesium stearate. * Examples include salts and alkylmagnesiums such as butylethylmagnesium. Moreover, a mixture of two or more of these compounds may be used. Preferably, magnesium halide is used, or magnesium halide is formed during catalyst formation. More preferably, the halogen is chlorine.

Examples of the titanium compound used in the present invention include those represented by the following general formula.

T i Xm (OR?) 1 Here, X is a halogen, R7 represents a hydrocarbon group having 36 or less carbon atoms, m and l are O to 4, and 1m+1 is 3 or 4.

Specific examples include titanium halides such as titanium tetrachloride, titanium trichloride, and titanium tetrabromide, titanium alkoxides such as titanium butoxide and titanium ethoxide, and alkoxytitanium halides such as phenoxytitanium chloride. It may also be a mixture of two or more of these compounds.

Preferred are tetravalent titanium compounds in which X is chlorine. Specific examples include titanium tetrachloride, butoxytrichlorotitanium, and tetrabutoxytitanium.

The halogen used in the present invention is fluorine, chlorine, bromine, or iodine, preferably chlorine.

The specific compounds of the halogen source actually exemplified depend on the catalyst preparation method, but include titanium halides such as titanium tetrachloride and titanium tetrabromide, silicon halides such as silicon tetrachloride and silicon tetrabromide, and silicon halides such as silicon tetrachloride and silicon tetrabromide. Typical examples include phosphorus halides such as phosphorus chloride and phosphorus pentachloride.

Depending on the preparation method, halogenated hydrocarbons, simple halogens,
1 m of hydrogen halide (HCI, HBr, HI
etc.) may be used. These may be common to titanium compounds and magnesium compounds.

When producing TM the solid catalyst component (A) used in the present invention, various electron donors (internal donors) may be added,
It is also preferable. Examples of the electron donor include oxygen-containing compounds and nitrogen-containing compounds. More specifically, (a) methanol, ethanol, propatool, butanol, pentanol, hexanol, octatool,
Alcohols having 1 to 20 carbon atoms, such as dodecanol, octadecyl alcohol, 2-ethylhexyl alcohol, benzyl alcohol, cumyl alcohol, diphenylmethanol, triphenylmethanol, (b)
Phenol, cresol, cumylphenol, ethylphenol, propylphenol.

Phenols having 6 to 25 carbon atoms that may have an alkyl group such as nonylphenol and naphthol, (c) acetone, methyl ethyl ketone, methyl isobutyl ketone,
Ketones having 3 to 15 carbon atoms such as acetophenone, benzophenone and cyclohexanone; (d) Aldehydes having 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, tolualdehyde and nathaldehyde; (e) methyl formate, ethyl formate; WIR Methyl,
Ethyl acetate, furovir #acid, octyl acetate, cyclohexyl acetate, methyl cellosolve acetate, cellosolve acetate, butyl cellosolve acetate, ethyl propionate, methyl n-butyrate, ethyl isobutyrate, isopropyl isobutyrate, ethyl valerate, butyl valerate, stearic acid Ethyl, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate,
Ethyl methacrylate, ethyl cyclohexanecarboxylate, propyl phenylbutyrate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate,
Benzyl benzoate, cellosolve benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethylbenzoate, methyl anisate.

Ethyl anisate, ethyl ethoxybenzoate, diethyl phthalate, diisobutyl phthalate, diheptyl phthalate,
Dineopentyl phthalate, γ-butyrolactone, γ~
valerolactone, coumarin, phthalide, diethyl carbonate,
Organic acid esters having 2 to 20 carbon atoms such as trimethyl orthoformate, ethyl orthoformate, (f) methyl borate, ethyl borate, methyl silicate, ethyl silicate, butyl silicate, butyl titanate, butyl phosphate, trimethyl phosphite ,
Inorganic acid esters with a carbon number of 30 or less, such as diethyl phosphite, di(2-phenyl) phosphorochlororizoite, dimethyl *acid, and diethyl sulfate, (g) methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran , anisole, diphenyl ether, ethylene glycol dimethyl ether,
Ethers with 2 to 25 carbon atoms such as ethylene glycol diethyl ether, ethylene glycol diphenyl ether, and 2,2-dimethoxypropane; acid amides with 2 to 20 carbon atoms such as (thi)acid azide, benzoic acid amide, and toluic acid amide. (1) Acid halides having 2 to 20 carbon atoms, such as acetyl chloride, benzoyl chloride, toluic acid chloride, anisyl chloride, phthaloyl chloride, isophthaloyl isochloride, (2) Carbon atoms, such as acetic anhydride, phthalic anhydride, etc. Acid anhydrides having a number of 2 to 20 carbon atoms, amines having 2 to 20 carbon atoms such as monomethylamine, monoethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline, and tetramethylethylenediamine; (wo) Acetonitrile.

Nitriles having 2 to 20 carbon atoms such as benzonitrile and tolnitrile; (iv) thiols having 2 to 20 carbon atoms such as ethyl mercaptan, butyl mercaptan, and phenylthiol; to 25 thioethers, (Y) Sulfonic acids having 2 to 20 carbon atoms such as phenylmethylsulfone and diphenylsulfone, (D) Phenyltrimethoxysilane, phenyltriethoxysilane, phenyltributoxysilane, vinyltriethoxysilane, diphenyl Dimethoxysilane, diphenyljethoxysilane, phenyldimethylmonoethoxysilane, triphenylmethoxysilane, hexamethyldisiloxane, octamethyltrisiloxane, hexamethylcyclotrisiloxane, trimethylsilanol, phenyldimethylsilanol, triphenylsilanol, diphenylsilane Examples include silicon-containing compounds having 2 to 24 carbon atoms such as diols.

Two or more types of these electron-donating compounds can be used. Among these, preferred are organic acid esters,
These include inorganic acid esters and silicon-containing compounds.

The catalyst preparation method used in the present invention is not particularly limited, but examples include the following.

A method for obtaining a catalyst component by bringing magnesium halide, titanium halide, and the above electron-donating compound into contact with each other by co-pulverization or by dispersing or dissolving in a solvent; may contain a compound),
A method for obtaining a catalyst component by sequentially contacting the electron-donating compound and a titanium compound (the order may be reversed), and a method for contacting the electron-donating compound with a magnesium compound (or further containing a titanium compound). , a method of obtaining a catalyst component by contacting with a titanium compound and/or halogenation treatment at the same time or in a subsequent stage (which includes the use of a titanium compound at any stage).

The above catalyst component may be produced by supporting or impregnating it on a material commonly used as a catalyst carrier, such as silica or alumina.

The quantitative relationship of each component in component (A) is arbitrary as long as the effect of the present invention is recognized, but the following range is preferable in terms of quantity. The content of magnesium in component (A) is 0.00 molar ratio to titanium. It may be within the range of 1 to 1000, preferably within the range of 2 to 200, and the halogen content may be in a molar ratio of 1 to 0 to titanium.
The content may be in the range of 0, and when an electron donating compound is used, the content is within the range of 10 or less in terms of molar ratio to titanium.

Preferably 0. It may be within the range of 1 to 5. One typical organoaluminum compound in the present invention is represented by the following formula (II) to IV).

AIR8R9R1e (■)R
11RI2A 1-0-A I RI'R” (
III) Lozososhi = Anchor = Ko oyohi / Ma or RI5- (A l -0) n-A I (R
15) 2 (IV) (IT) formula, (III) formula,
In formula (IV), R8, R9 and R1'' may be the same or different, and have at most 12 carbon atoms.
hydrocarbon groups, hydrogen atoms, or halogens, at least one of which is a hydrocarbon group,
RIRI2, R13 and R'' may be the same or different.

It is a hydrocarbon group having at most 12 carbon atoms. Also R1
5 is a hydrocarbon group having at most 12 carbon atoms, and n is an integer of 1 or more. Typical organoaluminum compounds represented by the formula (II) include trialkylaluminums such as triethylaluminum, tripropylaluminum, trihexylaluminum and trioctylaluminum, and alkyl compounds such as diethylaluminum hydride and diisobutylaluminum hydride. Mention may be made of aluminum hydride and alkyl aluminum halides such as diethyl aluminum chloride, diethyl aluminum bromide and ethyl aluminum sesquichloride. Further, among the organoaluminum compounds represented by the formula (m), representative examples include alkylalumoxanes such as tetraethyldialumoxane and tetrabutyldialumoxane. Also(
The formula rV) represents aluminoxane, which is a polymer of aluminum compounds. RI5 includes methyl, ethyl, propyl, butyl, pentyl, etc., and is preferably a methyl or ethyl group. n is preferably from 1 to 10.

Among these organoaluminum compounds, trialkylaluminums, alkylaluminum hydrides and alkylalumoxanes are preferred because they give preferable results.

In the polymerization of olefins, the amount of organic aluminum used in the polymerization system is generally 10-4 mmol/1 or more, preferably 10-2 mmol/1 or more. Also,
The proportion of titanium atoms used in the solid catalyst component is generally 0.5 or more, preferably 2 or more, particularly 10 or more in terms of 1 molar ratio. Note that if the amount of organic aluminum used is too small, the polymerization activity will be significantly reduced.

When the amount of organic aluminum used in the polymerization system is 20 mmol/1 or more and the ratio to titanium atoms is 1000 or more in molar ratio, the catalyst performance will not be further improved even if these values are increased. do not have.

Component (C) of the catalyst used in the present invention is as follows - large amount (1
) is an acetal compound with a structure represented by

RI R6 where R1 and R6 are hydrocarbon residues, preferably carbon number 1
It is an aliphatic hydrocarbon residue having 1 to 6 carbon atoms, more preferably a straight chain aliphatic hydrocarbon residue having 1 to 3 carbon atoms, and R1 and R
6 may be bonded to each other via a chain aliphatic hydrocarbon residue. Specific examples include methyl, ethyl, propyl, or ethylene groups. R2R5 is hydrogen,
is the residue of a hydrocarbon, halogenated hydrocarbon or compound containing a heteroatom, R2+ R5 may be wholly or partially the same or different, and R I
+ R6 may form a ring in whole or in part.

Preferably, a hydrogen atom, a hydrocarbon residue having 1 to 20 carbon atoms, a halogenated hydrocarbon residue having 1 to 20 carbon atoms,
or a residue of a compound containing a heteroatom of group 3B to 7B on the long period periodic table, more preferably a hydrocarbon residue having 1 to 15 carbon atoms, or a halogenated hydrocarbon residue having 1 to 10 carbon atoms. .

It is a residue of a compound containing a hydrogen atom or a heteroatom of groups 3B to 7B in the second to fourth periods of the long period periodic table.

A specific example of R2++ R6 is (a) a hydrogen atom.

(b) Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, S-butyl, t-butyl.

Neopentyl, phenyl, 4-methylphenyl.

Hydrocarbon residues such as 4-fluorophenyl, cyclohexyl, norbornyl, norbornenyl, adamantyl,
(c) Monofluoromethyl, difluoromethyl, trifluoromethyl, monochloromethyl, dichloromethyl,
Trichloromethyl, monobromomethyl, dibromomethyl, iodomethyl, 2-fluoroethyl92,2-
Difluoroethyl, 2, 2. 2-trifluoroethyl, 1. 2. 2゜2-tetrafluoroethyl,
l, 1. 2. 2. 2-perfluoroethyl, 2-chloroethyl, 2゜2-dichloroethyl, 2.
2. 2-) dichloroethyl, 1. 2. 2.
2-tetrachloroethyl, 1°1, 2. 2.
2-perchloroethyl, 2-bromoethyl, 1,2-
Halogenated hydrocarbon residues such as dibromoethyl and 2-iodoethyl; (d) fluoro, chloro, bromo and iodo; (v) alkoxy groups such as methoxy, ethoxy, propoxy, butoxy, t-butoxy and phenoxy; trimethylsilyl, triethylsilyl,
Residues of compounds containing group 4B elements such as trichlorosilyl, trimethylgermyl, triethylgermyl, trichlorogermyl, (t)cyano, isocyanate, carboxy.

These include amino and thiol groups.

Specific examples of the parts of the acetal compound excluding OR1 and OR6 include IH-indene, 9H-
Compounds having an unsaturated 5-membered ring skeleton in the molecule, such as fluorene, IH-cyclopenta[a]pentalene, IH-benz[f]indene, and 1,4-methanobiphenylene, and compounds derived therefrom may also be mentioned. .

Specific examples of such compounds are shown below, in which two or more molecules of each are fused (for example.

Diels-Alder product) compounds, specifically 5,5-dimethoxy-1,3-cyclopentadiene, 5,5-jethoxy-1°3-cyclopentadiene, 1,4-diethyl -2゜3-dimethyl-5,5
-Jethoxy-1,3-cyclopentadiene, 2-t-
Butyl-5,5-dimethoxy-1,3-cyclopentadiene, 2-t-butyl-5,5-jethoxy-1,3-
Cyclopentadiene, 1. 2. 3. 4-tetraphenyl-5,5-dimethoxy-1,3-cyclopentadiene, 1. 2. 3. 4-tetraphenyl-5,5
-Jethoxy-1,3-cyclopentadiene, 1゜4
-trimethylsilyl-2,3-diphenyl-5゜5-dimethoxy-1,3-cyclopentadiene, 2.3-)trimethylsilyl-1,4-diphenyl-5,5-dimethoxy-1,3-cyclopentadiene, 1. 2. 3
．． 4-tetrafluoro-5,5-dimethoxy-1,3
-Cyclopentadiene, 1°2, 3. 4-tetrafluoro-5,5-diethoxy-1,3-cyclopentadiene+1. 2. 3゜4-tetrachloro-5,
5-dimethoxy-1,3-cyclopentadiene, 1
．． 2. 3. 4-9trachloro-5,5-jethoxy-1,3-cyclopentadiene, 1. 2. 3.
4-tetrabromo-5゜5-dimethoxy-1,3-cyclopentadiene, 1, 2. 3. 4-tetrabromo-5,5-jethoxy-1,3-cyclopentadiene, 1. 2. 3゜4-tetrakis(trifluoromethyl)-5,5-dimethoxy-1,3-cyclopentadiene, 112, 3. 4-tetrakis(trifluoromethyl)-5,5-jethoxy-1,3-cyclopentadiene, 1,1-dimethoxy-IH-indene,
1゜1-jethoxy-IH-indene, 2.3-diphenyl-1,1-dimethoxy-IH-indene, 2.3-
diphenyl-1,1-jethoxy-IH-indene, 2
．． 3. 4. 5. 6. 7-hexachloro-1,
1-dimethoxy-IH-indene, 2°3, 4. 5
．． 6. 7-hexachloro-1,1-jethoxy-I
H-indene, 9,9-dimethoxy-9H-fluorene, 9,9-jethoxy-9H-fluorene, 3-bromo-9,9-dimethoxy-9H-fluorene, 3-bromo-9,9-dimethoxy-9H- Fluorene, 2. 3.
4. 5. 6゜7-Hexahydrito7.7-SimethoxyIH-cyclopenta[alpentalene, 9,9
-dimethoxy-1,4-methanobiphenylene and the like.

The amount of component (C) used is the molar ratio of component (C)/component (B).
) =0. 01-5, preferably 0.02-1.

The olefin used for polymerization is generally an olefin having at most 20 carbon atoms.

Typical examples are ethylene, propylene, butene-1
, 4-methylpentene-1, hexene-1, octene-
1, styrene, etc. In carrying out the polymerization, these olefins may be homopolymerized, or two or more types of olefins may be copolymerized. (For example, copolymerization of ethylene and propylene) In carrying out the polymerization, the solid catalyst component of the present invention, the organoaluminum compound and the acetal compound may be individually introduced into the polymerization vessel, but two or two of them may be introduced into the polymerization vessel. All may be mixed in advance.

Polymerization can be carried out either in an inert solvent, in a liquid monomer or in the gas phase. Moreover, it can be carried out in any of the batch, semi-continuous, and continuous methods. In addition, in order to obtain a polymer with a practical melt flow, the molecule tvR
The polymerization temperature, which may be accompanied by a moderating agent (generally hydrogen), is generally from -10°C to 180°C, and practically from 20°C to 130''C.

In addition, the presence or absence of prepolymerization and the form of the polymerization reactor.

Regarding the polymerization control method, fl& treatment method, etc., there are no limitations inherent to this catalyst system, and all known methods can be applied.

(5) Examples The present invention will be explained in more detail by the following examples. In addition, in Examples and Comparative Examples, heptane index (
(hereinafter abbreviated as HR) is boiling 11i? This is the residual amount expressed in % after the obtained polymer was extracted with n-heptane for 6 hours.

In each example, all of the compounds (organic solvent, olefin, hydrogen, titanium compound, magnesium compound, acetal compound, etc.) used in the production and polymerization of the solid catalyst component were substantially water-free.

Also, regarding the manufacturing method and polymerization of solid catalyst components.

The test was carried out in the absence of substantial moisture and under a nitrogen atmosphere.

Example 1 [Preparation of solid titanium catalyst component (A)] 1.71 g of anhydrous magnesium chloride, 9 ml of decane and 8.4 ml of 2-ethylhexyl alcohol were added to 130 ml of solid titanium catalyst component (A).
After heating the reaction at ℃ for 2 hours to obtain a homogeneous solution, 0.39 g of phthalic anhydride was added to this solution, and stirring and mixing was performed at 130'C for an additional 1 hour to dissolve phthalic anhydride into the homogeneous solution. let After cooling the homogeneous solution so obtained to room temperature.

After dropping the entire amount into 72 ml of titanium tetrachloride kept at -20°C over 1 hour, the temperature of this mixture was raised to 110°C over 4 hours, and when it reached 110°C, diisobutyl phthalate was added. ) 0.96 ml was added, and the mixture was kept at the same temperature for 2 hours without stirring. After the 2-hour reaction, the solid portion was collected by sieving, thoroughly washed with decane at 110°C and hexane at room temperature until no free titanium compound was detected during washing, and then dried under reduced pressure.

[Polymerization] In a 1.51 stainless steel autoclave, 20 mg of the solid component (A) produced by the above method and 1.5 mg as the component (C) were placed. 2. 3. 21.5 mg of 4-tetrachloro-5,5-dimethoxy-1,3-cyclopentadiene and 91 mg of triethylaluminum as component (B) were introduced, and then 380 g of propylene and 0.03 g of hydrogen were introduced.

The temperature of the autoclave was raised and the internal temperature was maintained at 70°C.

After 1 hour, the content gas was released to terminate the polymerization.

As a result, 217.1 g of polypropylene powder was obtained. The polymerization activity was 10900 g/g solid catalyst component/hour. The hebutane extraction residue (HR) of this polypropylene powder was 96.2%.

Comparative Example 1-2, Example 2-7 Catalyst production and polymerization were carried out in the same manner as in Example 1, except that the type of catalyst component (C) used was changed as shown in Table-1. The results are shown in Table-1.

Examples 8-10 A catalyst was prepared and polymerized in the same manner as in Example 1, except that the type and amount of catalyst component (C) used were changed as shown in Table 2. Vi fruits are also shown in Table 2.

Examples 11-16. Comparative Example 3-4 [Preparation of solid titanium catalyst component (A)] 20 g of anhydrous magnesium chloride and 7 g of benzoyl chloride were mixed into a porcelain ball with a diameter of 10 mm at an apparent volume of 50%.
The mixture was placed in 11 filled cylindrical containers, and co-milled for 12 hours at an amplitude of 9 mm using a vibrating ball mill.

Separately, in a flask with an internal volume of 500 ml, 120 ml of toluene, 83 g of titanium tetrachloride, and 65 g of di(2
-phenylphenyl) phosphorochlororizoite was added and reacted, and the mixture was heated to 60°C to form a homogeneous solution. The above-mentioned co-pulverized solid material was added to this solution and stirred at a temperature of 60° C. for 2 hours.

After filtering off the solid content, it was washed with toluene and dried under reduced pressure at 30°C to obtain a solid.

[Using 20 mg of the above solid component as the polymerization co(a) component, (
C) Ingredients: 1. 2. 3. 4-tetrachloro-
5,5-dimethoxy-1,3-cyclopentadiene 21
．． 5 mg, triethylaluminum as (B) 9
When propylene was polymerized using 1 mg under the same conditions as in Example 1, the polymerization activity was 3800 g/g・
The solid catalyst component/time and HR were 94.3%. (
Example 11) Hereinafter, polymerization was carried out by changing only the component (C). The results are shown in Table-3.

Example 17 9 mg of the solid component obtained in Example 1 (component A), 150 ml of triisobutylaluminum (component B), 1.2. 3.
Add 15 mg of 4-tetrachloro-5,5-dimethoxy-1,3-cyclopentadiene (component C), then add 40 mg of
0 g of isobutane was added and stirred at 70°C. Hydrogen was added to this so that the partial pressure was 2 kg/cm 2 . Furthermore, add ethylene so that the partial pressure becomes 5 kg/cm2.

Ethylene was continued to be supplied to maintain this pressure.

After 1 hour, the content gas was purged to complete the polymerization.

176 g of white odorless polyethylene was obtained. Polymerization activity is 3
It was 900 g/g solid catalyst component/hour/atm.

Examples 18-20 Polymerization was carried out in the same manner as in Example 17, except that the type and amount of catalyst component (C) used were changed as shown in Table 4. The results are shown in Table 4.

(Left below) Table 1 Example catalyst component (C) Amount used Polymerization activity HR (■) (g/gh) (X) 5.5-dimethoxy-1,3-cyclopentadiene/l -21,2 ,3,4-tetrabromo-32,0
5,5-dimethoxy-1,3-cyclopentadiene 8.813 84.8 // -32,3,4,5,8,7-hexachloro 2
7.70-1.1-dimethoxy-IH-indene 12.250 83.2 Table-2 Example catalyst component (C) Usage amount Polymerization activity HR (mg) (g/g-h) (X) Example- 8
1,2,3,4-tetrachloro-1O175,5-dimethoxy-1,3-cyclopentadiene 13.280 95.1 1! -1 21,5 10,85111 96,2 //-9 64,5 8,233 88,2 tt -10 107,5 4,850 88,0 IH-indene/l -69,9-dimethoxy-91( -113,4
Fluorene 12.9EIO 85,5 N -79,9-jethoxy-9)1-18゜4 Fluorene 10.320 93.0 Comparative Example-1 Cyclopentanone-3Methyl 1G,4 acetal 5.1339 88.9 //-2 diphenyldimethoxymeth 18.27.
158 58.6 Table-3 Table-4 Example catalyst component (C) Amount used Polymerization activity HR (■) (g/g・h) (X) Example-11 1,2,3,4-tetrachloro-21 ,55,5-dimethoxy-1,3-cyclopentadiene 3.805 84.3 // -121,2,3,4-tetrabromo-32,
05,5-dimethoxy-1,3-cyclopentadiene/l -132,3,4,5,8,7-hexachloro
27.70-1,1-dimethoxy-IH-indene/f-142,3,4,5,8,7-hexachloro
28.10-1.1-jetoxy-1)! -indene 3.550 4.013 4.518 93.8 94, O 92,1 8,8-dimethoxy-9)I- to fluorene 18.4, 12B 95.0 8.3-jethoxy-8H- fluorene 18 .4 3.890 94.2 Comparative Example-3 Cyclopentanone-dimethylacetal 10.4 2.2713 53.6 Diphenyldimethoxymeth 18.2 2.450 56.1 Example catalyst component (C) Example-i8 1.2,3.4-tetrachloro-5,5
-dimethoxy-1,3-cyclopentadiene II -192,3,4,5,8,7-hexachloro-1,1-dimethoxy- IH-indene II -209, f3-dimethoxy-9H-fluorene usage amount Polymerization Activity (mg) (g/g・h) 25.142 28.160 23.115 (6) Effect As described above, the method of the present invention can produce an olefin polymer with extremely high stereoregularity. It can be obtained in high yield. This is very useful for the economical production of olefin polymers.

[Brief explanation of drawings]

FIG. 1 is a flowchart for preparing a catalyst according to the present invention.

Claims (1)

[Claims] (1) In the method of producing an olefin polymer by polymerizing olefins in the presence of a catalyst, the catalyst used is (A) a solid catalyst component containing titanium, magnesium, and halogen as essential components; (B) organoaluminum Compounds, and (C) the following general formula (I), ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R^1 and R^6 are hydrocarbon residues, R^2-R^
5 is a residue of hydrogen, a hydrocarbon, a halogenated hydrocarbon, or a compound containing a heteroatom, R^2-R^5 may be the same or different in whole or in part, and R^ 1-R^6 may form a ring in whole or in part. ) A method for polymerizing an olefin, characterized in that it is formed from an acetal compound represented by: