JP2964424B2 - Olefin polymerization catalyst - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a high-performance catalyst composition and a polymerization method exhibiting high activity when subjected to polymerization or copolymerization of olefins, and particularly relates to a method having 3 or more carbon atoms. The present invention relates to an olefin polymerization catalyst and a polymerization method capable of obtaining a high stereoregular polymer in a high yield when applied to the polymerization of α-olefins.

[Conventional technology]

Hitherto, many production methods using a solid catalyst component containing magnesium, titanium, a halogen compound and an electron donor (internal donor) as essential components as a catalyst component have been proposed.

Organic carboxylic acid esters are often used (Japanese Patent Publication No. 47-9342), but there are many problems such as odors, and they are practically unsatisfactory in terms of stereoregularity, leaving room for improvement. The present applicant has proposed a method of overcoming these problems in the stereoregular polymerization of α-olefins (Japanese Patent Application No. 1-142717). Further, as a method for improving stereoregularity, many methods using an aromatic alkylalkoxysilane during catalyst preparation or polymerization have been proposed. However, a large amount of benzene, which is considered to have been produced by decomposition from the produced polymer, is detected in large quantities, and it is not preferable for safety, hygiene, and practical use.

On the other hand, the use of aliphatic hydrocarbon alkoxysilanes has been proposed (JP-A-61-78803, JP-A-63-258907, JP-A-2-84404, etc.). However, compared to aromatic alkylalkoxysilanes, the activity or stereoregularity is reduced, and a satisfactory result has not been obtained.

[Problems to be solved by the invention]

It is an object of the present invention to provide a polymer having high activity and high stereoregularity which does not cause problems in safety and health, and a high rigidity and high impact resistance propylene block copolymer which are insufficient and unsatisfactory in the conventional technology. It is intended to provide a catalyst system to provide.

[Means for solving the problem]

As a result of intensive studies to solve the above-mentioned problems, the present inventors have reached the present invention having the following points. That is, the present invention relates to the following: component (A) titanium, magnesium, halogen and the following general formula (I) (R ¹ O) _i (R ² O) _j (R ³ O) _k -Z-COOR ⁴ (I) Wherein R ¹ , R ² , R ³ and R ⁴ are a hydrocarbon group, Z is an aliphatic hydrocarbon group whose hydrogen atom may be substituted by an aromatic hydrocarbon, and i, j, k, are 0 to An integer of 3, i, j, k
Is 1 or more. Component (B), an organoaluminum compound, Component (C) at least one aliphatic hydrocarbon group having a secondary or higher α-carbon directly bonded to silicon. An aliphatic hydrocarbon alkoxysilane compound comprising: an olefin polymerization catalyst and a polymerization method.

 Hereinafter, the present invention will be described in detail.

Catalyst component (A) The magnesium compound used in the present invention includes magnesium halides such as magnesium chloride and magnesium bromide; alkoxy magnesiums such as methoxy magnesium, ethoxy magnesium and isopropoxy magnesium; magnesium laurate, magnesium stearate Magnesium carboxylate; alkyl magnesium such as butylethylmagnesium, and the like. Also, a mixture of two or more of these compounds may be used. Preferably, a magnesium halide is used, or a magnesium halide is formed during catalyst molding.
More preferably, the halogen is chlorine.

Examples of the titanium compound used in the present invention include titanium halides such as titanium tetrachloride, titanium trichloride, and titanium tetrabromide; titanium alkoxides such as titanium butoxide, titanium isopropoxide, and titanium ethoxide; and phenoxy titanium chloride. An alkoxytitanium halide and the like can be exemplified. In addition, two of these compounds
It may be a mixture of more than one species. Preferred is a tetravalent titanium compound containing halogen, and particularly preferred is titanium tetrachloride.

The halogen-containing compounds used in the present invention are those wherein the halogen is fluorine, chlorine, bromine, or iodine, preferably chlorine, and the specific compounds actually exemplified depend on the catalyst preparation method, titanium tetrachloride, Representative examples include titanium halides such as titanium tetrabromide, silicon tetrachloride, silicon halides such as silicon tetrabromide, phosphorus trichloride, and phosphorus halides such as phosphorus pentachloride. Halogenated hydrocarbons, halogen molecules, hydrohalic acids (eg, HCl, HBr, HI, etc.) may be used.

The alkoxyester compound used in the present invention is represented by the general formula (R ¹ O) _i (R ² O) _j (R ³ O) _k -Z-COOR ⁴ (I) (where i, j, k are 0 to An integer of 3, i, j, k
Is 1 or more. ). Here, R ¹ , R ² , R ³ and R ⁴ are hydrocarbon groups. R ¹ , R ² , R ³ and R ⁴ may be the same or different.

When any of R ¹ , R ² , R ³ or R ⁴ is an aliphatic or alicyclic hydrocarbon group, an aliphatic or alicyclic hydrocarbon group having 1 to 12 carbon atoms or 1 to 12 carbon atoms Is preferred. Specifically, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, pentyl, hexyl, 3-methylpentyl, tert-pentyl,
Heptyl, i-hexyl, octyl, nonyl, decyl,
2,3,5-trimethylhexyl, undenyl, dodecyl,
Vinyl, allyl, 42-hexenyl, 2,4-hexadienyl, isopropenyl, cyclobutyl, cyclopentyl,
Examples thereof include cyclohexyl, tetramethylcyclohexyl, cyclohexenyl, norbornyl, and the like.

These hydrogen atoms may be replaced by halogen atoms.

When any of R ¹ , R ² , R ³ , and R ⁴ is an aromatic or polycyclic hydrocarbon group, it has 6 to 18 carbon atoms or 7 to 18 carbon atoms.
Are preferred, or an aliphatic hydrocarbon group containing them. Specific examples include phenyl, tolyl, ethylphenyl, xyl, cumyl, trimethylphenyl, tetramethylphenyl, naphthyl, methylnaphthyl, anthranyl, benzyl, diphenylmethyl, indenyl and the like.

These hydrogen atoms may be replaced by halogen atoms.

Z is an aromatic group having a hydrogen atom of 6 to 18 carbon atoms, or
An aliphatic hydrocarbon group having 1 to 20 carbon atoms (including an alicyclic hydrocarbon group) which may be substituted with a polycyclic group having 7 to 18 carbon atoms is preferable, and specifically, methylene, ethylene , Ethylidene, trimethylene, tetramethylene, pentamethylene, hexamethylene, propenylene, and the like. Examples of the substituted substituents include methylmethylene, n-butylmethylene, ethylethylene, isopropylethylene, tert-butylethylene, and sec-butylethylene. Tert-amylethylene, adamantaneethylene, bicyclo [2,2,1] heptylethylene, phenylethylene, tolylethylene,
Examples include xylylethylene, diphenyltrimethylene, 1,2-cyclopentylene, 1,3-cyclopentylene, 3-cyclohexene-1,2-ylene, dimethylethylene, indenyl-1,2-ylene and the like. it can. A hydrogen atom may be replaced by a halogen atom.

Specific compounds include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, phenyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, butyl ethoxyacetate, phenyl ethoxyacetate, ethyl n-propoxyacetate, i-propoxy-acetic acid Ethyl, methyl n-butoxyacetate, ethyl i-butoxyacetate, ethyl n-hexyloxyacetate, octyl sec-hexyloxyacetate, methyl 2-methylcyclohexyloxyacetate, 3
-Methyl methoxypropionate, ethyl 3-methoxypropionate, butyl 3-methoxypropionate, 3-
Ethyl ethoxypropionate, butyl 3-ethoxypropionate, n-octyl 3-ethoxypropionate, 3
-Dodecyl ethoxypropionate, pentamethylphenyl 3-ethoxypropionate, 3- (i-propoxy)
Ethyl propionate, butyl 3- (i-propoxy) propionate, allyl 3- (n-propoxy) propionate, cyclohexyl 3- (n-butoxy) propionate, ethyl 3-neopentyloxypropionate, 3
-(N-octyloxy) butyl propionate, 3-
Methyl (2,6-dimethylhexyloxy) propionate, octyl 3- (3,8-dimethyldecyloxy) propionate, ethyl 4-ethoxybutyrate, cyclohexyl 4-ethoxybutyrate, octyl 5- (n-propoxy) valerate Ethyl 12-ethoxylaurate, ethyl 3- (1-indenoxy) propionate, methyl 3-methoxyacrylate, methyl 2-methoxyacrylate, methyl 2-ethoxyacrylate, ethyl 3-phenoxyacrylate,
Ethyl 2-methoxypropionate, n-butyl 2- (i-propoxy) butyrate, methyl 2-ethoxyisobutyrate, 2
Phenyl cyclohexyloxyisovalerate, butyl 2-ethoxy-2-phenylacetate, allyl 3-neopentyloxybutyrate, methyl 3-ethoxy-3- (o-methylphenyl) propionate, 3-ethoxy-2- (o -Methylphenyl) ethyl propionate, 3-ethoxy-2
-Ethyl mesitylpropionate, 3-ethoxy-2-te
rt-butyl propionate, 3-ethoxy-2-
Ethyl tert-amylpropionate, 3-ethoxy-2-
Ethyl adamantane propionate, 3-ethoxy-2-
Ethyl bicyclo [2,2,1] heptylpropionate, 3-
Ethyl ethoxy-3-phenylpropionate, ethyl 3-ethoxy-3-mesitylpropionate, ethyl 3-ethoxy-3-tert-butylpropionate, ethyl 3-ethoxy-3-tert-amylpropionate, 4-ethoxy Propyl 2- (tert-butyl) butyrate, 5-methoxy-
Ethyl 2-methyl-1-naphthyl nonanoate, ethyl 2-methoxycyclopentanecarboxylate, butyl 2-ethoxycyclohexanecarboxylate, 3-
(Ethoxymethyl) tetralin-2-acetic acid isopropyl ester, 8-butoxy-decalin-1-carboxylic acid ethyl ester, 3-ethoxynorbornane-2-carboxylic acid methyl ester, 2- (phenoxy) methyl acetate,
Ethyl 3- (p-cresoxy) propionate, 4- (2
Methyl-naphthoxy) butyrate, butyl 5-carbaclooxyvalerate, methyl 2-phenoxypropionate, 3- (4
-Methylphenoxy) -2-ethyl phenylpropionate, ethyl 2-phenoxy-cyclohexanecarboxylate, ethyl thiophen-3-oxyacetate and the like.

Of these, the following general formula (II) is preferred. Is an alkoxyester compound represented by the formula: here
R ⁵ and R ⁶ are an aliphatic hydrocarbon having 1 to 20 carbon atoms, R ⁷ and R ⁸ are a hydrogen atom or an aliphatic hydrocarbon having 1 to 20 carbon atoms, Y
Is a group in which a chain hydrocarbon having 1 to 4 carbon atoms is substituted with an aliphatic hydrocarbon, an aromatic hydrocarbon or a polycyclic hydrocarbon, or an alicyclic hydrocarbon group having 1 to 12 carbon atoms. Particularly preferred is an alkoxyester in which Y is a chain hydrocarbon and has a bulky substituent having 4 or more carbon atoms at the 2- or 3-position counted from the carboxyl group. Further, an alkoxyester compound having a 4- to 8-membered cycloalkane is also preferable. Specifically, ethyl 3-ethoxy-2-phenylpropionate, ethyl 3-ethoxy-2-tolylpropionate, ethyl 3-ethoxy-2-mesitylpropionate, 3-butoxy-2- (methoxyphenyl) propione Ethyl acrylate, methyl 3-i-propoxy-3-phenylpropionate, ethyl 3-ethoxy-3-phenylpropionate, ethyl 3-ethoxy-3-tert-butylpropionate, ethyl 3-ethoxy-3-adamantylpropionate Ethyl 3-ethoxy-2-tert-butylpropionate, ethyl 3-ethoxy-2-tert-aminopropionate, ethyl 3-ethoxy-2-adamantylpropionate, 3-ethoxy-2-bicyclo [2, 2,1)
Examples include ethyl heptylpropionate, ethyl 2-ethoxy-cyclohexanecarboxylate, methyl 2- (ethoxymethyl) -cyclohexanecarboxylate, methyl 3-ethoxy-norbornane-2-carboxylate, and the like.

Although the catalyst preparation method used in the present invention is not particularly limited, magnesium halide, titanium halide and an alkoxyester compound are co-ground,
Later, a halogenation treatment may be performed to achieve high activation. Alternatively, after a magnesium halide alone or a co-milling of a magnesium halide and a silicon compound or a phosphorus compound, a titanium compound treatment and a halogenation treatment may be performed in the presence of an alkoxyester compound.

Further, a magnesium carboxylate or an alkoxymagnesium, a titanium compound, a halogenating agent and an alkoxyester may be heat-treated to improve the performance. A magnesium halide may be dissolved in an organic solvent or the like, and an alkoxyester may be allowed to act during or after precipitation in the presence of a titanium compound.

Further, when the halogenating agent is allowed to act on the alkylmagnesium, a catalyst formed by adding an alkoxyester compound or a titanium compound to the preparation process may be used.

Further, a catalyst formed by adding an alkoxyester compound or a titanium compound to the preparation process when the metal magnesium and the halogenated hydrocarbon are allowed to act may be used.

The amount of the alkoxy ester compound remaining in the catalyst depends on the preparation method, but when the alkoxy ester compound of the present invention is abbreviated as ID, the titanium: magnesium: ID (molar ratio) is 1: 1 to 1000: 10 ^{-6 to} 100. And preferably in the range of 1: 2 to 100: 10 ^-4 to 10. If the ID is less than this range, the stereospecificity decreases, and it is impossible to increase rigidity. Conversely, if the amount is too large, the activity is undesirably reduced.

Catalyst component (B) The organoaluminum compound in the present invention is represented by the following general formulas (III) to (V) as general formulas.

AR ⁹ R ¹⁰ R ¹¹ ... (III) R ¹² R ¹³ A-O-AR ¹⁴ R ¹⁵ ... (IV) And / or In the formulas (III), (IV) and (V), R ⁹ , R
¹⁰ and R ¹¹ may be the same or different, and are a hydrocarbon group having at most 12 carbon atoms, a halogen atom or a hydrogen atom,
At least one of them is a hydrocarbon group, R ¹² ,
R ¹³ , R ¹⁴ and R ¹⁵ may be the same or different and are a hydrocarbon group having at most 12 carbon atoms.

R ¹⁶ is a hydrocarbon group having at most 12 carbon atoms, and is an integer of 1 or more.

Typical examples of the organoaluminum compound represented by the formula (III) include trialkylaluminums such as triethylaluminum, tripropylaluminum, tributylaluminum, trihexylaluminum and trioctylaluminum, and further, diethylaluminum hydride and diisobutylaluminum hydride. And alkylaluminum halides such as diethylaluminum chloride, diethylaluminum bromide and ethylaluminum sesquichloride.

Representative examples of the organoaluminum compound represented by the formula (IV) include alkyl dialumoxanes such as tetraethyl dialumoxane and tetrabutyl dialumoxane.

Formula (V) represents aluminoxane, which is a polymer of an aluminum compound. R ¹⁶ is methyl, ethyl,
Including propyl, butyl, pentyl and the like, preferably a methyl or ethyl group. Is preferably 1 to 10.

Of these organoaluminum compounds, trialkylaluminums, alkylaluminum hydrides and alkylalumoxanes are preferred, and trialkylaluminums are particularly preferred because they give favorable results.

Catalyst Component (C) An aliphatic hydrocarbon alkoxysilane compound containing at least one aliphatic hydrocarbon group having a secondary or higher α-carbon directly bonded to silicon used in the present invention is used.

Such an organosilicon compound has the general formula (VI)
R ¹⁷ Si (OR ¹⁸ ) ₃ or R ¹⁷ · R ¹⁹ Si (OR ¹⁸ ) ₂ (VI). Preferably R ¹⁷ is combined with the silicon with secondary or more carbons in the aliphatic hydrocarbon having 3 to 20 carbon atoms.

R ¹⁸ is an aliphatic hydrocarbon having 1 to 5 carbon atoms.

R ¹⁹ is composed of an aliphatic hydrocarbon having 1 to 20 carbon atoms.

Specifically, isopropyltrimethoxysilane, isopropyltriethoxysilane, isopropyltripropoxysilane, sec-butyltrimethoxysilane, sec-butyltriethoxysilane, tert-butyltrimethoxysilane, tert-butyltriethoxysilane, 1- Methylbutyltrimethoxysilane, 1-methylbutyltriethoxysilane, 3-pentyltrimethoxysilane, tert-pentyltrimethoxysilane, cyclopentyltrimethoxysilane, 1-methylpentyltrimethoxysilane, 1,3
-Dimethylbutyltrimethoxysilane, 1,2-dimethylbutyltrimethoxysilane, tert-hexyltrimethoxysilane, 1-ethyl1-methylpropyltrimethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclohexyltripropoxysilane, Cyclohexenyltrimethoxysilane, cyclohexenyltriethoxysilane, 3-methylcyclohexyltrimethoxysilane, 3-methylcyclohexyltriethoxysilane, norbornenetrimethoxysilane, norbornenetriethoxycinlan, norbornanetrimethoxysilane, norbornanetriethoxysilane, isopropylmethyl Dimethoxysilane, isopropylethyldimethoxysilane, propylisopropyldimethoxysilane, diisoprop Ropyldimethoxysilane, isobutylisopropyldimethoxysilane, butylisopropyldimethoxysilane, (sec-butyl) isopropyldimethoxysilane, (tert-butyl) isopropyldimethoxysilane, cyclopentylisopropyldimethoxysilane, cyclohexylisopropyldimethoxysilane, (sec-butyl) methyldimethoxy Silane, (sec-
(Butyl) ethyldimethoxysilane, (sec-butyl) propyldimethoxysilane, (sec-butyl) butyldimethoxysilane, di (sec-butyl) dimethoxysilane, (s
ec-butyl) (tert-butyl) dimethoxysilane, (se
c-butyl) cyclopentyldimethoxysilane, (sec-
(Butyl) cyclohexyldimethoxysilane, (sec-butyl) isobutyldimethoxysilane, (tert-butyl)
Methyldimethoxysilane, (tert-butyl) ethyldimethoxysilane, (tert-butyl) propyldimethoxysilane, di (tert-butyl) dimethoxysilane, (tert-
(Butyl) cyclopentyldimethoxysilane, (tert-butyl) cyclohexyldimethoxysilane, (tert-butyl) isobutyldimethoxysilane, (tert-butyl) butyldimethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylethyldimethoxysilane, cyclopentylpropyldimethoxysilane, cyclopentylbutyl Dimethoxysilane, dicyclopentyldimethoxysilane, cyclopentylcyclohexyldimethoxysilane, cyclopentylisobutyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylpropyldimethoxysilane, cyclohexylbutyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylisobutyldimethoxysilane Orchid, di (1,3-cyclopentadienyl) dimethoxysilane, (2-methylsilacyclopentane) dimethoxysilane, (2,5-dimethylsilacyclopentane) dimethoxysilane, (2,2-dimethylsilacyclopentane) Dimethoxysilane, (2,2,5,5-
Tetramethylsilacyclopentane) dimethoxysilane,
(2-ethylsilacyclopentane) dimethoxysilane,
(2,5-diethylsilacyclopentane) dimethoxysilane, (2-methylsilacyclohexane) dimethoxysilane, (2,6-dimethylsilacyclohexane) dimethoxysilane, (2,2-dimethylsilacyclohexane) dimethoxysilane, ( 2,2,6,6-tetramethylsilacyclohexane) dimethoxysilane and the like.
These may be used as a mixture of two or more.

In the present invention, preliminary polymerization may be performed prior to main polymerization. For the prepolymerization, the above-mentioned catalyst component (A), catalyst component (B), and in some cases, catalyst component (C) can be used. Any of these can be carried out with a higher concentration of catalyst than in the main polymerization. The produced polymer is preferably 0.1 to 200 g per 1 g of the catalyst. The reaction temperature is preferably in a range from a low temperature of -20 ° C to + 50 ° C.

Olefin The olefin used in the polymerization is generally an olefin having at most 18 carbon atoms. Representative examples thereof include ethylene, propylene, butene-1,4-methylpentene, 1, hexene-1, octene and the like. -1 and the like. In carrying out the polymerization, these olefins may be homopolymerized, or two or more olefins may be copolymerized (for example, copolymerization of ethylene and propylene).

Polymerization method and its conditions In carrying out the polymerization, the catalyst component (A) of the present invention,
The catalyst component (B) and the catalyst component (C) may be separately introduced into the polymerization vessel, or two or all of them may be mixed in advance.

Polymerization in an inert solvent, liquid monomer (olefin)
It can be performed in either the medium or gas phase. In order to obtain a polymer having a practical melt flow,
A molecular weight regulator (generally, hydrogen) may coexist.

Homopolymerization and copolymerization can be carried out in the presence of a catalyst comprising the catalyst components (A), (B) and (C).

Generally, the amount of organoaluminum used in the polymerization system is generally 10 ^-4 mmol / or more, and 10 ^-2 mmol /
The above is preferable. In addition, the molar ratio to the titanium atom in the catalyst component (A) is generally 0.5 or more,
Preferably 2 or more, especially 10 or more is suitable.

If the amount of the organic aluminum is too small, the polymerization activity is greatly reduced.

When the use of organoaluminum in the polymerization system is 20 mmol / or more and the ratio to the titanium atom is 1000 or more in molar ratio, even if these values are further increased, the catalytic performance is not further improved. .

The amount of the catalyst component (C) used varies slightly depending on whether or not the method of using the catalyst component (C) is used during the prepolymerization of the catalyst component (A). It is used in a molar, preferably 0.01 to 1, ratio.

The polymerization temperature is generally from -10 ° C to 180 ° C, and practically from 20 ° C to 130 ° C.

In addition, the form of the polymerization reactor, the method of controlling polymerization, the method of post-treatment, and the like are not limited to those specific to the present catalyst system, and all known methods can be applied.

〔Example〕

 Hereinafter, the present invention will be described in more detail with reference to examples.

In the examples and comparative examples, the heptane index (that is, HR) is boiling n-heptane, and represents the remaining amount after extracting the obtained polymer for 6 hours in%. Melt flow ratio (or MFR)
0.2% of 2,6-di-tert-butyl-4-methylphenol
The temperature of the mixed powder is 230 ° C according to JIS K-6758.
And the load was measured under the condition of 2.16 kg.

In each of the examples, each compound (organic solvent, olefin, hydrogen, titanium compound, magnesium compound, alkoxyester compound, organosilicon compound, etc.) used in the production and polymerization of the solid catalyst component is substantially water-free. It is.

Further, the production method and polymerization of the solid catalyst component were carried out in a nitrogen-free atmosphere substantially without water.

Example 1 9.5 g of anhydrous magnesium chloride was added to 50 ml of decane and 46.8 ml
Of 2-ethylhexyl alcohol was heated and dissolved at 130 ° C. for 2 hours in a round bottom flask under N ₂ atmosphere. 2.1 g of phthalic anhydride was added, and the mixture was further heated at 130 ° C. for 1 hour. The temperature of the solution was raised to 60 ° C., transferred to a dropping funnel in a nitrogen gas atmosphere, and allowed to reach room temperature. 410 ml of titanium tetrachloride was charged into the three-necked flask equipped with the dropping funnel,
Cooled to 0 ° C. The solution was dropped over 60 minutes, and the temperature rose to 100 ° C. in 5 hours. A solution of 5.5 g of ethyl 3-ethoxy-2-tert-butylpropionate in heptane was slowly added dropwise. The reaction was completed at 100 ° C. for 2 hours after the completion of the dropping. After the solid precipitates,
The supernatant was removed and 410 ml of fresh TiCl ₄ were introduced. 95 ℃
For 2 hours. Then 3 ml with 400 ml of n-decane
After washing twice, it was washed with n-hexane to obtain a solid catalyst. Ti
The supported amount was 2.2% by weight.

Preliminary polymerization A 200 ml three-necked flask was sufficiently replaced with a nitrogen gas atmosphere, and n-hexane 50 ml, triethyl aluminum 0.62
g, diisopropyldimethoxysilane 0.19 g, and catalyst component (A) 1.2 g were stirred at 5 ° C., and propylene was supplied over 3 hours to carry out prepolymerization (producing 2.3 g of polypropylene per 1 g of catalyst component (A)). After removing unreacted propylene, n-
After washing with hexane, a preactivated catalyst component was obtained.

Main polymerization In an autoclave having an internal volume of 3, 760 g of propylene was placed, and at room temperature, 91 mg of triethylaluminum, 14.7 mg of diisopropyldimethoxysilane, and a pre-activated catalyst 66
mg was charged. Further, 0.1 g of an aqueous system was added, and the temperature was raised to 80 ° C.
The reaction was performed for 1 hour.

The resulting polymer was dried and weighed 360 g. That is, the polymerization activity is 18000 g / g · solid catalyst component (A) · hour. This polypropylene powder had a boiling heptane extraction residue (HR) of 99.2% and an MFR of 2.3 g / 10 min. Analysis of the polymer also showed no detection of benzene.

Examples 2 to 8, Comparative Examples 1 and 2 In the homopolymerization of Example 1, the amount of the catalyst component (C) shown in Table 1 was changed instead of diisopropyldimethoxysilane.

Example 9 In a nitrogen stream, 5 g of diethoxymagnesium, 3-ethoxy-2-tert-
1.66 g of ethyl amylpropionate and 25 ml of 1,2-dichloropropane were obtained. Stirred at 70 ° C. for 1 hour, then pumped the suspension into 200 ml TiCl ₄ at room temperature. The temperature was gradually raised to 100 ° C., and the reaction was performed with stirring for 2 hours. After the reaction,
The precipitated solid was separated and washed three times with 200 ml of n-decane at 100 ° C. 200 ml of fresh TiCl ₄ was added and reacted at 100 ° C. for 2 hours. After completion of the reaction, the precipitated solid was separated, washed three times with 200 ml of n-decane at 80 ° C., and washed with n-hexane at room temperature until no chloride ion was detected.

 The Ti content of this catalyst component was 2.6% by weight.

 The prepolymerization was carried out according to Example 1.

For 1 g of the catalyst component (A), 1.9 g of polypropylene was produced.

Main Polymerization According to Example 1, propylene, triethylaluminum, diisopropyldimethoxysilane, and 43.5 mg of a preactivated catalyst were charged into an autoclave having an internal volume of 3. Further, 0.1 g of hydrogen was added, and polymerization was carried out at 80 ° C. for 1 hour.
The obtained polymer after drying was 390 g. That is,
The polymerization activity is 26000 g / g · solid catalyst (A) · hour. This polypropylene powder is boiling heptane extraction residue (HR)
Was 99.1% and the MFR was 1.8 g / 10 min.

Example 10 The main polymerization was carried out in the same manner as in Example 9 except that the preliminary polymerization was not carried out. From the obtained polymer, polymerization activity
28000g / g ・ Solid catalyst (A) ・ hour, HR = 99.1%, MFR
= 2.9 g / 10 minutes.

〔The invention's effect〕

When the polymerization of olefins is carried out using the catalyst component obtained according to the present invention, the catalyst residue is very high in activity, so that the catalyst residue in the produced polymer can be kept extremely low, so that the deashing step is omitted. be able to.

In addition, since the amount of residual halogen is small, the degree of corrosion of a molding machine or the like in a polymer processing step can be significantly improved.

Further, the residual catalyst causes deterioration of the polymer itself and yellowing, but since the concentration is necessarily low, these can be reduced.

In addition, since the stereoregularity is high, a polymer having practically usable mechanical strength can be obtained without removing a so-called atactic portion.

From the viewpoint of hygiene, benzene and the like generated by decomposition are detected in a product obtained from a polymer obtained by combining ordinary aromatic catalyst components, which is not preferable in terms of safety and health. When the catalyst component according to the present invention is used, the above problem does not occur because it does not have an aromatic substituent.

[Brief description of the drawings]

FIG. 1 is a flowchart showing one example of the production of an olefin polymerization catalyst and the olefin polymerization step according to the present invention.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁶ , DB name) C08F 4/60-4/70

Claims (2)

(57) [Claims] 1. Component (A) Titanium, magnesium, halogen and the following general formula (I) (R ¹ O) _i (R ² O) _j (R ³ O) _k -Z-COOR ⁴ (I) R ¹ , R ² , R ³ and R ⁴ are a hydrocarbon group, Z is an aliphatic hydrocarbon group whose hydrogen atom may be replaced by an aromatic hydrocarbon, and i, j, k, are 0 to 3 A catalyst component containing an alkoxyester compound represented by the following formula: Component (B) an organoaluminum compound, Component (C) α directly bonded to silicon. An olefin polymerization catalyst formed from an aliphatic hydrocarbon alkoxysilane compound containing at least one aliphatic hydrocarbon group having a secondary or higher carbon atom. 2. A method for polymerizing an olefin, comprising using a catalyst system containing the catalyst component according to claim 1.