JP2727117B2 - Olefin polymerization catalyst component and olefin polymerization method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (1) Industrial application field The present invention relates to a high-performance catalyst composition which has a high activity when used for polymerization or copolymerization of olefins, and particularly relates to α having 3 or more carbon atoms. The present invention relates to a catalyst component for olefin polymerization capable of obtaining a highly stereoregular polymer in a high yield when applied to olefin polymerization, and a method for polymerizing olefin.

(2) Prior Art 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. An organic carboxylic acid ester is often used, but there is a problem that an ester odor remains in the polymer unless an operation of removing the ester such as washing with an organic solvent is performed. It was also insufficient in terms of activity and stereospecificity. In order to overcome these disadvantages, some specific esters, that is, esters having an ether moiety have been proposed. Methods using anisates (JP-A-48-16986) and methods using furancarboxylates (JP-A-59-129205, 54)
JP-A-136590) and a method using 2-ethoxyethyl acetate (JP-A-61-287908, etc.) correspond thereto. However, even with these esters,
There has been a demand for the development of a catalyst that does not have industrially satisfactory performance in terms of activity and stereospecificity, and that has higher performance.

(3) Problems to be Solved by the Invention An object of the present invention is to provide a catalyst system which provides a polymer having high activity and high stereoregularity, which has been insufficient with the above prior art.

(4) Means for Solving the Problems As a result of earnest studies to solve the above problems, the present invention has been made, which has the following points. That is, the present invention provides, during or after the formation of a solid catalyst component comprising a titanium compound selected from a magnesium compound, a trivalent or tetravalent titanium halide, an alkoxide and an alkoxytitanium halide, and a halogen-containing compound as essential components.
The following general formula (I) (R ¹ O) _i (R ² O) _j (R ³ O) _k- Z-COOR ⁴ (I) (where R ¹ , R ² , R ³ and R ⁴ are aliphatic carbonized A group selected from hydrogen, an alicyclic hydrocarbon, an aromatic hydrocarbon, a polycyclic hydrocarbon, and a heterocyclic compound, and Z is an aliphatic whose hydrogen atom may be substituted with an aromatic group or a polycyclic group. Or an alicyclic hydrocarbon group, i, j, k is an integer of 0 to 3, and the sum of i, j, k is 1 or more.)
An olefin polymerization method characterized by using an olefin polymerization catalyst component obtained by treating in the presence of at least one species and a catalyst system containing the catalyst component.

 Hereinafter, the present invention will be used in detail.

Examples of the magnesium compound used in the present invention include magnesium halides such as magnesium chloride and magnesium bromide; alkoxymagnesiums such as ethoxymagnesium and isopropoxymagnesium; carboxylate salts of magnesium such as magnesium laurate and magnesium stearate. An alkylmagnesium such as butylethylmagnesium. 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 formation. 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 and titanium ethoxide; and alkoxy titanium halides such as phenoxytitanium chloride. Examples can be given.
Also, a mixture of two or more of these compounds may be used. 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. A halogenated hydrocarbon, a halogen molecule, or a hydrohalic acid (eg, HCl, HBr, HI, etc.) may be used.

As understood from the above, among the titanium compounds used in the present invention, titanium halide and alkoxytitanium halide are also halogen-containing compounds. Therefore, when these compounds are used, the use of one compound corresponds to the use of a titanium compound and the use of a halogen-containing compound.

Alkoxy ester compounds used in the present invention have the general formula represented by _{^{(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 groups composed of one or more of an aliphatic hydrocarbon, an alicyclic hydrocarbon, an aromatic hydrocarbon, a polycyclic hydrocarbon, and a heterocyclic compound. These may be the same or different. When this is an aliphatic or alicyclic hydrocarbon group, an aliphatic or alicyclic hydrocarbon group having 1 to 12 carbon atoms is preferable. 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, unenyl, dodecyl, vinyl, allyl,
2-hexenyl, 2,4 hexadienyl, isopropenyl, cyclobutyl, cyclopentyl, cyclohexyl,
Examples include 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, an aromatic or polycyclic hydrocarbon group having 6 to 18 carbon atoms is preferable. Specific examples include phenyl, tolyl, ethylphenyl, xyl, cumyl, trimethylphenyl, tetramethylphenyl, naphthyl, methylnaphthyl, and anthranil.

These hydrogen atoms may be replaced by halogen atoms.

When any of R ¹ , R ² , R ³ and R ⁴ is a heterocyclic compound, a heterocyclic compound having 4 to 18 carbon atoms is preferable. Specific examples include furyl, tetrahydrofuryl, thienyl, pyrrolyl, imidazolyl, indolyl, pyridyl, piperidyl and the like.

These hydrogen atoms may be replaced by halogen atoms.

When any one of R ¹ , R ² , R ³ and R ⁴ is linked to an aromatic hydrocarbon, a polycyclic hydrocarbon or a heterocyclic compound and an aliphatic hydrocarbon, the aromatic hydrocarbon having 6 to 18 carbon atoms is used. A group consisting of a hydrogen group, a polycyclic hydrocarbon or a heterocyclic compound having 4 to 18 carbon atoms and an aliphatic hydrocarbon group having 1 to 12 carbon atoms is preferable. Specific examples include benzyl, diphenylmethyl, indenyl, and furfuryl.

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 group having 1 to 20 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms, which may be substituted with a polycyclic group,
Specifically, methylene, ethylene, ethylidene, trimethylene, tetramethylene, pentamethylene, hexamethylene, propenylene, etc., and examples of substitution include methylmethylene, n-butylmethylene, ethylethylene, isopropylethylene, tertethylene -Butyl ethylene,
sec-butylethylene, tert-amylethylene, adamantaneethylene, bicyclo [2,2,1] heptylethylene, phenylethylene, tolylethylene, xylylethylene, diphenyltrimethylene, 1,2-cyclopentylene, 1,3- Cyclopentylene, 3-cyclohexane-
Examples thereof include 1,2-ylene, dimethylethylene, and indenyl-1. 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, ethyl 3-ethoxypropionate, butyl 3-ethoxypropionate, n-octyl 3-ethoxypropionate, 3-
Dodecyl ethoxypropionate, pentamethylphenyl 3-ethoxypropionate, ethyl 3- (i-propoxy) propionate, butyl 3- (i-propoxy) propionate, allyl 3- (n-propoxy) propionate, 3- ( n-butoxy) cyclohexyl propionate, ethyl 3-neopentyloxypropionate, 3-
(N-octyloxy) butyl propionate, 3- (2,
Methyl 3-dimethylhexyloxy) propionate, 3
Octyl (3-, 3-dimethyldecyloxy) propionate, ethyl 4-ethoxybutyrate, cyclohexyl 4-ethoxybutyrate, octyl 5- (n-propoxy) valerate, 12
Ethyl ethoxylaurate, ethyl 3- (1-indenoxy) propionate, methyl 3-methoxyacrylate, methyl 2-methoxyacrylate, methyl 2-ethoxyacrylate, ethyl 3-phenoxyacrylate, 2-
Ethyl methoxypropionate, 2- (i-propoxy)
N-butyl butyrate, methyl 2-ethoxyisobutyrate, phenyl 2-cyclohexyloxyisovalerate, 2-ethoxy-
Butyl 2-phenylacetate, allyl 3-neopentyloxybutyrate, methyl 3-ethoxy-3- (o-methylphenyl) propionate, ethyl 3-ethoxy-2- (o-methylphenyl) propionate, 3-ethoxy- Ethyl 2-mesitylpropionate, ethyl 3-ethoxy-2-tert-butylpropionate, ethyl 3-ethoxy-2-tert-amylpropionate, ethyl 3-ethoxy-2-adamantanepropionate, 3-ethoxy-2 -Ethyl bicyclo [2,2,1] heptylpropionate, ethyl 3-ethoxy-3-phenylpropionate, 3-ethoxy-3
-Ethyl mesitylpropionate, 3-ethoxy-3-tr
ethyl et-butyl propionate, 4-ethoxy-2-
Propyl (t-butyl) butyrate, ethyl 5-methoxy-2-methyl-1-naphthyl nonanoate, ethyl 2-methoxycyclobutanecarboxylate, butyl 2-ethoxycyclohexanecarboxylate, 3- (ethoxymethyl) tetralin- 2-butyric acid isopropyl ester,
8-butoxy, decalin-1-carboxylic acid ethyl ester, 3-ethoxynorbornane-2-carboxylic acid methyl ester, methyl 2- (phenoxy) acetate, ethyl 3- (p-cresoxy) propionate, 4- (2-naphthoxy) Methyl butyrate, butyl 5-carbaclooxyvalerate, 2
-Methyl phenoxypropionate, ethyl 3- (4-methylphenoxy) -2phenylpropionate, ethyl 2-phenoxy, cyclohexanecarboxylic acid, ethyl thiophen-3-oxyacetate, 2- (2-picolinoxymethyl) -cyclohexane Examples thereof include ethyl carboxylate and ethyl 3-furfuryloxypropionate.

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 12 carbons, R ⁷ and R ⁸ are a hydrogen atom or an aliphatic hydrocarbon having 1 to 20 carbons, Y
Is a group in which a chain hydrocarbon having 1 to 4 carbon atoms is substituted by an aliphatic hydrocarbon having 1 to 18 carbon atoms, an aromatic hydrocarbon having 6 to 18 carbon atoms or a polycyclic hydrocarbon, or a fatty acid having 3 to 12 carbon atoms. It is a cyclic hydrocarbon group. Particularly preferably, Y is a chain hydrocarbon, and an alkoxyester having a bulky substituent having 4 or more carbon atoms at the 2- or 3-position counted from the carboxyl group is preferable. Further, an alkoxyester compound having a 4- to 8-membered cycloalkane is also preferable. Specifically, ethyl 3-ethoxy-2-phenylpropionate, 3-ethoxy-2
-Ethyl tripropionate, ethyl 3-ethoxy-2-mesitylpropionate, ethyl 3-butoxy-2- (methoxyphenyl) propionate, 3-i-propoxy-
Methyl 3-phenylpropionate, 3-ethoxy-3-
Ethyl phenylpropionate, 3-ethoxy-3-tert
-Ethyl butylpropionate, ethyl 3-ethoxy-3-adamantylpropionate, 3-ethoxy-2-tert
-Ethyl butyl propionate, 3-ethoxy-2-tert
Ethyl-amylpropionate, ethyl 3-ethoxy-2-adamantylpropionate, ethyl 3-ethoxy-2-bicyclo [2,2,1] heptylpropionate, ethyl 2-ethoxy-cyclohexanecarboxylate, 2- (ethoxymethyl ) -Methyl 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: 2-100: 10 ^{-4 -10} . If the ID is less than this range, stereospecificity decreases, while if it is too large, the activity decreases, which is not preferable.

Polymerization of olefin The solid catalyst component of the present invention obtained as described above is
Olefin polymerization can be performed by combining with an organic aluminum compound.

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

AlR ⁹ R ¹⁰ R ¹¹ ... (III) R ¹² R ¹³ Al-O-AlR ¹⁴ R ¹⁵ ... (IV) 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 1 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. l 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.

A catalyst comprising a titanium-containing solid catalyst component according to the present invention and a catalyst component comprising an organoaluminum compound for the purpose of improving the stereoregularity of the resulting polymer when performing a polymerization reaction of an α-olefin having 3 or more carbon atoms. Many compounds which have been proposed for use in Ziegler polymerization catalysts and which have an effect on stereoregularity can be further added to the system. Compounds used for such purposes include aromatic monocarboxylic acid esters, Si-OC
Or a silicon compound having an Si-NC bond, an acetal compound, a germanium compound having a Ge-OC bond, a nitrogen or oxygen heterocyclic compound having an alkyl substituent, or the like.

Specifically, for example, ethyl benzoate, butyl benzoate, ethyl p-toluate, ethyl p-anisate, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, di-n- Propyldimethoxysilane, cyclohexylmethyldimethoxysilane, tetraethoxysilane, t-butylmethyldimethoxysilane, benzophenonedimethoxyacetal, benzophenonediethoxyacetal, acetophenonedimethoxyacetal, t-
Butyl-methylketone dimethoxyacetal, diphenyldimethoxygermane, phenyltriethoxygermane, 2,2,6,6-tetramethylpiperidine, 2,2,6,6-tetramethylpyran and the like. Of these, Si-OC
Alternatively, a silicon compound or an acetal compound having a Si-NC bond is preferable, and a combination with a compound having a Si-OC bond is particularly preferable.

In the polymerization of olefins, the amount of organoaluminum used in the polymerization system is generally 10 ⁻⁴ mmol / or more, preferably 10 ⁻² mmol / or more. Further, the usage ratio to the titanium atom in the solid catalyst component is generally 0.5 or more, preferably 2 or more, particularly 1 or more in molar ratio.
0 or more is preferable. If the amount of the organoaluminum is too small, the polymerization activity is greatly reduced.
In addition, 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, it can be seen that the catalyst performance is further improved even if these values are further increased. Absent.

The amount of the above-mentioned stereoregularity improver used for the purpose of improving the stereoregularity of the α-olefin polymer can be achieved with a very small amount by using the titanium-containing solid catalyst component of the present invention. It is usually used in a ratio of 0.001 to 5 mol, preferably 0.01 to 1, with respect to 1 mol of the organoaluminum compound.

Olefin The olefin used in the polymerization is generally an olefin having at most 18 carbon atoms, and typical examples thereof include ethylene, propylene, butene-1, 4-methylpentene-1, hexene-1, octene and octene. -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 solid catalyst component of the present invention, the organoaluminum compound or these and the stereoregularity improver may be separately introduced into a polymerization vessel, but two or all of them may be introduced. 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.

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.

(5) Examples 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, stereoregularity improver, etc.) used in the production and polymerization of the solid catalyst component is substantially water-free. .

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

[Example 1] Preparation of solid catalyst component Anhydrous magnesium chloride (obtained by calcining and drying commercially available anhydrous magnesium chloride in a dry hydrogen chloride gas stream at about 500 ° C for 15 hours) 20 g (0.21 mol), 3 -Ethoxy-2-phenyl, ethyl propionate 11.1 g (0.05 mol), titanium tetrachloride 3.3 ml, and silicon oil (TSS-451, 20CS manufactured by Shin-Etsu Chemical Co., Ltd.) 3.0 as a grinding aid
The ml was placed in a container for a vibrating ball mill (stainless steel cylindrical type, circular volume 1, magnetic balls having a diameter of 10 mm and apparently filled by about 50% by apparent volume) under a dry nitrogen stream. This was mounted on a vibrating ball mill having an amplitude of 6 mm and co-milled for 15 hours to obtain a co-milled solid. 15 g of the obtained co-ground product was suspended in 150 ml of 1,2-dichloroethane, and
After stirring at 0 ° C. for 2 hours, the solid portion was collected by filtration and washed sufficiently with hexane until free 1,2-dichloroethane was not detected in the washing solution. This is low temperature 30
After drying under reduced pressure at -40 ° C to remove hexane, a solid catalyst component was obtained. When the obtained solid catalyst component was analyzed,
The content of titanium atoms in this solid catalyst component was 2.3% by weight.

Polymerization and physical properties of the resulting polymer In a stainless steel autoclave having an internal volume of 3, 20 mg of the solid catalyst component produced in the above-described manner, 91 mg of triethylaluminum and 20 mg of diphenyldimethoxysilane, and immediately, 760 g of propylene and 0.1 g of 0.1 g Hydrogen was charged. The temperature of the autoclave was raised and the internal temperature was kept at 70 ° C. After one hour, the content gas was released to terminate the polymerization. As a result, 314 g of powdery polypropylene was obtained. That is, the polymerization activity is 15700 g / g · solid catalyst component · hour and 683 kg / g · Ti · hour. This propylene powder had an HR of 95.9%. The MFR was 8.6 g / 10 minutes.

[Example 2] Using the solid catalyst component of Example 1, the polymerization temperature was set to 80 ° C. Other than that is the same as the first embodiment. The obtained polymer was 408 g of a powdery polymer and the polymerization activity was 20400 g / g.
-Solid catalyst component-hour, 887 kg / g-Ti-hour. The HR of this polypropylene powder is 97.1% and the MFR is 3.4 g /
10 minutes.

Example 3 Using the solid catalyst component of Example 1, polymerization was carried out in the same manner as in Example 1 except that 20 mg of phenyltriethoxysilane was charged instead of diphenyldimethoxysilane during the polymerization. From the obtained powder polymer, the polymerization activity was 1430
0 g / g · solid catalyst component · time, 622 kg / g-Ti · time, HR 95.8%, MFR 12.3 g / 10 min.

[Examples 4 to 7] The same polymerization conditions as in Example 1 were used except that the solid catalyst component of Example 1 was used and the stereoregularity improver added during polymerization was changed as shown in Table 1. The results obtained are also shown in Table 1.

Example 8 9.5 g of anhydrous magnesium chloride (treated in the same manner as in Example 1) was mixed with 50 ml of decane and 46.8 ml of 2-ethylhexyl alcohol at 130 ° C. in a round bottom flask under N ₂ atmosphere. For 2 hours. 2.1 g of phthalic anhydride was added, and the mixture was further heated at 130 ° C. for 1 hour. The solution was cooled to room temperature, 20 ml was charged into a dropping funnel, and the temperature was lowered to -20 ° C over 30 minutes.
The solution was dropped into 80 ml of titanium tetrachloride, and the temperature was raised to 110 ° C. in 4 hours. A solution of 3.3 g of ethyl 3-ethoxy-2-phenylpropionate was slowly added dropwise. After dropping, 11
The reaction was performed at 0 ° C. for 2 hours. After removing the supernatant, add new TiC
The l ₄ introduced 80 ml, was heated at 110 ° C.. Then 100ml
Was washed three times with n-decane, and then washed with n-hexane to obtain a solid catalyst. The Ti loading was 2.8% by weight.

As a result of carrying out the polymerization in the same manner as in Example 1, the polymerization activity was
H was 12600 g / g-solid catalyst, 450 kg / g-Ti-hour.
R. was 96.7% and MFR was 2.0 g / 10 min.

[Example 9] In a nitrogen stream, a well-dried 300 ml round bottom flask was
100 ml of n-heptane, 9.5 g of MgCl _{2, and} 68 g of Ti (onBu) ₄ were added and reacted at 100 ° C. for 2 hours to obtain a homogeneous solution. After completion of the reaction, the temperature was lowered to 40 ° C., and then 15 ml of methylhydrogenpolysiloxane (of 2 centistokes) was added and reacted for 3 hours. After washing the formed solid catalyst with n-heptane, 150 ml of heptane was added, and a solution prepared by dissolving 28 g of SiCl ₄ in 80 ml of n-heptane was added dropwise over 1 hour at room temperature. After the completion of the dropwise addition, the reaction was further performed for 30 minutes. The obtained solid component was washed three times with 200 ml of n-heptane, and then cooled to -10 ° C. Thereto TiCl ₄ was introduced 100 ml, well after stirring, it was added dropwise 3-ethoxy-2-phenylpropionic acid ethyl 2.82 g. After the completion of the dropwise addition, the reaction was carried out at 90 ° C. for 2 hours. Remove the supernatant, introduce 100 ml of fresh TiCl ₄ and add 9 ml.
The reaction was performed at 0 ° C. for 2 hours. After completion of the reaction, the solid was washed with n-heptane to obtain a solid catalyst. Analysis of the amount of supported Ti was 2.4% by weight.

The polymerization was carried out in the same manner as in Example 1, and as a result, the polymerization activity was 1290
It was 0 g / g · solid catalyst · hour and 538 kg / g · Ti · hour.
The HR was 95.0% and the MFR was 23 g / 10 minutes.

[Example 10] In a nitrogen stream, a well-dried 300 ml round bottom flask was
5 g of diethoxymagnesium, 1.22 g of ethyl 3-ethoxy-2-phenylpropionate and 25 ml of methylene chloride were added. Stir at reflux for 1 hour and then suspend the suspension at room temperature.
It was pumped into 200ml TiCl ₄ in. Gradually raise the temperature to 110 ° C and 2
The reaction was performed while stirring for an hour. After completion of the reaction, the precipitated solid was separated and washed three times with 200 ml of n-decane at 110 ° C. 200 ml of fresh TiCl ₄ was added and reacted at 120 ° C. for 2 hours. After completion of the reaction, the precipitated solid was separated, washed three times with 200 ml of n-decane at 110 ° C., and washed with n-hexane at room temperature with hexane until no chloride ion was detected. The content of titanium in the catalyst component was 3.2%.

The polymerization was carried out in the same manner as in Example 1. Calculating from the results obtained, the polymerization activity was 20800 g / g · solid catalyst component · hour, 650 kg / g · Ti · hour, HR was 96.8%, and MFR was 1.7 g.
/ 10 minutes.

[Examples 11 to 21] Instead of the ethyl 3-ethoxy-2-phenylpropionate of Example 10, the components added during the preparation of the catalyst were changed. Other than that was prepared in the same manner as in Example 10. The polymerization method is Example 1.
The same was done. Table 2 shows the polymerization results.

[Comparative Examples 1-4] Prepared in the same manner as in Example 10 except that the compounds shown in Table 3 were used as components to be added at the time of preparing the catalyst in place of ethyl 3-ethoxy-2-phenylpropionate of Example 10. . The polymerization was carried out in the same manner as in Example 1.

Example 22 Using the solid catalyst of Example 1, polymerization was carried out in the same manner as in Example 1 without using diphenyldimethoxysilane. From the obtained polymer, the polymerization activity was 17300 g / g · solid catalyst component · hour and 752 kg / g · Ti · hour. The HR of this polypropylene powder was 51.3%. The MFR was 15.1 g / 10 minutes.

Comparative Example 5 A solid catalyst was prepared in the same manner as in Example 1 without using ethyl 3-ethoxy-2-phenylpropionate. Polymerization was carried out in the same manner as in Example 1 without using diphenyldimethoxysilane. The polymerization activity of the obtained polymer is 9110 g / g
Solid catalyst component / hour, 285 kg / g · Ti · hour. The HR of this polypropylene powder was 23.7%. MFR
It was 7.9 g / 10 minutes.

Comparative Example 6 A solid catalyst was prepared in the same manner as in Example 1 without using ethyl 3-ethoxy-2-phenylpropionate. Polymerization was carried out in the same manner as in Example 1. From the obtained polymer, the polymerization activity was 4910 g / g-solid catalyst component-time, 213 kg / g-Ti
Time. The HR of this polypropylene powder is 71.2%
Met. The MFR was 3.8 g / 10 minutes.

(7) Effect When olefins are polymerized by using the catalyst component obtained by the present invention, the catalyst is very high in activity, so that the catalyst residue in the produced polymer can be kept extremely low. In addition, the decalcification step can be omitted.
In addition, since the amount of remaining halogen (concentration) is small, the degree of corrosion of a molding machine or the like in a polymer processing step can be greatly improved. Further, the residual catalyst causes deterioration and yellowing of the polymer itself, 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.

These effects are of crucial significance in industrial processes.

[Brief description of the drawings]

FIG. 1 is a flow chart showing one method for preparing an olefin polymerization catalyst of the present invention.

Claims (2)

(57) [Claims] The present invention relates to a solid catalyst component comprising, as an essential component, a titanium compound selected from a magnesium compound, a trivalent or tetravalent titanium halide, an alkoxide and an alkoxytitanium halide, and a halogen-containing compound. (I) (R ¹ O) _i (R ² O) _j (R ³ O) _k- Z-COOR ⁴ (I) (where R ¹ , R ² , R ³ and R ⁴ are aliphatic hydrocarbons and fats A group selected from a cyclic hydrocarbon, an aromatic hydrocarbon, a polycyclic hydrocarbon, and a heterocyclic compound, and Z is an aliphatic or alicyclic ring whose hydrogen atom may be substituted with an aromatic group or a polycyclic group. A hydrocarbon group, i, j, k is an integer of 0 to 3 and the sum of i, j, k is 1 or more.) One or more alkoxy ester compounds represented by the formula: An olefin polymerization catalyst component obtained by the following treatment. 2. An olefin polymerization method comprising using a catalyst system containing the catalyst component according to claim 1.