JP2908866B2 - Solid catalyst component for olefin polymerization and olefin polymerization method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a high-performance catalyst composition having a high activity when used for polymerization or copolymerization of olefins. The present invention relates to a catalyst component for olefin polymerization capable of obtaining a high stereoregular polymer in a high yield when applied to olefin polymerization, and a method for polymerizing olefins using the same.

[Conventional technology]

Heretofore, many production methods using a solid catalyst component having 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, 54-13)
No. 6590) and a method using 2-ethoxyethyl acetate (JP-A-61-287908). However, even if these esters are used, they do not have industrially satisfactory performance in terms of activity and stereospecificity, and further development of a high-performance catalyst has been desired.

Against this background, the present applicant has previously described a method for producing an olefin polymerization catalyst using an alkoxyester compound as an internal donor and a method for polymerizing an olefin (Japanese Patent Application No. 1-14 / 1990).
No. 2717, hereinafter referred to as a prior invention)).
According to the method of the invention of the prior application, it has become possible to obtain a polymer having high stereoregularity with high activity.

[Problems to be solved by the invention]

An object of the present invention is to further improve the above-mentioned prior application invention and to provide a novel olefin polymerization catalyst component for producing a polymer having higher activity and higher stereoregularity and a method for polymerizing olefins using the same.

[Means for solving the problem]

As a result of diligent research to solve the above-mentioned problems, by using a transition metal compound of Group 7A and Group 8 of the periodic table at the time of preparing the same catalyst as in the prior application invention, it was compared with the polymer obtained by the method of the prior application invention. As a result, it has been found that a polymer having more excellent stereoregularity is produced, and the present invention has been made, which has the following points. That is, the present invention relates to the following general formula (I) (R ¹ O) _i (R ² O) _j (R ³ ) during or after the formation of a solid catalyst component containing a magnesium compound, a titanium compound and a halogen-containing compound as essential components. O) _k -Z-COOR ⁴ (I) (where R ¹ , R ² , R ³
And R ⁴ are hydrocarbon groups; Z is an aliphatic hydrocarbon group whose hydrogen atom may be substituted with an aromatic hydrocarbon; and i, j,
k is an integer of 0 to 3, and the sum of i, j, k is 1 or more. Olefin polymerization characterized by contacting and reacting one or more alkoxyester compounds represented by the formula) with one or more transition metal compounds belonging to Group 7A and Group 8 of the Periodic Table. An olefin polymerization method characterized by using a solid catalyst component and a catalyst system containing the solid catalyst component.

 Hereinafter, the present invention will be described in detail.

Preparation of Solid Catalyst Component for Olefin Polymerization The magnesium compound used in the preparation of the solid catalyst component in the present invention is not particularly limited, and is used as a raw material for preparing a highly active catalyst for ordinary olefin polymerization and copolymerization. Can be used. That is, magnesium halides such as magnesium chloride, magnesium bromide and magnesium iodide; alkoxymagnesiums such as dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium and diphenoxymagnesium; magnesium laurate, magnesium stearate , Magnesium acetate such as magnesium acetate; alkylmagnesium such as dimethylmagnesium, diethylmagnesium, and butylethylmagnesium. These various magnesium compounds can be used alone or in combination of two or more. Preferably, magnesium halide or alkoxymagnesium is used, or magnesium halide is formed during catalyst formation. Particularly preferably, the halogen is chlorine.

Examples of the titanium compound used in the present invention include titanium halides such as titanium tetrachloride, titanium trichloride, titanium tetrabromide, and titanium tetraiodide;
Alkoxy titanium such as tetraethoxytitanium, tetrapropoxytitanium, tetrabutoxytitanium, tetraphenoxytitanium; alkoxytitanium such as ethoxytitanium trichloride, butoxytitanium trichloride, phenoxytitanium trichloride, dibutoxytitanium dichloride, tributoxytitanium chloride Halide and the like can be exemplified. In addition, these various titanium compounds include 1
The seeds can be used alone or in combination of two or more. Preferably, it is a tetravalent titanium compound containing halogen, and particularly preferably, titanium tetrachloride.

In the halogen-containing compound used in the present invention, the halogen is fluorine, chlorine, bromine, or iodine, preferably chlorine, and specific compounds actually exemplified are titanium tetrachloride, Examples thereof include titanium halides such as titanium tetrabromide, silicon tetrachloride, silicon halides such as silicon tetrabromide, and phosphorus halides such as phosphorus trichloride and phosphorus pentachloride. Hydrocarbons, halogen molecules, and hydrohalic acids 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).

When any of R ¹ , R ² , R ³ , and R ⁴ is an aliphatic or alicyclic hydrocarbon group, it has 1 to 12 carbon atoms or 4 to 12 carbon atoms.
Are 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, unenyl, dodecyl, vinyl, allyl, 2-hexenyl, 2,4 hexadienyl, isopropenyl, cyclobutyl, cyclopentyl, 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-amyl ethylene, adamantane ethylene, bicyclo [2,2,1] butyl ethylene, phenyl ethylene, tolyl ethylene,
Xylylethylene, diphenyltrimethylene, 1,2-cyclopentylene, 1,3 cyclopentylene, 3-cyclohexene-1,2-ylene, dimethylethylene, indenyl-1,2-ylene and the like can be exemplified. 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, and ethyl i-propoxyacetate. Methyl n-butoxyacetate, ethyl i-butoxyacetate, ethyl n-hexyloxyacetate, octyl sec-hexyloxyacetate, methyl 2-methylcyclohexyloxyacetate,
-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,
Cyclohexyl 3- (n-butoxy) propionate, 3
-Ethyl neopentyloxypropionate, 3- (n-
Octyloxy) butyl propionate, methyl 3- (2,6 dimethylhexyloxy) propionate, 3- (3,3
-Dimethyloctyloxy) octyl propionate, 4-
Ethyl ethoxybutyrate, cyclohexyl 4-ethoxybutyrate, octyl 5- (n-propoxy) valerate, ethyl 12-ethoxylaurate, ethyl 3- (1-indenoxy) propionate, methyl 3-methoxyacrylate, 2-
Methyl methoxyacrylate, methyl 2-ethoxyacrylate, ethyl 3-phenoxyacrylate, ethyl 2-methoxypropionate, n-butyl 2- (i-propoxy) butyrate, methyl 2-ethoxyisobutyrate, 2-cyclohexyloxyisovalerate Phenyl, 2-ethoxy, 2-phenylbutyl acetate, allyl 3-neopentyloxybutyrate, 3
Methyl ethoxy, 3 (o-methylphenyl) propionate, ethyl 3-ethoxy, 2- (o-methylphenyl) propionate, ethyl 3-ethoxy, 2-mesitylpropionate, 3-ethoxy, 2-tertbutylpropionate ethyl,
Ethyl 3-ethoxy, 2-tert-amylpropionate,
Ethyl ethoxy, 2-adamantane ethyl propionate, 3-ethoxy, 2-bicyclo [2,2,1] ethyl butylpropionate, 3 ethoxy, ethyl 3-phenylpropionate, 3
Ethoxy, ethyl 3-mesitylpropionate, 3 ethoxy, ethyl 3-tert-butylpropionate, 3 ethoxy, 3
-Ethyl tert-amylpropionate, 4-ethoxy, 2-
Propyl (t-butyl) butyrate, 5-methoxy, 2-methyl, 1
-Ethyl 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,
Methyl 2- (phenoxy) acetate, ethyl 3- (p-cresoxy) propionate, methyl 4- (2-naphthoxy) butyrate, butyl 5-carbaclooxyvalerate, methyl 2-phenoxypropionate, 3- (4-methylphenoxy)
2-ethyl phenylpropionate, 2-phenoxy, ethyl cyclohexanecarboxylate, thiophene-
Examples thereof include ethyl 3-oxyacetate.

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 by an aliphatic hydrocarbon, an aromatic hydrocarbon or a polycyclic hydrocarbon, or an alicyclic hydrocarbon group having 5 to 12 carbon atoms. Particularly preferably, Y is a chain hydrocarbon and is 2% from the carboxyl group.
Alkoxy esters having a bulky substituent having 4 or more carbon atoms at the 3- or 3-position are preferred. 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, ethyl 2- (methoxyphenyl) propionate, 3-i-propoxy, methyl 3-phenylpropionate, ethyl 3-ethoxy, 3-phenylpropionate, 3
-Ethoxy, ethyl 3-tert-butylpropionate, 3-
Ethoxy, ethyl 3-adamantylpropionate, 3 ethoxy, ethyl 2-tert-butylpropionate, 3-ethoxy, ethyl 2-tert-amylpropionate, 3-ethoxy, 2
-Ethyl adamantyl propionate, 3-ethoxy, 2-
Ethyl bicyclo [2,2,1] heptylpropionate, 2-
Ethoxy, ethyl cyclohexanecarboxylate, 2 (ethoxymethyl), methyl cyclohexanecarboxylate, 3-
Ethoxy norbornane-2-carboxylate and the like can be exemplified.

The transition metal compounds of Group 7A and Group 8 of the periodic table used in the present invention include manganese of Group 7A, technetium, rhenium, iron of Group 8 and iron, ruthenium, osmium, cobalt,
Various compounds such as rhodium, iridium, nickel, palladium, and platinum can be exemplified. For example, these transition metal halides, alkoxides, carponates,
Chelate compounds represented by acetylacetonate salts and the like can be mentioned.

Preferably, manganese (II) chloride, technetium (III) chloride, rhenium (III) chloride, manganese (II) bromide,
Manganese (II) iodide, iron (II) chloride, iron (III) chloride,
Iron (II) bromide, iron (II) iodide, ruthenium chloride (II
I), osmium (III) chloride, osmium (IV) chloride,
Cobalt (II) chloride, cobalt (II) bromide, cobalt (II) iodide, rhodium (II) chloride, iridium chloride (II)
I), iridium (IV) chloride, nickel (II) chloride, nickel (II) bromide, nickel (II) iodide, palladium (II) chloride, palladium (II) bromide, platinum (II) chloride, platinum chloride (III), and halides of respective transition metals typified by platinum (IV) chloride and the like. These transition metal compounds may be used alone or in combination of two or more. However, the value in parentheses indicates the valence of the transition metal.

The use amount of each of the above components is arbitrary as long as the effect is recognized in the present invention, but is generally preferably in the following range.

The amount of the titanium compound to be used is preferably in the range of 1 × 10 ^{−4 to} 1000, and more preferably in the range of 0.01 to 100, in a molar ratio to the amount of the magnesium compound to be used. Halogen compounds are used as necessary.However, when used, the amount used depends on whether or not titanium compounds, magnesium compounds and transition metal compounds of Group 7A and 8 of the periodic table contain halogen. It is better to use a molar ratio of 1 × 10 ^{-2 to} 1000 with respect to the amount of magnesium used,
Preferably it is in the range of 0.1-100.

The use amount of the alkoxyester compound represented by the formulas (I) and (II) is preferably in a range of 1 × 10 ⁻³ to 10 in terms of a molar ratio with respect to the use amount of the magnesium compound, and is preferably 0.01 to 10%. 5 is within the range.

The amount of the transition metal compound of Group 7A and Group 8 of the periodic table is 1 × 10 ⁻³ or more in a molar ratio to the amount of the magnesium compound.
The range of 5 is preferable, and the range of 0.01 to 1 is preferable.

The method for preparing a solid catalyst component according to the present invention is a conventional method obtained by temporarily or stepwise contacting and reacting a magnesium compound, a titanium compound, an electron donor and, if necessary, an auxiliary such as a halogen-containing compound. Known solid catalyst component preparation methods can be applied. That is, at the time of or after the formation of the known solid catalyst component (I), (II)
One or more of the transition metal compounds of Group 7A and Group 8 of the periodic table, which are brought into contact with one or more of the alkoxyester compounds represented by the formulas and reacted with them in a temporary or stepwise manner. is there. Specific examples of applying a known method include: (1) contacting and reacting magnesium chloride, a titanium compound, an alkoxyester compound, and a transition metal compound of Group 7A or 8 in the periodic table in any order, and then reacting a liquid hydrocarbon; Washing method as appropriate.

(2) A method of contacting and reacting an alkoxymagnesium, a titanium compound, a halogen-containing compound, an alkoxyester compound, and a transition metal compound of Groups 7A and 8 of the periodic table in an arbitrary order, and then appropriately washing with a liquid hydrocarbon.

(3) A method in which a magnesium compound or a transition metal compound of Groups 7A and 8 of the periodic table is dissolved with a titanium tetraalkoxide and an alkoxyester compound, and is contacted with a halogen-containing compound or a solid titanium compound precipitated with a titanium halide.

Etc., the solid catalyst component of the present invention can be prepared.

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.

As the organoaluminum compound in the present invention, a compound represented by AlR ⁹ _z X _3-z may be mentioned as a general formula. In the above formula, R ⁹ represents a hydrocarbon group having 1 to 20 carbon atoms, particularly preferably an aliphatic hydrocarbon group. X represents a halogen, and z represents a number of 1 to 3. Specific examples of the organoaluminum compound include trimethylaluminum,
Triethyl aluminum, tripropyl aluminum,
Tributyl aluminum, trihexyl aluminum,
Trioctylaluminum, dimethylaluminum dichloride, diethylaluminum dichloride, methylaluminum dichloride, ethylaluminum dichloride and the like can be mentioned. Preferably, trialkylaluminum is used. 2 bonded through an O or N atom
Organoaluminum compounds containing one or more Al atoms, typically aluminoxanes, can also be used.

Further, dialkylaluminum alkoxides, alkylaluminum sesquihalides, alkylaluminum sesquialkoxides and the like are also used.

When a polymerization reaction of an α-olefin having 3 or more carbon atoms is carried out, a catalyst system comprising a titanium-containing solid catalyst component and an organoaluminum compound according to the present invention is provided for the purpose of improving the stereoregularity of the produced polymer. Up to now, many compounds which have been proposed for use in olefin polymerization catalysts and which have an effect on stereoregularity can be further added. Representative compounds used for such purposes include aromatic carboxylic acid esters, Si-OC or
Examples thereof include a silicon compound having an Si—N—C bond, an acetal compound, a germanium compound having a Ge—O—C bond, and a nitrogen or oxygen heterocyclic compound having an alkyl substituent.

Specific examples of these compounds include, for example, ethyl benzoate, butyl benzoate, ethyl p-toluate, ethyl p-anisate, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and diphenyldiethoxysilane. -N-propyldimethoxysilane, cyclohexylmethyldimethoxysilane, tetraethoxysilane, t-butylmethyldimethoxysilane, benzophenone, dimethoxyacetal, benzophenonediethoxyacetal, acetophenonedimethoxyacetal, t-butylmethylketonedimethoxyacetal, diphenyldimethoxygerman, phenyl Triethoxygermane, 2,2,6,6-tetramethylpiperidine, 2,2,6,6-tetramethylpyran and the like. Among these, silicon compounds and acetal compounds having a Si—O—C or Si—N—C bond are preferable, and particularly, Si—O—
A combination with a compound having a C bond is preferred.

In the polymerization of olefins, the amount of the organoaluminum compound used in the polymerization system is generally at least 10 ^-4 mmol / l, preferably at least 10 ^-2 mmol / l. Further, the usage ratio to the titanium atom in the solid catalyst component is generally 0.5 or more, preferably 2 or more, particularly 10
The above is preferable. If the amount of the organoaluminum compound is too small, the polymerization activity is greatly reduced. When the amount of the organoaluminum compound used in the polymerization system is 20 mmol / l or more and the ratio to the titanium atom is 1000 or more in molar ratio, the catalyst performance is further improved even if these values are further increased. Is not seen.

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 solid catalyst component of the present invention. However, it is usually used in a molar ratio of 0.001 to 5 mol, preferably 0.01 to 1, with respect to 1 mol of the organic aluminum compound.

Olefins The olefins used in the polymerization include ethylene, propylene, 1-butene, 4-methyl-1-pentene,
-Methyl-1-pentane, 1-hexene, 1-octene and the like. Of these, α-olefins having 3 or more carbon atoms, particularly propylene, are preferred. The polymerization can be suitably applied to not only homopolymerization but also generally known random or block copolymerization.

Polymerization Method and Its Conditions In carrying out the polymerization, the solid catalyst component, the organoaluminum compound or the steric regularity improver of the present invention may be separately introduced into a polymerization vessel. May be mixed in advance.

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

The polymerization temperature can be generally selected from the range of -10 ° C to 180 ° C, and is practically 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 Examples and Comparative Examples, the stereoregularity (isotacticity) of the produced polymer was evaluated by a boiling heptane extraction method. That is, the resulting polymer was extracted with boiling heptane for 6 hours, and the weight% of the insoluble portion was defined as isotactic index (II). The melt flow index (MFI) of the resulting polymer is 2,6-
The powder containing 0.2% of di-tert-butyl-4-methylphenol was measured according to JIS K-6758 at a temperature of 230 ° C. and a load of 2.16 kg.

In each Example, each compound (organic solvent, olefin, hydrogen, titanium compound, magnesium compound, alkoxyester compound, transition metal compound of Group 7A and 8 of the periodic table, halogen-containing compound) used in the production and polymerization of the solid catalyst component was used. Compounds, stereoregularity improvers, etc.) are all substantially water-removed.

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

Example 1 Solid Preparation anhydrous magnesium chloride catalyst components: MgCl ₂ (those obtained by heat drying for 15 hours at about 500 ° C. in a nitrogen stream to dry commercially available anhydrous magnesium chloride) 30 g (315 mm
ol), anhydrous ferrous chloride: FeCl ₂ (commercially available ferrous chloride tetrahydrate: obtained by heating and dehydrating FeCl ₂ .4H ₂ O at about 200 ° C. for 8 hours in a stream of hydrogen chloride. ) 2.85g
(22.5 mmol) and 4.65 g (23 mmol) of ethyl 3-ethoxy-2-phenylpropionate were placed in a container for a vibrating ball mill (stainless steel cylindrical type, 1 in content, porcelain balls having a diameter of 10 mm in apparent volume of about 50). % Filling). This was mounted on a vibrating ball mill with an amplitude of 6 mm and a frequency of 30 Hz.
Co-ground was obtained by co-milling for 0 hours. 5 g of the obtained co-ground product is mixed with 100 ml of titanium tetrachloride: TiCl ₄
And reacted at 120 ° C. for 2 hours. The solid product was collected by filtration and filtered with n-decane (100 ml) at 80 ° C.
It was washed four times with n-hexane (100 ml) at room temperature four times. This was dried under reduced pressure at 40 ° C. to obtain a target solid catalyst component. When the obtained solid catalyst component was analyzed by atomic absorption spectrometry, the content of titanium atoms in the solid catalyst component was 2.0% by weight.

Polymerization of propylene and physical properties of the resulting polymer 20 g of the solid catalyst component prepared in the above manner, 91 mg of triethylaluminum and 20 mg of diphenyldimethoxysilane were placed in a stainless steel autoclave having a volume of 3 l, and immediately thereafter, 760 g of propylene and 0.1 g Of hydrogen. 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, 374 g of polypropylene was obtained. That is, the polymerization activity is 18700-polypropylene / g-solid catalyst component / time (hereinafter abbreviated as g-PP / g-Cat / h), 935 kg-
It was titanium / hour (hereinafter abbreviated as kg-PP / g-Ti-h) in the polypropylene / g-solid catalyst component. Formed polymer II
Was 97.4%. MFI was 7.8 g-polypropylene / 10 minutes (hereinafter abbreviated as g-PP / 10 min).

Comparative Example 1 Preparation of Solid Catalyst Component The same method and preparation conditions as in Example 1 were used except that MgCl ₂ and ethyl 3-ethoxy-2-phenylpropionate were not used in co-grinding FeCl _2. Was used to prepare a solid catalyst component. The content of titanium atoms in the obtained solid catalyst component was 2.4% by weight.

Polymerization of Propylene and Evaluation of Produced Polymer Propylene polymerization was performed in the same manner and under the same polymerization conditions as in Example 1. 320 g of polypropylene was obtained, and the polymerization activity was
16000 g-PP / g-Cat.h and 670 kg-PP / g-Ti-h. II of the produced polymer was 95.7%. MFI is 5.8g-PP / 10min
Met.

Examples 2 to 10 Instead of ethyl 3-ethoxy-2-phenylpropionate, a solid catalyst component was prepared in the same manner and under the same preparation conditions as in Example 1, using the alkoxyester compounds shown in Table 1. Propylene polymerization was carried out under the same method and under the same polymerization conditions as in Example 1.

Comparative Examples 2 to 10 Instead of ethyl 3-ethoxy-2-phenylpropionate, a solid catalyst component was prepared in the same manner and under the same conditions as in Comparative Example 1, except that the alkoxyester compounds shown in Table 1 were used. Propylene polymerization was carried out under the same method and under the same polymerization conditions as in Example 1.

Examples 11 to 14 Using the solid catalyst component of Example 1, except that the stereoregularity improver added during the polymerization was changed to those shown in Table 2,
Propylene polymerization was carried out in the same manner and under the same polymerization conditions as in Example 1.

Examples 15-16 7A, during the preparation of the solid catalyst component, the transition metal compound component of the group 8
A solid catalyst component was prepared in the same manner as in Example 1, except that anhydrous manganese chloride (MnCl ₂ ) and anhydrous cobalt chloride (CoCl ₂ ) were used instead of FeCl ₂ . Mn
Cl ₂ and CoCl ₂ were each obtained by heating and dehydrating a commercially available anhydride at about 200 ° C. for 8 hours in a stream of hydrogen chloride. Propylene polymerization was performed in the same manner and under the same polymerization conditions as in Example 1 (Table 3).

Example 17-20 a solid MgCl ₂ catalyst component preparation, FeCl _2, 3- ethoxy-2-
A solid catalyst component was prepared in the same manner and under the same conditions as in Example 1, except that the amount of ethyl phenylpropionate used was changed to that shown in Table 4. Propylene polymerization was performed according to Example 1.
The polymerization was carried out in the same manner and under the same polymerization conditions.

Comparative Examples 11 to 13 Using electron donors (internal donors) shown in Table 5 instead of ethyl 3-ethoxy-2-phenylpropionate,
A solid catalyst component was prepared in the same manner and under the same preparation conditions as in Example 1. Propylene polymerization was carried out under the same method and under the same polymerization conditions as in Example 1.

Example 21 Preparation of solid catalyst component 9.50 g (100 mmol) of anhydrous magnesium chloride (Example 1)
50 ml of 1.80 g (14.2 mmol) of anhydrous iron chloride (treated in the same manner as in Example 1) and 1.80 g (14.2 mmol) of anhydrous iron chloride
Of n-decane and 47 ml of 2-ethylhexyl alcohol were dissolved in a round bottom flask at 130 ° C. for 2 hours under a nitrogen atmosphere. To this solution, 2.1 g of phthalic anhydride was added, and further heated at 130 ° C. for 1 hour. The solution was cooled to room temperature, 50 ml was charged into a dropping funnel, and the temperature was lowered to -20 ° C over 1 hour.
The solution was dropped into 200 ml of titanium tetrachloride, and the temperature was increased to 110 ° C. over 4 hours. 2.78 g (12.5 mmol) of ethyl 3-ethoxy-2-phenylpropionate was slowly added dropwise. After the completion of the dropwise addition, the reaction was carried out at 80 ° C. for 2 hours. After the reaction, the supernatant was removed, and 200 ml of titanium tetrachloride was newly introduced.
The reaction was carried out at 2 ° C. for 2 hours. Then remove the supernatant, 100 ℃
6 times with n-decane (100 ml) at room temperature and n-hexane (1
(00 ml) and dried under reduced pressure at 40 ° C. to obtain the desired solid component. The content of titanium atoms in the obtained solid catalyst component was 1.8% by weight.

Polymerization of Propylene and Physical Properties of Produced Polymer Propylene polymerization was carried out in the same manner as in Example 1. 400 g of polypropylene is obtained and the polymerization activity is 20,000 g-PP / g-cat
h and 1110 kg-PP / g-Ti · h. I. of the resulting polymer I.
Was 98.0%. MFI of produced polymer is 5.2g-PP / 10min
Met.

Examples 22 to 23 A transition metal compound component of Group 7A
A solid catalyst component was prepared in the same manner and under the same preparation conditions as in Example 21, except that anhydrous manganese chloride (MnCl ₂ ) and anhydrous cobalt chloride (CoCl ₂ ) were used instead of FeCl ₂ . Propylene polymerization was performed under the same method and polymerization conditions as in Example 1 (Table 6).

[Effects of the Invention] When olefins are polymerized using the catalyst component of the present invention, the polymerization activity is extremely high, and the catalyst residue in the produced polymer can be kept extremely low. Can be omitted. Further, since the amount (concentration) of the remaining halogen is small, the degree of corrosion of a molding machine or the like in the polymer processing step can be significantly improved. Further, the remaining catalyst causes deterioration and coloring of the polymer itself, but since the concentration is necessarily low, these can be reduced.

Further, since the resulting polymer has a very high stereoregularity, a polymer having practically usable mechanical strength can be obtained without removing a so-called non-stereoregular polymer portion.

These effects are of crucial significance in industrial processes.

[Brief description of the drawings]

FIG. 1 is a flowchart showing a method for preparing a catalyst for olefins polymerization, which is one of 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] The present invention relates to the following general formula (I) (R ¹ O) _i (R ² O) _j (R ³ ) when or after the formation of a solid catalyst component comprising a magnesium compound, a titanium compound and a halogen-containing compound as essential components. O) _k -Z-COOR ⁴ (I) (where R ¹ , R ² , R ³ and R ⁴ are a hydrocarbon group, and Z is an aliphatic hydrocarbon whose hydrogen atom may be substituted with an aromatic hydrocarbon) And i, j, k is an integer of 0 to 3, and the sum of i, j, k is 1 or more.) And one or more alkoxyester compounds represented by the following formula: A solid catalyst component for olefin polymerization, which is obtained by contacting and reacting with two or more transition metal compounds of Groups 7A and 8 of the periodic table. 2. A method for polymerizing an olefin, comprising using a catalyst system containing the catalyst component according to claim 1.