JP2881341B2 - 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 an olefin polymerization catalyst component capable of obtaining a high stereoregular polymer in a high yield when applied to olefin polymerization, and to an olefin polymerization method using a catalyst system containing this catalyst component.

[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. Although an organic carboxylic acid ester is often used as an internal donor, 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. Further, there has been a demand for the development of a catalyst having no industrially satisfactory performance in terms of polymerization activity and stereoregularity of the produced polymer, and further having high performance.

Against this background, the present applicant has previously described a method for producing an olefin polymerization catalyst using a ketoester compound as an internal donor and a method for polymerizing an olefin (JP-A-3-43407).
In 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 provide a catalyst which provides an olefin polymer having a high activity and a high stereoregularity, and a method for polymerizing an olefin, which were insufficient with the above prior art.

[Means for solving the problem]

As a result of intensive studies to solve the above-mentioned problems, a transition metal selected from iron (II), cobalt (II), nickel (II) and manganese (II) during the preparation of a solid catalyst similar to the prior application invention (however, , () Indicates the valency of the transition metal) to produce a polymer having more excellent stereoregularity than the polymer obtained by the method of the prior application. And arrived at the present invention having the following points. That is, the present invention relates to the following general formula (I) 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. (Where R ¹ , R ² and Z are groups selected from aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and polycyclic hydrocarbons). Or contacting and reacting with two or more compounds in the presence of one or more compounds of transition metals selected from iron (II), cobalt (II), nickel (II) and manganese (II) A solid catalyst component for olefin polymerization obtained by the above method and a catalyst system containing the 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 And carboxylic acid salts of magnesium such as magnesium acetate; alkyl magnesium 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 ketoester compound used in the present invention has the general formula Is represented by

R ^{1 in the} general formula (I) is a hydrocarbon group having 1 to 20 carbon atoms,
It is a group consisting of one or more of an aliphatic hydrocarbon, an alicyclic hydrocarbon, an aromatic hydrocarbon, and a polycyclic hydrocarbon. Specifically, methyl, ethyl, n-propyl, i-propyl, sec-butyl, tert-butyl, tert-amyl, 2-
Hexenyl isopropenyl, cyclopentyl, cyclohexyl, tetramethylcyclohexyl, cyclohexenyl, melbonylphenyl, tolyl, ethylphenyl,
Examples include xyl, cumyl, trimethylphenyl, tetramethylphenyl, pentamethylphenyl, naphthyl, methylnaphthyl, anthranyl, benzyl, diphenylmethyl, indenyl and the like.

These hydrogen atoms may be replaced by halogen atoms.

Among them, a group having an aromatic hydrocarbon or a polycyclic hydrocarbon is preferably used. Z in the general formula (I) is a hydrocarbon group having 1 to 30 carbon atoms, and is a group consisting of one or more of an aliphatic hydrocarbon, an alicyclic hydrocarbon, an aromatic hydrocarbon, and a polycyclic hydrocarbon. . Specifically, methylene, ethylene, trimethylene, propylenecyclohexane-diyl, tetramethylcyclohexane-diyl, o-phenylene, m-phenylene, p-phenylene, dimethyl-o
-Phenylene, 1,2-naphthylene, 2,3-naphthylene, 1,
Examples thereof include 8-naphthylene, biphenylene, binaphthylene, and 1,9-fluorenediyl. These hydrogen atoms may be replaced by halogen atoms. Among them, a group having an aromatic hydrocarbon group having 1 to 20 carbon atoms or a polycyclic hydrocarbon group is preferably used.

R ^{2 in the} general formula (I) is a hydrocarbon group having 1 to 20 carbon atoms, and is a group consisting of one or more of an aliphatic hydrocarbon, an alicyclic hydrocarbon, an aromatic hydrocarbon, and a polycyclic hydrocarbon. is there. Specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-
Ethylhexyl, cyclohexyl, phenyl, tolyl,
Xylyl, naphthyl and the like can be exemplified.

These hydrogen atoms may be replaced by halogen atoms. Among them, a group having an aliphatic hydrocarbon having 1 to 12 carbon atoms is preferably used.

Specific examples of the ketoester compound of the general formula (I) include methyl 2-benzoylbenzoate, ethyl 2-benzoylbenzoate, n-butyl 2- (2'-methylbenzoyl) benzoate, and 2- (4'-methyl Ethyl benzoyl) benzoate, ethyl 2- (2 ', 4'-dimethylbenzoyl) benzoate, ethyl 2- (2', 4 ', 6'-trimethylbenzoyl) benzoate, 2- (pentamethyl-benzoyl) benzoic acid Propyl, ethyl 2- (triethyl-benzoyl) benzoate, ethyl 2 (4'benzoyl chloride) benzoate, methyl 2- (trimethylbenzoyl) -4,5 dimethylbenzoate, 2-benzoyl-3,6 dimethylbenzoate n Propyl, (1'-naphthyl) phenylketone-2-ethyl carboxylate, (1'-naphthyl) 4,5-dimethylphenylketone-
Methyl 2-carboxylate, propyl (2'-naphthyl) phenylketone-2-carboxylate, butyl phenyl-1-naphthylketone-2-carboxylate, ethyl mesityl 2-naphthylketone-3-carboxylate, 8-benzoylnaphthalenecarboxy Propyl acid, octyl 8-trioylnaphthalenecarboxylate, isobutyl 2'-trioylbiphenyl-2-carboxylate, methyl 2'-benzoylbiphenyl-2-carboxylate, ethyl 2'-benzoylbinaphthyl-2-carboxylate, 5'-indenyl) phenyl ketone-2-carboxylate, n-butyl 2-benzoylfluorene-carboxylate, ethyl 9-benzoylfluorene-carboxylate, n-butyl 6 (4'-trioyl) indene-5-carboxylate, 10 -Benzoylphenanthrene-10 Carboxylic acid ethyl, and the like can be exemplified.

The iron (II), cobalt (I
Examples of the transition metal compound selected from I), nickel (II), and manganese (II) include, for example, chelate compounds represented by halides, alkoxides, carboxylate salts, and acetylacetonate salts of these transition metals. And the like.

Preferably, iron (II) chloride, iron (II) bromide, iron (II) iodide, cobalt (II) chloride, cobalt (II) bromide, cobalt (II) iodide, nickel (II) chloride, The halide of each transition metal represented by nickel (II) iodide, nickel (II) iodide, manganese (II) chloride, manganese (II) bromide, manganese (II) iodide, etc. is mentioned.
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 ketoester compound represented by the formula (I) 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 5%.
Is within the range.

The amount of the transition metal compound to be used is preferably in the range of 1 × 10 ^{−3 to} 5 and more preferably in the range of 0.01 to 1 in a molar ratio to the amount of the magnesium compound.

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 or after the formation of a known solid catalyst component, one or more ketoester compounds represented by the formula (I) and a compound of a transition metal selected from iron, cobalt, nickel and manganese And one or two or more of them are contacted or reacted temporarily or stepwise. Specific examples of applying a known method include: (1) magnesium chloride, titanium compound, ketoester compound and iron (II), cobalt (II), nickel (I
A method in which a compound of a transition metal selected from I) and manganese (II) is contacted and reacted in an arbitrary order, and then appropriately washed with a liquid hydrocarbon.

(2) An alkoxymagnesium, a titanium compound, a halogen-containing compound, a ketoester compound and a compound of a transition metal selected from iron (II), cobalt (II), nickel (II) and manganese (II) in any order After contacting and reacting, a method of appropriately washing with a liquid hydrocarbon.

(3) Magnesium compounds, iron (II), cobalt (I
I), a compound of a transition metal selected from nickel (II) and manganese (II) is dissolved in a titanium tetraalkoxide and a ketoester compound, and the titanium compound is precipitated on a solid containing a halogen-containing compound or a titanium halide. How to make contact.

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
By combining with an organic aluminum compound, olefin polymerization can be performed.

As the organoaluminum compound, a compound represented by AlR ³ _y X _3-y is exemplified as a general formula. In the above formula, R ³ represents a hydrocarbon group having 1 to 20 carbon atoms,
Particularly, an aliphatic hydrocarbon group is preferred. X represents a halogen, and y represents a number of 1 to 3. Specific examples of the organoaluminum compound include trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum, dimethylaluminum dichloride, diethylaluminum dichloride, methylaluminum dichloride, ethylaluminum dichloride and the like. However, a trialkylaluminum is preferably used. An organoaluminum compound containing two or more Al atoms bonded through an O or N atom, and aluminoxane as a typical example, 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 used 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 Si-O-C.
Examples include a silicon compound having an -NC bond, an acetal compound, a germanium compound having a Ge-OC 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 10 ^-4 mmol / mol.
More preferably, the concentration is 10 ⁻² mmol / or more. In addition, the usage ratio to the titanium atom in the solid catalyst component,
The molar ratio is generally 0.5 or more, preferably 2 or more,
Particularly, 10 or more 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 / 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. can not see.

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 the 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, ketoester, iron (II), cobalt (II), nickel (II) and A transition metal compound selected from manganese (II),
Halogen-containing 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 Preparation of solid catalyst component Anhydrous magnesium chloride: MgCl ₂ (obtained by heating and drying a commercially available anhydrous magnesium chloride in a dry nitrogen stream at about 500 ° C. for 15 hours) 30 g (315 mmo)
l), ferrous chloride anhydride: FeCl ₂ (commercially available ferrous chloride tetrahydrate: FeCl ₂ · 4H ₂ O and at about 200 ° C. in a hydrogen chloride stream 8
2.85 g (obtained by heating and dehydrating for 2 hours)
2.5 mmol), 5.84 g of ethyl 2-benzoylbenzoate (23 mm
ol) was placed in a container for a vibrating ball mill (stainless steel cylindrical type, inner volume 1, porcelain balls having a diameter of 10 mm, which were filled by about 50% by apparent volume). When the amplitude is 6mm and the frequency is 3
A co-ground solid was obtained by attaching to a 0 Hz vibrating ball mill and performing co-ground for 20 hours. 5 g of the obtained co-ground product
Was suspended in 100 ml of titanium tetrachloride: TiCl ₄ and reacted at 80 ° C. for 2 hours. The solid product was collected by filtration and washed six times with n-decane (100 ml) at 80 ° C. and n-hexane (100 ml) at room temperature.
ml) for 4 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 Produced Polymer In a stainless steel autoclave having an internal volume of 3, 20 mg of the solid catalyst component prepared as described above, 91 mg of triethylaluminum and 20 mg of diphenyldimethoxysilane, and immediately, 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, 268 g of polypropylene was obtained. That is, the polymerization activity is 13400 g-polypropylene / g-solid catalyst component / time (hereinafter abbreviated as g-PP / g-cat · h), 670 kg
-Polypropylene / g-titanium-time in the solid catalyst component (hereinafter abbreviated as kg-PP / g-Ti-h). II of the produced polymer was 96.5%. MFI was 4.4 g-polypropylene / 10 minutes (hereinafter abbreviated as g-PP / 10 min).

Comparative Example 1 Preparation of solid catalyst component The solid catalyst component was prepared in the same manner and under the same preparation conditions as in Example 1, except that FeCl ₂ was not used when MgCl ₂ and ethyl 2-benzoylbenzoate were co-ground. Was prepared. The content of titanium atoms in the obtained solid catalyst component is 3.
2 wt%.

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. 220 g of polypropylene was obtained, and the polymerization activity was
11000 g-PP / g-cat · h and 340 kg-PP / g-Ti · h. II of the produced polymer was 95.0%. MFI is 4.8g-P
It was P / 10min.

Examples 2 to 7 Instead of ethyl 2-benzoylbenzoate, solid catalyst components were prepared in the same manner and under the same preparation conditions as in Example 1, except that the ketoester 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.

Comparative Examples 2 to 7 Instead of ethyl 2-benzoylbenzoate, a solid catalyst component was prepared in the same manner and under the same preparation conditions as in Example 1 using the ketoester compounds shown in Table 1. Propylene polymerization was carried out under the same method and under the same polymerization conditions as in Example 1.

Examples 8 to 11 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.

Example 12-13 The solid catalyst component prepared during the transition metal compound components instead of anhydrous manganese chloride FeCl ₂ (MnCl _2), except for using anhydrous cobalt chloride (CoCl _2), and the same manner as in Example 1 A solid catalyst component was prepared under the preparation conditions. In addition, MnCl ₂ , Co
Cl ₂ is obtained by converting a commercially available anhydride into a hydrogen chloride stream at about 200
The product obtained by heating and dehydrating at 8 ° C. for 8 hours was used. Propylene polymerization was performed in the same manner and under the same polymerization conditions as in Example 1 (Table 3).

Examples 14 to 17 The solid catalyst was prepared in the same manner and under the same conditions as in Example 1 except that the amount of MgCl ₂ , FeCl ₂ , ethyl 2-benzoylbenzoate used in the preparation of the solid catalyst component was changed to that shown in Table 4. The components were prepared. Propylene polymerization was carried out under the same method and polymerization conditions as in Example 1.

Comparative Example 8 Preparation of Solid Catalyst Component A solid catalyst component was prepared in the same manner and under the same conditions as in Example 1 except that ethyl benzoate was used instead of ethyl 2-benzoylbenzoate. The content of titanium atoms in the obtained solid catalyst component was 2.3% 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. 392 g of polypropylene was obtained, and the polymerization activity was
19400 g-PP / g-cat · h and 840 kg-PP / g-Ti · h. II of the produced polymer was 83.1%. Of the resulting polymer
MFI was 6.8 g-PP / 10 min.

Example 18 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. 3.18 g (12.5 mmol) of ethyl 2-benzoylbenzoate was slowly added dropwise. After dropping, 80
The reaction was carried out at 2 ° C. for 2 hours. After the reaction, remove the supernatant and
200 ml of titanium tetrachloride was introduced and reacted at 80 ° C. for 2 hours. Then, the supernatant was removed and n-decane at 100 ° C. (100 m
The resultant was washed 6 times with l) and 4 times with n-hexane (100 ml) at room temperature, and dried at 40 ° C. under reduced pressure to obtain a target 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. 410 g of polypropylene was obtained and the polymerization activity was 20500 g-PP / g-cat
H was 1140 kg-PP / g-Ti · h. I. of the resulting polymer
I. was 97.5%. The MFI of the resulting polymer is 6.7 g-PP / 10 mi
n.

Comparative Example 9 Preparation of solid catalyst component A solid catalyst was prepared in the same manner and under the same preparation conditions as in Example 2 except that FeCl ₂ was not used when dissolving MgCl ₂ in n-decane and 2-ethylhexyl alcohol by heating. The components were prepared. The content of titanium atoms in the obtained solid catalyst component was 2.2% by weight.

Polymerization of Propylene and Physical Properties of Produced Polymer Propylene polymerization was carried out in the same manner and under the same polymerization conditions as in Example 1. 280 g of polypropylene are obtained, with a polymerization activity of 14
000 g-PP / g-cat · h and 640 kg-PP / g-Ti · h.
II of the produced polymer was 96.5%. MFI is 7.0g-PP /
It was 10 min.

Examples 19 to 20 Solid catalyst components were prepared in the same manner as in Example 18, except that MnCl ₂ and CoCl ₂ were used instead of FeCl _{2 as} the transition metal compound component during the preparation of the solid catalyst components. Propylene polymerization was carried out under the same method and polymerization conditions as in Example 1 (Table 5).

〔The invention's effect〕

When the polymerization of olefins is carried out using the catalyst component obtained by the present invention, the polymerization activity is very high, and the catalyst residue in the produced polymer can be kept extremely low, so that the deashing step is omitted. be able to. 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 flow chart illustrating a method for preparing an olefin polymerization catalyst according to one embodiment of the present invention.

Continuation of the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) C08F 4/60-4/70 CAS ONLINE

Claims (2)

(57) [Claims] 1. The method according to claim 1, wherein a solid catalyst component comprising a magnesium compound, a titanium compound and a halogen-containing compound as essential components is formed or after the formation thereof. (Where R ¹ , R ² and Z are groups selected from aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and polycyclic hydrocarbons). Or, a compound of a transition metal selected from iron (II), cobalt (II), nickel (II), and manganese (II) with two or more kinds (however, the parentheses indicate the valence of the transition metal) A solid catalyst component for olefin polymerization obtained by contacting and reacting in the presence of one or more of the following. 2. A method for polymerizing an olefin, comprising using a catalyst system containing the catalyst component according to claim 1.