JP2922923B2 - Method for producing olefin polymerization catalyst and method for polymerizing olefin - Google Patents

Description

The present invention relates to a method for producing an olefin polymerization catalyst and a method for polymerizing an olefin. More specifically, the present invention makes it possible to obtain a highly stereoregular polymer with a high yield when applied to the polymerization of olefins, particularly α-olefins having 3 or more carbon atoms, by using a specific catalyst. is there.

[Conventional technology]

Conventionally, as a stereoregular polymerization catalyst for olefins,
Ziegler-type catalysts are well known, and various methods have been proposed to further improve the polymerization activity and stereoregularity of the resulting polymer.

Among these various improvement methods, those relating to solid catalyst components are extremely large, and various metal compounds have been studied.

[Problems to be solved by the invention]

 A typical example of a conventional study has been described below.

“History of Polyolefins”, RBSeymour, T. Cheng Ed
s., P.243 (1986), D.Reidel Publishing Co., Dordrecht
Discloses the relationship between the electronegativity of metal ions of metal chlorides and the polymerization activity from propion polymerization using various metal chlorides as catalyst supports, and these are shown. Poly
In Mer Journal, 5 , 128 (1973), propylene polymerization is carried out using various hydroxy metal chlorides as solid catalyst carriers. The ionic radius of the metal ions of the hydroxy metal chloride used and the stereoregularity of the resulting polymer are described. Is related to Also, U.S. Pat.No. 3,238,146 states that polypropylene with high crystallinity can be obtained using a solid catalyst in which titanium tetrachloride is thin-film coated on the surface of a metal chloride such as cobalt chloride, manganese chloride, and iron chloride. It has been disclosed. Further, US Pat. No. 4,439,538 discloses that polypropylene having high stereoregularity can be obtained by using an iron chloride solid catalyst carrier containing a benzoate as an electron donor.

However, in these methods, since the polymerization activity and the stereoregularity of the produced polymer are low, a step of deashing the catalyst residue after polymerization and a step of removing the non-stereoregular polymer portion are required, and therefore, industrially, It was hardly a satisfactory method.

An object of the present invention is to solve the problems in the prior art and to provide a novel method for producing an olefin polymerization catalyst and a method for polymerizing olefins, which produce a more active and highly stereoregular polymer. I do.

[Means for solving the problem]

As a result of intensive studies to solve the above-mentioned problems, the present inventors have reached the present invention which has the following points. That is, the present invention relates to iron (I
Reaction of a transition metal compound selected from I), cobalt (II), and manganese (II) (however, the parentheses indicate the valence of the transition metal), a titanium compound, a halogen-containing compound, and an electron donor. A method for producing a solid catalyst component for olefin polymerization, comprising contacting and reacting in the presence of a magnesium compound during or after the formation of the solid catalyst component by the method described above, and using a catalyst system containing the solid catalyst component. Olefin polymerization method.

 Hereinafter, the present invention will be described in detail.

Preparation of Solid Catalyst Component for Olefin Polymerization Iron (II), cobalt (I
Compounds of transition metals selected from I) and manganese (II) (however, the parentheses indicate the valence of the transition metal)
For example, halides, alkoxides, carboxylates,
Chelate compounds represented by acetylacetonate salts and the like can be mentioned.

Preferably, iron (II) chloride, iron (II) bromide, iron (II) iodide, cobalt (II) chloride, cobalt (II) bromide, cobalt (II) iodide, manganese (II) chloride, Each halide is typified by manganese (II) iodide, manganese (II) iodide 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.

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. Further, these various titanium compounds 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 depend on the catalyst preparation method and the like. Titanium halides such as titanium tetrabromide, silicon halides such as silicon tetrachloride, phosphorus trichloride, phosphorus halides such as phosphorus pentachloride can be exemplified, but depending on the preparation method of the catalyst, halogenated hydrocarbons, A halogen molecule or hydrohalic acid may be used.

As the electron donor used in the present invention, generally, a phosphorus-containing compound, a sulfur-containing compound, an oxygen-containing compound, a nitrogen-containing compound and the like can be mentioned. Of these, oxygen-containing compounds are preferred.

Examples of the oxygen-containing compound include ethers, esters, ketones, and acid anhydrides.

Preferably, ethyl acetate, ethyl propionate, ethyl acrylate, ethyl oleate, ethyl stearate, ethyl phenylacetate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, methyl toluate, ethyl toluate, Propyl toluate, butyl toluate, methyl ethyl benzoate, ethyl ethyl benzoate, ethyl xylene carboxylate, methyl anisate,
Carboxyls such as ethyl anisate, methyl ethoxybenzoate, ethyl ethoxybenzoate, ethyl cinnamate, dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, diisobutyl phthalate, dihexyl phthalate, dioctyl phthalate Examples thereof include acid esters, cyclic esters such as γ-butyrolactone, and acid anhydrides such as maleic anhydride and phthalic anhydride. These may be used alone or in combination of two or more.

Examples of the magnesium compound used in the present invention include magnesium halides such as magnesium chloride, magnesium bromide, and magnesium iodide; alkoxy compounds such as dimethoxy magnesium, diethoxy magnesium, dipropoxy magnesium, dibutoxy magnesium, and diphenoxy magnesium. Magnesium; carboxylic acid salts of magnesium such as magnesium acetate, magnesium laurate and magnesium stearate; and alkyl magnesium such as dimethylmagnesium, diethylmagnesium and butylethylmagnesium. These 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.

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 used is a transition metal compound selected from iron (II), cobalt (II), and manganese (II) (however, the parentheses indicate the valence of the transition metal).
The molar ratio is preferably in the range of 1 × 10 ^{−4 to} 1000, and more preferably in the range of 0.01 to 100. Halogen compounds are used as necessary, but if used, the amount used is a titanium compound or a compound of a transition metal selected from iron (II), cobalt (II) and manganese (II). The transition metal selected from iron (II), cobalt (II), and manganese (II) to be used regardless of whether or not halogens are included in the parentheses. (Where the parentheses indicate the valence of the transition metal) in a molar ratio of 1 × 10 ^-2 to 10
It is preferably in the range of 00, preferably in the range of 0.1 to 100.

The amount of electron donor used is iron (II), cobalt (II),
The molar ratio of the transition metal compound selected from manganese (II) (the parentheses in parentheses indicate the valence of the transition metal) is preferably in the range of 1 × 10 ^-3 to 10. , Preferably in the range of 0.01 to 5.

The amount of the magnesium compound used is based on the amount of the transition metal compound selected from iron (II), cobalt (II) and manganese (II) (however, the parentheses indicate the valence of the transition metal). On the other hand, the molar ratio is preferably in the range of 1 × 10 ^{−3 to} 5,
Preferably it is in the range of 0.01 to 1.

The method for preparing the solid catalyst component is not particularly limited, and generally, a method for preparing a catalyst for olefin polymerization can be used as a reference. For example, a specific example is as follows.

(1) A halide, a titanium compound, an electron of a transition metal compound selected from iron (II), cobalt (II), and manganese (II) (however, parentheses indicate the valence of the transition metal) A method in which a donor and a magnesium compound are contacted and reacted in an arbitrary order, and then appropriately washed with a liquid hydrocarbon.

(2) a compound of a transition metal selected from iron (II), cobalt (II), and manganese (II) (however, the parentheses indicate the valence of the transition metal), a titanium compound, an electron donor,
A method in which a halogen-containing compound and a magnesium compound are contacted and reacted in an arbitrary order, and then appropriately washed with a liquid hydrocarbon.

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 ¹ _y X _3-y is exemplified as a general formula. In the above formula, R ¹ represents a hydrocarbon group having 1 to 20 carbon atoms, particularly preferably an aliphatic hydrocarbon group. X represents a halogen, and y 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. In addition, organoaluminum compounds containing two or more Al atoms bonded via O or N atoms, and aluminoxane as a typical example, can also be used.

Further, dialkylaluminum alkoxides, alkylaluminum sesquihalides, alkylaluminum sex alkoxides 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. On the other hand, 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 organoaluminum compound.

Olefins The olefins used in the polymerization include ethylene, propylene, 1-butene, 4-methyl-1-pentene,
-Methyl-1-pentene, 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 of the present invention, the organoaluminum compound or the steric regularity improver and these 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. 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).

In each example, each compound (organic solvent, olefin, hydrogen,
A transition metal compound selected from a titanium compound, a magnesium compound, iron (II), cobalt (II), and manganese (II) (provided that the valence of the transition metal is shown in parentheses);
Steric regularity improvers, etc.) are all substantially dewatered.

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 (TiCl ₄ / n-BP / FeCl ₂ .MgCl ₂ catalyst) Anhydrous ferrous chloride: FeCl ₂ (commercially available ferrous chloride tetrahydrate: F
30 g (obtained by heating and dehydrating eCl ₂ .4H ₂ O in a hydrogen chloride stream at about 200 ° C. for 8 hours)
l), anhydrous magnesium chloride: MgCl ₂ (a commercially available anhydrous magnesium chloride is dried at about 500 ° C. in a dry nitrogen stream at 15 ° C.)
1.63 g)
(0.017 mol), di-n-butyl phthalate: n-BP 4.78 g
(0.017 mol) was placed in a container for a vibrating ball mill (stainless steel cylindrical type, internal volume 1, porcelain balls having a diameter of 10 mm, and apparent volume filled by about 50%). This was mounted on a vibrating ball mill having an amplitude of 6 mm and a frequency of 30 Hz, and co-milled for 20 hours to obtain a co-milled solid. 5 g of the obtained co-ground product was suspended in 60 ml of titanium tetrachloride: TiCl ₄ and reacted at 120 ° C. for 2 hours. The solid product is collected by excess,
Washed 10 times with toluene (80 ml) at 60 ° C. 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 magnesium atoms in this solid catalyst component was
The content of 0.9% by weight, the content of iron atoms was 36.6% by weight, and the content of titanium atoms was 1.7% by weight.

Polymerization of Propylene and Stereoregularity 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 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, 195 g of polypropylene was obtained. That is, the polymerization activity is 9750 g-polypropylene / g-solid catalyst component / time (hereinafter abbreviated as g-PP / g-cat · h), 574
kg-polypropylene / g-titanium-time in the solid catalyst component (hereinafter abbreviated as kg-PP / g-Ti-h). II of the produced polymer was 97.5%.

Example 2 Preparation of solid catalyst component (TiCl ₄ / n-BP / FeCl ₂ · MgCl ₂ catalyst) 22.0 g (174 mmol) of FeCl ₂ , 6.7 g (70 mmol) of MgCl ₂ , n
A solid catalyst component was prepared in the same manner as in Example 1 except that 4.79 g (17.2 mmol) of -BP was used at the time of grinding with a vibration ball mill. When the obtained solid catalyst component was analyzed by atomic absorption spectrometry, the content of magnesium atom in this solid catalyst component was 6.5% by weight, the content of iron atom was 28.2% by weight, and the content of titanium atom was 2.1% by weight. %Met.

Propylene polymerization and stereoregularity of formed polymer Propylene polymerization was carried out under the same polymerization conditions as in Example 1 except that 20 mg of the TiCl ₄ / n-BP / FeCl ₂ .MgCl ₂ catalyst obtained above was used. And II of the produced polymer was measured. As a result, 220 g of polypropylene was obtained.

That is, the polymerization activity is 11000 g-PP / g-cath, 524 kg.
-PP / g-Ti · h. II of the produced polymer was 98.1%.

Example 3 Preparation of solid catalyst component (TiCl ₄ / n-BP / FeCl ₂ .MgCl ₂ catalyst) 15.2 g (120 mmol) of FeCl ₂ , 11.4 g (120 mmol) of MgCl ₂ ,
A solid catalyst component was prepared in the same manner as in Example 1 except that 4.78 g (17 mmol) of n-BP was used at the time of grinding in a vibration ball mill. When the obtained solid catalyst component was analyzed by atomic absorption spectrometry, the content of magnesium atom in this solid catalyst component was 11.3% by weight, the content of iron atom was 19.8% by weight, and the content of titanium atom was 2.0% by weight. %Met.

Propylene polymerization and stereoregularity of formed polymer Propylene polymerization was carried out under the same polymerization conditions as in Example 1 except that 20 mg of the TiCl ₄ / n-BP / FeCl ₂ .MgCl ₂ catalyst obtained above was used. And II of the produced polymer was measured. As a result, 300 g of polypropylene was obtained.

That is, the polymerization activity is 15000 g-PP / g-cat.h, 750 kg
-PP / g-Ti · h. II of the produced polymer was 98.6%.

Comparative Example 1 Preparation of solid catalyst component (TiCl ₄ / n-BP / FeCl ₂ catalyst) Anhydrous ferrous chloride: FeCl ₂ (commercial ferrous chloride tetrahydrate: F
30 g (obtained by heating and dehydrating eCl ₂ .4H ₂ O in a hydrogen chloride stream at about 200 ° C. for 8 hours)
l), di-n-butyl phthalate: n-BP 4.78 g (0.017mo
l) 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, apparently filled by about 50% by 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
The suspension was suspended in 60 ml of titanium tetrachloride: TiCl ₄ and reacted at 120 ° C. for 2 hours. The solid product was collected by filtration and washed 10 times with toluene (80 ml) at 60 ° C. 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 iron atoms in this solid catalyst component was 37.6% by weight, and the content of titanium atoms was 2.1% by weight.

Propylene Polymerization and Stereoregularity of Produced Polymer Propylene polymerization was carried out under the same polymerization conditions as in Example 1 except that 20 mg of the TiCl ₄ / n-BP / FeCl ₂ catalyst obtained above was used. The II of the polymer was measured. Result 38
g of polypropylene was obtained.

That is, the polymerization activity is 1900 g-PP / g-cat.h, 90 kg-
PP / g-Ti · h. II of the produced polymer was 76.0%.

Example 4 Preparation of Solid Catalyst Component (TiCl ₄ / n-BP / MnCl ₂ .MgCl ₂ Catalyst) Anhydrous manganese chloride: MnCl ₂ (commercially available manganese chloride tetrahydrate: MnCl ₂ .4H ₂ O in hydrogen chloride stream) At about 200 ℃
30 g (obtained by heating and dehydrating for 0.2 hours)
A solid catalyst component was prepared in the same manner as in Example 1 except that 4 mol) was used in the vibration ball milling instead of 30 g (0.24 mol) of FeCl ₂ . When the obtained solid catalyst component was analyzed by atomic absorption spectrometry, the content of magnesium atom in this solid catalyst component was 1.0% by weight, the content of manganese atom was 34.2% by weight, and the content of titanium atom was 1.4% by weight. %Met.

Propylene Polymerization and Stereoregularity of Produced Polymer Propylene polymerization was carried out under exactly the same polymerization conditions as in Example 1 except that 20 mg of the TiCl ₄ / n-BP / MnCl ₂ .MgCl ₂ catalyst obtained above was used. And II of the produced polymer was measured. As a result, 262 g of polypropylene was obtained.

That is, the polymerization activity is 13100 g-PP / g-cath, 936 kg
-PP / g-Ti · h. II of the produced polymer was 96.4%.

Comparative Example 2 The solid catalyst component _{(TiCl 4 / n-BP /} MnCl 2 catalyst) Preparation of anhydrous manganese chloride: MnCl ₂ (a commercially available manganese chloride tetrahydrate: MnCl about 200 ₂ · 4H ₂ O in the hydrogen chloride stream 16 ° C
30 g (obtained by heating and dehydrating for 0.2 hours)
A solid catalyst component was prepared in the same manner as in Comparative Example 1, except that 4 mol) was used in the vibration ball milling instead of 30 g (0.24 mol) of FeCl ₂ . When the obtained solid catalyst component was analyzed by atomic absorption spectrometry, the content of manganese atoms in this solid catalyst component was 35.4% by weight, and the content of titanium atoms was 1.2% by weight.

Propylene Polymerization and Stereoregularity of Produced Polymer Propylene polymerization was carried out under exactly the same polymerization conditions as in Example 1 except that 20 mg of the TiCl ₄ / n-BP / MnCl ₂ catalyst obtained above was used. The combined II was measured. as a result,
79 g of polypropylene were obtained.

That is, the polymerization activity is 3940 g-PP / g-cath, 328 kg
-PP / g-Ti · h. II of the produced polymer was 69.6%.

Example 5 Preparation of solid catalyst component (TiCl ₄ / n-BP / CoCl ₂ .MgCl ₂ catalyst) Anhydrous cobalt chloride: CoCl ₂ (commercially available anhydrous cobalt chloride: C
30 g (0.24 mol) obtained by heating and dehydrating oCl ₂ in a stream of hydrogen chloride at about 200 ° C. for 8 hours.
A solid catalyst component was prepared in the same manner as in Example 1 except that 30 g (0.24 mol) of Cl ₂ was used during pulverization by a vibration ball mill. When the obtained solid catalyst component was analyzed by atomic absorption spectrometry, the content of magnesium atoms in this solid catalyst component was 1.1% by weight, and the content of cobalt atoms was 3%.
8.0 wt% and the content of titanium atoms was 1.8 wt%.

Propylene Polymerization and Stereoregularity of Produced Polymer Propylene polymerization was carried out under exactly the same polymerization conditions as in Example 1 except that 20 mg of the TiCl ₄ / n-BP / CoCl ₂ .MgCl ₂ catalyst obtained above was used. And II of the produced polymer was measured. As a result, 112 g of polypropylene was obtained.

That is, the polymerization activity is 5600 g-PP / g-cat.h, 311 kg
-PP / g-Ti · h. II of the produced polymer was 85.2%.

Example 6 Preparation of solid catalyst component (TiCl ₄ / n-BP / CoCl ₂ .MgCl ₂ catalyst) CoCl ₂ 21.4 g (165 mmol), MgCl ₂ 7.6 g (80 mmol), n
A solid catalyst component was prepared in the same manner as in Example 1 except that 4.87 g (17.5 mmol) of -BP was used at the time of grinding with a vibration ball mill. When the obtained solid catalyst component was analyzed by atomic absorption spectrometry, the content of magnesium atom in this solid catalyst component was 7.3% by weight, the content of cobalt atom was 27.5% by weight, and the content of titanium atom was 2.0% by weight. %Met.

Propylene Polymerization and Stereoregularity of Produced Polymer Propylene polymerization was carried out under exactly the same polymerization conditions as in Example 1 except that 20 mg of the TiCl ₄ / n-BP / CoCl ₂ .MgCl ₂ catalyst obtained above was used. And II of the produced polymer was measured. As a result, 152 g of polypropylene was obtained.

That is, the polymerization activity is 7600 g-PP / g-cat
-PP / g-Ti · h. II of the produced polymer was 95.2%.

Example 7 Preparation of solid catalyst component (TiCl ₄ / n-BP / CoCl ₂ · MgCl ₂ catalyst) 15.6 g (120 mmol) of CoCl ₂ , 11.4 g (120 mmol) of MgCl ₂ ,
A solid catalyst component was prepared in the same manner as in Example 1 except that 4.78 g (17 mmol) of n-BP was used at the time of grinding in a vibration ball mill. When the obtained solid catalyst component was analyzed by atomic absorption spectrometry, the content of magnesium atom in this solid catalyst component was 11.3% by weight, the content of cobalt atom was 20.4% by weight, and the content of titanium atom was 1.9% by weight. %Met.

Propylene Polymerization and Stereoregularity of Produced Polymer Propylene polymerization was carried out under exactly the same polymerization conditions as in Example 1 except that 20 mg of the TiCl ₄ / n-BP / CoCl ₂ .MgCl ₂ catalyst obtained above was used. And II of the produced polymer was measured. As a result, 190 g of polypropylene was obtained.

That is, the polymerization activity is 9500 g-PP / g-cat.h, 500 kg
-PP / g-Ti · h. II of the produced polymer was 98.2%.

Comparative Example 3 Preparation of solid catalyst component (TiCl ₄ / n-BP / CoCl ₂ catalyst) Anhydrous cobalt chloride: CoCl ₂ (commercially available anhydrous cobalt chloride: C
30 g (0.24 mol) obtained by heating and dehydrating oCl ₂ in a stream of hydrogen chloride at about 200 ° C. for 8 hours.
A solid catalyst component was prepared in the same manner as in Comparative Example 1 except that 30 g (0.24 mol) of Cl ₂ was used during the vibration ball milling. When the obtained solid catalyst component was analyzed by atomic absorption spectrometry, the content of cobalt atom in the solid catalyst component was 38.3% by weight, and the content of titanium atom was 1.7% by weight.

Propylene Polymerization and Stereoregularity of Produced Polymer Propylene polymerization was carried out under exactly the same polymerization conditions as in Example 1 except that 20 mg of the TiCl ₄ / n-BP / CoCl ₂ catalyst obtained above was used. The combined II was measured. As a result 35
g of polypropylene was obtained.

That is, the polymerization activity is 1750 g-PP / g-cath, 103 kg
-PP / g-Ti · h. II of the produced polymer was 68.1%.

〔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. I can do it. 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 extremely 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.

Claims (2)

(57) [Claims] (1) Iron (II), cobalt (II), manganese (I)
Compounds of transition metals selected from I) (provided that
() Indicates the valence of the transition metal), titanium compound,
A method for producing a solid catalyst component for olefin polymerization, comprising contacting and reacting in the presence of a magnesium compound during or after the formation of a solid catalyst component by the reaction of a halogen-containing compound and an electron donor. 2. A method for polymerizing an olefin, comprising using a catalyst system containing the solid catalyst component according to claim 1.