JPH04180903A - Production of olefin polymerization catalyst and polymerization of olefin - Google Patents

Abstract

PURPOSE:To obtain a highly active catalyst which can give a highly stereoregular olefin polymer by using a specified ketoester compound and a specified transition metal in the preparation of a solid catalyst component comprising a magnesium compound, a titanium compound and a halogen compound. CONSTITUTION:The purpose catalyst component is prepared by performing contact and reaction in the presence of a ketoester compound of the formula and a compound of a transition metal of group VII A or VIII of the periodic table during or after preparing a solid catalyst component essentially consisting of a magnesium compound, a titanium compound and a halogen compound. In the formula, R<1>, R<2> and Z are each an aliphatic hydrocarbon group, an alicyclic hydrocarbon group or a polycyclic hydrocarbon group. When an olefin is polymerized in the presence of the above catalyst component, catalyst residues in the formed polymer can greatly be reduced because of very high polymerization activity and therefore the deashing step can be omitted.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a high-performance catalyst composition that exhibits a highly active action when subjected to the polymerization or copolymerization of olefins, and particularly relates to α- The present invention relates to a method for producing a catalyst component for olefin polymerization and a method for polymerizing olefins, which can yield a highly stereoregular polymer in high yield when applied to olefin polymerization.

[Conventional technology]

Conventionally, many manufacturing methods have been proposed that use solid catalyst components containing magnesium, titanium, a halogen compound, and an electron donor (internal donor) as essential components. Although organic carboxylic acid esters are often used as internal donors, there is a problem in that the ester odor remains in the polymer unless the ester is removed, such as by washing with an organic solvent. Furthermore, it does not have industrially satisfactory performance in terms of polymerization activity and stereoregularity of the resulting polymer, and there has been a desire to develop a catalyst with even higher performance.

Against this background, the applicant has previously established an internal donor,
A method for producing an olefin polymerization catalyst using a ketoester compound and a method for polymerizing olefins (Japanese Patent Application No. 1-178)
No. 620 (hereinafter referred to as the "prior invention"),
According to the method of the prior invention, it has become possible to obtain a highly stereoregular polymer with high activity.

[Problem to be solved by the invention]

An object of the present invention is to provide a method for producing a catalyst and a method for polymerizing olefins, which provide a highly active and highly stereoregular olefin polymer, which were insufficient in the prior art.

[Means to solve the problem]

As a result of intensive research to solve the above problems, it was found that by using transition metal compounds of Groups 7A and 8 of the periodic table in the preparation of a solid catalyst similar to that of the earlier invention, the polymer obtained by the method of the earlier invention was improved. It was discovered that a polymer having even better stereoregularity was produced in comparison, and the present invention, which has the following outline, was achieved.

That is, the present invention provides the following general formula (where R1, R
2 and 2 are groups selected from aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and polycyclic hydrocarbons. ) and one or more ketoester compounds represented by: and one or two transition metal compounds of Groups 7A and 8A of the Periodic Table.
The present invention provides a method for producing a catalyst component for olefin polymerization, which is characterized by carrying out contact and reaction treatment in the presence of more than one species, and a method for polymerizing olefin, which is characterized by using a catalyst system containing this catalyst component.

The present invention will be explained in detail below.

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 the preparation of high-activity catalysts for ordinary olefin polymerization and copolymerization. can be used. That is,
Magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide; alkoxymagnesiums such as dimethoxymagnesium, jetoxymagnesium, dipropoxymagnesium, dibutoxymagnesium, diphenoxymagnesium; magnesium laurate, magnesium stearate, acetic acid Examples include magnesium carboxylates such as magnesium; alkylmagnesiums such as dimethylmagnesium, diethylmagnesium, butylethylmagnesium, and the like.

Moreover, these various magnesium compounds can also be used individually by 1 type, and can also be used in combination of 2 or more types. Preferably, magnesium halide,
Those that use alkoxymagnesium or those that form magnesium halide during catalyst formation. Particularly preferably, the halogen is chlorine.

Titanium compounds used in the present invention include titanium halides such as titanium tetrachloride, titanium trichloride, titanium tetrabromide, and titanium tetrachloride; tetramethoxytitanium, tetrabutoxytitanium, tetrapropoxytitanium, and tetrabutoxytitanium. , alkoxytitanium such as tetraphenoxytitanium; ethoxytitanium trichloride, butoxytitanium trichloride, phenoxytitanium trichloride,
Examples include alkoxytitanium halides such as dibutoxytitanium dichloride and tributoxytitanium chloride. Moreover, these various titanium compounds can also be used individually by 1 type, and can also be used in combination of 2 or more types. Preferred is a halogen-containing tetravalent titanium compound, particularly titanium tetrachloride.

In the halogen-containing compound used in the present invention, the halogen is fluorine, chlorine, bromine, or iodine, preferably chlorine, and the specific compounds actually exemplified depend on the catalyst preparation method, but include titanium tetrachloride, Examples include titanium halides such as titanium tetrabromide, silicon halides such as silicon tetrachloride and silicon tetrabromide, and phosphorus halides such as phosphorus trichloride and phosphorus pentachloride. Hydrocarbons, halogen molecules, and hydrohalic acids may also be used.

The ketoester compound used in the present invention has the general formula %Formula % R1 in the general formula (I) is a hydrocarbon group having 1 to 2 carbon atoms, such as an aliphatic hydrocarbon, an alicyclic hydrocarbon, an aromatic hydrocarbon,
A group consisting of one or more polycyclic hydrocarbons.

Specifically, methyl, ethyl, n-propyl, i-propyl, 5ec-butyl, tert-butyl, tert
-amyl, 2-hexenylisopropenyl, cyclopentyl, cyclohexyl, tetramethylcyclohexyl,
cyclohexenyl, melbornylphenyl, tolyl, ethylphenyl, xyl, cumyl, trimethylphenyl,
Tetramethylphenyl, pentamethylphenyl, naphthyl, methylnaphthyl, anthranyl, benzyl, di
Examples include phenylmethyl and indenyl.

These hydrogen atoms may be substituted with halogen atoms.

Among these, groups having aromatic hydrocarbons or polycyclic hydrocarbons are preferably used. 2 in general formula (I) is a hydrocarbon group having 1 to 30 carbon atoms, and is a group consisting of one or more of aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and polycyclic hydrocarbons. .

Specifically, methylene, ethylene, trimethylene, propylenecyclohexane-diyl, tetramethylcyclohexane-diyl, 0-phenylene, m-phenylene, p
-phenylene, dimethyl-0-phenylene, 1,2-naphthylene, 2,3-naphthylene, 1,8-naphthylene,
Examples include biphenylene, biphelene, 1,9-fluorenediyl and the like. These hydrogen atoms may be substituted with halogen atoms. Among these, groups having an aromatic hydrocarbon group or a polycyclic hydrocarbon group having 1 to 20 carbon atoms are preferably used.

R2 in general formula (I) is a hydrocarbon group having 1 to 20 carbon atoms,
A group consisting of one or more of aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and polycyclic hydrocarbons. Specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, 5ec-butyl, jer
Examples include t-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, cyclohexyl, phenyl, tolyl, xylyl, naphthyl, and the like.

These hydrogen atoms may be substituted with halogen atoms. Among these, groups having an aliphatic hydrocarbon having 1 to 12 carbon atoms are preferably used.

Specific examples of the ketoester compound of general formula (I) include methyl 2-benzoylbenzoate, ethyl 2-benzoylbenzoate, n-butyl 2-(2'-methylbenzoyl)benzoate, and 2-(4'-methyl). benzoyl)ethyl benzoate, 2-
(2',4'-dimethylbenzoyl)ethyl benzoate, 2- (2',4',6'-trimethylbenzoyl)
Ethyl benzoate, 2-(pentamethyl-benzoyl)propyl benzoate, 2-(triethyl-benzoyl)ethyl benzoate, 2(4'benzoyl chloride)ethyl benzoate, 2-(trimethylbenzoyl)-4,5 dimethylbenzoic acid Methyl, n-propyl 2-benzoyl-3,6dimethylbenzoate, ethyl (1'-naphthyl)phenylketone-2-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-benzoylnaphthalenecarboxylate propyl acid, peptyl 8-trioylnaphthalenecarboxylate, isobutyl 2'-trioylbiphenyl-2-carboxylate, methyl 2'-benzoylbiphenyl-2-carboxylate, ethyl 2'-benzoylbinaphthyl-2-carboxylate, ( Butyl 5'-indenyl)phenylketone-2-carboxylate, n-butyl 2-benzoylfluorene-carboxylate, ethyl 9-benzoylfluorene-carboxylate, 6(4
Examples include n-butyl'-trioyl)indene 5-carboxylate, ethyl lO-benzoylphenanthrene-10carboxylate, and the like.

The transition metal compounds of Groups 7A and 8 of the periodic table used in the present invention include manganese, technetium, and
Examples include various compounds such as rhenium, group 8 iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, and platinum. For example, chelate compounds typified by enogenides, alkoxides, carboxylates, and acetylacetonate salts of these transition metals can be mentioned.

Preferably, manganese chloride (■), technetium chloride (
■), rhenium chloride (■), manganese bromide (■), manganese iodide (■), iron chloride (II), iron chloride (■), iron bromide (■), iron iodide (■), chloride Ruthenium (■), Osmium chloride (■), Osmium chloride (■), Cobalt chloride (■), Cobalt bromide (■), Cobalt iodide (■),
Rhodium chloride (■), iridium chloride (■), iridium chloride (■), nickel chloride (■), nickel bromide (■)
), nickel iodide (■), palladium chloride (■), palladium bromide (■), platinum (II) chloride, platinum chloride (■)
, platinum (IV) chloride, and the like, halides of transition metals can be mentioned.

These transition metal compounds may be used alone or in combination of two or more. However, the numbers in parentheses indicate the valence of the transition metal.

The amount of each component to be used is arbitrary as long as the effect is enhanced in the present invention, but it is preferably within the following range for boat fishing.

The amount of the titanium compound to be used is preferably in the range of I x 10' to 1000, preferably in the range of 0.01 to 100, in terms of molar ratio to the amount of the magnesium compound used. Halogen compounds are used as necessary, but when used, the amount used is determined by titanium compounds,
Regardless of whether the magnesium compound and the transition metal compound of Group 8 of Periodic Table 7A contains a halogen, the molar ratio relative to the amount of magnesium used is lXl0'~
It is preferably within the range of 1000, preferably within the range of 0.1 to 100.

The amount of the ketoester compound represented by the formula (I) to be used is preferably within the range of 1X10' to 10 in terms of molar ratio to the amount of the magnesium compound used. O
It is within the range of 1 to 5.

The amount of the transition metal compound of Group 8 of Periodic Table 7A to be used is IXl[
l-3 to 5 is good, preferably 0.01 to 1.

The method for preparing the solid catalyst component used in the present invention is as follows:
magnesium compounds, titanium compounds and electron donors,
Furthermore, if necessary, a conventionally known method for preparing a solid catalyst component obtained by contacting and reacting with an auxiliary agent such as a halogen-containing compound temporarily or stepwise can be applied. That is, during or after the formation of a known solid catalyst component, one or more ketoester compounds that can be represented by formula (I) and one or two transition metal compounds of Group 8 of Periodic Table 7A. In the above manner, contact and reaction are carried out temporarily or in stages. As a specific example of applying a known method, (1) Magnesium chloride, a titanium compound, a ketoester compound, and a transition metal compound of group 7A or 8 of the periodic table are brought into contact and reacted in any order, and then treated with a liquid hydrocarbon. How to wash properly.

(2) A method of contacting and reacting an alkoxymagnesium, a titanium compound, a halogen-containing compound, a ketoester compound, and a transition metal compound of Groups 7A and 8 of the Periodic Table in any order, followed by washing as appropriate with a liquid hydrocarbon.

(3) A method in which a magnesium compound, a transition metal compound of group 7A, group 8 of the periodic table is dissolved in a titanium tetraalkoxide and a ketoester compound, and the titanium compound is brought into contact with a halogen-containing compound or a solid precipitated with a titanium halide.

The solid catalyst component of the present invention can be prepared by the method described above.

Olefin polymerization The solid catalyst component of the present invention obtained as described above can be combined with an organoaluminum compound to perform olefin polymerization.

Typical organoaluminum compounds in the present invention include compounds represented by the general formula AA'R,X3□. In the above formula, R3 has 1 to 2 carbon atoms
0 hydrocarbon groups are shown, and aliphatic hydrocarbon groups are particularly preferred. X represents halogen, and y represents a number from 1 to 3. Specific examples of this organoaluminum compound include trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum, dimethylaluminum dichloride, diethylaluminium dichloride,
Examples include methylaluminum dichloride and ethylaluminum dichloride, but trialkylaluminum is preferably used. Organoaluminum compounds containing two or more AI atoms bonded via O or N atoms, typically aluminoxanes, can also be used.

Furthermore, dialkylaluminum alkoxides, alkylaluminum sesquihalides, alkylaluminum sesquialkoxides, and the like may also be used.

When carrying out a polymerization reaction of α-olefins having 3 or more carbon atoms, this is added to the catalyst system consisting of the titanium-containing solid catalyst component and the organoaluminum compound according to the present invention for the purpose of improving the stereoregularity of the resulting polymer. Many compounds that have been proposed for use in olefin polymerization catalysts and have effects on stereoregularity can be further added. Typical compounds used for this purpose include aromatic carboxylic acid esters, 5i-0-C or 5
Examples include silicon compounds having an i-N-C bond, acetal compounds, germanium compounds having a Ge-0-C bond, and nitrogen or oxygen heterocyclic compounds having an alkyl substituent.

Specific examples of these compounds include ethyl benzoate, butyl benzoate, ethyl p-toluate, ethyl p-anisate, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, diphenyljethoxysilane, Di-n-propyldimethoxysilane, cyclohexylmethyldimethoxysilane, tetraethoxysilane, t-butylmethyldimethoxysilane, benzophenone, dimethoxyacetal, benzophenone jetoxyacetal, acetophenone dimethoxyacetal, t-butylmethylketone dimethoxyacetal, diphenyldimethoxygermane, These include phenyltriethoxygermane, 2,2.6.6-titramethylpiperidine, 2.2.6.6-tetramethylpyran, and the like. Among these, Si-0-C or Si-
Silicon compounds and acetal compounds having an N-C bond are preferred, and combinations with compounds having an Si-0-C bond are particularly preferred.

In the polymerization of olefins, the amount of organoaluminum compound used in the polymerization system is generally 10-4 mmol/
1 or more, preferably 10 −2 mmol/1 or more. The molar ratio of the titanium atoms used in the solid catalyst component is generally 0.5 or more, preferably 2.
Above, especially 10 or more is suitable. Note that if the amount of the organoaluminum compound used is too small, the polymerization activity will be significantly reduced. In addition, when the amount of the organoaluminum compound used in the polymerization system is 20 mmol/1 or more and the ratio to titanium atoms is 1000 or more in molar ratio, the catalyst performance will be further improved even if these values are further increased. cannot be seen.

The amount of the stereoregularity improver used for the purpose of improving the stereoregularity of the α-olefin polymer is:
When the solid catalyst component of the present invention is used, the purpose can be achieved even in a very small amount, but it is usually 0.001 to 5 mol, preferably 0.001 to 5 mol per mol of the organoaluminum compound. O is used in a molar ratio of 1 to 1.

The olefins used in olefin polymerization include ethylene, propylene, 1-butene, 4-methyl-1-pentene, 3
-Methyl-1-pentane, 1-hexene, 1-octene and the like. Among these, preferred is a-olefin having 3 or more carbon atoms, especially propylene. In addition to homopolymerization, commonly known random or block copolymerization can also be suitably applied.

Polymerization method and conditions In carrying out the polymerization, the solid catalyst component of the present invention, the organoaluminum compound, or these and the stereoregularity improver may be separately introduced into the polymerization vessel, but among them, two
Some or all may be mixed in advance.

Polymerization can be carried out either in an inert solvent, in a liquid monomer (olefin) or in the gas phase. Further, in order to obtain a polymer having a practically usable melt flow, a molecular weight regulator (generally hydrogen) may be present.

The polymerization temperature can generally be selected from the range of -10°C to 180°C, and is practically 20°C to 130°C.

In addition, there are no limitations inherent to this catalyst system with respect to the form of the polymerization reactor, polymerization control method, post-treatment method, etc., and all known methods can be applied.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples.

In the Examples and Comparative Examples, the stereoregularity (isotacticity) of the produced polymer was evaluated by boiling hebutane extraction. That is, by extracting the produced polymer with boiling hebutane for 6 hours, the weight percent of the insoluble portion was determined as the isotactic index (1,1,). The melt flow index (MFI) of the produced polymer is
JIS K-6758 for powder mixed with 0.2% of 2,6-sheettett-butyl-4-methylphenol
Measurements were made under conditions of 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,
7A of the Periodic Table, Group 8 transition metal compounds, halogen-containing compounds, stereoregularity improvers, etc.) are all those from which water has been substantially removed.

Furthermore, the manufacturing method and polymerization of the solid catalyst component were carried out in the absence of substantial moisture and in a nitrogen atmosphere.

Example 1 Preparation of solid catalyst component Anhydrous magnesium chloride: MgC/2 (obtained by heating and drying commercially available anhydrous magnesium chloride in a stream of dry nitrogen at about 500°C for 15 hours)
30g (315mmol), anhydrous ferrous chloride: Fe
Cl2 (commercially available ferrous chloride tetrahydrate: F e C1.
(Obtained by heating and dehydrating 4H20 in a hydrogen chloride stream at about 200°C for 8 hours) 2.85g
(22.5 mmol) and ethyl 2-benzoylbenzoate 5 = 84 g (23 mmol) in a vibrating ball mill container (cylindrical stainless steel, internal volume 111, diameter 1
amm porcelain ball (approximately 50% filled in apparent volume). This has an amplitude of 6m and a frequency of 30H! A co-pulverized solid was obtained by attaching the powder to a vibrating ball mill and performing co-pulverization for 20 hours. 5 g of the obtained co-pulverized material was 1 (lo
ml titanium tetrachloride: suspended in T I C414
The reaction was carried out at 0°C for 2 hours. The solid product was collected by filtration and washed successively six times with n-decane (100 ml) at 80°C and four times with n-hexane (100 ml) at room temperature. This was dried under reduced pressure at 40°C to obtain the desired solid catalyst component. When the obtained solid catalyst component was analyzed by atomic absorption spectrophotometry, the content of titanium atoms in this solid catalyst component was 2.0% by weight.

Polymerization of propylene and physical properties of the resulting polymer A solid catalyst component prepared by the above method was placed in a stainless steel autoclave with an internal volume of 31 cm, and 91 cm of triethylaluminum.
and 20 μm of diphenyldimethoxysilane were added, and then immediately 760 g of propylene and 0.1 g of hydrogen were charged. The temperature of the autoclave was raised and the internal temperature was maintained at 70°C. After 1 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 13,400 g-polypropylene/g-
Solid catalyst component/time (hereinafter referred to as g-P P/g-ci
(abbreviated as jlIh), 670kg-polypropylene/g
-Titanium in the solid catalyst component (hereinafter referred to as dazzling-P P
/g-Ti・h).

1. of the produced polymer. I was 96.5%. Midfielder
I is 4.4 g-polypropylene/10 minutes (hereinafter referred to as g-
PP/IQmin) Tea Tsuta.

Comparative Example 1 Preparation of solid catalyst component A solid catalyst component was prepared by the same method and preparation conditions as in Example 1, except that FeCl2 was not used when co-pulverizing MgCl2 and ethyl 2-benzoylbenzoate. I did it. The content of titanium atoms in the obtained solid catalyst component was 3.2vt%.

Polymerization of propylene and evaluation of the resulting polymer Propylene polymerization was carried out using the same method and polymerization conditions as in Example 1. 22
0 g of polypropylene was obtained, and the polymerization activity was 11,000.
g -P P/ g -ell-h.

It was 340 kg-PP/g-Ti-h. I of the produced polymer, 1. was 95.0%. MFI is 4.8g
-P P / 10m1nte was there.

Examples 2 to 7 Solid catalyst components were prepared using the same method and preparation conditions as in Example 1, using the ketoester compounds shown in Table 1 instead of ethyl 2-benzoylbenzoate. Propylene polymerization was carried out using the same method and polymerization conditions as in Example 1.

Comparative Examples 2 to 7 Solid catalyst components were prepared using the same method and preparation conditions as in Example 1, using the ketoester compounds shown in Table 1 instead of ethyl 2-benzoylbenzoate. Propylene polymerization was carried out using the same method and polymerization conditions as in Example 1.

Examples 8 to 11 Using the solid catalyst component of Example 1, propylene was produced in the same manner and under polymerization conditions as in Example 1, except that the stereoregularity improver added during polymerization was changed to those shown in Table 2. Polymerization was performed.

Examples 12 to 13 When preparing the solid catalyst component, anhydrous manganese chloride (MnC1
), a solid catalyst component was prepared using the same method and preparation conditions as in Example 1, except that anhydrous cobalt chloride (Co C12) was used. In addition, MnC1, CoC1, and the like are commercially available anhydrides that are heated to 80° C. in a hydrogen chloride stream at about 200°C.
The one obtained by heating and dehydrating for a period of time was used.

Propylene polymerization was carried out using the same method and polymerization conditions as in Example 1 (Table 3).

- Examples 14 to 17 Solid catalyst components were prepared in the same manner and under the same preparation conditions as in Example 1, except that the amount of MgC1, FeC12゜2-benzoylbenzoate ethyl used in preparing the solid catalyst components was changed to that shown in Table 4. was prepared. Propylene polymerization was carried out using 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, using ethyl benzoate instead of ethyl 2-benzoylbenzoate. The content of titanium atoms in the obtained solid catalyst component was 2.3vj%.

Polymerization of propylene and evaluation of the resulting polymer Propylene polymerization was carried out using the same method and polymerization conditions as in Example 1. 39
2g of polypropylene was obtained, and the polymerization activity was 19400.
g -P P/ g -cxt-h.

It was 1140 kg-PP/g-Ti-h. 1. of the produced polymer. I was 83.1%. M of the produced polymer
FI was 6.8 g -P P/1 (lain).

Example 18 Preparation of solid catalyst component 9, Sag (100 isol) of anhydrous magnesium chloride (treated in the same manner as in Example 1) and 1.80 g
(14,2111(II) anhydrous iron chloride (treated in the same manner as in Example 1) was mixed with 50 ml of n-decane and 47
ml of 2-ethylhexyl alcohol were both heated and dissolved at 130° C. for 2 hours in a round bottom flask under a nitrogen atmosphere. Add 2.1 g of phthalic anhydride to this solution, and add 13 g of phthalic anhydride.
Heated at 0°C for 1 hour. Cool the solution to room temperature and
0 ml of titanium tetrachloride was placed in a dropping funnel, and dropped into 200 ml of titanium tetrachloride at -20°C over 1 hour.
The temperature was increased to 0°C. 3.18g (12.5mm
o Ethyl 2-benzoylbenzoate from I) was slowly added dropwise. After the dropwise addition was completed, the mixture was reacted at 80° C. for 2 hours. After the reaction, the supernatant liquid was removed, and 200 ml of titanium tetrachloride was newly introduced, followed by reaction at 80° C. for 2 hours. Next, the supernatant was removed, washed six times with n-decane (lOQml) at 100°C and four times with n-hexane (lOQml) at room temperature, and dried under reduced pressure at 40°C to obtain the desired solution. A solid component was obtained. The content of titanium atoms in the obtained solid catalyst component was 1.8% by weight.

Polymerization of propylene and physical properties of the resulting 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 205
00g -P P/g -cxf・h, lILDkg
-PP/g-Ti-h. 1.1. of the produced polymer.
was 97.5%. The MFI of the produced polymer is 6.7g.
-PP/10mln.

Comparative Example 9 Preparation of solid catalyst component All methods and preparation conditions were the same as in Example 2, except that F e C12 was not used when dissolving M g CI 2 in n-decane and 2-ethylhexyl alcohol. A solid catalyst component was prepared.

The content of titanium atoms in the obtained solid catalyst component was 2.2
It was wt%.

Polymerization of propylene and physical properties of the resulting polymer Propylene polymerization was carried out using the same method and polymerization conditions as in Example 1. 280
g of polypropylene was obtained, and the polymerization activity was 140 fl.
Og -P P/ g -csj・h1fi40kg-
It was PP/g-Ti·h. 1.1. of the produced polymer. was 96.5%. MFI is 7.0g -P P
/ IQ+ain.

Examples 19-20 During the preparation of the solid catalyst component, Mn C12 was used instead of FeCl2 for the group 7A and 8 transition metal compound components.

A solid catalyst component was prepared using the same method and preparation conditions as in Example 18, except that CoCj2 was used. Propylene polymerization was carried out using the same method and polymerization conditions as in Example 1 (Table 5
).

〔Effect of the invention〕

When olefins are polymerized using the catalyst component obtained by the present invention, the polymerization activity is very high, so the amount of catalyst residue in the produced polymer can be kept extremely low, so the deashing step can be omitted. be able to. Furthermore, since the amount (concentration) of remaining halogen is small, the degree of corrosion of molding machines and the like during the polymer processing process can be significantly improved. In addition, the residual catalyst causes deterioration and coloration of the polymer itself, but since the concentration is necessarily low, these can also be reduced.

Moreover, since the stereoregularity of the produced polymer is very high, a polymer having mechanical strength that can be used in practical use can be obtained without removing the so-called non-stereoregular polymer portion.

These effects have extremely important meaning in industrial processes.

[Brief explanation of drawings]

FIG. 1 is a flow chart relating to a method for preparing a catalyst for polymerizing olefins, which is one aspect of the present invention.

Claims (2)

[Claims] (1) During or after the formation of a solid catalyst component whose essential components are a magnesium compound, a titanium compound, and a halogen-containing compound, the following general formula (I)▲mathematical formula, chemical formula, table, etc.▼(I) (here , R^1, R^2 and Z are groups selected from aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and polycyclic hydrocarbons. 2 or more types, and 1 type or 2 of transition metal compounds of group 7A and 8 of the periodic table.
1. A method for producing a solid catalyst component for olefin polymerization, which comprises carrying out contact and reaction treatment in the presence of more than one species. (2) A method for polymerizing olefins, which comprises using a catalyst system containing the catalyst component according to claim (1).