JPH0350207A - Production of olefin polymerization catalyst and polymerization of olefin - Google Patents

Abstract

PURPOSE:To produce an olefin polymerization catalyst which can give a highly stereoregular polymer in high activity by reacting a well-known magnesium- supported titanium-containing solid catalyst component by contact in the presence of a specified transition metal compound during or after the formation of this component. CONSTITUTION:A solid catalyst component for olefin polymerization is prepared by reacting a catalyst component essentially consisting of a magnesium compound, a titanium compound, a halogenated compound and an electron donor by contact in the presence of at least one transition metal compound of group VII A or VIII of the periodic table during or after the formation of this component. A catalyst system for olefin polymerization is formed by combining the obtained catalyst component with an organometallic compound and optionally a stereoregularity improver. Examples of the transition metal compound include halides, alkoxides and carboxylates of these metals and chelate compounds represented by acetylacetonates.

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 a high-performance catalyst composition having a carbon number of 3 or more. 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.

[Prior Art] In recent years, titanium halides, etc. have been supported on magnesium chloride together with electron donors in place of the titanium trichloride catalyst component, which has been commonly used as a solid catalyst component in catalysts for polymerizing olefins such as propylene. Many solid catalysts have been developed and reported.

Among these, the ones that were initially actively developed were:
Co-pulverized product of aromatic monocarboxylic acid ester and magnesium chloride as an electron donor treated with titanium tetrachloride, or magnesium chloride as a complex of aromatic monocarboxylic acid ester and titanium tetrachloride as an electron donor There are some that have been co-pulverized.

Various methods have been proposed to further improve activity and stereoregularity. For example, in JP-A-59-94590, a solid catalyst prepared from magnesium halide, an organoaluminum compound, an organic carboxylic acid ester, and a Si
JP-A-57-63310 discloses a method of combining compounds having a -0-R group, etc., in which various organic carboxylic acid monoesters and diesters as electron donors, activated magnesium chloride, and a titanium compound are combined. A method of preparing a solid catalyst in combination and using a compound having a 5i-0 bond or a 5i-N bond and an organoaluminum compound has been proposed as an improved patent.

However, although these solid catalysts have high polymerization activity when combined with organoaluminum compounds, they are not sufficient in terms of the industrial necessity of obtaining stereoregular polymers in high yields; The problem remained that an electron-donating compound such as a carboxylic acid ester had to be used in combination.

Furthermore, a method that does not use an electron donating compound during polymerization is also described in JP-A-58-138715, but this method has the problem that the amount of organoaluminum compound used during polymerization is extremely excessive. No satisfactory results have been obtained.

[Problem to be solved by the invention J When polymerizing olefins such as propylene using the solid catalyst having magnesium chloride as a carrier,
In order to obtain a stereoregular polymer in high yield, it is necessary to use an organoaluminum compound and an electron donor not only during the preparation of the solid catalyst but also during the polymerization. It is necessary to use a large amount of such an electron donor, which poses the problem of imparting odor and coloring peculiar to the electron donor used to the resulting polymer.

-a The amount of electron donor contained in the solid catalyst component is reduced to such an extent that the odor problem of the produced polymer can be ignored by contact treatment with titanium halide or other halides or washing with an organic solvent. . However, the electron donor used together with the organoaluminum compound during polymerization is extremely large compared to that contained in the solid catalyst component mentioned above, and most of it is contained in the resulting polymer. As long as an electron donor is sometimes used, it is considered that the problem of odor of the produced polymer is inevitable.

The purpose of the present invention is to solve the problems in the conventional techniques and provide a novel method for producing an olefin polymerization catalyst and a method for polymerizing olefins that produce a polymer with higher activity and stereoregularity. shall be.

[Means for Solving the Problems] As a result of intensive research to solve the above-mentioned problems, we have arrived at the present invention, which has the following outline. That is, the present invention provides a method for forming a solid catalyst component containing a magnesium compound, a titanium compound, a halogen-containing compound, and an electron donor as essential components during or after the formation of a solid catalyst component containing one or more transition metal compounds of Group 8 of Periodic Table 7A or 2F. ! The present invention provides a method for producing a solid catalyst component for olefin polymerization, which is characterized by carrying out contact and reaction treatment in the presence of the above, and a method for polymerizing olefins, which is characterized by using a catalyst system containing this solid catalyst component.

Hereinafter, one aspect of the present invention will be explained in detail.

Preparation of Olefin Polymer A Catalyst The magnesium compound used in the preparation of the solid catalyst component in the present invention is not particularly limited, and may be those used as a raw material for preparing 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, those using magnesium halide or alkoxymagnesium,
Alternatively, it forms 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 tetrahydride; tetramethoxytitanium, tetraethoxytitanium, tetrapropoxytitanium, and tetrabutoxytitanium. , alkoxytitanium such as tetraphenoxytitanium; ethoxytitanium trichloride, butoxytitanium trichloride, phenoxytitanium trichloride,
Examples include alkoxytitanium halides such as dibutoxytitanium dichloride and tributoxytitanium chloride. Further, these various titanium compounds can be used alone or in combination of two or more. Preferred is a tetravalent titanium compound containing a halogen, particularly preferred is titanium tetrachloride.
be.

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 electron donor used in the present invention generally includes phosphorus-containing compounds, sulfur-containing compounds, oxygen-containing compounds, nitrogen-containing compounds, and the like. Among these, oxygen-containing compounds are preferred.

Examples of oxygen-containing compounds 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, ethyl anisate, methyl ethoxybenzoate, ethyl ethoxybenzoate, ethyl cinnamate, dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate,
Esters of carboxylic acids such as diisobutyl phthalate, dihexyl phthalate, dioctyl phthalate or γ-
Examples include cyclic esters such as butyrolactone and acid anhydrides such as maleic anhydride and phthalic anhydride.

These may be used alone or in combination of two or more.

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. Examples include chelate compounds represented by halides, alkoxides, carboxylates, and acetylacetonate salts of these transition metals.

Preferably, manganese chloride (■), technetium chloride (
■), rhenium chloride (■), manganese bromide (■), manganese iodide (■), iron chloride (■), iron chloride (■), iron bromide (■), iron iodide (■), chloride Ruthenium (■), osmium chloride (m), osmium chloride (IV), cobalt chloride (■), cobalt bromide (■), cobalt iodide (■),
Rhodium chloride (■), iridium chloride (■), iridium chloride (■), nickel chloride (■), nickel bromide (T
I) Nickel iodide (■), palladium chloride (■),
Palladium bromide (■), platinum chloride (■), platinum chloride (m
), platinum chloride (rV), and other halides of transition metals. 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 recognized in the present invention, but it is preferable to use the following range.

The amount of the titanium compound used is l x 10-' to 1000 in molar ratio to the amount of the magnesium compound used.
It is preferably within the range of 0.01 to ioo. A halogen compound is used as necessary, and when used, the amount used depends on whether the titanium compound, magnesium compound, and transition metal compound of Group 7A and 8 of the periodic table contain halogen. First, the molar ratio of lXl0- to the amount of magnesium used is
” to 1000, preferably 0.1-10
It is within the range of 0.

The amount of the electron donor to be used is preferably in the range of 1X10-'' to 1O, preferably in the range of 0.1 to 5 in molar ratio to the amount of the magnesium compound used.

The amount of the transition metal compound of Group 8 of Periodic Table 7A is 1Xl0 in molar ratio to the amount of the magnesium compound used.
-'' to 5, preferably 0.01-1.

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 transition metal compounds of Groups 7A and 8 of the Periodic Table are brought into contact and reacted temporarily or in stages. As a specific example of applying a known method.

(11 A method of contacting and reacting magnesium chloride, a titanium compound, an electron donor, and a transition metal compound of Group 8 of Periodic Table 7A in any order, and then washing as appropriate with liquid hydrocarbon.

(2) A method of contacting and reacting an alkoxymagnesium, a titanium compound, a halogen-containing compound, an electron donor, and a transition metal compound of group 7A or group 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 an electron donor, 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.

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

A typical example of the organoaluminum compound in the present invention is a compound represented by the general formula APR'yXs-y. In the above formula, R' has 1 to 2 carbon atoms
0 hydrocarbon groups, particularly preferably aliphatic hydrocarbon groups, X is a halogen, and y is 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 Aε atoms bonded via zero 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, silicon compounds having Si-0-C or Si-N-C bonds, acetal compounds, and germanium having Ge-0-C bonds. compounds, nitrogen or oxygen heterocyclic compounds having an alkyl substituent, and the like.

Specific examples of these compounds include ethyl benzoate, butyl benzoate, ethyl p-toluate, ethyl p-anisate, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, diphenyljethoxysilane, -n-propyldimethoxysilane, cyclohexylmethyldimethoxysilane, tetraethoxysilane, t-butylmethyldimethoxysilane, benzophenone, dimethoxyacecool, benzophenonejethoxyacetal, acetophenone dimethoxyacetal, t-butylmethylketonedimethoxyacecool, diphenyldimethoxygermane , phenyltriethoxygermane, 2,2,6,6-titramethylbiveridine, 2,2,6,6-tetramethylbilane, and the like.

Among these, Si-0-C or Si-N-
Silicon compounds and acetal compounds having a C bond are preferred, and combinations with compounds having a 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/
I2 or more, preferably 101 mmol/I2 or more. Further, the molar ratio of the titanium atoms used in the solid catalyst component is generally 0.5 or more, preferably 2 or more, particularly 10 or more. 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 organoaluminum compound used in the polymerization system is 20 mmol/e or more and the ratio to titanium atoms is 1000 or more in molar ratio, the catalyst performance will further improve 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 0.0 to 5 mol, preferably 0.01 to 5 mol, preferably 0.01 to 1 mol, per mol of the organoaluminum compound. used in a molar ratio of

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

In carrying out the polymerization method and its 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 two or two of them may be introduced into the polymerization vessel. All may be mixed beforehand.

Polymerization can be carried out either in an inert solvent, in a liquid 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 addition, in the Examples and Comparative Examples, the stereoregularity (isotacticity) of the produced polymer was evaluated by the boiling hebutane extraction method. That is, the produced polymer was extracted with boiling hebutane for 6 hours, and 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
2. JIS K-6758 for powder mixed with 0.2% of 6-tert-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 used in the production and polymerization of the solid catalyst component (organic solvent, olefin, hydrogen, titanium compound, magnesium compound, electron donor, periodic table 7A, group 8 transition metal compound, halogen (containing compounds, stereoregularity improvers, etc.) are all substantially water-free.

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.

Anhydrous magnesium chloride: MgCIx (obtained by heating and drying commercially available anhydrous magnesium chloride in a nitrogen stream at about 500°C for 15 hours) 20 g (210 mmol), anhydrous ferrous chloride:
FeCL- (commercially available ferrous chloride tetrahydrate: FeClz
- Obtained by heating and dehydrating 4HaO at approximately 200°C for 8 hours in a hydrogen chloride stream) 1.90
g (15 mmol), di-n-butyl phthalate: n
- 4.45 g (16 mmol) of BP was placed in a container for a vibratory ball mill (cylindrical stainless steel, internal volume 12, porcelain balls with a diameter of 10 mm filled to about 50% by apparent volume). The amplitude is 6ffIII+ and the frequency is 3.
A co-pulverized solid was obtained by attaching it to a 0 Hz vibrating ball mill and performing co-pulverization for 20 hours. 5 g of the obtained co-pulverized material was mixed with 50 mQ of titanium tetrachloride: T1. It was suspended in C14 and reacted at 120°C for 2 hours. The solid product was collected by filtration and diluted with toluene (80 mg) at 60°C.
Washed 0 times. 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.

20 mg of the solid catalyst component prepared by the above method was placed in a stainless steel autoclave with an internal volume of 3 I2 containing heavy A of propylene and the product mold, and 91 mg of triethylaluminum.
mg and 20 mg of diphenyldimethoxysilane, then immediately add 760 g of propylene and 1 g of
of hydrogen was charged. Raise the temperature of the autoclave and bring the internal temperature to 7.
It was kept at 0°C. After 1 hour, the content gas was released to terminate the polymerization. As a result, 542 g of polypropylene was obtained.

That is, the polymerization activity is 27100g-polypropylene/
PP solid catalyst component/time (hereinafter referred to as g-PP7g-cat
,・h), 1360kg-polypropylene/
g-Titanium in the solid catalyst component time (hereinafter, kg-PP
7g-Ti-h) of the produced polymer.
．． was 97.2%. MFI is 10.5g-polypropylene/10min (hereinafter referred to as g-PP/10m1n
).

! Wataru■1 Preparation of catalytic acid - "Anhydrous cobalt chloride (commercially available anhydrous cobalt chloride) is used in place of anhydrous ferrous chloride (FeCl) in a hydrogen chloride stream for about 200 ml of
A solid catalyst component was prepared in the same manner as in Example 1 except that 1.95 g (15 mmol) of the solid catalyst component (obtained by heating and dehydrating at 0° C. for 8 hours) was used. The content of titanium in the solid catalyst component is 2.2% by weight
Met.

Polymerization of propylene and molded propylene was carried out in the same manner as in Example 1.

5: 10g of polypropylene was obtained, and the polymerization activity was 26
500g-PP/g-cat-h, 1210kg
-PP/g -Ti·h. 1. of the produced polymer.
1. was 96.8%. MFI is 9.7 g −
PP/10mln.

Instead of FeCl2, 1.89 g of anhydrous manganese chloride (obtained by heating and dehydrating commercially available anhydrous manganese chloride at a hydrogen chloride flow width of about 200°C for 8 hours)
A solid catalyst component was prepared in the same manner as in Example (2) except that (15 mmol) was used. The content of titanium in the solid catalyst component was 1.9% by weight.

Polymerization of propylene was carried out in the same manner as in Example 1.

496 g of polypropylene was obtained, and the polymerization activity was 248
00g-PP/g-cat-h, 1305kg
-PP/g -Ti·h. 1. of the produced polymer.
1. was 96.2%. MFI is 11.5g −
PP/10mln.

Anhydrous ferrous chloride: 0.95g FeC1z (7,5
mmol), 4.31 g (15,5
A solid catalyst component was prepared in the same manner as in Example 1 except that 1 mmol) was used. The content of titanium in the solid catalyst component was 2.0% by weight.

Polymerization of heavy A and raw A of propylene was carried out in the same manner as in Example 1.

640 g of polypropylene was obtained, and the polymerization activity was 320
00g-PP/g-caih, 1600kg-P
P/g-Ti·h. T of the produced polymer, 1.
was 96.4%. MFI is 11.0g-PP
/ 10m1n.

3.80g (30mmol) of FeC1z
A solid catalyst component was prepared in the same manner as in Example 1 except that 4.78 g (17.1 mmol) of n-BP was used. The content of titanium in the solid catalyst component was 1.9% by weight.

Polymer A of propylene and physical properties of product 4 Propylene polymerization was carried out in the same manner as in Example 1.

468 g of polypropylene was obtained, and the polymerization activity was 234.
00g-PP/g-cat-h, 1230k
g -PP/g -T'i·h. 1.1. of the produced polymer. was 97.4%. MFt is 9.9
g-PP/lomin.

8.88g (70mmol) of FeC1g,
A solid catalyst component was prepared in the same manner as in Example 1 except that 5.57 g (20 mmol) of n-roP was used. The content of titanium in the solid catalyst component was 11% by weight.

Polymerization of heavy A and raw A of propylene was carried out in the same manner as in Example 1.

392g of polypropylene was obtained and the 1 polymerization activity was 196
00g-PP/g-cat-h, 1150k
g-PP/g-Ti·h. 1.1. of the produced polymer. was 98.1%. MFI is 6.0 g
-PP/10mln.

15.2g (160mmol) of ugclz, Fe
C1, 11.4g (145mmol), n-B
P6. A solid catalyst component was prepared in the same manner as in Example 1 except that log (22 mmol) was used. The content of titanium in the solid catalyst component was 1.8% by weight.

Polymerization of heavy A of propylene and the product of propylene was carried out in the same manner as in Example 1.

310 g of polypropylene was obtained, and the polymerization activity was 155
0 mouth g-PP/g-cat-h, 861
kg-PP/g-Ti·h. 1, ■, of the produced polymer was 98.6%. The MFI of the resulting polymer is 3.4 g -PP/101! It was Iin.

3.41 g (26.3 mmol) of CaCl2
A solid catalyst component was prepared in the same manner as in Example 1 except that 4.73 g (17 mmol) of n-BP was used. The content of titanium in the solid catalyst component is 2.2
% by weight.

Physical properties of propylene polymer A and product type A Propylene polymerization was carried out in the same manner as in Example 1.

432 g of polypropylene was obtained, with a polymerization activity of 216
00 g-PP/g-cat-h, 980 kg
-PP/g -Ti·h. 1. of the produced polymer.
1. was 97.0%. The MFI of the produced polymer is 8.
It was 6g-PP/l mouth min.

12.9 g (100 mmol) of CoC1z, i
Jg (: 12.4 g (130 mmol) of l-, n-
A solid catalyst component was prepared in the same manner as in Example 1 except that 4.73 g (17 mmol) of BP was used. The content of titanium in the solid catalyst component was 2.1% by weight.

Polymerization of propylene and product polymerization Propylene polymerization was carried out in the same manner as in Example 1.

244 g of polypropylene was obtained, and the polymerization activity was 122
00g-PP7g-cat-h, 580kg-PP
It was 7g-Ti·h. 1.1. of the produced polymer. is 9
It was 8.2%. The MFI of the produced polymer is 3.1 g −
It was PP/10mln.

Comparative Example 1 Preparation of Catalyst In Example 1, a solid catalyst component was prepared without using FeCl2. The amounts of MgC1z and n-BP used are the same as in Example 1. The content of titanium in the solid catalyst component was 1.9% by weight.

Polymerization of propylene was carried out in the same manner as in Example 1.

342 g of polypropylene was obtained, and the polymerization activity was 171
00 g-PP/g-cat-h, 900kg
-PP/g -Ti·h. 1 of the produced polymers
．． 1. was 95.4%. The MFI of the produced polymer is l
O,5g-PP/10mln.

Hereinafter, in Examples 10-13, propylene polymerization was performed using the solid catalyst prepared in Example 1.

Propylene polymerization was carried out in the same manner as in Example 1 except that 20 mg of phenyltriethoxysilane was used instead of diphenyldimethoxysilane. , 536 g of polypropylene was obtained, and the polymerization activity was 26800 g-PP/g.
-caih, 1340kg -PP/g-
It was Ti-h. 1.1. of the produced polymer. is 97.4%
Met. The MFI of the produced polymer is 9.7 g -PP/
It was 10m1n.

Propylene polymerization was carried out in the same manner as in Example 1 except that 19 mg of benzophenone dimethyl acetal was used instead of diphenyldimethoxysilane.

450 g of polypropylene was obtained, and the polymerization activity was 225
00g-PP/g-cat-h, 1125kg-
PP/g-Ti·h. 1.1 of the produced polymer
．． was 96.0%. The MFI of the produced polymer is 8.8
g-PP/lOn+in.

Propylene polymerization and raw polymerization Propylene polymerization was carried out in the same manner as in Example 1, except that 2,2,6,6-titramethylbiperidine 12B was used instead of diphenyldimethoxysilane. . 488 g of polypropylene was obtained, and the polymerization activity was 24400 g -PP/g -c
at-h, 1220 kg-PP7g-Ti-h. 1.1. of the produced polymer. was 96.5%.

The MFI of the produced polymer was 9.6 g-PP/10 m1n.

The polymerization temperature of the heavy A and produced human body of LL eupropylene is 80
Propylene polymerization was carried out in the same manner as in Example 1, except that the temperature and polymerization time were 30 minutes. 510 g of polypropylene was obtained, and the polymerization activity was 51000 g-PP/g-cai
h, 2550 kg-PP/g-Ti-h. 1.1. of the produced polymer. was 98.2%. The MFI of the produced polymer is 10.6 g-PP/10mln
Met.

Ethyl benzoate instead of di-n-butyl phthalate 2.4
Example 1 except that 0 g (16 mmol) was used.
A solid catalyst component was prepared in a similar manner. The content of titanium in the solid catalyst component was 1.9% by weight.

Physical properties of propylene polymer A and product type A Propylene polymerization was carried out in the same manner as in Example 1.

286 g of polypropylene was obtained, and the polymerization activity was 243
00g-PP/g-caih, 1280kg-P
P/g Ti・h. 1. of the produced polymer. t,
was 853%. The MFI of the produced polymer is 24.6
g-PP/t.

It was min.

Comparative Example 2 Preparation of Catalyst In Example 14 above, a solid catalyst component was prepared without using Feel□. The amounts of lJgclg and ethyl benzoate used are the same as in Example 14. The content of titanium in the solid catalyst component was 2.0% by weight.

Physical properties of propylene polymer A and product type A Propylene polymerization was carried out in the same manner as in Example 14.

390 g of polypropylene was obtained, and the polymerization activity was 195
00 g-PP/g-cat-h, 975 kg
-PP/g -Ti·h. 1. of the produced polymer.
1. was 77.5%. The MFI of the produced polymer is 30
．． It was 0 g-PP/10mln.

9.50 g (100++ mol) of anhydrous magnesium chloride (treated in the same manner as in Example 1) and 1.80 g
g (14.2 mmol) of anhydrous iron chloride (treated in the same manner as in Example 1) was mixed with 5012 decane and 47 m2 of 2
- Ethylhexyl alcohol was dissolved by heating 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 2.1 g of phthalic anhydride to this solution.
heated for an hour. Cool this solution to room temperature and add 50 mQ
into a dropping funnel and heated to 200℃ at -20℃ for 1 hour.
m112! Dropped into titanium titanium chloride, 1 was added over 4 hours.
The temperature was increased to 10°C. 3.48g (12,5
mmoL) of di-n-butyl phthalate (n-BP) was slowly added dropwise. After the dropwise addition, the reaction was carried out at 110°C for 2 hours. After the reaction, the supernatant was removed and a new 200 tml solution was added.
2 titanium tetrachloride was introduced and reacted at 110° C. for 2 hours. The supernatant was then removed and the solution was poured into decane (100°C) at 100°C.
By washing 6 times with 0nl) and 4 times with hexane (100n+42) at room temperature, and drying this under reduced pressure at 40°C,
The desired solid component was obtained.

The amount of titanium supported in the obtained solid catalyst component was 1.8% by weight.

Propylene Polymer A and Propylene Propylene polymerization was carried out in the same manner as in Example 1.

374 g of polypropylene was obtained, and the polymerization activity was 187
00g-pp/g-cat-h, 1040k10
It was 4O/g-Ti·h. 1.1 of the produced polymer
．． was 98.7%. MFt of the produced polymer is 6.6
g-PP/10ml 1 mouth.

In Example 15, the solid catalyst component was prepared without using FeCl2. MgC1z, phthalic anhydride, n
-The amount of BP used is the same as in Example 1. The content of titanium in the solid catalyst component was 2.0% by weight.

Propylene @A and the resulting polymer Propylene polymerization was carried out in the same manner as in Example 15.

294 g of polypropylene was obtained, and the polymerization activity was 147.
0 mouth g-PP/g-cat-h, 7
It was 35 kg-PP/g-Tlh. 1.1. of the produced polymer. was 96.7%. MFI of produced polymer
was 5.0 g-1'P/10 m1n.

[Effect of the invention 1] When olefins are polymerized using the catalyst component obtained by the present invention, the polymerization activity is extremely high, so it is possible to suppress the catalyst residue in the produced polymer to an extremely low level. Therefore, the deashing step can be omitted. Also, since the agitation (concentration) of residual halogen is low, the degree of corrosion of molding machines, etc. 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.

Furthermore, since the produced polymer has very high stereoregularity, a polymer having mechanical strength suitable for 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 containing a magnesium compound, a titanium compound, a halogen-containing compound, and an electron donor as essential components, one or more transition metal compounds of Group 8 of Periodic Table 7A are added. 1. A method for producing a solid catalyst component for olefin polymerization, which comprises contacting and reacting in the presence of a catalyst. (2) A method for polymerizing olefins, which comprises using a catalyst system containing the solid catalyst component according to claim (1).