JPH04173811A - Production of olefinic polymerization catalyst and polymerization of olefin - Google Patents

Abstract

PURPOSE:To obtain the title catalytic component providing a polymer having high stereoregularity in high yield by molding a solid catalytic component comprising an Mg compound, a Ti compound and a halogen-containing compound as essential components and treating the molded component plural times in the presence of a specific keto-ester compound. CONSTITUTION:During or after molding of a solid catalytic component comprising a magnesium compound (e.g. anhydrous magnesium chloride), a titanium compound (e.g. titanium tetrachloride) and a halogen-containing compound as essential components, the solid catalytic component is subjected to contact treatment twice or more times in the presence of one or more keto-ester compounds (e.g. 2-benzoylbenzoic acid ethyl ester) shown by the formula (R<1>, R<2> and Z are aliphatic hydrocarbon, alicyclic hydrocarbon, aromatic hydrocarbon or polycyclic hydrocarbon) to give the objective catalytic component for olefinic polymerization.

Description

Detailed Description of the Invention (1) Industrial Application Field 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, when applied to the polymerization of olefins, allows a highly stereoregular polymer to be obtained in high yield.

(2) Prior Art Conventionally, many manufacturing methods have been proposed using solid catalyst components containing magnesium, titanium, a halogen compound, and an electron donor (internal donor) as essential catalyst components. In many cases, an organic carboxylic acid ester is used as an internal donor, and there is a problem in that the ester odor remains in the polymer unless the ester is removed by washing with a solvent. In addition, it does not have industrially satisfactory performance in terms of polymerization activity and stereoregularity of the resulting polymer, and there is a desire to develop a catalyst with further high performance.

Against this background, the present applicant has previously proposed a method for producing an olefin polymerization catalyst using a ketoester compound as an internal toner and a method for polymerizing olefins (Japanese Patent Application No. 1-17111).
No. 620, hereinafter referred to as the prior invention), and according to the method of the prior invention, it became possible to obtain highly stereoregular polymers with high activity.

(3) Problems to be Solved by the Invention The purpose of the present invention is to provide a method for producing a catalyst and a method for polymerization which provide a polymer with high activity and high stereoregularity, which were insufficient in the prior art. It is something to do.

(4) Means for Solving the Problems As a result of intensive research to solve the above problems, the method of the earlier invention was developed by treating with a ketoester compound two or more times during or after the formation of the solid catalyst similar to the earlier invention. It was discovered that a polymer having even better stereoregularity was produced compared to the polymer obtained by the above method, and the present invention, which has the following outline, was achieved. That is, the present invention provides the following during or after the formation of a solid catalyst component containing a magnesium compound, a titanium compound, and a haloken-containing compound as essential components (where R1, R2 and Z are aliphatic hydrocarbons) , alicyclic hydrocarbons, aromatic hydrocarbons, and polycyclic hydrocarbons). The present invention provides a method for producing a catalyst component for olefin polymerization, and a method for polymerizing olefins, characterized by using a catalyst system containing this catalyst component.

The present invention will be explained in detail below.

Magnesium compounds used in the present invention include magnesium halides such as magnesium chloride and magnesium bromide; alkoxymagnesiums such as Etquin magnesium and isopropoxymagnesium; Carphonate, alkylmagnesium such as butylmagnesium chloride: n-alkylmagnesium halide such as butylmagnesium chloride, n
Examples include alkylalkoxymagnesium such as -butylethoxymagnesium. Moreover, a mixture of two or more of these compounds may be used. Preferably, magnesium halide is used or magnesium halide is formed during catalyst formation.

More preferably, the halogen is chlorine.

The titanium compounds used in the present invention include titanium halides such as titanium tetrachloride, titanium trichloride, and titanium tetrabromide; titanium alkoxides such as titanium butoxide and titanium ethoxide; and alkoxytitanium halides such as phenoxytitanium chloride. I can give an example. or,
A mixture of two or more of these compounds may be used. Preferably, it is a tetravalent titanium compound containing a halogen,
Particularly preferred is titanium tetrachloride.

The halokene-containing compound used in the present invention is halogen, fluorine, chlorine, bromine, or iodine, preferably chlorine. Typical 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. is a halogenated hydrocarbon, a halogen molecule, a hydrohalic acid (e.g., HC
g, HBr, Hl, etc.) may also be used.

The ketoester compound used in the present invention has the general formula %Formula % R1 in the general formula (1) is a hydrocarbon group having 1 to 20 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, 5ee-butyl, tert-butyl, tert-
Amyl, 2-hexenylisopropenyl, cyclopentyl, cyclohexyl, tetramethylsif-0hexyl, cyclohexenyl, melbornylphenyl, tolyl, ethylphenyl, xyl, cumyl, trimethylphenyl, tetramethylphenyl, pentamethylphenyl, naphthyl, methyl Examples include naphthyl, anthranyl, hensyl, diphenylmethyl, and indenyl.

These hydrogen atoms may be substituted with halogen atoms.

Among these, groups having aromatic hydrocarbons or polycyclic hydrocarbons are preferably used. Z in general formula (1) 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, and 9-fluorenediyl. 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 (1) 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, 5ee-butyl, ter
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 (1) 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',[1°-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-3,6-dimethylbenzoate, 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-hendiylfluorene-carboxylate, 6(4
Examples include n-butyl'-trioyl)indene 5-carboxylate, ethyl 10-benzoylphenanthrene-10carboxylate, and the like.

The catalyst preparation method used in the present invention is not particularly limited, but magnesium halide, titanium halide, and ketoester compound may be co-pulverized and then halogenated to achieve high activation. Alternatively, magnesium halide alone or co-pulverization of magnesium halide and a silicon compound or phosphorus compound may be treated with a titanium compound or halogenated in the presence of a ketoester compound.

Further, magnesium carboxylate or alkoxymagnesium, titanium compound, halogenated JFI and ketoester may be heat treated to improve performance.

Magnesium halosaponide may be dissolved in an organic solvent or the like, and then allowed to precipitate in the presence of a titanium compound, or after the precipitation, a ketoester may be applied.

Alternatively, a catalyst produced by adding a ketoester compound or a titanium compound to the preparation process when a halogenating agent is applied to alkylmagne/ram may be used.

Alternatively, magnesium metal may be reacted with a halogenated hydrocarbon and reacted with a ketoester compound or a titanium compound during the preparation process using the resulting magnesium halide as a raw material. Furthermore, the polymerization activity of the catalyst is improved by treating the solid catalyst component with the ketoester compound and then continuously treating it with the titanium compound or halogen-containing compound described above.

Although the amount of the ketoester compound remaining in the catalyst depends on the preparation method, the ketoester compound of the present invention was used in I and D.

Abbreviated as titanium/magnesium 1. D.

(Molar ratio) is in the range of 1:1-1000.10-6-100, preferably in the range of 1:2-100:10'-10. 1. D: If the amount is less than this range, the stereospecificity will decrease, and if it is too much, the activity will decrease, which is not preferable.

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 are represented by the following formulas (A1) to (A3).

Ap R"Ra2R"' (A 1 )
A4 A5 A6 a7RRAn
)-0-ApRR(A2) In formulas (A1), (A2) and (A3), R
al, RA2. RA3 may be the same or different and are a hydrocarbon group, a halogen atom, or a hydrogen atom having at most 12 carbon atoms, at least one of which is a hydrocarbon group, and Ra4. Ra5. Ra6 and Ra7 may be the same or different and are hydrocarbon groups having at most 12 carbon atoms. Further, Ra8 is a hydrocarbon group having at most 12 carbon atoms, and na is an integer of 1 or more.

Typical organoaluminum compounds represented by the formula (A1) include trialkylaluminum such as triethylaluminum, tripropylaluminum, tributylaluminum, trihexylaluminum and trioctylaluminum, as well as diethylaluminum hydride and diisobutylaluminum hydride. and alkylaluminum halides such as diethylaluminum chloride, diethylaluminum bromide and ethylaluminum sesquicrite.

Among the organoaluminum compounds represented by formula (A2),
Typical examples include alkylalumoxanes such as tetraethylene alumoxane and tetrabutyldialumoxane.

Further, formula (A3) represents aluminoxane, which is a polymer of an aluminum compound. Ra8 is methyl, ethyl,
It includes propyl, butyl, pentyl, etc., but methyl and ethyl groups are preferred. na is preferably 1 to IO.

Among these organoaluminum compounds, trialkylaluminums, alkylaluminum hydrides, and alkylalumoxanes are preferred, and trialkylaluminums are particularly preferred because they give favorable results.

In order to improve the stereoregularity of the produced polymer when performing a polymerization reaction of α-olefin having 3 or more carbon atoms, a catalyst comprising a titanium-containing solid catalyst component and a catalyst component comprising an organoaluminum compound according to the present invention is used. The system can further include a number of compounds that have hitherto been proposed for use in Ziegler polymerization catalysts and have effects on stereoregularity. Compounds used for this purpose include aromatic monocarphonic acid ester, Sl -0-
Examples include silicon compounds having a C or Si-N-C bond, acetal compounds, germanium compounds having a Ge-○-C bond, and nitrogen or oxygen heterocyclic compounds having an alkyl substituent.

Specifically, for example, ethyl benzoate, butyl benzoate, ethyl p-toluate, ethyl p-anisate, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxyrane, diphenylshedoxinrane, she-n-propyl Dimethoxysilane, cyclohexylmethyldimethoxysilane, tetraethoxysilane, t-butylmethyldimethoxysilane, benzophenone dimethoxy acetal, benzophenone jetoxy acetal, acetophenone dimethoxy acetal, t-butyl, methyl ketone dimethoxy acetal, diphenyl dimethoxy germane, phenyl triethoxy kermane ,
2.2,6.6-titramethylpiveridine, 2,2,6
．． 6-titramethylpyran and the like. Among these, S
Silicon compounds and acetal compounds having t -0-C or St -N-C bonds are preferred, especially St
A combination with a compound having a -0-C bond is preferred.

In the polymerization of olefins, the amount of organic aluminum used in the polymerization system is generally +o-' mmol/g or more, preferably 1o-2 mmol/g or more. or,
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 organoaluminium used is too small, the polymerization activity will be significantly reduced. Furthermore, if the use of organoaluminum in the polymerization system is 20 mmol/g or more and the ratio to titanium atoms is 1000 or more in terms of molar ratio, it is not seen that the catalyst performance will further improve even if these values are further increased. I can't.

The amount of the aforementioned stereoregularity improver used for the purpose of improving the stereoregularity of the α-olefin polymer is
When the titanium-containing solid catalyst component of the present invention is used, the purpose can be achieved even in a very small amount.It is usually 0.001 to 5 mol, preferably 0, O1 to 1 mol per mol of the organoaluminum compound. used in the ratio of

The olefins used in olefin polymerization are generally olefins having at most 18 carbon atoms, and typical examples include ethylene, propylene, butene-1,4-methylpentene-1, hexene-1, and octene. -1st grade is given. In carrying out the polymerization, these olefins may be homopolymerized, or two or more olefins may be copolymerized (for example, copolymerization of ethylene and propylene).

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 introduced into the polymerization vessel separately, or two or all of them may be introduced into the polymerization vessel. 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 is generally from -10°C to 180°C,
Practically speaking, the temperature is 20°C or more and 130°C or less.

In addition, the configuration of the polymerization reactor, polymerization control method, post-treatment method, etc. are not limited to the present catalyst system, and all known methods can be applied.

5) Examples 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, after the obtained polymer was extracted for 6 hours, the weight percent of the insoluble portion was defined as the isotactic index (1, 1,). The melt flow index (i.e., MFI) is determined according to JIS K-6758 for a powder mixed with 0.296 of 2,6-sheet tCrt-butyl-4 methylphenol at a temperature of 230°C and a load of 2.16 kg. It was measured.

In each example, all the compounds (organic solvent, olefin, hydrogen, titanium compound, magnesium compound, stereoregularity improver, etc.) used in the production and polymerization of the solid catalyst component were substantially free of moisture. .

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

[Example 1 Preparation of solid catalyst component Anhydrous magnesium chloride: MgCΩ2 (obtained by heating and drying commercially available anhydrous magnesium chloride in a stream of dry nitrogen at about 500°C for 15 hours)
30g (315an+of) and 5.84g (23a+moN) of ethyl 2-benzoylbenzoate in a container for a vibrating ball mill (stainless steel cylindrical, internal volume 1g, porcelain balls with a diameter of 1OIlll filled to about 50% of the apparent volume) I put it in. This was attached to a vibrating ball mill with an amplitude of 6 mm and a frequency of 30 degrees, and co-pulverization was carried out for 20 hours to obtain a co-pulverized solid.

5 g of the obtained co-pulverized material was mixed with 100 ml of titanium tetrachloride:T
It was suspended in ICi' 4 and reacted at 80°C for 2 hours.

The solid product obtained was dissolved in n-decane (loOml) at 80°C.
) 6 times, and then diluted with ethyl 2-benzoylbenzoate lJ5.
g (54 smoi)) at 80°C for 1 hour.

After the reaction, 100ml of TiCΩ4 was added to the system and the
The reaction was carried out at ℃ for 2 hours. The solid product was reacted again with 100 ml of TiCR4 at 80°C for 2 hours, and after the reaction was completed,
6 times with n-decane (LOOML) at 80°C and n-decane at room temperature.
Washed successively four times with hexane (100 ml).

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 catalyst component was 2.6% by weight (vt%).

Polymerization of propylene and physical properties of the resulting polymer In a stainless steel autoclave with an internal volume of 3 g, 2 hg of the solid catalyst component prepared by the above method, 91 mg of t-ethylaluminum, and 20 II g of diphenyldimethoxysilane were placed.
and then immediately add 7 BOg of propylene and 0
．． 1 g of hydrogen was charged. The temperature of the autoclave was raised and the internal temperature of the dust was maintained at 70°C.

Propylene polymerization was carried out for 1 hour, and the polymerization was stopped by releasing the content gas. As a result, 300 fr polypropylene was obtained. That is, the polymerization activity is 1500 g-polypropylene/pe solid catalyst component/time (hereinafter referred to as g-P
P/g-cat・h), 580kg-polypropylene/g-titanium in the solid catalyst component・h (hereinafter, kg
-PP/g-Ti-h). The I,I, of the produced polymer was 968%. MFI is 4,6 g-polypropylene/10 minutes (hereinafter referred to as g-PP/10
＋++i 口).

[Comparative Example 1] Preparation of Solid Catalyst Component 5 g of a co-pulverized product of MgCl2 and ethyl 2-benzoylbenzoate obtained in the same manner as in Example 1 was suspended in 100 ml of T t CD 4 and mixed at 80°C. Allowed time to react. The solid product obtained was heated in n-decane (loOm
l) 6 times and room temperature n-hexane (loOml) 4 times.
Washed twice consecutively. This was dried under reduced pressure at 40°C to obtain a solid catalyst component. The content of titanium atoms in this catalyst component was 3.2 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. 220
g of polypropylene was obtained, and the polymerization activity was 11,000 g.
-PP/g-eat-h, 340kg-PP/g-
It was Ti-h. 1 of the produced polymers. is 95,
It was 0%. MFI is 4.8g - P P / 10
It was m1n.

[Example 2 Preparation of solid catalyst component 9.50 r (roommoΩ) of anhydrous magnesium chloride ~ M g Ci) 2 (subjected to the same heat drying treatment as in Example 1) was mixed with 50 ml of n-decane and 47 m
1 in 2-ethylhexyl alcohol under a nitrogen atmosphere.
The mixture was heated and dissolved at 30°C for 2 hours. Next, add 2.0% of phthalic anhydride to this solution. IK was added and the mixture was further heated at 130°C for 1 hour. The solution was cooled to room temperature and
Drop into TICD 4 (200 ml) at 4°C.
The temperature was raised to 80°C over time. Temperature 80
℃, 3.18 g (12.5 mmo
Ethyl 2-benzoylbenzoate (g) was slowly added dropwise.

After completion of the dropping, the reaction was carried out at 80° C. for 2 μl. The obtained solid product was washed six times with n-decane (loOml) at 80°C and reacted with 3.18 g (12,5 gmoΩ) of ethyl 2-benzoylbenzoate at 80°C for 1 hour. After the reaction, 200ml of TiCΩ4 was added to the system at 80°C.
The mixture was allowed to react for 2 hours. Remove the supernatant liquid and make a new 200ml
of TiCΩ4 was introduced and reacted at 80° C. for 2 hours. After the reaction was completed, the obtained solid product was heated to 80°C in n-decane (l
n-hexane (loOml) at room temperature 6 times
It was washed four times consecutively. This was dried under reduced pressure at 40°C to obtain the desired solid catalyst component. The amount of titanium supported in the obtained solid catalyst component was 1.9 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. 334
g of polypropylene was obtained, and the polymerization activity was 16,700 g.
-PP/ g -eat-h, 880kg-PP/
There was g-Ti-h. 1.1. of the produced polymer. is 97
．． It was 9%. MFI is 73g-P P / 10m
It was 1n.

[Comparative Example 2] Preparation of solid catalyst component Solubilized MgCg2 obtained by the same method as Example 2
The solution was incubated at -20°C TIC for 1 hour (20°C).
0ml) and the temperature was raised to 80°C over 4 hours. When the temperature reached 80℃, 3.18
g (12,5 gmoN) of ethyl 2-benzoylbenzoate was slowly added dropwise. After dropping, heat at 80℃ for 2 hours.
Allowed time to react. Remove the supernatant and add 200ml of T
I Cil 4 was introduced and reacted at 80°C for 2 hours.

After the reaction was completed, the obtained solid product was mixed with n-decane (loOml) at 80°C six times and n-hexane (loOml) at room temperature.
1) four times successively. This was dried under reduced pressure at 40°C to obtain the desired solid catalyst component. The amount of titanium supported in the obtained solid catalyst component was 2.2 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 14,000 g.
-PP/g-cat-h, 840kg-PP/g-
It was Ti-h. 1.1. of the produced polymer. is 96.5
%Met. MFI is 7.0g -P P -/lo
It was a+in.

[Example 3 Preparation of Solid Catalyst Component 5, I] [lf<44txmoI] of jetoxymagnesium, 1.40 g (5,51110 g) of ethyl 2-benzoylbenzoate was added to 25 ml of methylene chloride under a nitrogen atmosphere for 1 hour. Stir at reflux for an hour. The resulting suspension was then pumped into T ICD 4 (200 ml) at room temperature.

The temperature was gradually raised to 110° C., and the mixture was reacted with stirring for 2 hours.

After the reaction, the precipitated solid was heated to 110°C with n-decane (2
00ml) three times and 1.40g (5,5irAo
N) with ethyl 2-benzoylbenzoate and 1 at 110 °C.
Allowed time to react. Then add 200 ml of TIC into the system.
j74 was added and reacted at 110°C for 2 hours. The supernatant liquid was removed, and 200 ml of TicΩ4 was newly introduced and reacted at 110° C. for 2 hours. After completion of the reaction, the obtained solid product was washed three times with n-decane (200 ml) at io<0>C and then with n-hexane (200 ml!) at room temperature until no chloride ions were detected. This was dried under reduced pressure at 40°C to obtain the desired solid catalyst component. The amount of titanium supported in the obtained solid catalyst component was 2.6%.

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. 470
g of polypropylene was obtained, and the polymerization activity was 23,500 g.
-PP/g-cat-h, 900J-PP/g-T
It was i-h. 1.1. of the produced polymer. is 97.5
%Met. MFI is 11.2g - P P / lo
Ivy at min.

[Comparative Example 3] Preparation of solid catalyst component A jetoxymagnesium-containing suspension obtained in the same manner as in Example 3 was added to T L C14 (200 ml) at room temperature.
It was pumped inside. The temperature was gradually raised to 110°C and the mixture was stirred for 2 hours before reacting. After the reaction was completed, the precipitated solid was
Washed three times with n-decane (200 ml) at 0°C. Add 200ml of TICi' 4 and heat at 110℃ for 2 hours.
Allowed time to react. After the reaction, the precipitated solid was heated to 110°C.
Washed 3 times with n-decane (200 ml) and washed with n-decane at room temperature.
It was washed with hexane (200 ml) until no chlorine ions were detected. The content of titanium atoms in the ground solid catalyst component was 3.3 vt%.

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. 408
g of polypropylene was obtained, and the polymerization activity was 20,400 g.
-PP/g-Cat-h, 620y-PP/g -
It was Ti-h. 1.1. of the produced polymer. is 96.1%
Met. MFI is 10.7g - P P / lom
It was in.

[Examples 4 to 9] Catalyst preparation and propylene polymerization were performed in the same manner as in Example 3, using the ketoester compounds shown in Table 1 instead of ethyl 2-benzoylbenzoate.

[Comparative Examples 4 to 9] Catalyst preparation and propylene polymerization were performed in the same manner as in Comparative Example 3, using the ketoester compounds shown in Table 1 instead of ethyl 2-benzoylbenzoate.

[Comparative Example 10] Catalyst preparation and propylene polymerization were performed in the same manner as in Comparative Example 3, using ethyl benzoate instead of ethyl 2-benzoylbenzoate. The content of titanium atoms in the obtained solid catalyst component was 2.3 wt%. 320 g of polypropylene was obtained, and the polymerization activity was 15,300 g-PP/g-
eaL-h, 670 kg-pp/g-Ti-h. 1.1. of the produced polymer. was 80.1%. M
FI was 3.2 g-PP/lOa+in.

[Examples IO to 13] Using the solid catalyst component of Example 1, propylene was produced under the same conditions as in Example 1, except that the stereoregularity improver added during propylene polymerization was changed to the compound shown in Table 2. Polymerization was performed.

〔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 R (concentration) of the remaining halogen is also small, the degree of corrosion of molding machines, etc. during the polymer processing process can be significantly improved. In addition, the residual catalyst may cause deterioration and coloring of the polymer itself, and 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. Figure 1

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. A catalyst component for olefin polymerization, characterized in that it is treated twice or more in the presence of two or more types. (2) A method for polymerizing olefins, which comprises using a catalyst system containing the catalyst component according to claim (1).