JPH08143619A - Solid catalyst component for polymerization of olefin, its production and production of olefin polymer - Google Patents

Abstract

PURPOSE: To economically and safely obtain the subject component having high activity and high stereospecificity by treating a solid catalyst derived from a reaction of an Mg compound, a Ti compound and a halogen compound with an electron-donating compound. CONSTITUTION: In forming or after forming a solid catalyst component derived from a reaction of an Mg compound such as magnesium chloride, a Ti compound such as titanium tetrachloride and a halogen compound such as titanium halide, silicon halide, phosphorus halide or halogenated alcohol, the objective component is obtained by treating it in the presence of one or more kinds of electron-donating compound of the formula (R<1> is a 1-10C hydrocarbon; R<2> and R<3> are each a 1-20C hydrocarbon; R<4> is a >=3C branched hydrocarbon). As a compound of the formula, 2,2-diisobutyl-3-methoxy-propionic acid ethyl ester or 2-propyl-2-isopentyl-3-methoxy-propionic acid methyl ester, etc., is exmplified.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solid catalyst component for olefin polymerization, a catalyst for olefin polymerization and a method for producing an olefin polymer for producing a homopolymer of ethylene or .alpha.-olefin or a copolymer thereof. .

[0002]

2. Description of the Related Art Heretofore, many solid catalyst components have been proposed, which contain magnesium compounds, titanium compounds, halogen compounds and electron-donating compounds as essential components. It is well known that these catalysts have high activity in the polymerization of olefins and exhibit high stereospecificity in the polymerization of α-olefins. In particular, it is also known that when a phthalic acid ester compound is used as an electron-donating compound when preparing the above-mentioned solid catalyst component, excellent performance is exhibited.

By the way, in the catalyst system using the phthalic acid ester compound as an electron donating compound, it is necessary to use a large amount of an organosilicon compound as a promoter component other than the organoaluminum compound. However, the organosilicon compound used for the above purpose is expensive because of its complicated structure, and thus has a serious problem of increasing the catalyst cost. In addition, since siloxanes or inorganic silicic acids generated by the decomposition of the organosilicon compound remain in the polymer in a microdispersed state, there is a problem that the physical properties of the polymer are greatly affected.

The present inventors have previously used an organic compound having a specific structure as an electron-donating compound for a catalyst, and thus can exhibit a certain degree of stereoregularity without using an organosilicon compound as a promoter component. Was found (EP38334A2), but the performance of practical use level was not obtained only with this solid catalyst and the organoaluminum compound. Therefore, in actual use, the organosilicon compound should be used in a small amount. I had no choice.

Recently, studies have been made on the use of a diether compound as an electron-donating compound (Japanese Patent Laid-Open No. 3-2943).
02), the diether compound has a high possibility of having physiological activity due to its structure. Therefore, there are safety and health problems such as the need for careful handling. Therefore,
It has been earnestly desired to develop a catalyst system which does not use an organosilicon compound as a co-catalyst component and has no safety and health problems.

[0006]

Olefin polymerization which exhibits high activity and high stereospecificity without using any expensive organosilicon compound as a cocatalyst component and without having any problems in safety and hygiene. For solid catalyst component,
It is an object of the present invention to provide a catalyst for olefin polymerization and a method for producing an olefin polymer.

[0007]

Means for Solving the Problems As a result of various investigations for solving these problems, the present inventors have found that the solid catalyst component is formed by or after the reaction of a magnesium compound, a titanium compound, and a halogen compound. Polymerization or copolymerization of olefins using a solid catalyst component for olefin polymerization, which is characterized in that treatment is carried out in the presence of one or more electron donating compounds represented by general formula (I). As a result, they have found that the above problems can be solved, and have reached the present invention.

The solid catalyst component for olefin polymerization, the catalyst for olefin polymerization and the method for producing an olefin polymer according to the present invention will be specifically described below. The solid catalyst component for olefin polymerization according to the present invention is a magnesium compound,
It can be obtained by treating in the presence of one or more electron donating compounds represented by the following general formula (I) during or after the solid catalyst component is formed by the reaction of a titanium compound and a halogen compound. .

Embedded image (Here, R ¹ is a hydrocarbon group having 1 to 10 carbon atoms, R ²
Is a hydrocarbon group having 1 to 20 carbon atoms, and R ³ is 1 to 12 carbon atoms.
20 is a hydrocarbon group, and R ⁴ is a branched hydrocarbon group having 3 or more carbon atoms. )

Magnesium compounds used in the present invention include magnesium halides such as magnesium chloride and magnesium bromide: alkoxy magnesium such as ethoxy magnesium and isopropoxy magnesium; magnesium laurate and magnesium stearate. Examples of carboxylates of magnesium: alkylmagnesium such as butylethylmagnesium, and the like. Also, 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.

Examples of the titanium compound used in the present invention include titanium tetrachloride, titanium trichloride, titanium tetrabromide, and other titanium halides: titanium butoxide, titanium ethoxide, and other titanium alkoxides: phenoxytitanium chloride, and the like. Examples thereof include alkoxytitanium halides. Also, a mixture of two or more of these compounds may be used. A tetravalent titanium compound containing halogen is preferable, and titanium tetrachloride is particularly preferable.

In the halogen-containing compound used in the present invention, the halogen is fluorine, chlorine, bromine or iodine, preferably chlorine, and the specific compound actually exemplified depends on the catalyst preparation method. Titanium halides such as titanium tetrachloride and titanium tetrabromide, silicon halides such as silicon tetrachloride and silicon tetrabromide, phosphorus halides such as phosphorus trichloride and phosphorus pentachloride, 2,2,2-trichloroethanol,
Halogen-containing alcohols such as 2,2,2-trifluoroethanol are typical examples, but depending on the preparation method, halogenated hydrocarbons, halogen molecules, hydrohalic acids (eg, HCl, HBr, HI, etc.) may be used. You may use.

The electron donating compound used in the present invention is a compound represented by the general formula (I).

Embedded image In the formula, R ¹ is a hydrocarbon group having 1 to 10 carbon atoms, preferably a hydrocarbon group having 1 to 5 carbon atoms, and more preferably a hydrocarbon group having 1 to 3 carbon atoms. A methyl group, an ethyl group and a propyl group.

R ² is a hydrocarbon group having 1 to 20 carbon atoms, preferably a hydrocarbon group having 1 to 15 carbon atoms, and more preferably a hydrocarbon group having 1 to 10 carbon atoms. Examples thereof include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, isopentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, cyclopentyl group and cyclohexyl group.

R ³ is a hydrocarbon group having 1 to 20 carbon atoms, preferably a hydrocarbon group having 1 to 15 carbon atoms, specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl. Group, pentyl group, isopentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, decyl group, pentadecyl group, cyclopentyl group,
A cyclohexyl group and the like.

R ⁴ is a hydrocarbon group having 3 or more carbon atoms, preferably a branched hydrocarbon group having 3 or more carbon atoms, specifically, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group. Group, isopentyl group, sec-pentyl group, tert-pentyl group, 2-ethylhexyl group, texyl group, cyclopentyl group, cyclohexyl group and the like.

As the above compound, 2-methyl-
Methyl 2-isopropyl-3-methoxy-propionate, ethyl 2-methyl-2-isopropyl-3-methoxy-propionate, 2-methyl-2-isopropyl-3
-Methoxy-iso-butyl propionate, 2-methyl-2-isopropyl-3-methoxy-tert-butyl propionate, 2-methyl-2-isopropyl-3-methoxy-propionic acid (2-ethylhexyl), 2-methyl 2-Methyl-2-isopropyl-3-ethoxy-propionate, ethyl 2-methyl-2-isopropyl-3-ethoxy-propionate, butyl 2-methyl-2-isopropyl-3-ethoxy-propionate, 2-ethyl-2
-Ethyl isopropyl-3-methoxy-propionate,
2-Ethyl-2-isopropyl-3-methoxy-butyl propionate, 2-ethyl-2-isopropyl-3-methoxy-tert-butyl propionate, 2-ethyl-
2-Isopropyl-3-methoxy-propionic acid (2-
Ethylhexyl), 2,2-diisopropyl-3-methoxy-ethyl propionate, 2,2-diisopropyl-
3-Methoxy-butyl propionate, 2-isopropyl-2-isobutyl-3-methoxy-methyl propionate, 2-isopropyl-2-isobutyl-3-methoxy-ethyl propionate, 2-isopropyl-2-isobutyl-3- Butyl methoxy-propionate, 2-isopropyl-2-isobutyl-3-methoxy-propionic acid (2-ethylhexyl), methyl 2-isopropyl-2-isopentyl-3-methoxy-propionate, 2-isopropyl-2-isopentyl- 3-Methoxy-ethyl propionate, 2-isopropyl-2-isopentyl-
Butyl 3-methoxy-propionate, 2-isopropyl-2-isopentyl-3-methoxy-propionic acid (2
-Ethylhexyl), methyl 2-isopropyl-2-cyclopentyl-3-methoxy-propionate, ethyl 2-isopropyl-2-cyclopentyl-3-methoxy-propionate, 2-isopropyl-2-cyclopentyl-3-methoxy-propionic acid Butyl, 2-isopropyl-2-cyclopentyl-3-methoxy-propionic acid (2-ethylhexyl), 2-isopropyl-2-cyclohexyl-3-methoxy-butyl propionate, 2-
Isopropyl-2-cyclohexyl-3-methoxy-propionic acid (2-ethylhexyl), 2-butyl-2-
Isopropyl-3-methoxy-propionic acid (2-ethylhexyl), ethyl 2-butyl-2-isobutyl-3-methoxy-propionate, 2-butyl-2-isobutyl-3-methoxy-propionic acid (2-ethylhexyl), 2-Butyl-2-isopentyl-3-methoxy-
Ethyl propionate, 2-butyl-2-isopentyl-
3-methoxy-propionic acid (2-ethylhexyl),
Ethyl 2-butyl-2-cyclopentyl-3-methoxy-propionate, ethyl 2,2-diisobutyl-3-methoxy-propionate, 2,2-diisobutyl-3-methoxy-propionic acid (2-ethylhexyl), 2- Isobutyl-2-isopentyl-3-methoxy-ethyl propionate, 2-isobutyl-2-isopentyl-3-
Methoxy-propionic acid (2-ethylhexyl), 2-
Ethyl isobutyl-2-cyclopentyl-3-methoxy-propionate, 2-isobutyl-2-cyclopentyl-3-methoxy-propionic acid (2-ethylhexyl), methyl 2-cyclopentyl-2-isopentyl-3-methoxy-propionate, 2-cyclopentyl-2
-Isopentyl-3-methoxy-ethyl propionate,
Butyl 2-cyclopentyl-2-isopentyl-3-methoxy-propionate, 2-Cyclopentyl-2-isopentyl-3-methoxy-propionic acid (2-ethylhexyl), 2,2-dicyclopentyl-3-methoxy-
Examples include ethyl propionate and the like.

The catalyst preparation method used in the present invention is not particularly limited, but magnesium halide,
Titanium halide and the electron-donating compound of the present invention may be co-ground and then halogenated to achieve high activation. After the magnesium halide alone or the magnesium halide and the silicon compound or the phosphorus compound are co-ground, the titanium compound treatment and the halogenation treatment may be performed in the coexistence of the electron donating compound. Further, magnesium carboxylate or alkoxy magnesium and a titanium compound, a halogenating agent and an electron donating compound may be heat-treated to be highly activated. It is also possible to dissolve magnesium halide in an organic solvent or the like and allow the electron-donating compound of the present invention to act during or after precipitation in the presence of a titanium compound. Further, a catalyst prepared by adding an electron-donating compound and a titanium compound to the preparation process when the halogenating agent acts on alkylmagnesium may be used. The amount of the electron-donating compound remaining in the catalyst depends on the preparation method.
, The titanium: magnesium: ED (molar ratio) is in the range of 1: 1 to 1000: 10 ^{−6 to} 100, preferably 1: 2 to 100: 10 ⁻⁴ to 10. If the ED is less than this range, the stereoregularity decreases, and conversely if the ED is too large, the activity decreases, which is not preferable.

Typical organoaluminum compounds in the present invention are represented by the following general formulas (II) to (IV). AlR ⁵ R ⁶ R ⁷ (II) R ⁸ R ⁹ Al-O-AlR ¹⁰ R ¹¹ ... (III)

[Chemical 4]

Embedded image

In formulas (II), (III) and (IV),
R ⁵ , R ⁶ and R ⁷ may be the same or different and each is a hydrocarbon group having at most 12 carbon atoms, a halogen atom or a hydrogen atom, at least one of which is a carbon hydrogen group, and R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ may be the same or different and each is a hydrocarbon group having at most 12 carbon atoms. R ¹² is a hydrocarbon group having at most 12 carbon atoms,
n is an integer of 1 or more.

Typical of the organoaluminum compounds represented by the formula (II) are trialkylaluminums such as triethylaluminum, tripropylaluminum, tributylaluminum, triisobutylaluminum, trihexylaluminum and trioctylaluminum, and Alkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride and alkyl aluminum halides such as diethyl aluminum chloride, diethyl aluminum bromide and ethyl aluminum sesquichloride.

Further, among the organoaluminum compounds represented by the formula (III), typical ones include alkyl dialumoxanes such as tetraethyl dialumoxane and tetrabutyl dialumoxane.

The formula (IV) represents an aluminoxane, which is a polymer of an aluminum compound. R ¹² includes a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and the like, but a methyl group and an ethyl group are preferable. The value of n is preferably 1-10.

Of these organoaluminum compounds,
Trialkylaluminums, alkylaluminum halides and alkylalumoxanes are preferred, especially trialkylaluminums as they give the preferred results.

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

In the polymerization of olefins, the amount of the organoaluminum compound used in the polymerization system is generally 10 ^-4 mmol / L or more, preferably 10 ^-2 mmol / L or more. The molar ratio of titanium atom in the solid catalyst component is generally 0.5 or more, preferably 2 or more, and more preferably 10 or more. If the amount of the organoaluminum compound used is too small, the polymerization activity will be significantly reduced. When the amount of the organoaluminum compound used in the polymerization system is 20 mmol / L or more and the ratio with respect to titanium atoms is 1000 or more in molar ratio, the catalyst performance is further improved even if these values are further increased. There is nothing to do.

When the above-mentioned titanium-containing solid catalyst component used for the purpose of improving the stereoregularity of the α-olefin polymer is used, the object can be achieved even in a very small amount. 0.01 to 5 mol, preferably 0.01 to 1 mol, relative to 1 mol of the compound
Used in the ratio of

In the olefin polymerization method according to the present invention,
It is preferable to prepolymerize the olefin in the olefin polymerization catalyst. The olefin used in the preliminary polymerization may be the same as or different from the olefin used in the main polymerization described later, but it is preferable to use propylene. The reaction temperature during the prepolymerization is -20 to 10
It is in the range of 0 ° C, preferably -20 to 60 ° C. In the prepolymerization, a molecular weight modifier such as hydrogen can be used. It is desirable that the prepolymerization is carried out so that 0.1 to 1000 g, preferably 0.3 to 500 g, particularly preferably 1 to 200 g of a polymer is produced per 1 g of the olefin polymerization catalyst. In carrying out the polymerization, the solid catalyst component of the present invention and the organoaluminum compound may be separately introduced into the polymerization vessel, or they may be mixed in advance. The 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 practical melt flow, a molecular weight modifier (generally hydrogen) may coexist. The polymerization temperature is generally -10 ° C to 180 ° C, and practically 20 ° C to 130 ° C. In addition, with respect to the form of the polymerization reactor, the method of controlling the polymerization, the method of post-treatment, etc., there is no limitation specific to the present catalyst system, and all known methods can be applied.

[0028]

The present invention will be described in more detail with reference to the following examples. The melt index (ie, MFR) in the examples and comparative examples was measured according to JIS K-6758-1968. The heptane index, i.e., HR (%), which is a measure of the stereoregularity of a polymer, represents the remaining amount in% after the obtained polymer was extracted with boiling n-heptane for 6 hours. The polymerization activity RR is represented by the polymer yield (g) per 1 hour of the solid catalyst component per hour. In each of the examples, each of the compounds (organic solvent, olefin, hydrogen, titanium compound, magnesium compound, etc.) used for the production and polymerization of the solid catalyst component was substantially dewatered. Further, the production method and the polymerization of the solid catalyst component were carried out in the presence of substantially no water and in an inert atmosphere such as nitrogen.

The names and the abbreviations or abbreviations of the organoaluminum compounds and electron donating compounds (ED) used in the examples and comparative examples are shown below.
Triethylaluminum (TEA), triisobutylaluminum (TIBA), 2-isopropyl-2-isopentyl-3-methoxy-ethylpropionate (A),
2-Isopropyl-2-isopentyl-3-methoxy-
Methyl propionate (B), 2-cyclopentyl-2-
Ethyl isopentyl-3-methoxy-propionate (C), 2,2-dicyclopentyl-3-methoxy-propionate (D), diisobutylphthalate (E), 2-tert-butyl-3-methoxy-propionate. (F), 2,2-diisobutyl-1,3-
Dimethoxypropane (G).

Example 1 Preparation of solid catalyst component 1 20 g of anhydrous magnesium chloride (obtained by calcining and drying commercially available anhydrous magnesium chloride in a dry hydrogen chloride gas stream at about 500 ° C. for 15 hours) (0.2
1 mol), 2-isopropyl-2-isopentyl-3-
Methoxy-ethyl propionate 12.2g (0.05m
ol), 3.0 ml of titanium tetrachloride and silicon oil (TSS-451, 20c manufactured by Shin-Etsu Chemical Co., Ltd.) as a grinding aid.
s) 3.0 ml of a vibrating ball mill container (stainless steel cylindrical type, circular volume 1 L, diameter 10
mm magnetic balls were placed in an apparent volume of about 50%). Attach this to a vibrating ball mill with an amplitude of 6 mm,
A co-milled solid was obtained by co-milling for 15 hours. 15 g of the obtained co-ground product was suspended in 150 ml of 1,2-dichloroethane and stirred at 80 ° C. for 2 hours, and then a solid portion was collected by filtration and washed with hexane to obtain 1,2 which was free during washing. -Wash thoroughly until no dichloroethane is detected. This was dried under reduced pressure at 30 ° C. to 40 ° C. and hexane was removed to obtain a solid catalyst component. When the obtained solid catalyst component was analyzed, the content of titanium atoms in this solid catalyst component was 2.4% by weight. Physical properties of polymerized and produced polymer In a stainless steel autoclave having an internal volume of 3 L, 17 mg of the solid catalyst component produced by the above method and 91 mg of triethylaluminum were put, and then 760 g of propylene and 0.1 g of hydrogen were charged. The temperature of the autoclave was raised and the internal temperature was kept at 70 ° C. After 1 hour, the content gas was released to terminate the polymerization. The polymerization results are shown in Table 1.

(Example 2, Comparative Examples 1 and 2) A solid catalyst component was prepared in the same manner as in Example 1 except that the compounds shown in Table 1 were used as the electron donating compound, and the polymerization was evaluated. . The results are shown in Table 1.

(Example 3) Production of solid catalyst component 2 9.5 g of anhydrous magnesium chloride (treated in the same manner as in Example 1)
50 ml of decane and 48.6 ml
2-ethylhexyl alcohol together under a nitrogen atmosphere,
It was heated and dissolved in a round bottom flask at 130 ° C. for 2 hours. Nothing
Add 2.1 g of water phthalic acid and heat at 130 ° C for 1 hour.
Was. Cool this solution to room temperature and add 20 ml dropping funnel.
, 30 ml of -20 ° C 80 ml of tetrachloride titanium
The solution was added dropwise to the flask and the temperature was raised to 110 ° C. in 4 hours. 2-
Isopropyl-2-isopentyl-3-methoxy-pro
1.22 g (0.005 mol) of ethyl pionate and
A solution of 5 ml of xanthan was slowly added dropwise. End of dripping
Then, the mixture was reacted at 110 ° C. for 2 hours. After removing the supernatant,
80 ml of titanium tetrachloride is newly introduced, and it is 2:00 at 110 ° C.
Heated for a while. Then, wash 3 times with 100 ml of decane
Then, it was washed with hexane to obtain a solid catalyst. Titanium loading
Was 2.6% by weight.Polymerization and physical properties of polymer If you use a stainless steel autoclave with an internal volume of 3 L
8.8 mg of solid catalyst component produced by the method, triethyl
Add 91 mg of aluminum, then add 760 g of propylene
Ren and 0.1 g of hydrogen were charged. Autoclave
The temperature was raised and the internal temperature was kept at 80 ° C. 1 hour later,
It was released to terminate the polymerization. The polymerization results are shown in Table 1.

(Examples 4 and 5, Comparative Examples 3 and 4) Solid catalyst components were prepared in the same manner as in Example 3 except that the compounds shown in Table 1 were used as electron donating compounds.
Polymerization was evaluated. The results are shown in Table 1.

(Example 6) Production of solid catalyst component 3 A well-dried 300-mL round bottom flask in a nitrogen stream
And 5.0 g of diethoxy magnesium, 2-isopropyl
Lu-2-isopentyl-3-methoxy-propionic acid
1.22 g (0.005 mol) of chill and methylene chloride
25 ml was added. Stir at reflux for 1 hour, then suspend this suspension
The liquid was pumped into 200 ml of titanium tetrachloride at room temperature. Xu
Individually raise the temperature to 110 ° C. and react for 2 hours with stirring
Was. After completion of the reaction, after precipitation, the precipitated solid was separated by filtration and kept at 110 ° C.
It was washed 3 times with 200 ml of decane. New titanium tetrachloride
200 ml was added and reacted at 120 ° C. for 2 hours. reaction
After the completion, the precipitated solid was separated by filtration, and the decane at 110 ° C was 200 m.
Wash 3 times with 1 l, and detect chlorine ions in hexane at room temperature.
Wash with hexane until no more. This catalyst component
The tan atomic weight content was 3.3% by weight.Polymerization and physical properties of polymer If you use a stainless steel autoclave with an internal volume of 3 L
2.5 mg of solid catalyst component produced by the method, triethyl
Add 91 mg of aluminum, then add 760 g of propylene
Ren and 0.1 g of hydrogen were charged. Autoclave
The temperature was raised and the internal temperature was kept at 80 ° C. 1 hour later,
It was released to terminate the polymerization. The polymerization results are shown in Table 1.

(Examples 7 and 8, Comparative Examples 5 and 6) Solid catalyst components were prepared in the same manner as in Example 6 except that the compounds shown in Table 1 were used as the electron-donating compound.
Polymerization was evaluated. The results are shown in Table 1.

(Example 9) Production of solid catalyst component 4 Metallic magnesium 12.8g, ethyl orthoformate 88m
1 (0.53 mol) and 1, 2 as a reaction initiator
-0.5 ml of dibromoethane was added and the suspension was brought to 55 ° C.
Hold, and add n-butyl chloride 8 to 100 ml of hexane.
Add 5 ml of a solution containing 0 ml (0.80 mol)
For 50 minutes and the rest was added dropwise over 80 minutes. Stirring
The reaction was carried out at 70 ° C. for 4 hours to obtain a solid product. 5
It was washed 6 times with hexane at 0 ° C. The solid product 6.
3 g and 50 ml of decane were placed in a reactor and kept at room temperature for 2,2,2.
2.0 ml of 2-trichloroethanol and 11 ml of decane
The mixed solution of was added dropwise over 30 minutes, and after completion, stirred at 80 ° C for 1 hour.
Stirred. After separating the solid matter, wash 4 times with 100 ml of hexane
Then, it was washed twice with 100 ml of toluene. The solid
40 ml of toluene and 60 ml of titanium tetrachloride are added to 90
The temperature was raised to ℃, 2-isopropyl-2-isopentyl-3
-Methoxy-ethyl propionate 1.83 g (0.00
75 mol) and 5 ml of toluene was added dropwise over 5 minutes.
After that, the mixture was stirred at 120 ° C. for 2 hours. After that,
The mixture was filtered at 0 ° C and washed twice with toluene at 90 ° C. further
40 ml of toluene and 60 ml of titanium tetrachloride were added to the solid substance.
The mixture was stirred at 120 ° C. for 2 hours, and the resulting solid was 110 ° C.
It is separated by filtration and washed with 100 ml of hexane at room temperature 7 times to give a solid.
A titanium catalyst component was obtained.Polymerization and physical properties of polymer If you use a stainless steel autoclave with an internal volume of 3 L
4.6 mg of solid catalyst component produced by the method, triethyl
Add 91 mg of aluminum, then add 760 g of propylene
Ren and 0.1 g of hydrogen were charged. Autoclave
The temperature was raised and the internal temperature was kept at 80 ° C. 1 hour later,
It was released to terminate the polymerization. The polymerization results are shown in Table 1.

(Examples 10 to 14 and Comparative Examples 7 and 8) As electron donating compounds and organoaluminum compounds, Table 1
A solid catalyst component was prepared in the same manner as in Example 9 except that the compound shown in 1 was used, and the polymerization was evaluated. The results are shown in Table 1.

[0038]

[Table 1]

[0039]

EFFECT OF THE INVENTION A solid catalyst component for olefin polymerization which does not use an expensive organosilicon compound as a co-catalyst component at all, has no safety and health problems, and exhibits high activity and high stereoregularity. It has become possible to provide a catalyst for olefin polymerization and a method for producing an olefin polymer.

[Brief description of drawings]

FIG. 1 is a flow chart diagram to assist in understanding the present invention.

Claims (5)

[Claims] 1. In the presence of one or more electron donating compounds represented by the following general formula (I) during or after the formation of a solid catalyst component by the reaction of a magnesium compound, a titanium compound and a halogen compound. A method for producing a solid catalyst component for offine polymerization, which comprises performing treatment with. Embedded image (Here, R ¹ is a hydrocarbon group having 1 to 10 carbon atoms, R ²
Is a hydrocarbon group having 1 to 20 carbon atoms, and R ³ is 1 to 12 carbon atoms.
20 is a hydrocarbon group, and R ⁴ is a branched hydrocarbon group having 3 or more carbon atoms. ) 2. R ¹ of the electron-donating compound represented by the general formula (I) is a methyl group, an ethyl group or a propyl group, and R 1.
² is a hydrocarbon group having 1 to 10 carbon atoms, R ³ is a methyl group, an ethyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, an isopentyl group, a hexyl group, a heptyl group,
Octyl group, 2-ethylhexyl group, decyl group, pentadecyl group, cyclopentyl group, cyclohexyl group, and R ⁴ is isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, sec -Pentyl group, tert-pentyl group, 2-ethylhexyl group, texyl group, cyclopentyl group, cyclohexyl group, The manufacturing method of the solid catalyst component for olefin polymerization of Claim 1 characterized by the above-mentioned. 3. The electron-donating compound represented by the general formula (I) is ethyl 2,2-diisobutyl-3-methoxy-propionate, 2-isopropyl-2-isopentyl-3.
-Methoxy-methyl propionate, 2-isopropyl-
Ethyl 2-isopentyl-3-methoxy-propionate, Methyl 2-isopropyl-2-cyclopentyl-3-methoxy-propionate, Ethyl 2-isopropyl-2-cyclopentyl-3-methoxy-propionate, 2
-Cyclopentyl-2-isopentyl-3-methoxy-
Methyl propionate, 2-Cyclopentyl-2-isopentyl-3-methoxy-ethyl propionate, 2,2-
The solid catalyst component for olefin polymerization according to claim 1 or 2, which is one of methyl dicyclopentyl-3-methoxy-propionate and ethyl 2,2-dicyclopentyl-3-methoxy-propionate. Production method. 4. A solid catalyst component for olefin polymerization obtained by the production method according to claim 1. 5. A method for producing an olefin polymer, which comprises polymerizing olefins using the catalyst comprising the solid catalyst component for olefin polymerization according to claim 4 and an organoaluminum compound.