JPH08157521A - Production of solid catalyst component for olefin polymerization, catalyst for olefin polymerization, and production of olefin polymer - Google Patents

Abstract

PURPOSE: To obtain a solid catalyst component for olefin polymerization, which is nonproblematic in safety and hygienics, and shows high activity and high stereoregularity. CONSTITUTION: This component is prepared by treating a solid catalyst component prepared by reacting a magnesium compound with a titanium compound and a halogen compound during or after its preparation with at least one electron-donating compound represented by the formula (wherein R<1> and R<2> are each 1-10 C linear or branched hydrocarbon group, provided that they may be the same or different from each other; and R<3> and R<5> are each a 3-20 C saturated hydrocarbon group having at leas one sec. or tert. carbon atom, provided that they may be the same or different from each other).

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 an aromatic ester represented by a phthalic acid ester compound is used as an electron donating compound in the preparation of the solid catalyst component, excellent performance is exhibited. However, compounds having an aromatic ring are not used for safety and health reasons.

A method of using a malonate derivative as an electron-donating compound has also been reported. For example, Japanese Patent Application Laid-Open No. 6-12216 proposes a compound having a structure in which R ³ and R ⁴ of the general formula (I) in the present invention described later are connected to form a ring. Further, in JP-A-6-279517, one or both of R ³ and R ^{4 in} the general formula (I) is a linear hydrocarbon group, and one or both of R ³ and R ⁴ are Is hydrogen, and one of R ³ and R ⁴ is a hydrocarbon group containing an aromatic ring. These methods significantly reduce the yield. Although methods for using other non-aromatic diester compounds as electron-donating compounds have also been reported (JP-A-3-124705, JP-A-3-168207), these methods show high stereoregular polymer yields. Not always satisfactory enough to get at a rate.

[0004]

The object of the present invention is to provide an electron-donating compound without any safety and health problems.
Further, it is to provide a solid catalyst component for olefin polymerization that exhibits high activity and high stereospecificity, a catalyst for olefin polymerization, and a method for producing an olefin polymer.

[0005]

Means for Solving the Problems As a result of various investigations for solving the above problems, the present inventors have found that a solid catalyst component formed by or after the reaction of a magnesium compound, a titanium compound, and a halogen compound has the following general Using a solid catalyst component for olefin polymerization characterized by performing the treatment in the presence of an electron-donating compound represented by the formula (I),
The present invention has been completed by finding that an olefin polymer can be produced by solving all the above problems by polymerizing or copolymerizing an olefin.

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 forming a solid catalyst component by the reaction of a titanium compound and a halogen compound. .

Embedded image (Here, R ¹ and R ² are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, and they may be the same or different from each other. R ³ and R ⁴ are each 1 Two or more
It is a saturated hydrocarbon group having 3 to 20 carbon atoms or a cyclic saturated hydrocarbon group containing a primary carbon or a tertiary carbon, which may be the same or different from each other. )

Magnesium compounds used in the present invention include magnesium halides such as magnesium chloride and magnesium bromide: ethoxy magnesium, alkoxy magnesium such as isopropoxy magnesium; magnesium laurate and magnesium stearate. Carboxylic acid salt of magnesium: alkyl magnesium such as butylethyl magnesium can be exemplified. 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.

Titanium compounds 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.

The halogen-containing compound used in the present invention has a halogen of 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 , 2,
Typical examples are halogen-containing alcohols such as 2,2-trifluoroethanol, but depending on the preparation method, halogenated hydrocarbons, halogen molecules, hydrohalic acids (for example,
HCl, HBr, HI, etc.) may be used.

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 and R ² are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, and they may be the same or different from each other. More preferably, it is a hydrocarbon group having 1 to 8 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, and a 2-ethylhexyl group.

R ³ and R ⁴ are saturated hydrocarbon groups having 3 to 20 carbon atoms or cyclic saturated hydrocarbon groups each containing at least one secondary carbon or tertiary carbon, and they may be the same or different. May be. Preferably, it is a saturated hydrocarbon group having 3 to 10 carbon atoms or a cyclic hydrocarbon group containing one or more secondary carbons or tertiary carbons, specifically, isopropyl group, isobutyl group, isopentyl group, isohexyl group, Examples include isoheptyl group, cyclopentyl group, cyclohexyl group, 2-cyclopentylethyl group, 2-cyclohexylethyl group.

Examples of the above compounds include dimethyl diisopropylmalonate, diethyl diisopropylmalonate, dipropyl diisopropylmalonate, diisopropyl diisopropylmalonate, dimethyl diisobutylmalonate, diethyl diisobutylmalonate, dipropyldiisobutylmalonate, diisopropyldiisobutylmalonate. Dimethyl diisopentylmalonate, diethyl diisopentylmalonate, dipropyl diisopentylmalonate, diisopropyl diisopentylmalonate, dimethyl diisohexylmalonate, diethyl diisohexylmalonate, dipropyldiisohexylmalonate, Diisopropyl diisohexylmalonate, dimethyl diisoheptylmalonate, diethyl diisoheptylmalonate, diisodiisoheptylmalonate Pill, diisopropyl diisoheptyl malonate, dimethyl di (2-cyclopentylethyl) malonate, diethyl di (2-cyclopentylethyl) malonate, dipropyl di (2-cyclopentylethyl) malonate, di (2-cyclopentylethyl) malon Acid diisopropyl, dimethyl di (2-cyclohexylethyl) malonate, diethyl di (2-cyclohexylethyl) malonate,
Dipropyl di (2-cyclohexylethyl) malonate, Diisopropyl di (2-cyclohexylethyl) malonate,
Dimethyl isopropyl isobutylmalonate, Diethyl isopropylisobutylmalonate, Dipropyl isopropylisobutylmalonate, Diisopropyl isopropylisobutylmalonate, Dimethyl isopropylisopentylmalonate, Dimethyl isopropylisopentylmalonate, Dipropyl isopropylisopentylmalonate, Isopropylisopentylmalonate Diisopropyl, dimethyl isopropylisohexylmalonate, diethyl isopropylisohexylmalonate, dipropyl isopropylisohexylmalonate, diisopropyl isopropylisohexylmalonate, dimethyl isopropylisoheptylmalonate, diethyl isopropylisoheptylmalonate, diisopropylisopropylisoheptylmalonate ,
Isopropyl isoheptyl malonate diisopropyl, isopropyl (2-cyclopentylethyl) malonate dimethyl, isopropyl (2-cyclopentylethyl) malonate diethyl, isopropyl (2-cyclopentylethyl) malonate dipropyl, isopropyl (2-cyclopentylethyl) malonate diisopropyl Dimethyl isopropyl (2-cyclohexylethyl) malonate, Diethyl isopropyl (2-cyclohexylethyl) malonate, Dipropyl isopropyl (2-cyclohexylethyl) malonate, Diisopropyl isopropyl (2-cyclohexylethyl) malonate, Isobutyl isopentylmalonic acid Dimethyl, diethyl isobutyl isopentyl malonate, dipropyl isobutyl isopentyl malonate, isobutyl isopentyl malonate Ropil, dimethyl isobutylisohexylmalonate, diethyl isobutylisohexylmalonate, dipropyl isobutylisohexylmalonate, diisopropyl isobutylisohexylmalonate, dimethyl isobutylisoheptylmalonate, diethyl isobutylisoheptylmalonate, dipropylisobutylisoheptylmalonate , Isobutyl isoheptyl malonate diisopropyl, isobutyl cyclopentyl malonate dimethyl, isobutyl cyclopentyl malonate diethyl, isobutyl cyclopentyl malonate dipropyl,
Isobutyl cyclopentylmalonate diisopropyl, isobutylcyclohexylmalonate dimethyl, isobutylcyclohexylmalonate diethyl, isobutylcyclohexylmalonate dipropyl, isobutylcyclohexylmalonate diisopropyl, isobutyl (2-cyclopropylethyl) malonate diethyl, isobutyl (2-cyclohexylethyl) malon Diethyl acid, dimethyl isopentylisohexylmalonate, diethyl isopentylisohexylmalonate, dipropyl isopentylisohexylmalonate, diisopropyl isopentylisohexylmalonate, dimethyl isopentylisoheptylmalonate,
Isopentyl isoheptyl malonate diethyl, isopentyl isoheptyl malonate dipropyl, isopentyl isoheptyl malonate diisopropyl, isopentyl cyclopentyl malonate diethyl, isopentyl cyclohexylmalonate diethyl, isopentyl (2-cyclopentylethyl) malonate diethyl, isopentyl Diethyl (2-cyclohexylethyl) malonate, dimethyl isohexylisoheptylmalonate, diethyl isohexylisoheptylmalonate, dipropyl isohexylisoheptylmalonate, diisopropyl isohexylisoheptylmalonate, diethyl isohexylcyclopentylmalonate, iso Hexyl diethyl cyclohexyl malonate, isohexyl (2-cyclopentylethyl) diethyl malonate, isohexyl (2 -Cyclohexylethyl) diethyl malonate, cyclopentyl cyclohexyl diethyl malonate, cyclopentyl (2-cyclopentylethyl) malonate diethyl, cyclopentyl (2-cyclohexylethyl) malonate diethyl, cyclohexyl (2-cyclopentylethyl) malonate diethyl, cyclohexyl (2 Examples include diethyl-cyclohexylethyl) malonate and diethyl (2-cyclopentylethyl) (2-cyclohexylethyl) malonate. Especially preferred is diethyl isopropyl isopentyl malonate.

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 formula (I) may be co-ground and then halogenated to achieve high activation. After the magnesium halide alone or the co-ground of the magnesium halide and the silicon compound or the phosphorus compound, the titanium compound treatment and the halogenation treatment may be performed in the coexistence of the electron donating compound of the formula (I). Further, magnesium carboxylate or alkoxy magnesium, a titanium compound, a halogenating agent and an electron donating compound of the formula (I) may be heat-treated to be highly activated. The magnesium halide may be dissolved in an organic solvent or the like, and the electron-donating compound of the formula (I) may be allowed to act during or after the precipitation in the presence of the titanium compound. Further, a catalyst prepared by adding an electron-donating compound of the formula (I) or a titanium compound to the preparation process when the halogenating agent acts on alkylmagnesium may be used. Although the amount of the electron donating compound of the formula (I) remaining in the catalyst depends on the preparation method, when the electron donating compound of the formula (I) is abbreviated as ED, titanium: magnesium: ED (molar ratio) is
1: 1 to 1000: in the range of 10 ^{-6 to} 100, preferably
1: 2 to 100: 10 ^- in the range of ⁴ -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]

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, and 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), representative ones include alkyl dialumoxane 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 preferable, and trialkylaluminums are particularly preferable because they give preferable results.

The olefin used for the polymerization is generally an olefin having at most 18 carbon atoms, and typical examples thereof include ethylene, propylene, 1-butene, 4-
Methyl-1-pentene, 1-hexene, 1-octene 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. Further, the usage ratio of titanium atoms in the solid catalyst component is generally 0.5 or more in terms of molar ratio, preferably 2
Above all, 10 or more is particularly preferable. If the amount of the organoaluminum compound used is too small, the polymerization activity will be significantly reduced. It should be noted that 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 purpose can be achieved even in a very small amount, but usually 1 mol of the organoaluminum compound is used. It is used in a ratio of 0.01 to 5 mol, preferably 0.01 to 1.

An electron donating compound (D2) is optionally used in the preparation of the olefin polymerization catalyst according to the present invention. The electron donating compound (D2) is an organosilicon compound having an alkoxy group. , Nitrogen-containing compounds,
A phosphorus-containing compound and an oxygen-containing compound can be used. Among these, it is particularly preferable to use an organosilicon compound having an alkoxy group.

The electron-donating compound (D2) is used in a molar ratio of 0.001 to organoaluminum compound.
5, preferably in the range of 0.01-1.

Specific examples of the organosilicon compound having an alkoxy group include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraisobutoxysilane, trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane and triethylethoxysilane. , Ethylisopropyldimethoxysilane, propylisopropyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, isopropylisobutyldimethoxysilane, di (te
rt-Butyl) dimethoxysilane, tert-butylmethyldimethoxysilane, tert-butylethyldimethoxysilane, tert-butylpropyldimethoxysilane, tert-butylisopropyldimethoxysilane, tert-butylbutyldimethoxysilane, tert-butylisobutyldimethoxysilane, tert -Butyl (sec-butyl) dimethoxysilane, tert-butylamyldimethoxysilane, tert-butylhexyldimethoxysilane, tert-butylheptyldimethoxysilane, tert-butyloctyldimethoxysilane, tert-butylnonyldimethoxysilane, tert-butyldecyldimethoxysilane Silane, tert-butyl (3,3,3-trifluoromethylpropyl) dimethoxysilane, tert-
Butyl (cyclopentyl) dimethoxysilane, tert-butyl (cyclohexyl) dimethoxysilane, dicyclopentyldimethoxysilane, bis (2-methylcyclopentyl) dimethoxysilane, bis (2,3-dimethylcyclopentyl) dimethoxysilane, diphenyldimethoxysilane, phenyltriethoxy Silane, methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, isopropyltrimethoxysilane, butyltrimethoxysilane, i-butyltrimethoxysilane,
tert-butyltrimethoxysilane, sec-butyltrimethoxysilane, amyltrimethoxysilane, isoamyltrimethoxysilane, cyclopentyltrimethoxysilane, cyclohexyltrimethoxysilane, norbornanetrimethoxysilane, indenyltrimethoxysilane,
2-methylcyclopentyltrimethoxysilane, cyclopentyl (tert-butoxy) dimethoxysilane, isopropyl (tert-butoxy) dimethoxysilane, tert-butyl (isobutoxy) dimethoxysilane, tert-butyl (tert-butoxy) dimethoxysilane, texyltrimethoxy Examples thereof include silane, thexyl (i-propoxy) dimethoxysilane, and texyl (tert-butoxy) dimethoxysilane.

Specific examples of the nitrogen-containing compound include 2,
6-diisopropylpiperidine, 2,6-diisopropyl-4-
2,6-Substituted piperidines such as methylpiperidine, N-methyl-2,2,6,6, -tetramethylpiperidine, 2,5-diisopropylazolidine, N-methyl-2,2,5,5-tetra 2,5-Substituted azolidines such as methyl azolidine, N, N, N ', N'-tetramethylmethylenediamine, N, N, N', N'-substituted methylenediamines such as tetraethylmethylenediamine, 1, Substituted imidazolines such as 3-dibenzylimidazolidine and 1,3-dibenzyl-2-phenylimidazolidine are included. Specific examples of the phosphorus-containing compound include triethyl phosphite, tri n-propyl phosphite, triisopropyl phosphite, tri n-butyl phosphite, triisobutyl phosphite, diethyl n-butyl phosphite, and diethyl phenyl phosphite. Such as phosphite ester.

As the oxygen-containing compound, specifically, 2,
2,6-Substituted tetrahydrofurans such as 2,6,6-tetramethyltetrahydrofuran and 2,2,6,6-tetraethyltetrahydrofuran, 1,1-dimethoxy-2,3,4,5-tetrachlorocyclopentadiene, 9 Examples include dimethoxymethane derivatives such as 9,9-dimethoxyfluorene and diphenyldimethoxymethane.

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 prepolymerization is -20 to 100.
C., preferably in the range of -20 to 60.degree. In prepolymerization, a molecular weight modifier such as hydrogen can be used. Prepolymerization is 0.1 per 1 g of olefin polymerization catalyst.
~ 1000g, preferably 0.3-500g, particularly preferably 1-
Preference is given to producing 200 g of polymer. In carrying out the polymerization, the solid catalyst component of the present invention,
The organoaluminum compounds may be introduced separately into the polymerization vessel or they may be premixed. 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 ℃ to 180 ℃, practically 20 ℃ or more 13
It is below 0 ° 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.

[0027]

The present invention will be described in more detail with reference to the following examples. The melt flow rate (that is, MFR) in the examples and comparative examples is JIS K-6758.
Measured according to -1968. The heptane index (that is, HR) is the remaining amount in% after the obtained polymer was extracted with boiling n-heptane for 6 hours. 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.
Diethyl isopropyl isopentyl malonate (A), diethyl diisobutyl malonate (B), diethyl dicyclopentyl malonate (C), diethyl cyclobutane-1,1-dicarboxylate (D), diethyl isopropylmalonate (E), di-n -Diethyl butyl malonate (F).

(Example 1) Preparation of solid catalyst component 1 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) 20 g (0.21 mol), diethyl isopropyl isopentyl malonate 13.
6 g (0.05 mol), 3.0 ml of titanium tetrachloride and silicon oil as a grinding aid (Shin-Etsu Chemical TSS -451, 20 cs
) 3.0 ml under dry nitrogen flow, container for vibration ball mill (stainless steel cylindrical type, circular volume 1 L, diameter 10 mm
The magnetic balls of No. 2 were filled in about 50% by apparent volume). This was attached to a vibrating ball mill with an amplitude of 6 mm and co-pulverized for 15 hours to obtain a co-pulverized solid. 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 the solid portion was collected by filtration and washed with hexane to give 1 It was washed thoroughly until 1,2-dichloroethane was not detected. 30 this
After drying under reduced pressure at 40 ° C to 40 ° C to remove hexane, a solid catalyst component was obtained. When the obtained solid catalyst component was analyzed,
The titanium atom content of this solid catalyst component was 2.4% by weight. Polymerization and Physical Properties of Polymer 17 mg of solid catalyst component prepared by the above method, 91 mg of triethylaluminum, 61 mg of dicyclopentyldimethoxysilane were placed in a stainless steel autoclave with an internal volume of 3 L.
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.

(Examples 2 and 3, Comparative Examples 1 to 3) 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 electron donating compounds, and the polymerization was evaluated. I did. The results are shown in Table 1.

(Example 4) Preparation of solid catalyst component 2 9.5 g of anhydrous magnesium chloride (processed in the same manner as in Example 1) was added together with 50 ml of decane and 48.6 ml of 2-ethylhexyl alcohol under a nitrogen atmosphere. It was heated and dissolved in a round bottom flask at 130 ° C for 2 hours. Phthalic anhydride 2.
1 g was added and the mixture was further heated at 130 ° C. for 1 hour. The solution is cooled to room temperature, charged with 20 ml in a dropping funnel, added dropwise to 80 ml titanium tetrachloride at -20 ° C over 30 minutes, and the solution is added for 11 hours in 4 hours.
Raised to 0 ° C. Diethyl isopropyl isopentyl malonate 1.36 g (0.005 mol) and hexane 5 ml
Was slowly added dropwise. After dripping, 110 ℃, 2
Reacted in time. After removing the supernatant, 80 ml of titanium tetrachloride was newly introduced and heated at 110 ° C for 2 hours. Then,
The solid catalyst was washed 3 times with 100 ml of decane and then with hexane to obtain a solid catalyst. The amount of titanium supported was 2.6% by weight. Polymerization and physical properties of polymer The solid catalyst component produced by the above method was placed in a stainless steel autoclave with an internal volume of 3 L.
8.8 mg, triethylaluminum 91 mg, and dicyclopentyldimethoxysilane 61 mg were added, 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.

(Examples 5 and 6, Comparative Examples 4 to 6) Solid catalyst components were prepared in the same manner as in Example 4 except that the compounds shown in Table 1 were used as the electron-donating compounds, and the polymerization was evaluated. I did. The results are shown in Table 1.

Example 7 Production of Solid Catalyst Component 3 A 300 ml round bottom flask that had been thoroughly dried in a nitrogen stream was charged with 5.0 g of diethoxymagnesium, 1.36 g (0.005 mol) of diethyl isopropylisopentylmalonate and methylene chloride. 25 ml was added. It was stirred under reflux for 1 hour and then the suspension was pumped into 200 ml of titanium tetrachloride at room temperature. The temperature was gradually raised to 110 ° C. and the reaction was carried out with stirring for 2 hours.
After completion of the reaction, after precipitation, the precipitated solid was filtered and decane at 110 ℃ was added.
Washed 3 times with 200 ml. 200 ml of new titanium tetrachloride
Was added and reacted at 120 ° C. for 2 hours. After the reaction was completed, the precipitated solid was separated by filtration and washed 3 times with 200 ml of decane at 110 ° C,
It was washed with hexane at room temperature until chlorine ions were not detected with hexane. The content of titanium atoms in this catalyst component was 3.3% by weight. Polymerization and physical properties of polymer 2.5 g of solid catalyst component produced by the above method in a stainless steel autoclave with an internal volume of 3 L, 91 mg of triethylaluminum, 61 of dicyclopentyldimethoxysilane.
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.

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

Example 10 Production of Solid Catalyst Component 4 12.8 g of magnesium metal, 88 ml of ethyl orthoformate (0.53
mol) and and 1,2-dibromoethane as reaction initiator
Add 0.5 ml to keep the suspension at 55 ° C and add 1 more hexane.
5 ml of a solution prepared by dissolving 80 ml (0.80 mol) of n-butyl chloride in 00 ml was added and stirred for 50 minutes, and the rest was added dropwise over 80 minutes. The reaction was carried out at 70 ° C for 4 hours with stirring to obtain a solid product. It was washed 6 times with hexane at 50 ° C. Charge 6.3 g of the solid product and 50 ml of decane into the reactor at room temperature 2,
A mixed solution of 2.0 ml of 2,2-trichloroethanol and 11 ml of decane was added dropwise over 30 minutes, and after the completion, the mixture was stirred at 80 ° C for 1 hour. The solids were filtered, washed with 100 ml of hexane four times, and further washed with 100 ml of toluene twice. Toluene 4 in the solid
Add 0 ml and 60 ml titanium tetrachloride and raise the temperature to 90 ° C. Diethyl isopropyl isopentylmalonate 2.04 g (0.0075 m
ol) and toluene (5 ml) added dropwise over 5 minutes, then
The mixture was stirred at 0 ° C for 2 hours. Then, the solid matter was filtered at 90 ° 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, and the mixture was stirred at 120 ° C for 2 times.
The solid substance obtained by stirring for 1 hour was filtered at 110 ° C. and washed with 100 ml of hexane at room temperature seven times to obtain a solid titanium catalyst component. Polymerization and physical properties of the polymer 4.6 mg of the solid catalyst component produced by the above method, 91 mg of triethylaluminum, and 61 of dicyclopentyldimethoxysilane were placed in a stainless steel autoclave with an internal volume of 3 L.
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 80 ° C. After 1 hour, the content gas was released to terminate the polymerization. The polymerization results are shown in Table 1.

(Examples 11 and 12, Comparative Examples 10-1)
2) A solid catalyst component was prepared in the same manner as in Example 10 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.

[0037]

[Table 1]

[0038]

EFFECTS OF THE INVENTION It is possible to provide a solid catalyst component for olefin polymerization, a catalyst for olefin polymerization, and a method for producing an olefin polymer which exhibit high activity and high stereoregularity without having any safety and health problems. Became.

[Brief description of drawings]

FIG. 1 is a flowchart showing a manufacturing process of the present invention.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shintaro Inazawa, Oita City, Oita Prefecture, No. 2 Nakasu, Showa Denko K.K.

Claims (7)

[Claims] 1. In the presence of one or more electron donating compounds represented by the following general formula (I) during or after molding 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 and R ² are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, and they may be the same or different from each other. R ³ and R ⁴ are each 1 Two or more
It is a saturated hydrocarbon group having 3 to 20 carbon atoms or a cyclic saturated hydrocarbon group containing a primary carbon or a tertiary carbon, which may be the same or different from each other. ) 2. An electron-donating compound represented by the general formula (I) wherein R ¹ and R ² are a methyl group, an ethyl group, a propyl group,
R ³ and R ⁴ which are the same or different hydrocarbon groups selected from isopropyl group, butyl group, isobutyl group, tert-butyl group and 2-ethylhexyl group.
Is an identical or different saturated hydrocarbon group having 3 to 10 carbon atoms, each containing one or more secondary carbon or tertiary carbon, and the solid catalyst for olefin polymerization according to claim 1. Method of manufacturing ingredients. 3. An electron donating compound represented by formula (I) wherein R ¹ and R ² are a methyl group, an ethyl group, a propyl group,
The solid catalyst component for olefin polymerization according to claim 1, which is the same or different hydrocarbon group selected from isopropyl groups, R ³ is an isopropyl group, and R ⁴ is an isopentyl group. Manufacturing method. 4. An olefin polymerization catalyst containing a solid catalyst component for olefin polymerization obtained by the method according to claim 1 and an organoaluminum compound. 5. An olefin polymerization catalyst comprising the solid catalyst component for olefin polymerization obtained by the method according to claim 1, an organoaluminum compound, and an electron donating compound as a third component. 6. The third component, which is an electron-donating compound, is at least one compound selected from an organosilicon compound having an alkoxy group, a nitrogen-containing compound, a phosphorus-containing compound, and an oxygen-containing compound. Olefin polymerization catalyst. 7. A method for producing an olefin polymer, in which olefins are polymerized using the catalyst for olefin polymerization according to any one of claims 4 to 6.