JPH04178406A - Production of catalyst for polymerizing olefin and method for polymerizing olefin - Google Patents

Abstract

PURPOSE:To obtain the subject catalyst capable of providing a highly stereoregular polymer in high yield by carrying out contact treatment of a solid catalyst component consisting essentially of an Mg compound, a Ti compound and a halogen-containing compound with a specific alkoxy ester and a transition metallic compound in forming the aforementioned solid catalyst component, etc. CONSTITUTION:A solid catalyst component consisting essentially of a magnesium compound (e.g. anhydrous magnesium chloride), a titanium compound (e.g. titanium tetrachloride) and a halogen-containing compound is subjected to contact and reaction treatment with an alkoxy ester compound (e.g. ethyl 3-ethoxy-2- phenylpropionate) expressed by the formula (R<1> to R<4> are hydrocarbon group; Z is aliphatic hydrocarbon group in which H thereof may be replaced by aromatic hydrocarbon; i, j and k are integers of 0-3; the sum total of i, j and k is >=1) and a transition metallic compound of group 7A or 8 (e.g. ferrous chloride) of the periodic table to afford the objective catalyst component.

Description

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

[Conventional technology]

Conventionally, many manufacturing methods have been proposed that use solid catalyst components containing magnesium, titanium, a halogen compound, and an electron donor (internal donor) as essential components. Organic carboxylic acid esters are often used, but
Unless the ester is removed by washing with an organic solvent, the ester odor remains in the polymer.

It was also insufficient in terms of activity and stereospecificity.

In order to overcome these drawbacks, several proposals have been made regarding specific esters, ie, esters having an ether moiety. A method using anisate esters (Japanese Unexamined Patent Publication No. 16986/1986), a method using furancarboxylic esters (Japanese Unexamined Patent Publication No. 129205/1989,
The methods using 2-ethoxyethyl acetate (Japanese Patent Application Laid-open No. 61-287908, etc.) fall under this category. However, even when these esters are used, they do not have industrially satisfactory performance in terms of activity and stereospecificity, and there has been a desire to develop catalysts with even higher performance.

Against this background, the present applicant has previously proposed a method for producing an olefin polymerization catalyst using an alkoxy ester compound as an internal donor and a method for polymerizing olefins (Patent Application No. 1-1-1).
42717 (hereinafter referred to as the prior invention), and according to the method of the prior invention, it was possible to obtain a highly stereoregular polymer with high activity.

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

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

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

[Means to solve the problem]

As a result of intensive research to solve the above-mentioned problems, by using transition metal compounds of Groups 7A and 8 of the periodic table in the same catalyst preparation as in the earlier invention, a polymer obtained by the method of the earlier invention was obtained. It was discovered that a polymer having even better stereoregularity was produced by doing so, and the present invention, which has the following outline, was achieved. That is, in the present invention, during or after the formation of a solid catalyst component containing a magnesium compound, a titanium compound, and a halogen-containing compound as essential components, the hydrogen atom of the following formula group 2 may be substituted with an aromatic hydrocarbon. aliphatic hydrocarbon group, and i, j, k are 0 to 3
is an integer, and the sum of i, j, is 1 or more. ) A solid catalyst for olefin polymerization, characterized by contacting and reacting one or more alkoxy ester compounds represented by the following with one or more transition metal compounds of Groups 7A and 8 of the Periodic Table. The present invention provides a method for producing the component and a method for polymerizing olefins, which is characterized by using a catalyst system containing the solid catalyst component.

The present invention will be explained in detail below.

Preparation of solid catalyst component for olefin polymerization The magnesium compound used in the preparation of the solid catalyst component in the present invention is not particularly limited, and is used as a raw material for the preparation of high-activity catalysts for ordinary olefin polymerization and copolymerization. can be used. That is,
Magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide; alkoxymagnesiums such as dimethoxymagnesium, jetoxymagnesium, dipropoxymagnesium, dibutoxymagnesium, diphenoxymagnesium; magnesium laurate, magnesium stearate, acetic acid Examples include magnesium carboxylates such as magnesium; alkylmagnesiums such as dimethylmagnesium, diethylmagnesium, butylethylmagnesium, and the like.

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

Titanium compounds used in the present invention include titanium halides such as titanium tetrachloride, titanium trichloride, titanium tetrabromide, and titanium tetrahydride; tetramethoxytitanium, tetraethoxytitanium, tetrapropoxytitanium, and tetrabutoxytitanium. , alkoxytitanium such as tetraphenoxytitanium; ethoxytitanium trichloride, butoxytitanium trichloride, phenoxytitanium trichloride,
Examples include alkoxytitanium halides such as dibutoxytitanium dichloride and tributoxytitanium chloride. Further, these various titanium compounds can be used alone or in combination of two or more. Preferred is a halogen-containing tetravalent titanium compound, particularly titanium tetrachloride.

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

The alkoxy ester compound used in the present invention has the general formula: (R'O), CR20), (R30)k-Z-C
It is expressed as OOR' (1).

When any one of R1, R2, R3, and R4 is an aliphatic or alicyclic hydrocarbon group, an aliphatic group having 1 to 12 carbon atoms or an alicyclic hydrocarbon group having 4 to 12 carbon atoms is preferable. Specifically, methyl, ethyl, n-propyl, i-propyl, n
-butyl, i-butyl, 5ec-butyl, tert-butyl, pentyl, hexyl, 3-methylpentyl, je
rt-pentyl, heptyl, i-hexyl, octyl,
Nonyl, decyl, 2.3.5-)limethylhexyl, undenyl, dodecyl, vinyl, allyl, 2-hexenyl, 2.4hexagenyl, impropenyl, cyclobutyl, cyclopentyl, cyclohexyl, tetramethylcyclohexyl, cyclohexenyl, Examples include norbornyl.

These hydrogen atoms may be substituted with halogen atoms.

When any of R1, R2, R3, and R4 is an aromatic or polycyclic hydrocarbon group, an aromatic group having 1 to 1 B carbon atoms or a polycyclic hydrocarbon group having 7 to 18 carbon atoms, or an aliphatic group containing them; Group hydrocarbon groups are preferred. Specific examples include phenyl, tolyl, ethylphenyl, xyl, cumyl, trimethylphenyl, tetramethylphenyl, naphthyl, methylnaphthyl, anthranyl, benzyl, diphenylmethyl, and indenyl.

These hydrogen atoms may be substituted with halogen atoms.

2 is an aromatic group whose hydrogen atom has 6 to 18 carbon atoms, or
An aliphatic hydrocarbon group having 1 to 20 carbon atoms (including an alicyclic hydrocarbon group) which may be substituted with a polycyclic group having 7 to 18 carbon atoms is preferable, and specifically, methylene, ethylene, etc. ,
Ethylidene, trimethylene, tetramethylene, pentamethylene, hexamethylene, propenylene, etc. Substituted examples include methylmethylene, n-butylmethylene, ethylethylene, isopropylethylene, teI
l-butylethylene, 5ec-butylethylene, lerl
−Amylethylene, adamantaneethylene, bicyclo(
2,2,1) Heptylethylene, phenylethylene, tolylethylene, xylylethylene, diphenyltrimethylene, 1,2cyclopentylene, 1.3cyclopentylene, 3-cyclohexene-1,2ylene, dimethylethylene, indenyl 1 , 2ylene, etc. can be exemplified. Hydrogen atoms may be substituted with halogen atoms.

Specific compounds include methyl methoxy acetate, ethyl methoxy acetate, butyl methoxy acetate, phenyl methoxy acetate, methyl ethoxy acetate, ethyl ethoxy acetate, butyl ethoxy acetate, phenyl ethoxy acetate, ethyl n-propoxy acetate, i-propoxy-acetic acid. Ethyl, methyl n-butoxyacetate, i-butoxyethyl acetate, n-hexyloxyethyl acetate, 5eC-hexyloxyoctyl acetate, 2-methylcyclohexyloxymethyl acetate, 3
-Methyl methoxypropionate, ethyl 3-methoxypropionate, butyl 3-methoxypropionate, ethyl 3-ethoxypropionate, butyl 3-ethoxypropionate, n-octyl 3-ethoxypropionate, 3-
Dodecyl ethoxypropionate, Pentamethylphenyl 3-ethoxypropionate, Ethyl 3-(i-propoxy)propionate, Butyl 3(i-propoxy)propionate, Allyl 3-(n-propoxy)propionate, 3-(n -butoxy)cyclohexyl propionate, ethyl 3-neopentyloxypropionate, 3-(
Butyl n-octyloxy)propionate, 3-(2,
Methyl 6dimethylhexyloxy)propionate, 3-
(3,3-dimethyldecyloxy)octyl propionate, ethyl 4-ethoxybutyrate, cyclohexyl 4-ethoxybutyrate, 5-(n-propoxy)octyl valerate,
Ethyl 12-ethoxylaurate, ethyl 3-(1-indenoxy)propionate, methyl 3-methoxyacrylate, methyl 2-methoxyacrylate, methyl 2-ethoxyacrylate, ethyl 3-phenoxyacrylate, 2
-ethyl methoxypropionate, 2- n-butyl (i-propoxy)butyrate, 2-methyl ethoxyisobutyrate, 2-
Phenyl cyclohexyloxyisovalerate, 2-ethoxy, butyl 2-phenylacetate, allyl 3-neopentyloxybutyrate, 3-ethoxy, methyl 3(0-methylphenyl)propionate, 3-ethoxy, 2-(o-methylphenyl) ) Ethyl propionate, 3-ethoxy.

Ethyl 2-mesitylpropionate, 3-ethoxy.

2-ter+ethyl butylpropionate, 3-ethoxy, ethyl 2-tertamylpropionate, 3-ethoxy, ethyl 2-adamantanepropionate, 3-ethoxy, ethyl 2-bicyclo(2,2,I)butylpropionate , 3ethoxy, ethyl 3-phenylpropionate, 3ethoxy, ethyl 3-mesitylpropionate, 3
Ethoxy, 31ert-butylpropionate ethyl, 3
Ethoxy, ethyl 3-teu amylpropionate, 4-
Ethoxy, 2-(t-butyl)propyl butyrate, 5-methoxy, 2-methyl, ethyl 1-naphthylnonanoate, 2-methoxycyclopentanecarboxylic acid ethyl ester, 2-ethoxycyclohexanecarboxylic acid butyl ester, 3-
(Ethoxymethyl)tetralin-2-acetic acid isoprobyl ester, 8-butoxy.

Decalin-1-carboxylic acid ethyl ester, 3-ethoxynorbornane-2-carboxylic acid methyl ester, 2-
Methyl (phenoxy)acetate, ethyl 3-(p-flexoxy)propionate, methyl 4-(2-naphthoxy)butyrate, butyl 5-carbacroxyvalerate, methyl 2-phenoxypropionate, 3-(4methylphenoxy)-2-phenoxy Examples include ethyl enylpropionate, 2-phenoxy, cyclohexanecarboxylic acid ethyl ester, and ethyl thiophene-3-oxyacetate.

Among these, an alkoxy ester compound represented by the following general formula (n) is preferred.

Here, R5 and R6 are aliphatic hydrocarbons having 1 to 20 carbon atoms, R7 and R8 are hydrogen atoms or aliphatic hydrocarbons having 1 to 20 carbon atoms, and Y is a chain hydrocarbon having 1 to 4 carbon atoms. A group in which hydrogen is substituted with an aliphatic hydrocarbon, an aromatic hydrocarbon, or a polycyclic hydrocarbon, or a ring hydrocarbon group having 1 to 12 carbon atoms. Particularly preferred is an alkoxy ester in which Y is a chain hydrocarbon and has a bulky substituent having 4 or more carbon atoms at the 2nd or 3rd position counting from the carboxyl group. Also preferred are alkoxy ester compounds having a 4- to 8-membered cycloalkane. Specifically, 3-ethoxy, ethyl 2-phenylpropionate, 3-ethoxy,
Ethyl 2-tolylpropionate, 3-ethoxy, ethyl 2-mesitylpropionate, 3-butoxy, ethyl 2-(methoxyphenyl)propionate, 3-1-propoxy, methyl 3-phenylpropionate, 3-ethoxy, Ethyl 3-phenylpropionate, 3-ethoxy 23
-rerr-butylpropionate ethyl, 3-ethoxy.

Ethyl 3-adamantylpropionate, 3ethoxy, 2
-terf ethyl butylpropionate, 3-ethoxy,
2-1crtethyl amylpropionate, 3-ethoxy, ethyl 2-adamantylpropionate, 3-ethoxy, 2-bicyclo[2,2,I)butylpropionate, 2-ethoxy, ethyl cyclohexanecarboxylate, 2( ethoxymethyl), methyl cyclohexanecarboxylate, methyl 3-ethoxy norbornane-2-carboxylate, and the like.

The transition metal compounds of Groups 7A and 8 of the periodic table used in the present invention include manganese, technetium, and
Examples include many compounds such as rhenium, group VIII iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, and platinum. Examples include chelate compounds represented by halides, alkoxides, carboxylates, and acetylacetonate salts of these transition metals.

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

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

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

The amount of the titanium compound to be used is preferably in the range of 1xlO' to 1000 in molar ratio to the amount of the magnesium compound used, preferably in the range of 1,QI to 100.If necessary, a halogen compound However, when used, the amount used depends on the amount of magnesium used, regardless of whether the titanium compound, magnesium compound, or transition metal compound of Group 7A or 8 of the Periodic Table contains halogen. lX1O-2~ in molar ratio to the amount used
It is good within the range of 1000, preferably Q, I~I(1(
It is within the range of l.

The amount of the alkoxy ester compound that can be represented by the formulas (I) and (II) is preferably in the range of 1X10' to 10, preferably in the range of 001 to 5, based on the amount of the magnesium compound used. It is within.

The amount of the transition metal compound of Group 8 of Periodic Table 7A is 1Xl0 in molar ratio to the amount of the magnesium compound used.
It is preferably within the range of '~5 (and preferably within the range of 0.01~1).

The method for preparing the solid catalyst component used in the present invention is as follows:
magnesium compounds, titanium compounds and electron donors,
Furthermore, if necessary, a conventionally known method for preparing a solid catalyst component obtained by contacting and reacting with an auxiliary agent such as a halogen-containing compound temporarily or stepwise can be applied. That is, (I) during or after the formation of a known solid catalyst component.

(II) One or more alkoxy ester compounds that can be represented by formula (II) and 7A of the periodic table.

Temporarily with one or more group 8 transition metal compounds,
Alternatively, contact and reaction may be carried out in stages. As a specific example of applying a known method, (1) Magnesium chloride, a titanium compound, an alkoxy ester compound, and a transition metal compound of group 7A or 8 of the periodic table are brought into contact and reacted in any order, and then a liquid hydrocarbon is formed. How to wash properly.

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

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

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

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

Typical organoaluminum compounds in the present invention have the general formula AI R, X3-! Examples include compounds represented by: In the above formula, R9 has 1 to 2 carbon atoms
0 hydrocarbon groups are shown, and aliphatic hydrocarbon groups are particularly preferred. X represents halogen, and 2 represents a number from 1 to 3. Specific examples of this organoaluminum compound include trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum, dimethylaluminum dichloride, diethylaluminium dichloride,
Examples include methylaluminum dichloride and ethylaluminum dichloride, but trialkylaluminum is preferably used. Organoaluminum compounds containing two or more AI atoms bonded via zero or N atoms, typically aluminoxanes, can also be used.

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

When carrying out a polymerization reaction of α-olefins having 3 or more carbon atoms, this is added to the catalyst system consisting of the titanium-containing solid catalyst component and the organoaluminum compound according to the present invention for the purpose of improving the stereoregularity of the resulting polymer. Many compounds that have been proposed for use in olefin polymerization catalysts and have effects on stereoregularity can be further added.

Typical compounds used for this purpose include:
Aromatic carboxylic acid ester, 5i-0-C or 5i-
Silicon compounds having N-C bonds, acetal compounds,
Examples include germanium compounds having a Ge-0-C bond, nitrogen or oxygen heterocyclic compounds having an alkyl substituent, and the like.

Specific examples of these compounds include ethyl benzoate, butyl benzoate, ethyl p-toluate, ethyl p-anisate, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, diphenyljethoxysilane, -n-propyldimethoxysilane, cyclohexylmethyldimethoxysilane, tetraethoxysilane, t-butylmethyldimethoxydisilane, benzophenone, dimethoxyacetal, benzophenone jetoxyacetal, acetophenone dimethoxyacetal, t-butylmethylketone dimethoxyacetal, diphenyldimethoxygermane , phenyltriethoxygermane, 2,2.6.6-titramethylpiperidine, 2.2.6.6-tetramethylpyran, and the like.

Among these, Si-0-C or Si-N
Silicon compounds and acetal compounds having a -C bond are preferred, and combinations with compounds having a Si-0-C bond are particularly preferred.

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

The amount of the stereoregularity improver used for the purpose of improving the stereoregularity of the α-olefin polymer is:
When the solid catalyst component of the present invention is used, the purpose can be achieved even in a very small amount, but it is usually 0.001 to 5 mol, preferably 0.01 to 1 mol, per 1 mol of the organoaluminum compound. used in molar proportions.

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

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

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

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

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

〔Example〕

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

In addition, in the Examples and Comparative Examples, the stereoregularity (isotacticity) of the produced polymer was evaluated by the boiling hebutane extraction method. That is, by extracting the produced polymer with boiling hebutane for 6 hours, the weight percent of the insoluble portion was determined as the isotactic index (1,1,). The melt flow index (MFI) of the produced polymer is
JIS K-6758 for powder mixed with 0.2% of 2,6-sheette+t-butyl-4-methylphenol
Measurements were made under conditions of a temperature of 230° C. and a load of 2.16 kg.

In each example, each compound (organic solvent, olefin, hydrogen,
Titanium compounds, magnesium compounds, alkoxy ester compounds, periodic table 7A, group 8 transition metal compounds,
(halogen-containing compounds, stereoregularity improvers, etc.) are all substantially water-free.

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

Example 1 Preparation of solid catalyst component Anhydrous magnesium chloride: M g C12 (obtained by heating and drying commercially available anhydrous magnesium chloride in a nitrogen stream at about 500°C for 15 hours) 30 g (315 mol) , anhydrous ferrous chloride:
FeCl2 (commercially available ferrous chloride tetrahydrate: F e C1
(obtained by heating and dehydrating 4HO at about 200°C for 8 hours in a hydrogen chloride stream) 2.
85g (22.5mmol), 3-ethoxy-2-
Ethyl phenylpropionate 4.65g (23mmo
1) was placed in a container for a vibrating ball mill (cylindrical stainless steel, filled with porcelain balls having an internal volume of 11 and a diameter of ]0nnn, approximately 50% by apparent volume). This was attached to a vibrating ball mill with an amplitude of 6 and a frequency of 3 Hr, and co-pulverization was performed for 20 hours to obtain a co-pulverized solid. 5 g of the obtained co-pulverized material was mixed with I (10 ml of titanium tetrachloride: T I
Cj! 4 and reacted at 120°C for 2 hours. The solid product was collected by filtration and diluted with n-decane (1000ml) at 80'C and n-hexane (1000ml) at room temperature for 6 times.
1) four times successively. This was dried under reduced pressure at 40°C to obtain the desired solid catalyst component. When the obtained solid catalyst component was analyzed by atomic absorption spectrophotometry, the content of titanium atoms in this solid catalyst component was 2.0% by weight.

Polymerization of propylene and physical properties of the resulting polymer A solid catalyst component prepared by the above method was placed in a stainless steel autoclave with an internal volume of 31 cm, and 91 cm of triethylaluminum.
and 20 μm of diphenyldimethoxysilane were added, and then immediately 760 g of propylene and 0.1 g of hydrogen were charged. The temperature of the autoclave was raised and the internal temperature was maintained at 70°C. After 1 hour, the content gas was released to terminate the polymerization.

As a result, 374 g of polypropylene was obtained. That is, the polymerization activity is +8700-polypropylene/g-solid catalyst component/time (hereinafter, g-P P/g-cat
・H), 935 kg-polypropylene/g-titanium in the solid catalyst component ・H (hereinafter referred to as dazzling-PP/g-T
(abbreviated as i-h).

1.1. of the produced polymer. was 97.4%. MFI is 7.8g-polypropylene 10 minutes (hereinafter referred to as g-P
P/l0II+in).

Comparative Example 1 Preparation of solid catalyst component Solid was prepared in the same manner and preparation conditions as in Example 1, except that FeCl2 was not used when co-pulverizing MgCl2 and ethyl 3-ethoxy-2-phenylpropionate. The catalyst components were prepared.

The content of titanium atoms in the obtained solid catalyst component was 2.4
wj%.

Polymerization of propylene and evaluation of the resulting polymer Propylene polymerization was carried out using the same method and polymerization conditions as in Example 1. 32
0 g of polypropylene was obtained, and the polymerization activity was 16 [IQ
(Ig-P P/g-cat ・h.

It was 670 kg-PP/g-Ti-h. The I, I, of the produced polymer was 957%. MFI is 5.8
g - P P / 10 m1n.

Examples 2 to 10 Using the alkoxy ester compounds shown in Table 1 instead of ethyl 3-ethoxy-2-phenylpropionate,
A solid catalyst component was prepared using the same method and preparation conditions as in Example 1. Propylene polymerization was carried out using the same method and polymerization conditions as in Example 1.

Comparative Examples 2 to 10 Using the alkoxy ester compounds shown in Table 1 instead of ethyl 3-ethoxy-2-phenylpropionate,
A solid catalyst component was prepared using the same method and preparation conditions as in Example 1. Propylene polymerization was carried out using the same method and polymerization conditions as in Example 1.

Examples 11 to 14 Using the solid catalyst component of Example 1, propylene was produced in the same manner and under polymerization conditions as in Example 1, except that the stereoregularity improver added during polymerization was changed to those shown in Table 2. Polymerization was performed.

Example 15~! 6 When preparing the solid catalyst component, anhydrous manganese chloride (M
n Cl 2 ), anhydrous cobalt chloride (Co Cl 2 )
) was used, but a solid catalyst component was prepared using the same method and preparation conditions as in Example 1. Furthermore, MnC1! , C
oCJ2 was obtained by heating and dehydrating commercially available anhydrides at about 200° C. for 8 hours in a hydrogen chloride stream.

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

Examples 17 to 20 The same method and preparation as in Example 1 except that the amount of MgCl, Fe (12゜ethyl 3-ethoxy-2-phenylpropionate used) was changed to that shown in Table 4 for preparing the solid catalyst component. A solid catalyst component was prepared under the following conditions.Propylene polymerization was carried out under the following conditions.
The polymerization was carried out using the same method and polymerization conditions as in Example 1.

Comparative Examples 11 to 13 Solid catalyst components were prepared using the same method and preparation conditions as in Example 1, using the electron donor (internal donor) shown in Table 5 instead of ethyl 3-ethoxy-2-phenylpropionate. . Propylene polymerization was carried out using the same method and polymerization conditions as in Example 1.

Example 21 Preparation of solid catalyst component 9, 5[1 g (10(1+n+nol)) of anhydrous magnesium chloride (treated in the same manner as in Example 1) and 1
．． 80 g (14,2+nmol) of anhydrous iron chloride (treated in the same manner as in Example 1) was mixed with 50 ml of n-decane and 47 ml of 2-ethylhexyl alcohol in a round bottom flask under a nitrogen atmosphere at 130°C. The mixture was heated and dissolved for 2 hours. 2.1 g of phthalic anhydride was added to this solution, and the mixture was further heated at 130° C. for 1 hour. Cool this solution to room temperature, add 50ml to a dropping funnel, and add 12ml over 1 hour.
The mixture was dropped into 200 ml of titanium tetrachloride at 0°C, and the temperature was raised to 110°C over 4 hours. 278g (12,5
mmol) of ethyl 3-ethoxy-2-phenylpropionate was slowly added dropwise. After dropping, heat at 80℃ for 2 hours.
Allowed time to react. After the reaction, remove the supernatant and add a new
ml of titanium tetrachloride was introduced and reacted at 80°C for 2 hours. The supernatant was then removed, and n-decane (l
n-hexane (looml) at room temperature 6 times
The target solid component was obtained by washing the product four times with water and drying it under reduced pressure at 40'C.

The content of titanium atoms in the obtained solid catalyst component was 18% by weight.

Polymerization of propylene and physical properties of the resulting polymer Propylene polymerization was carried out in the same manner as in Example 1.

400 g of polypropylene was obtained, and the polymerization activity was 200
00g-PP/g-cal-h, IIlOkg-P
It was P/g-Ti·h. I, I, of the produced polymer
was 98.0%. The MFI of the produced polymer is 52g-
There was PP/l11m1n.

Examples 22 to 23 When preparing the solid catalyst component, anhydrous manganese chloride (MnCj!) was used instead of FeCl20 for the group 7A and 8 transition metal compound components.
), a solid catalyst component was prepared using the same method and preparation conditions as in Example 21, except that anhydrous cobalt chloride (Co C12) was used. Propylene polymerization was carried out using the same method and polymerization conditions as in Example 1 (Table 6).

〔Effect of the invention〕

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

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

These effects have extremely important meaning in industrial processes.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a flowchart 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 containing a magnesium compound, a titanium compound, and a halogen-containing compound as essential components, the following general formula (I) (R^1O)_i
(R^2O)_j(R^3O)_k-Z-COOR^4
(I) (where R^1, R^2, R^3 and R^4
is a hydrocarbon group, Z is an aliphatic hydrocarbon group whose hydrogen atom may be substituted with an aromatic hydrocarbon, and i, j, k are integers from 0 to 3, and the sum of i, j, k is 1 or more. ) and one or more alkoxy ester compounds represented by 7A of the periodic table.
, a method for producing a solid catalyst component for olefin polymerization, which comprises contacting and reacting with a Group 8 transition metal compound. (2) A method for polymerizing olefins, which comprises using a catalyst system containing the catalyst component according to claim (1).