JPH02289604A - Preparation of olefin polymerization catalyst and polymerization of olefin - Google Patents

Abstract

PURPOSE:To prepare the subject polymerization catalyst giving highly stereoregular polymers in high yields by forming a solid catalyst component comprising a Mg compound, a Ti compound and a halogen-containing compound as essential components and subsequently treating the catalytic component with a specific alkoxy ester compound. CONSTITUTION:A solid catalyst component comprising a magnesium compound (e.g. magnesium chloride), a titanium compound (e.g. titanium tetrachloride) and a halogen-containing compound (e.g. 1,2-dichloroethane) as essential components is formed and simultaneously or subsequently treated with one kind or more of alkoxy ester compounds (e.g. 3-ethoxy-2-phenylpropionic acid ethyl ester) of the formula [R<1>-R<4> are aliphatic hydrocarbon, alicyclic hydrocarbon, aromatic hydrocarbon, heterocyclic hydrocarbon, etc.; Z is H, (substituted) aliphatic or alicyclic hydrocarbon; i, j, k are 0-3; the sum of i, j and k is 1 or more] to provide the objective polymerization catalyst component.

Description

Detailed Description of the Invention (1) Industrial Application Field The present invention relates to a high-performance catalyst composition that exhibits a highly active action when subjected to the polymerization or copolymerization of olefins, and particularly relates to a high-performance catalyst composition having a carbon number of 3 or more. - This invention relates to a method for producing a catalyst component for olefin polymerization and a method for polymerizing olefins, which can provide a highly stereoregular polymer in high yield when applied to the polymerization of olefins.

(2) Prior Art 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 catalyst 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. Methods using anisate esters (Japanese Unexamined Patent Publication No. 48-16986), methods using furancarboxylic esters (Japanese Unexamined Patent Publications Nos. 59-129205 and 54-136590), 2-ethoxyethyl acetate A method using
Publication No. 7908 (Kasa) falls 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.

(3) Problems to be Solved by the Invention The purpose of the present invention is to provide a catalyst system that provides a highly active and highly stereoregular pfr a form, which was insufficient in the prior art. .

(4) Means for Solving the Problems As a result of intensive research to solve the above problems, we have arrived at the present invention, which has the following outline. That is, in the present invention, the following general formula (1) fR'ol. fR20) j (R30
1 , -Z-(:0011'(here 11', 11
2. R3 and R4 are groups selected from aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, polycyclic hydrocarbons, and heterogeneous compounds, and Z is a group whose hydrogen atom is an aromatic group or a polycyclic group. an aliphatic or alicyclic hydrocarbon group which may be substituted with , and i, j, k are integers from ro to 3, and the sum of j, h is 1 or more. ) A method for producing a catalyst component for olefin polymerization, characterized in that the treatment is carried out in the presence of 1f weight or 2 fI or more of an alkoxy ester compound represented by It's in the method.

The present invention will be explained in detail below.

Magnesium compounds used in the present invention include magnesium halides such as magnesium chloride and magnesium bromide; alkoxymagnesiums such as ethoxymagnesium and isobropoxymagnesium; magnesium carboxylates such as magnesium laurate and magnesium stearate. ; Examples include alkylmagnesiums such as butylethylmagnesium. Moreover, a mixture of two or more of these compounds may be used. Preferably, magnesium halide is used or magnesium halide is formed during catalyst formation. More preferably, the halogen is chlorine.

Titanium compounds used in the present invention include titanium halides such as titanium tetrachloride, titanium trichloride, and titanium tetrabromide; titanium alkoxides such as titanium butoxide and titanium ethoxide; and alkoxytitanium halides such as phenoxytitanium chloride. etc. can be exemplified. Moreover, a mixture of two or more of these compounds may be used. Preferred is a halogen-containing tetravalent titanium compound, particularly titanium tetrachloride.

The halogen-containing compounds used in the present invention are those in which the halogen is fluorine, chlorine, bromine, or iodine, preferably chlorine, and in fact. Examples of specific compounds include titanium halides such as titanium tetrachloride and titanium tetrabromide, silicon halides such as silicon tetrachloride and silicon tetrabromide, phosphorus trichloride, and pentachloride, although they depend on the catalyst preparation method. Phosphorus halides such as phosphorus are typical examples, but depending on the preparation method, halogenated hydrocarbons, halogen molecules, and hydrohalic acids (e.g., H (Jl, HBr, HI, etc.) may also be used. .

The alkoxy ester compound used in the present invention has the general formula (R O). (RO). (RO)-Z-CO
It is expressed as OR'I J k (I).

Rl, R2, R3, and R4 are groups consisting of one or more of aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, polycyclic hydrocarbons, and heterocyclic compounds. These may be the same or different. When this is an aliphatic or alicyclic hydrocarbon group, it is preferably an aliphatic or alicyclic hydrocarbon group having 1 to 12 carbon atoms. Specifically, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-
Butyl, See-butyl, L-butyl, pentyl, hexyl, 3-methylpentyl, L-pentyl, hebutyl, i-hexyl, octyl, nonyl, decyl, 2,3.5-trimethylhexyl, undenyl, dodecyl, vinyl, Examples include allyl, 2-hexenyl, 2.4-hexadienyl, isopropenyl, cyclobutyl, cyclobentyl, cyclohexyl, tetramethylcyclohexyl, cyclohexenyl, norbornyl.

These hydrogen atoms may be substituted with halogen atoms.

R1, R2. R3. When any of R4 is an aromatic or polycyclic hydrocarbon group, it is preferably an aromatic or polycyclic hydrocarbon group having 1 to 18 carbon atoms. Specific examples include phenyl, tolyl, ethyl phenyl, quinl, cumyl, trimethyl phenyl, tetramethyl phenyl, naphthyl, methylnaphthyl, anthranyl, and the like.

These hydrogen atoms may be substituted with halogen atoms.

Rl. R2. When either R3 or R4 is a polycyclic compound, a heterocyclic compound having 1 to 18 carbon atoms is preferable. Specific examples include frill, tetrahydrofuryl, chenyl, virolyl, imidazolyl, indolyl, pyridyl, and piveridyl.

These hydrogen atoms may be substituted with halogen atoms.

R1, R2. R3. If any of R4 is a link between an aromatic hydrocarbon, a polycyclic hydrocarbon, or a heterocyclic compound and an aliphatic hydrocarbon, the number of carbon atoms is 1~! 8 aromatic hydrocarbon group, polycyclic hydrocarbon or heterocyclic compound and carbon number 1 to 1
A group consisting of two aliphatic hydrocarbon groups connected is preferred. Specifically, benzyl, diphenylmethyl, indenyl,
An example is a full frill.

These hydrogen atoms may be substituted with halogen atoms.

Z is an aromatic group whose hydrogen atom has 1 to 18 carbon atoms, or
An aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, which may be substituted with a polycyclic group, is preferable, and specifically,
Methylene, ethylene, ethylidene, trimethylene, tetramethylene, pentamethylene, hexamethylene, propenylene, etc. Substituted examples include methylmethylene, n-butylmethylene, ethylethylene, isobrobylethylene, tert-butylethylene, soc-butylethylene, tert-amylethylene, adamantaneethylene, bicyclo(2.2.1)hebutylethylene, phenylethylene, tolylethylene, xylylethylene, diphenyltrimethylene, ■,2cyclopentylene, l, 3-cyclopentylene, 3-cyclohexene 1.2
Examples include ylene, dimethylethylene, and indenyl-1,2-ylene. 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-bropoxy acetate, ethyl l-proboxy acetate. , n-butoxymethyl acetate, i-butoxyethyl acetate, n-hexyloxyethyl acetate, sec-hexyloxyoctyl acetate, 2-methylcyclohexyloxymethyl acetate, 3
-Methyl methoxypropionate, ethyl 3-methoxybropionate, butyl 3-methoxybropionate, ethyl 3-ethoxybropionate, butyl 3-ethoxypropionate, n-octyl 3-ethoxypropionate, 3-ethoxybropionate dodecyl bionate, pentamethylphenyl 3-ethoxybropionate, ethyl 3-(i-broboxy)propionate, butyl 3(i-broboxy)propionate, allyl 3-(n-broboxy)propionate, 3
Cyclohexyl -(n-butoxy)propionate, 3-
Ethyl neopentyloxypropionate, 3-Cn-octyloxy)butyl propionate, 312, methyl [i dimethylhexyloxy)propionate, 3-(3.
Octyl 3-dimethyldecyloxy)propionate, 4
-ethyl ethoxyacetate, cyclohexyl 4-ethoxyacetate, octyl 5-(n-broboxy)valerate, 12-
Ethyl ethoxylaurate, 3-(1-indenoxy)
Ethyl propionate, methyl 3-methoxyacrylate,
Methyl 2-methoxyacrylate, methyl 2-ethoxyacrylate, ethyl 3-phenoxyacrylate, ethyl 2-methoxybrobionate, n-butyl 2-(i-bropoxy)butyrate, methyl 2-ethoxyisobutyrate, 2- Phenyl cyclohexyloxyisovalerate, 2-ethoxy. 2
-butyl phenyl acetate, allyl 3-neobentyloxybutyrate, methyl 3-ethoxy, 3(0-methylphenyl)propionate, 3-ethoxy, 2-(o-methylphenyl)
Ethyl bromionate, 3-ethoxy, 2-mesityl ethyl bromionate, 3-ethoxy, 2-tart butylprobionic acid ethyl, 3-ethyloxy, 2-tert
Ethyl amylbrobionate, 3-ethoxy, 2-adamantanepropionate, 3-ethoxy, 2-bicyclo(2.2,+3heptylbrobionate, 3-ethoxy, 3-phenylpropionate, 3-ethoxy ，
Ethyl 3-mesitylbropionate, 3-ethoxy, 3-t
ethyl ert-butylbrobionate, 3-ethoxy, 3-
Ethyl tert-amylpropionate, 4-ethoxy, 2
-(t-butyl)brovyl butyrate, 5-methoxy, 2-methyl. Ethyl 1-naphthylnonanoate, ethyl 2-methoxypentanecarboxylate, 2-ethyl butyl hexanecarboxylate 2-ethoxyhexane, 3-(ethoxymethyl)tetralin-2-acetic acid isobrobyl ester,
8-Butoxy, decalin-1-carboxylic acid ethyl ester, 3-ethoxynorbornane-2-carboxylic acid methyl ester, 2-(phenoxy)methyl acetate, 3-(p-
ethyl cresoxy)brobionate, methyl 4-(2-naphthoxy)acetate, butyl 5-rubacuroxyvalerate, 2
-methyl phenoxybropionate, ethyl 3-(4methylphenoxy)-2phenylbropionate, 2-phenoxy, cyclohexanecarboxylic acid ethyl ester, ethyl thiophene-3-oxyacetate, 2-<2-p-ylinoxymethyl) Ethyl monocyclohexanecarboxylate, 3
-Furfuryloxypropionate and the like can be exemplified.

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, and R7. R8 is a hydrogen atom or an aliphatic hydrocarbon having 1 to 20 carbon atoms, and Y is a chain hydrocarbon having 1 to 4 carbon atoms substituted with an aliphatic hydrocarbon, an aromatic hydrocarbon, or a polycyclic hydrocarbon. or an alicyclic 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, ethyl 3-ethoxy, 2-phenylpropionate, 3-ethoxy. Ethyl 2-tolylbropionate, 3-ethoxy. 2-
Ethyl mesitylbropionate, 3-butoxy, 2- (
ethyl methoxyphenyl)propionate, 3-i-broboxy, methyl 3-phenylbrobionate, 3-ethoxy, ethyl 3-phenylbrobionate, 3-ethoxy,
Ethyl 3-tert-butylbrobionate, 3-ethoxy, ethyl 3-adamantylbrobionate, 3-ethoxy, ethyl 2-tert-butylbropionate, 3-ethoxy, 2-Lert-ethyl amylbropionate, 3-ethoxy, 2 -Ethyl adamantylpropionate, 3-ethoxy, 2-bicyclo(2,2.13heptylpropionate, 2-ethoxy, ethyl cyclohexanecarboxylate, 2(ethoxymethyl), methyl cyclohexanecarboxylate, 3-ethoxynorbornane Examples include methyl -2-carboxylate.

The catalyst preparation method used in the present invention is not particularly limited, but magnesium halide, titanium halide, and alkoxy ester compound may be co-pulverized and then halogenated to achieve high activation. Or after co-pulverizing magnesium halide alone or co-pulverizing magnesium halide with a silicon compound or a phosphorus compound,
Titanium compound treatment and halogenation treatment may be performed in the presence of an alkoxy ester compound.

Further, magnesium carboxylate or alkoxymagnesium, titanium compound, halogenating agent and alkoxy ester may be heat treated to improve performance. Magnesium halide may be dissolved in an organic solvent or the like, and an alkoxy ester may be applied during or after precipitation in the presence of a titanium compound.

Alternatively, a catalyst produced by adding an alkoxy ester compound or a titanium compound to the preparation process when a halogenating agent is applied to the alkylmagnesium may be used.

Alternatively, a catalyst produced by adding an alkoxy ester compound or a titanium compound to the preparation process when metallic magnesium and a halogenated hydrocarbon are reacted may also be used.

The amount of the alkoxy ester compound remaining in the catalyst depends on the preparation method, but the amount of the alkoxy ester compound of the present invention remaining in the catalyst may vary depending on the preparation method.
D, abbreviated as: Titanium: Magnesium: I. D, (molar ratio) is 1:
The range is 1 to 1000: to' to 100, preferably 1:2 to 100: 10-4 to 1O.

I. If D is less than this range, the stereospecificity will be reduced, and if it is too large, the activity will be reduced, which is not preferable.

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

Typical organoaluminum compounds in the present invention are represented by the following formulas (m) to (V).

AgR9R10R11・・・・・・・・・・・・・・・
...Town...(III) R R Ag-0-A
IIR"R15 ...... (mV) (m) formula, (I
In formula V) and formula (V), R9, R10.
R11 may be the same or different, and has at most 12 carbon atoms.
at least one of them is a hydrocarbon group, R
t2, R13, R14 and R1.5 may be the same or different and are hydrocarbon groups having at most 12 carbon atoms.

Further, R16 is a hydrocarbon group having at most 12 carbon atoms, and ρ is an integer of 1 or more.

Typical organoaluminum compounds represented by the formula (III) include trialkylaluminum such as triethylaluminum, tribubylaluminum, tributylaluminium, trihexylaluminum and 1-lioctylaluminium, as well as diethylaluminum hydride and Mention may be made of alkyl aluminum hydrides such as 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 (■), representative examples include alkyldialumoxanes such as tetraethyldialumoxane and tetrabutyldialumoxane.

Further, formula (V) represents aluminoxane, which is a subaggregate of an aluminum compound. R16 is methyl, ethyl,
It includes probyl, butyl, bentyl, etc., but methyl and ethyl groups are preferred. g is preferably 1 to 10.

Among these organoaluminum compounds, 1-realkylaluminum, alkylaluminum hydride, and alkylalumoxane are preferred, and trialkylaluminum is particularly preferred because it gives preferable results.

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

Specifically, for example, ethyl benzoate, butyl benzoate, p-ethyl toluate, p-ethyl anisate, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, di-n-propyldimethoxysilane, cyclohexylmethyldimethoxysilane, tetraethoxysilane, 1-butylmethyldimethoxysilane, penzophenone dimethoxy acecool, penzophenone diethoxy acetal, acetophenone dimethoxy acetal, t-butyl, methylketone dimethoxy Acetal, diphenyldimethoxygermane, phenyltriethoxygermane,
2,2. G,6-tetramethylpiperidine, 2.2. G
．． G-tetramethylpyran and the like. Among these, silicon compounds and acetal compounds having st -o-c or St -N-C bonds are preferred, and in particular Si
A combination with a compound having a -0-C bond is preferred.

In the polymerization of olefins, the amount of organic aluminum used in the polymerization system is generally at least xo-' mmol/g, preferably at least 10-2 mmol/1. Furthermore, the molar ratio of the titanium atoms used in the solid catalyst component is generally 0.5 or more, preferably 2 or more,
In particular, IO or more is preferable. Note that if the amount of organoaluminium used is too small, the polymerization activity will be significantly reduced. In addition, when the use of organoaluminum in the polymerization system is 20 mmol/p or more and the ratio to titanium atoms is 1000 or more in molar ratio, it is not seen that the catalyst performance is further improved even if these values are further increased. I can't do it.

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

The olefin used in olefin polymerization is generally an olefin having at most 18 carbon atoms, and representative examples thereof include ethylene, propylene, butene-1,4-methylbentene-1, hexene-1, and octene-1. 1 etc. In conducting the polymerization, these olefins may be subjected to Sino-German polymerization, or two or more types of olefins may be copolymerized (for example, copolymerization of ethylene and brobylene).

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 two or two of them may be introduced into the polymerization vessel. 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. Also,
In order to obtain a polymer with a practical melt flow, a molecular m regulator (generally hydrogen) may be present.

The polymerization temperature is generally -10°C to 180°C,
Practically speaking, the temperature is 20°C or more and 130°C or less.

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.

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

In addition, in the examples and comparative examples, the hebutane index (i.e., H. R, ) is 4@n-hebutane, and is the residual amount after extracting the obtained polymer for 6 hours, expressed in %. . Melt flow ratio (i.e.
MFR) is JIS K- for powder containing 0.2% of 2.6-di-tert-butyl-4 methylphenol.
Temperature is 230℃ and load is 2.16 by 6758
The measurement was carried out under the condition of kg.

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

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 20 g of anhydrous magnesium chloride (obtained by calcining and drying commercially available anhydrous magnesium chloride in a stream of dry hydrogen chloride gas at about 500'C for 15 hours)
0.21 mol), 3-ethoxy, 2-phenyl, ethyl propionate 11,Ig (0.05 mol), 3.3 ml of titanium tetrachloride, and silicone oil (TSS-451 manufactured by Shin-Etsu Chemical Co., Ltd.) as a grinding aid. .20C S )3.
Container for vibrating ball mill (stainless steel cylindrical type, circular volume IN, diameter 1 on) under a nitrogen stream with dry On+1
+ magnetic balls were placed in the container (approximately 50% filled in terms of apparent volume). This was attached to a vibrating ball mill with an amplitude of 6 m, and
A co-milled solid was obtained by co-milling for 5 hours. 15 g of the obtained co-pulverized material was suspended in 150 ml of 1,2-dichloroethane and stirred at 80°C for 2 hours. The solid portion was collected by filtration and washed with hexane. The sample was thoroughly washed until 1,2-dichloroethane was no longer detected. This was dried under reduced pressure at a low temperature of 3Q'C to 40C to remove hexane, and then a solid catalyst component was obtained. Analysis of the obtained solid catalyst component revealed that the content of titanium atoms in this solid catalyst component was 2.3% by weight.

Polymerization and Physical Properties of the Produced Polymer Into a stainless steel autoclave with an internal volume of 3 g, 20 mg of the solid catalyst component produced by the above method, 91s+g of triethylaluminum and 20+ag of diphenyldimethoxysilane were placed, and then immediately 760g of propylene and O ．． 1g of hydrogen was 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, 314 g of powdered polypropylene was obtained. That is, the polymerization activity was 15,700 r/f-solid catalyst component/hour and 683 kg/g-/Tre time.

H. of this polypropylene powder. R. was 95.9%. MFR was 8.6 g/to min.

[Example 2] Using the solid catalyst component of Example 1, the polymerization temperature was set at 80°C. The rest is the same as in Example 1.

The obtained polymer was 408 g of powdered polymer with a polymerization activity of 20,400 K/f/solid catalyst component/hour and 887 kg/g-Ti pot hour. The H, R, of this polybropylene powder is 97.1%, and VF
R was 3.4 g/10 minutes.

[Example 3] Using the solid catalyst component of Example 1, polymerization was carried out in the same manner as in Example 1 except that 20 mg of phenyltriethoxysilane was charged instead of diphenyldimethoxysilane during polymerization. From the obtained powder polymer, the polymerization activity was 1
4300g/g・Solid catalyst component・Time, 822}c
g/g − Ti·hour, H, R. 95.8%
, MFR was 12.3 g/10 minutes.

[Examples 4 to 7] The same polymerization conditions as in Example 1 were used except that the solid catalyst component of Example 1 was used and the stereoregularity improver added during polymerization was changed as shown in Table 1. The results obtained are also shown in Table 1.

(Left below) [Example 8] 9.5 g of anhydrous magnesium chloride (treated in the same manner as in Example 1) was mixed with 50 ml of decane and 4B. 8ml
of 2-ethylhexyl alcohol under N2 atmosphere,
The mixture was heated and dissolved in a round bottom flask at 130°C for 2 hours. Phthalic anhydride 2.1. was added and further heated at 130°C for 1 hour. This liquid was cooled to room temperature, 20 ml was placed in a dropping funnel, and dropped into 80 ml of titanium tetrachloride at -20°C over 30 minutes, and the temperature was raised to 110°C over 4 hours. 0
．． 98g of 3-ethoxy. A solution of ethyl 2-phenylpropionate was slowly added dropwise. After dropping, 110℃
, the reaction was carried out for 2 hours.

After removing the supernatant, 80 ml of T iCl 4 was newly introduced and heated at 110° C. for 2 hours. Next, the solid catalyst was washed three times with 100 ml of n-decane and then with n-hexane. The amount of T1 supported was 2.8% by weight.

As a result of polymerization carried out in the same manner as in Example 1, the polymerization activity was 1
2BOOg/g ・Solid catalyst, 450}cg/g
- It was Tre time. H. R. is 96.7%, MF
R was 2.0 g/10 minutes.

[Example 9] In a nitrogen stream, 100 ml of n-hebutane (MgCjl) was added to a sufficiently dried 300 ml round bottom flask.
g, TI (o-n Bu) 48gg was added, ioo
The mixture was reacted at ℃ for 2 hours to form a homogeneous solution. After the reaction is completed, 4
The temperature was lowered to 0° C., and then 15 ml of methylhydrodiene polysiloxane (20 centistokes) was added and reacted for 3 hours. After washing the produced solid catalyst with n-hebutane, 150 ml of hebutane was added, and 80 ml of n-hebutane was added.
A solution of 28 g of St C II 4 in hebutane was added dropwise at room temperature over 1 hour. After the dropwise addition was completed, the reaction was continued for an additional 30 minutes. The obtained solid component was poured into 200 ml of n
After washing three times with -hebutane, it was cooled to -10'C.

100 ml of T iC 41 4 was introduced into the mixture, and after thorough stirring, 2.82 g of ethyl 3-ethoxy, 2-phenylbrobionic acid was added dropwise. After the dropwise addition was completed, the reaction was carried out at 90'C for 2 hours. Remove the supernatant and add 100% new
mlT i C#, was introduced and reacted for 2 hours at 90"C. After the reaction was completed, it was washed with n-heptane to obtain a solid catalyst. The amount of TI supported was analyzed and found to be 2,4 % by weight.

Polymerization was carried out in the same manner as in Example 1, and as a result, the polymerization activity was 129
00g/g・Solid catalyst・Time, 538kg/g ”T
It was i time. H. R, is 95. θ%, MFR was 23 g/10 min.

[Example 10] In a nitrogen stream, 5 g of diethoxymagnesium 13-ethoxy. 1.22 g of ethyl 2-phenylpropionate and 25 ml of methylene chloride were added. Stir under reflux for 1 hour, then pump the suspension into 200 ml T i CI, at room temperature.

The temperature was gradually raised to 110° C., and the mixture was reacted with stirring for 2 hours. After the reaction was completed, the precipitated solid was separated and washed three times with 200 ml of n-decane at 11.0°C. New T iC
200 ml of D4 was added, and the mixture was reacted at 120°C for 2 hours. After the reaction, the precipitated solid was separated and heated at 110°C.
- Washed three times with 200 ml of decane, and then washed with hexane at room temperature with n-hexane until no chloride ions were detected. The titanium atomic content of this catalyst component was 3.2%.

Polymerization was carried out in the same manner as in Example 1. Calculating from the obtained results, the polymerization activity is zogoo g/g・solid catalyst component・hour, 650 kg/g-Ti・hour, H
,R. is 9G. 8%, MFR was 1.7 g/10 min.

[Examples 11-211 3-Ethoxy of Example IO. In place of ethyl 2-phenylbrobionate, the components added during catalyst preparation were changed. Other than that, it was prepared in the same manner as in Example 10.

The polymerization method was carried out in the same manner as in Example 1. The polymerization results are shown in Table 2.

(The following is a blank space) [Comparative Examples 1 to 4] Example 10 except that the compounds shown in Table 3 as components added during catalyst preparation were used in place of ethyl 3-ethoxy, 2-phenylbrobionic acid in Example 1O. Prepared in the same manner.

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

(The following is a blank space) [Example 22] Polymerization was carried out in the same manner as in Example 1 using the solid catalyst of Example 1 but without using diphenyldimethoxysilane. From the obtained polymer, the polymerization activity is 17,300 g/g·solid catalyst component·hr and 752 kg/g·Ti·hr.

H, R of this polypropylene powder. is 5l. It was 3%. MFR was 15.1 g/10 minutes.

[Comparative Example 5] A solid catalyst was prepared in the same manner as in Example 1 without using ethyl 3-ethoxy,2-phenylpropionate. Polymerization was carried out in the same manner as in Example 1 without using diphenyldimethoxysilane. The polymerization activity from the obtained polymer was 9110 g.
/g・solid catalyst component・time, 285kg/z-Ti・
It's time. H. of this polypropylene powder. R.
was 23.7%.

MFR was 7-9 g/to min.

[Comparative Example 6] A solid catalyst was prepared in the same manner as in Example 1 without using ethyl 3-ethoxy,2-phenylpropionate. Example 1
Polymerization was carried out in the same manner. The polymerization activity of the obtained polymer was 4910 g/g, solid catalyst component, time, 213 k.
g/g・Ti・time.

H. of this polypropylene powder. R. is 71.29i
It was i. MFR was 3.8 g/10 minutes.

(7) Effects When olefins are polymerized using the catalyst component obtained by the present invention, since the catalyst is very highly active, the catalyst residue in the produced polymer is removed. Since the amount of halogen can be kept low, the deashing process can be omitted.Also, since the amount (concentration) of residual halogen is small, the degree of corrosion of molding machines, etc. during the polymer processing process can be greatly reduced. Shieru.

In addition, the residual catalyst causes deterioration and yellowing of the polymer itself, but since the concentration is necessarily low, these can also be reduced.

Furthermore, because of the high stereoregularity, it is possible to obtain a polymer having mechanical strength that can be put to practical use without removing the so-called active portion.

These effects have extremely important meaning in industrial processes.

[Brief explanation of drawings]

FIG. 1 is a flowchart relating to method 10 of the present invention for preparing a catalyst for polymerizing olefins.

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 are aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, polycyclic hydrocarbons, hetero A group selected from cyclic compounds, Z is an aliphatic or alicyclic hydrocarbon group whose hydrogen atom may be substituted with an aromatic group or a polycyclic group, and i, j, k are integers from 0 to 3. and the sum of i, j, k is 1 or more.) One or two alkoxy ester compounds represented by
1. A method for producing a catalyst component for olefin polymerization, characterized in that the treatment is carried out in the presence of more than one species. (2) A method for polymerizing olefins, which comprises using a catalyst system containing the catalyst component according to claim (1).