JPH04185613A - Olefin polymerization catalyst - Google Patents

Abstract

PURPOSE:To obtain a highly active catalyst system giving a propylene block copolymer having high stereoregularity, high rigidity, and high impact strength by combining a component consisting of Ti, Mg, a halogen, and an alkoxy ester, an organoaluminum compd., and a specific silane compd. CONSTITUTION:An olefin polymn. catalyst is prepared from a component consisting of Ti, Mg, a halogen, and an alkoxy ester compd. of the formula:(R<1> O)i(R<2>O)j(R<3>O)k-Z-COOR<4>(wherein R<1> to R<4> are each a hydrocarbon group;Z is an aliph. hydrocarbon group optionally substd. by one or more arom. hydrocarbon groups; and (i), (j), and (k) are each 0-3 provided that their sum is 1 or higher)(e.g. ethyl 3-ethoxy-2-t-butylpropionate), an organoaluminum compd. (e.g. triethylaluminum), and an alkoxysilane having at least one aliph. hydrocarbon group wherein an alpha-carbon atom directly sttached to the Si atom is secondary or higher (e.g. diisopropyldimethoxysilane).

Description

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

[Conventional technology]

Conventionally, many production 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 (Japanese Patent Publication No. 47-9342), but they have many problems such as odor and are unsatisfactory in practical terms in terms of stereoregularity, leaving room for improvement. The present applicant has proposed a method for overcoming these problems in stereoregular polymerization of α-olefins (Japanese Patent Application No. 1-142717).

Furthermore, as one method for improving stereoregularity, many methods have been proposed in which aromatic alkyl alkoxylans are used during catalyst preparation or polymerization. However, a large amount of benzene, which is thought to have been produced by decomposition, was detected in the produced polymer, which is undesirable from safety and hygiene considerations, making it impossible to use it practically.

In response, it has been proposed to use aliphatic hydrocarbon alkoxysilanes (Japanese Patent Application Laid-Open No. 78803/1983).
, JP-A-63-258907, JP-A-2-84404, etc.). However, compared to aromatic alkyl alkoxyranes, the activity or stereoregularity is lower, and fully satisfactory results have not been obtained.

[Problem to be solved by the invention]

The object of the present invention is to create a polymer with high activity and stereoregularity that does not cause safety and health problems, and a propylene block copolymer with high rigidity and high impact resistance, which were insufficient and unsatisfactory with the prior art. The aim is to provide a catalyst system that gives

[Means to solve the problem]

As a result of intensive research to solve the above three problems, we have arrived at the present invention, which has the following main points. That is, the present invention comprises component (A) titanium, magnesium, halogen and the following general formula (I) % formula % (wherein R, R, R and R4 are hydrocarbon groups, and Z is an aromatic carbide hydrogen atom). an aliphatic hydrocarbon group which may be substituted with hydrogen; also i, j;

k is an integer from 0 to 3, and the sum of i, j, is 1
That's all. ) A catalyst component containing an alkoxy ester compound represented by Component (B) an organoaluminum compound, Component (C) containing one or more a-carbon or secondary or higher aliphatic hydrocarbon groups directly bonded to silicon. The invention features a catalyst for polymerizing an olefin formed from an aliphatic hydrocarbon alkoxysilane compound, and a polymerization method.

The present invention will be explained in detail below.

Catalyst component (A) Magnesium compounds used in the present invention include magnesium halides such as magnesium chloride and magnesium bromide; alkoxymagnesiums such as methoxymagnesium, ethoxymagnesium, and isobroboxymagnesium; lauric acid Examples include magnesium, magnesium carboxylates such as magnesium stearate; alkylmagnesiums such as butylethylmagnesium; and the like. 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 butoxide, titanium isobropoquine,
Examples include titanium alkoxides such as titanium ethoxide, and alkoxytitanium halides such as phenoxytitanium chloride. Moreover, a mixture of two or more of these compounds may be used. 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 examples thereof depend on the catalyst preparation method, but tetrachloride Representative examples include titanium halides such as titanium and titanium tetrabromide, silicon halides such as silicon tetrachloride and silicon tetrabromide, and phosphorus halides such as phosphorus trichloride and phosphorus pentachloride. In some cases, halogenated hydrocarbons, halogen molecules, and hydrohalic acids (eg, HCN, HBr, Hl, etc.) may be used.

The alkoxy ester compound used in the present invention has the general formula, (R'O), (R20), CR30) -Z-C
ci, j, expressed as OOR' (I) Jk, are integers from 0 to 3, and the sum of i, j, is 1 or more. ). Here R, R
, R and R4 are hydrocarbon groups. R, R, R and R4 may be the same or different.

When any one of R, R, R or R4 is an aliphatic or polycyclic 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, 5ee-butyl, tert-butyl, pentyl, hexyl, 3-methylpentyl, tc
rt-pentyl, heptyl, i-hexyl, octyl,
nonyl, decyl, 2,3.5-trimethylhexyl,
Examples include undenyl, dodecyl, vinyl, allyl, 2-hexenyl, 2.4hexadienyl, isopropenyl, cyclobutyl, cyclopentyl, cyclohexyl, tetramethylcyclohexyl, cyclohexenyl, norbornyl.

These hydrogen atoms may be substituted with halogen atoms.

When any of Rl, R2, R3, R4 is an aromatic or polycyclic hydrocarbon group, an aromatic group having 6 to 18 carbon atoms or a polycyclic hydrocarbon group having 7 to J8 carbon atoms, or an aliphatic group containing them. Group hydrocarbon groups are preferred. Specifically, phenyl,
Tolyl, ethylphenyl, xyl, cumyl, trimethylphenyl, tetramethylphenyl, naphthyl, methylnaphthyl, anthranyl, benzyl, diphenylmethyl,
Examples include indenyl.

These hydrogen atoms may be substituted with halogen atoms.

Z is an aromatic group whose hydrogen atom has 6 to 18 carbon atoms, or
Aliphatic hydrocarbon groups (including alicyclic hydrocarbon groups) having 20 to 20 carbon atoms, which may be substituted with a polycyclic group having 7 to 8 carbon atoms, are preferable, and specifically, methylene, ethylene, etc. ,
Ethylidene, trimethylene, tetramethylene, pentamethylene, hexamethylene, propenylene, etc. Substituted examples include methylmethylene, n-butylmethylene, ethylethylene, isopropylethylene, ter
t-butylethylene, 5ee-butylethylene, te
rt-amylethylene, adamantaneethylene, bicyclo[2,2,1)butylethylene, phenylethylene, tolylethylene, xylylethylene, diphenyltrimethylene, l,2cyclobentylene, 1.3nclopentylene, 3-cyclohexene] , 2-ylene, dimethylethylene, indenyl-1,2-ylene, and the like. 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, 5ee-hexyloxyoctyl acetate, 2-methylcyclohexyloxymethyl acetate, 3
-Methyl methoxypropionate, ethyl 3-methoxypropionate, butyl 3-methoxypropionate, ethyl 3-ethoxypropionate, butyl 3-ethoxypropionate, n-octyl 3-ethquinpropionate, 3-
Dodecyl ethoxypropionate, Pentamethylphenyl 3-ethoxypropionate, Ethyl 3-(i-propoxy)propionate, Butyl 3(i-propoxy)propionate, Allyl 3-(n-propoxy)propionate, 3-(n-propoxy) -butoxy)cyclohexyl propionate,
Ethyl 3-neopentyloxypropionate, 3-(n
-octyloxy)butyl propionate, 3- (2,
6 dimethyl hequinluoquine) methyl propionate, 3-
Octyl (3,3-dimethyldecyloxy)propionate, Ethyl 4-Ethoxybutyrate, Cyclohexyl 4-Ethoquinybutyrate, Octyl 5-(n-'7''lopoxy)valerate, Ethyl J2-ethoxylaurate, 3-(I -indenoquine) ethyl propionate, methyl 3-methoxyacrylate, methyl 2-methoxyacrylate, methyl 2-ethoxyacrylate, ethyl 3-phenoxyacrylate, ethyl 2-methoxypropionate, 2-(i-propoxy)butyric acid n-butyl, methyl 2-ethoxyisobutyrate, phenyl 2-cyclohexyloxyisovalerate, 2-
Ethoxy, butyl 2-phenylacetate, allyl 3-neopentyloxybutyrate, 3-ethoxy, methyl 3(o-methylphenyl)propionate, 3-ethoxy, ethyl 2-(o-methylphenyl)propionate, 3-ethoxy.

Ethyl 2-mesitylpropionate, 3-ethoxy.

Ethyl 2-tertbutylpropionate, 3-ethoxy, ethyl 2-tertamylpropionate, 3-ethoxy, ethyl 2-adamantanepropionate, 3-ethoxy, ethyl 2-bicyclo[2,2,I]heptylpropionate, 3-ethoxy, ethyl 3-phenylpropionate, 3-ethoxy, ethyl 3-mesitylpropionate, 3
ethoxy, ethyl 3-tert-butylpropionate,
3-ethoxy, ethyl 3-tert-amylpropionate,
4-ethoxy, 2-(t-butyl)propyl butyrate, 5-
Metquin, 2 methyl, ethyl 1-naphthylnonanoate, 2
Methoxine clopentane carboxylic acid ethyl ester 2-
Nidoxin chlorhexane carboxylic acid butyl ester, 3
- (Ethoxymethyl)tetralin-2-acetic acid isopropyl 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-carbaculoquine valerate, methyl 2-phenoxypropionate, 3-(4methylphenoxy)-2
Ethyl phenylpropionate, 2-phenoxy, cyclohexanecarboxylic acid ethyl ester, thiophene-3-
Examples include ethyl oxyneacetate.

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

Here, R5 and Rfi are aliphatic hydrocarbons having 1 to 20 carbon atoms, and R7 and R8 are hydrogen atoms or aliphatic hydrocarbons having 1 to 20 carbon atoms.
20 aliphatic hydrocarbons, and Y is a group in which a chain hydrocarbon having 1 to 4 carbon atoms is substituted with an aliphatic hydrocarbon, an aromatic hydrocarbon, or a polycyclic hydrocarbon, or a group having 1 to 4 carbon atoms] 2 is an alicyclic hydrocarbon group. 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. in particular,
3-ethoxy, ethyl 2-phenylpropionate, 3-
Ethoxy, ethyl 2-tolylpropionate, 3-ethoxy, ethyl 2-mesitylpropionate, 3-butoxy,
2-(methoxyphenyl)ethyl propionate, 3-
i-propoxy, methyl 3-phenylpropionate, 3
-ethoxy, ethyl 3-phenylpropionate, 3-ethoxy, ethyl 3-tert-butylpropionate, 3
-Ethoxy.

Ethyl 3-adamantylpropionate, 3-ethquine, 2
-tertbutyl ethyl propionate, 3-tert-butylpropionate, 2-tert-amyl ethyl propionate, 3-tert-butyl ethyl propionate, 3-
Ethoxy 1 Ethyl 2-adamantylpropionate, 3
-ethoxy, 2-bicyclo(2.2.1)ethylbutylpropionate, 2-ethoxy, ethyl cyclohexanecarboxylate, 2(ethoxymethyl), methyl cyclohexanecarboxylate, 3-ethoxy norbornane-2-
Examples include methyl 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, the magnesium carboxylate or alphoxymagnesium, the titanium compound, the halogenating agent, and the alcoquine ester may be heat-treated to improve their 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 in 1. D.
Abbreviated as: Titanium: Magnesium 1. D, (molar ratio) is 1:1~
The range is 1000: 10' to 100, preferably 2 to 100: 0' to 10. When J and D are less than this range, the stereospecificity decreases and it becomes impossible to increase the rigidity.

On the other hand, if it is too large, the activity will decrease, which is not preferable.

Catalyst Component (B) The organoaluminum compound in the present invention is typically represented by the following formulas (m) to V).

A11 R9RIOR11・・・・・・・・・・・・・
・・・・・・・・・・・・ (III) RRAp-0-A
11R"R+5... (TV) (m) formula, (
In formula IV) and formula (V), R9, R10, R1
1 may be the same or different, and the number of carbon atoms is at most 2 hydrocarbon groups, hydrogen atoms, or hydrogen atoms,
At least one of them is a hydrocarbon group, R1
2, R13, R14 and R15 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 p is an integer of 1 or more.

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

Further, among the organoaluminum compounds represented by the formula (rV), representative examples include alkylalumoxanes such as tetraethyldialumoxane and tetrabutyldialumoxane.

Further, formula (V) represents aluminoxane, which is a polymer of an aluminum compound. RlG is methyl, ethyl,
It includes propyl, butyl, pentyl, etc., preferably methyl and ethyl groups. g is preferably 1 to ]0.

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

Catalyst component (C) α directly bonded to silicon used in the present invention
- An aliphatic hydrocarbon alkoxysilane compound containing one or more aliphatic hydrocarbon groups in which carbon atoms are secondary or higher is used.

Such organosilicon compounds are represented by the general formula %. Preferably, R17 is an aliphatic hydrocarbon having 3 to 20 carbon atoms and is bonded to silicon through a secondary carbon.

R18 is an aliphatic hydrocarbon having 1 to 5 carbon atoms.

R19 consists of an aliphatic hydrocarbon having 1 to 20 carbon atoms.

Specifically, isopropyltrimethoxysilane, isopropyltrimethoxysilane, isopropyltripropoxinlan, 5ee-butyltrimethoxysilane, 5eC
-butyltriethoxysilane, tert-butyltrimethquine silane, tert-butyltrinidoxinane,
]-Methylbutyltrimethoxysilane 1-Methylbutyltriethoxysilane, 3-pentyltrimethoxysilane, tert-pentyltrimethoxysilane, cyclopentyltrimethoxysilane, ]-methylpentyltrimethoxysilane, ], 3-dimethylbutyltrimethoxysilane Methoxysilane, tert-hexyltrimethoxysilane, 1-nityl]-methylbrobyltrimethoxysilane, cyclot
＼Quinrutrimethoxysilane, cyclohexyltriethoxysilane, cyclohexyltribropoxinlan, cyclohexyltrimethoxysilane, cyclohexenyltriethoxysilane, 3-methylcyclohexyltrimethoxysilane, 3-methylcyclohexyltriethoxysilane, norbornenetrimethoxysilane , norbornenetriethoxysilane, norbornanetrimethoxysilane, norbornanetriethoxysilane, isopropylmethyldimethoxysilane, isopropylethyldimethoxysilane, propylisopropyldimethoxysilane, diisopropyldimethoxysilane, isobutylisopropyldimethoxysilane, butylisopropyldimethoxysilane, (SeC- butyl) isopropyl dimethoxine silane, (tert-butyl) isopropyl dimethoxine silane, cyclopentyl isopropyl dimethoxine lan, cyclohexyl isopropyl dimethoxine lan, (sec
-butyl)methyldimethoxyrane, (sec-butyl)ethyldimethoxinerane, (see-butyl)propyltonmethoxysilane, (see-butyl)butyltrimethoxysilane, di(see-butyl)dimethoxinerane, (see-butyl) (tert-butyl)dimethoxysilane, (see-butyl)cyclopentyldimethoxysilane, (see-butyl)cyclohexyldimethoxysilane, (see-butyl)isobutyldimethoxysilane% (tert-butyl)methyldimethoxysilane, (tert-butyl)ethyl Dimethoxylan, (tert-butyl)propyldimethoxysilane, di(tert-butyl)dimethoxysilane, (tert-butyl)dimethoxysilane, (tert-butyl)propyldimethoxysilane, (tert-butyl)dimethoxysilane,
t-butyl)cyclopentyldimethoxysilane, (t-butyl)cyclopentyldimethoxysilane, (t
ert-butyl)cyclohexyldimethoxysilane, (
tert-butyl)isobutyldimethoxysilane, (t
ert-butyl)butyldimethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylethyldimethoxysilane, cyclopentylpropyldimethoxylan, cyclopentylbutyldimethoxysilane, cyclopentyldimethoxysilane, cyclopentylcyclohexyldimethoxysilane, cyclopentylisobutyldimethoxysilane, cyclohexylmethyldimethoxysilane, Cyclohexyl ethyldimethoxysilane, cyclohexylbropyldimethoxysilane, cyclohexylbutyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylisobutyldimethoxysilane, di(
I. 3-cyclopentadienyl) dimethoxine, (
2-Methylsilane clopentane) dimethoxysilane, (
2,5-dimethylcyclobentane)dimethoxysilane, (2,2-dimethylcyclopentane)dimethoxysilane, (2,2.5.5-tetramethylcyclopentane)dimethoxysilane, (2-ethylsilacyclopentane) ) dimethoxysilane, (2,5-diethylsilaneclopentane)dimethoxysilane, (2-methylsilacyclohexane)dimethoxysilane, (2,6-
dimethylsilacyclohexane) dimethoxysilane, (2
, 2-dimethylsilacyclohexane), ;methoxysilane, (2.2,Ili.B-tetramethylsilcyclohexane)dimethoxysilane, and the like.

These may be used as a mixture of two or more types.

In the present invention, preliminary polymerization may be performed prior to main polymerization. For pre-Q polymerization, the above catalyst component (A) and catalyst component (B) are used.
, a catalyst component (C) may be used depending on the case. Both can be carried out using a higher concentration of catalyst than the main polymerization. The amount of polymer produced is 0.1-200g per 1g of catalyst.
is preferred. The reaction temperature is preferably in the range of -20°C to +50°C.

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

Polymerization method and conditions In carrying out the polymerization, the catalyst component (A), catalyst component (B) and catalyst component (C) of the present invention may be introduced separately into the polymerization vessel, or two types of them may be introduced. 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. Also,
In order to obtain a polymer with a practical melt flow, a molecular weight regulator (generally hydrogen) may be present.

Homopolymerization and copolymerization can be carried out in the presence of a catalyst consisting of catalyst components (A), (B) and (C).

Generally, the amount of organoaluminum used in the polymerization system is generally 10-' mmol/g or more, preferably 10-2 mmol/g or more. Further, the molar ratio of the titanium atoms used in the catalyst component (A) is generally 0.5 or more, preferably 2 or more, particularly 10 or more.

Note that if the amount of organoaluminium used is too small, the polymerization activity will be significantly reduced.

Furthermore, when the use of organic aluminum in the polymerization system is 20 mmol/β or more and the ratio to titanium atoms is 1000 or more in molar ratio, it is not seen that the catalytic performance is further improved even if these values are further increased. do not have.

The amount of catalyst component (C) to be used depends on whether a method is used in which catalyst component (C) is used during prepolymerization of catalyst component (A).
Although it varies slightly, 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. Used in a ratio of O1-1.

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

In addition, 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 Examples and Comparative Examples, the heptane index (i.e., H, R,) is the residual amount after 6 hours of extraction of the obtained polymer with boiling @n-heptane, expressed in %. Melt flow ratio (i.e. MFR
) is JIS K-675 for powder mixed with 0.2% of 2,6-tert-butyl-4 methylphenol.
8 under conditions of a temperature of 230° C. and a load of 2.16 kg.

In each example, all compounds (organic solvents, olefins, hydrogen, titanium compounds, magnesium compounds, alkoxy ester compounds, organosilicon compounds, etc.) used in the production and polymerization of the solid catalyst component were substantially free of moisture. It is.

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] 9.5 g of anhydrous magnesium chloride was mixed with 50 ml of decane and 46.8 ml of 2-ethylhexyl alcohol together with N.
The mixture was heated and dissolved at 130° C. for 2 hours in a round bottom flask under two atmospheres. Add 2.1g of phthalic anhydride and further heat to 130°C.
, heated for 1 hour. This liquid was heated to 60°C, transferred into a dropping funnel in a nitrogen gas atmosphere, and left to stand until it reached room temperature. In this 30 flask with a dropping funnel, 410
ml of titanium tetrachloride was added and cooled to -20°C. 6
It was added dropwise over 0 minutes, and the temperature rose to 100°C in 5 hours. 5
．． 5g of 3-ethoxy.

A hebutane solution of ethyl 2-tert-butylpropionate was slowly added dropwise. After completion of the dropwise addition, the mixture was reacted at 100° C. for 2 hours. After the solid had precipitated, the supernatant was removed and 4410 ml of fresh T i C1) was introduced. 95℃
The mixture was heated and stirred for 2 hours. Next, the catalyst was washed three times with 400 ml of n-decane and then washed with n-hexane to obtain a solid catalyst. The amount of TN supported was 2.2% by weight.

A 3-day flask containing 200 ml of prepolymerization was thoroughly replaced with a nitrogen gas atmosphere, and 50 ml of n-hexane and 0 triethylaluminum were added.
．． 62g, diisopropyldimethoxine run 0.19g
, 1.2 g of catalyst component (A) was stirred at 5°C, and propylene was supplied over 3 hours to prepolymerize (catalyst component (A)
) 2.3 g of polypropylene produced per Ig). After removing unreacted propylene, it was washed with n-hexane to obtain a preactivated catalyst component.

760 g of propylene was placed in an autoclave having an internal volume of 3 II for the main polymerization, and 14.7 g of triethylaluminum former-g1 diisopropyl dimethoxysilane and 66 g of a preactivated catalyst were charged at room temperature. Furthermore, 0.1 g of aqueous system was added, the temperature was raised to 80'C, and the reaction was carried out for 1 hour.

When the resulting polymer was dried, it weighed 360 g. That is, the polymerization activity was 18,000 g/g/solid catalyst component (A)/hour. This polypropylene powder had a boiling hebutane extraction residue (H, R6) of 99.2% and an MFR of 2.3 g/10 minutes. Furthermore, no benzene was detected when the polymer was analyzed.

Examples 2 to 8, Comparative Examples 1 to 2 In the homopolymerization of Example 1, the amount of catalyst component (C) shown in Table 1 was changed in place of diisopropyldimethoxysilane.

Example 9 5 g of diethoxymagunium, 2-t of 13-ethoxy, was placed in a thoroughly dried 200 ml round bottom flask in a nitrogen stream.
art Ethyl amylpropionate 1.66g Yohi 1.
25 ml of 2-dichloropropane was added. 70℃.

Stir for 1 hour, then add the suspension to 200 ml of room temperature
s pumped into CD 4. The temperature was gradually raised to 100° C. and the reaction was carried out with stirring for 2 hours. After the reaction was completed, the precipitated solid was separated in a furnace and washed three times with 200 ml of n-decane at 100°C. Added a new T i Cfl 4200ml,
The reaction was carried out at 100°C for 2 hours. After the reaction, the precipitated solid was separated from the furnace and washed three times with 200 ml of n-decane at 80°C.
Washing was performed with n-hexane at room temperature until chlorine ions were no longer detected.

The Ti content of this catalyst component was 2.6% by weight.

Preliminary polymerization was carried out according to Example 1.

1.9 g of polypropylene per 1 g of catalyst component CA)
was generated.

According to Example 1, propylene, triethylaluminum, diisopropyldimethoquine silane, and 43.5 g of a preactivated catalyst were charged into an autoclave having a polymerization capacity of 1. Furthermore, hydrogen o and +r were added, and polymerization was carried out at 80° C. for 1 hour. The obtained dried polymer weighed 390 g. That is, the polymerization activity is 26000g/r・solid catalyst (
A) ・It is time. This polypropylene powder has a boiling hebutane extraction residue (H, R,) of 99.19 ci and M
FR was 1.8 g/10 minutes.

Example 10 Main polymerization was carried out according to Example 9 without performing the preliminary polymerization. From the obtained polymer, polymerization activity 2
8000g/g・Solid catalyst (A)・Time, H,
R, -99.1%, MFR-2.9g/10 min.

(Effects of the Invention) When olefins are polymerized using the catalyst component modified by the present invention, the amount of catalyst residue in the produced polymer can be kept extremely low because the catalyst has very high activity. Additionally, the demineralization step can be omitted.

Furthermore, since the amount of residual halogen is small, the degree of corrosion of molding machines, etc. during polymer processing steps can be significantly improved.

In addition, the residual catalyst causes deterioration and yellowing and coloring 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 suitable for practical use without removing so-called active parts.

From the viewpoint of hygiene, benzene and the like produced by decomposition are detected in products obtained from polymers obtained by combining ordinary aromatic catalyst components, which is unfavorable from a health and safety standpoint. If the catalyst component according to the present invention is used, the above problem does not occur because it does not have an aromatic substituent.

[Brief explanation of drawings]

FIG. 1 is a flowchart showing an example of the production of an olefin polymerization catalyst and the olefin polymerization process according to the present invention.

Claims (1)

[Claims] 1. Component (A) titanium, magnesium, halogen and the following general formula (I) (R^1O)_i(R^2O)_j(R^3O)_k-
Z-COOR^4 (I) (here R^1, R^2, R
^3 and R^4 are hydrocarbon groups, Z is an aliphatic hydrocarbon group whose hydrogen atoms may be substituted with aromatic hydrocarbons, and i, j, k are integers from 0 to 3, i ,j,k
The sum of is 1 or more. ) A catalyst component containing an alkoxy ester compound represented by (B) an organoaluminum compound, and (C) a catalyst component containing one or more aliphatic hydrocarbon groups in which the α-carbon directly bonded to silicon is secondary or higher. A catalyst for the polymerization of olefins formed from an aliphatic hydrocarbon alkoxysilane compound. 2. A polymerization method characterized by using a catalyst system containing the catalyst component according to claim 1.