JPS63248804A - Catalyst for polymerization of olefin - Google Patents

Abstract

PURPOSE:To obtain an olefin polymerization catalyst capable of producing a highly stereoregular polymer, by combining an organic Al compound with a solid catalyst component obtained by contacting a solid component composed essentially of Ti, Mg and a halogen with an Si compound and an organic Zn compound. CONSTITUTION:The objective catalyst is composed of (A) a solid catalyst component produced by contacting (i) a solid component containing Ti, Mg and a halogen as essential components [e.g. a composition containing Ti(OC2H5)Cl3, dialkoxymagnesium and an Al halide as essential components], (ii) an Si compound of formula (R<1> and R<2> are hydrocarbon residue; X is halogen; 0<=m<=3; 0<=n<=3; 0<=m+n<=3) [e.g. (CH3)Si(OCH3)3] and (iii) an organic Zn compound [e.g. (CH3)2Zn or (C2H5)Zn(OCH3)] and (B) an organic Al compound (e.g. trimethylaluminum).

Description

[Detailed description of the invention]

BACKGROUND OF THE INVENTION Technical Field The present invention relates to catalysts for olefin polymerization. More specifically, when the present invention is applied to the polymerization of olefins, especially α-olefins having 3 or more carbon atoms, by using a specific catalyst, it is possible to produce a highly stereoregular polymer under stable polymerization conditions, which is advantageous for industrial production. This makes it possible to manufacture Conventionally proposed catalysts for olefin polymerization consisting of a solid catalyst component containing titanium, magnesium, and halogen as essential components and organoaluminum have extremely high activity, but cannot be used when the stereoregularity of the product polymer is a problem. It was necessary to use electron-donating compounds during polymerization. However, such catalysts that use an electron donating compound as the third component (external donor) have the disadvantage that the polymerization rate decreases due to the reaction between the organoaluminum compound and the electron donating compound, and that the polymerization rate is increased in order to increase the polymerization rate. Raising the temperature to There is a problem in that it is difficult to control product polymer performance. Therefore, it is desired to develop a catalyst system that can solve the door problem and produce a high tr-regular small polymer at a high catalytic yield without using an electron-donating compound as a third component (external donor). . Prior art JP-A-58-138715 discloses a titanium composite (i) which does not use an external donor and declares tetravalent titanium, magnesium, halogen and an electron donor as essential components.
and an organosilicon compound (2) having a 5i-0-C bond
and a solid component obtained by reacting the titanium complex under the co-reaction of an organoaluminum compound (j) or by treating the titanium complex with an organoaluminum compound and then reacting it with the organosilicon compound; A method for polymerization using a catalyst system has been disclosed. There are still many points to be improved, such as deterioration of the catalyst over time and limitations on the 1a ratio between the titanium component and the white aluminum compound during polymerization. The first objective is to provide a solution to the following points. That is, the first nofine polymerization catalyst according to the present invention consists of the following components (A) and (B). Component (A) Component (i): a solid component containing titanium, magnesium and halogen as essential components, component (i1) 2 general formula (only 17, R1 and R~ are hydrocarbon residues, X
is a halogen, m and n are 0≦m≦3 and 0≦n≦3, respectively, and 0≦m-1-n≦3. ) silicon compound, component ciio
: Organic zinc compound, solid catalyst component obtained by contacting. Component (B) Organoaluminum compound. Effects of the Invention The oleinoin commercial catalyst of the present invention does not use an electron-donating compound (external donor) during polymerization, so there is no decrease in the polymerization rate, and therefore the polymerization temperature can be raised.

It solves the problems of known catalysts, such as no problem even with [2]. These characteristics are extremely advantageous in industrial production and are important characteristics of catalysts. Although the reason for such a catalyst has not yet been fully analyzed, it is thought to be due to the interaction between the silicon compound of component (i1) and the organozinc compound of component (i11) used in the present invention. [Detailed Description of the Invention] [Catalyst] The catalyst of the present invention consists of a specific component (A) and a component (B). Here, “more” means,
This does not imply that the components are only those listed (ie, A and B), but does not exclude the coexistence of an expedient third component. Component (A) Component (A) of the catalyst of the present invention is a solid catalyst component obtained by contacting the above components (i) to (iii) with -C. Here, ``-1 that can be brought into contact with
This does not mean that only >, and does not exclude the coexistence of a purposeful fourth component. Component (i) The solid component used in component (i), which includes titanium, magnesium and halogen as essential components and has 3G=T, is a known solid component. For example, JP-A-53-45688, JP-A-54-3894, JP-A-54-31092, JP-A-54
-39483, 54-94591, 54-11
No. 8484, No. 54-131589, No. 55-754
No. 11, No. 55-90510, No. 55-90511, No. 55-127405, No. 55-147507,
No. 55-155003, No. 56-18609, No. 5
No. 6-70005, No. 56-72001, No. 56-8
No. 6905, No. 56-90807, No. 56-1552
No. 06, No. 57-3803, No. 57-34103,
No. 57-92007, No. 57-121003, No. 5
No. 8-5309, 1, i+ No. 58-5310, 58
-5311, 58-8706, 58-2773
No. 2, No. 58-32604, No. 58-32605,
No. 58-67703, No. 58-117206, No. 5
No. 8-127708, No. 58-183708, No. 58
-183709, 59-149905, 59-
Those described in various publications such as No. 149905 are used. Examples of the magnesium compound serving as a magnesium source used in the present invention include magnesium halide, dialkoxymagnesium, alkoxymagnesium halide, magnesium oxyhalide, dialkylmagnesium, magnesium oxide, magnesium hydroxide, magnesium carboxylate, and the like. In addition, the titanium compound serving as a titanium source has the general formula Ti(O
R) ) can be mentioned. Specific examples include TlC14, T t B r 4, T
i (OC2H5)C13, Ti (OC2H5)2C12, Ti (OC2H5)3C1, Ti (0-ic3H7)C13, Ti (0-nC4H9)C13, Ti(On C4H9) 2 CI 2, Ti(OC
2H5)Br3, Ti(OCH)(OC4H9)2C11Tt (0-n
c4ag)3C1゜Ti(0-C6H5)C13, Ti(0-1C4H9)2C12, Ti(OC5H1l)C13, Ti(OC6H13)C13, Ti(OC2H5)4, Ti(o-nC3H7)4, Ti(0- nC4Hg) 4, Ti(0-1C4H9)4, Ti(0-nC6H13)4, Ti(0-nC8H17)4, Ti[OCHCH(C2H5)C4H9]4, etc. Further, a molecular compound obtained by reacting T IX' 4 (herein, X' represents a halogen) with an electron donor described later can also be used. As a specific example, TiC1-CHC
OC2H5, T I Cl4・CH3CO2C2H5, TiCl4
・C6H5NO2, TiCl4 CH3C0CL TiCI4・C6H5COCl. TiCl4・C6H5CO2C2H5, TiClhCI
Examples include COC2H5, T i C14・C4H40, and the like. The halogen source is usually supplied from the above-mentioned magnesium and/or titanium halogen compounds, but it may also be supplied from known halogenating agents such as aluminum halides, silicon halides, and phosphorous halides. You can also do it. Halogens contained in catalyst components include fluorine, chlorine, bromine,
It may be iodine or a mixture thereof, with chlorine being particularly preferred. In addition to the above-mentioned essential components, the solid components used in the present invention include Si
CI CHS t CI 3, silicon compounds such as methyl hydride 0 diene polysiloxane, AI (OiCH)
AlCl 3 8 3' 3ゝAlBr A
l(OC2H5)3. 3' AI (OCH3: Aluminum compounds such as 12C1 and B (OCH) B (OC2H5) 3.3
It is also possible to use other components such as boron compounds such as 3' B (OC6H5) 3, and these may remain in the solid component as components such as silicon, aluminum and boron. Furthermore, when producing this solid component, an electron donor can be used as an internal donor (7). As an electron donor (internal donor) that can be used for producing this solid component, alcohol oxygen electron donors such as phenols, ketones, aldehydes, carboxylic acids, organic or inorganic acids such as Nisdels, ethers, acid amides, acid anhydrides, ammonia, amines, nitriles Examples include nitrogen-containing electron groups such as , isocyanates, etc. More specifically, (a) methanol, ethanol, propatool, pentanol, hexanol, octatool, dodecanol, octadecyl alcohol, benzyl alcohol , alcohols having 1 to 18 carbon atoms such as phenylethyl alcohol, cumyl alcohol, isopropylbenzyl alcohol, (b) phenol, cresol, xyl-1nonol, ethyl ether, propylphenol, cumylphenol, nonylphenol, naphthol Any alkyl group with 6 to 2 carbon atoms, such as
(c) Ketones having 3 to 15 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, bensif 5, and non, (d) acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, naph Aldehydes having 2 to 15 carbon atoms such as I. aldehyde, methyl (e)formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate , ethyl stearate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate,
Ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl delta benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, L-ethylbenzoate, methyl anisate, ethyl ethoxybenzoate, diethyl phthalate, dibutyl phthalate, dihebutyl phthalate, γ-butyrolactone, a-valerolactone, coumarin, phthalide, ethylene carbonate, etc. number of carbon′
, 2 to 20 white organic acid esters, (h) inorganic acid esters such as silicic acid esters such as ethyl silicate, butyl silicate, phenyltriethoxysilane, (th) acetyl chloride, benzoyl chloride, toluyl Acid halides with 2 or 15 carbon atoms such as acid chloride, anisyl chloride, phthaloyl chloride, isophthaloyl isochloride, (th) methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether,
720 ethers with 2 carbon atoms such as hydrofuran, anisole, diphenyl ether, (su) acid amides such as acetic acid amide, benzoic acid amide, toluic acid amide, (nu) methylamine, ethylamine, diethylamine, tributylamine, piperidine , tribenzylamine, aniline, pyridine, picoline, diamine, and the like; (l)acetonitrile, benzonitrile, lnitrile, and other chlorides. These electron donors are 2
1, 7 (H) used. Among these, preferred are nail esters and acid halides, and particularly preferred are phthalic esters and phthalic halides. 1-Registered components The amount of titanium compound used can be any value as long as the efficacy of the present invention is recognized, but it is generally preferable to fall within the following range: The amount of titanium compound used is 12% of the amount of magnesium compound used. The molar ratio is preferably within the range of 1X10' to 1000, and preferably 1. titanium compound and/or
Regardless of whether the magnesium compound contains halogen or not, the molar ratio to the amount of magnesium used is preferably within the range of 1 x 10-2 to 1000, preferably within the range of 0.1 to 100. . The amount of silicon, aluminum, and boron compounds to be used is preferably within the range of I.times.10@-3 to 100, preferably within the range of 0.01 to 1, in molar ratio to the amount of the magnesium compound used. The electron-donating compound may be used in a molar ratio of 1.times.10@-3 to 10, preferably 0.01 to 5, relative to the amount of the magnesium compound used. Component (i) is produced using the above-mentioned titanium source, magnesium source and halogen source, and if necessary, other components such as an electron donor, for example, by the following production method. (a) Magnesium halide (b) A method of treating alumina or magnesia with a halogenated phosphorus compound and then contacting it with a magnesium halide, an electron donor, and a titanium-halogen-containing compound. (c) A method of contacting a titanium halogen compound and/or a silicon halogen compound with a solid component obtained by contacting a magnesium halide with a titanium tetraalkoxide and a specific polymer silicon compound.The polymer silicon compound is one represented by the following formula. is appropriate. 1 + 5i - 0 mo. (Here, R is a hydrocarbon residue having about 1 to 10 carbon atoms, n
indicates a degree of polymerization such that the viscosity of this polymeric silicon compound is about 1 to 100 centistics. A method in which a titanium compound is brought into contact with the precipitated solid component. (e) A method in which an organomagnesium compound such as a Grignard reagent is reacted with a halogenating agent, a reducing agent, etc., and then an electron donor and a titanium compound are brought into contact with the organomagnesium compound. (v) A method of contacting an alkoxymagnesium compound with a halogenating agent and/or a titanium compound in the presence or absence of an electron donor. Among these, methylhydrodiene polysiloxane, 1,3,5.7 tetramethylcyclotetrasiloxane, and 1,3,5,7.9 pentamethylcyclopentasiloxane are particularly preferred. Component (II) Component (i1) used to produce component (A) R and R2 are hydrocarbon residues, X is a halogen,
m and n are 0≦m≦3 and 0≦n≦3, respectively, and 0≦m + n≦3). R1 and R2 are each 1 to
It is preferred that there are about 20, preferably 1 to 10, hydrocarbon residues. As for X, chlorine is preferable, at least from an economic point of view. Specific examples include (CH3)5i(OCH3)3, (CH)Si(OC2H5)3, (C2H5)2Si(OCH3)2, (n-C6H11)Si(OCH3)3, (CH)Si
(OC2H5)3, (n-CH) S i (QC2H,,) 3, (CH
2-CH)Si (OCH3) 3, C1(CH2)3
Si(OCH3)3.5i(OCH) 5i(OC2
H5)3C1134ゝ(C2H5)2Si(OC2H5)2, (CH)Si(
OCH3)3, Si(OC2H5)4, (C6H5)Si(OCH3)3. 5i(OCH3)2C12, (C6H5)2Si(OCH3)2, (C6H5)(CH3)Si(OCH3)2, (C6H
5) Sl(OC2H5)3, (C6H5)2Si(OC2H5)2, NC(CH2)
2Si(OC2H5)3, (C6H5) (CH3)
S 1 (OC2R5)2, (n-C3H7)St
(OC2H5) 3, (CH3)5i(OC3H7)3
, (C6H5)(CH2)Si(OC2H5)3, (CH
3) 3C3i (CH3) (OCH3)2, (CH3
) 3C5i (HC(CH3) 2)(OCH3)
2, (CII) C3i (CH3) (OC2H
5) 2, (C2H5) 3esi (CH3) (OC
H3) 2, (CH3)(C2H5)CH5i(CH3
)(OCH3)2, ((CH) CHCH2)Si
(OCH3) 2, C2H5C(CH3) 2Si (
CH3) (OCH3) 2, CHC(CH) 5i(C
H3) (OC2H5)2. (CH3)3C8i(OCH
3) 3, (CH3)3C8i(OC2H5)3, (C2H5)3
C-8i(OC2H5)3, (CH)(CH)CH3l
(OCH3)3 etc. are mentioned. Among these, preferable are branched hydrocarbon residues in which the carbon at the α position of R1 is secondary or tertiary and has 3 to 20 carbon atoms, especially those in which the carbon at the α position of R1 is tertiary and has a carbon number of 3 to 20. It is an ionic compound having 4 to 1,0 branched hydrocarbon residues. Component (ill) Component (ill) used to produce component (A) is an organozinc compound. The organic zinc compound has the general formula RZX (where R3 is hydrocarbon residual sulfur, 2-an
a Suitably, X is a halogen or alkoxide group, and a represents a number of O≦a<2. R3 preferably has about 1 to 10 carbon atoms. The alkyl portion of the alkoxide group preferably has about 1 to 6 carbon atoms. As for the halogen, chlorine is preferable at least from economical point of view. Specific examples include (CH3)2Zn1 (CH) Zn, (i-C4H9) 2Zn, (n-
CH) Z(i-(C2H5)ZnCl, (n-C
4H9) Z n C1-. Examples include (CH)Zn (OC2H5), (CH)Zn (OCH3), and the like. The contact conditions for components (i) to (iii) described in Production of Component (A)-L may be arbitrary as long as the effects of the present invention are observed, but the following conditions are generally preferred. . The contact temperature is -5
The temperature is about 0 to 200°C, preferably 0 to 100°C. Contact method and 1. Examples include a mechanical method using a rotary ball mill, a vibration mill, a jet mill, a media agitation pulverizer, etc., and a method of contacting by stirring in the presence of an inert diluent. The inert diluents used at this time include aliphatic or aromatic pupil hydrogen and halocarbohydrate 7J4.
, polysiloxane (for example, a polymeric silicon compound), etc. The quantitative ratio of components (i) to (iii) may be arbitrary as long as the effects of the present invention are recognized, but generally,
It is preferably within the following range. The ratio of component O) to component (Ii) is the ratio of component (Ii) to the titanium component constituting component (i).
I) atomic ratio of silicon (silicon/'titanium) is 0.01
-1000, preferably 0. 1-10
It is within the range of 0. The amount of component (lii) used is
The atomic ratio (zinc/titanium) of zinc in component (III) to the titanium component constituting i) is preferably in the range of 0.01 to 100, preferably in the range of 0.1 to 30. Component (B) Component (B) is an organoaluminium compound. A hydrocarbon residue or a hydrogen atom having about 1 to 20 carbon atoms, which may be the same or different, R7 is a hydrocarbon residue, X is a halogen, n and m are each a number of 0≦n and 3.0<m<3 It is. ). in particular,(
(b) Trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, etc., (b) diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride, ethylaluminum Examples include alkyl aluminum halides such as dichloride, (3) aluminum alkoxides such as diethylaluminum hydride, diisobutyl aluminum hydride, and (d) diethylaluminum ethoxide and diethylaluminum phenoxide. In addition to these (a) to (c) organoaluminum compounds, other organometallic compounds, for example, R8 and R9 may be the same or different and have 1 to 1 carbon atoms.
There are about 20 hydrocarbon residues. ) can also be used in combination with an alkyl aluminum alkoxide. For example, combinations of triethylaluminum and diethylaluminium ethoxide, combinations of diethylaluminum monochloride and diethylaluminum ethoxide, combinations of ethylaluminum dichloride and ethylaluminum jetoxide, and combinations of triethylaluminum, diethylaluminum ethoxide, and diethylaluminum chloride. Can be used in combination. The amount of component (B) used is component (B)/component (A) in weight ratio.
) is in the range of 0.1 to 1000, preferably 1 to 100. [Use of Catalyst/Polymerization] The catalyst of the present invention can be applied not only to ordinary slurry polymerization, but also to liquid-phase solvent-free polymerization, solution polymerization, or gas-phase polymerization that uses substantially no solvent. also applies. It is also applicable to continuous polymerization, batch polymerization or preliminary polymerization. As the polymerization solvent in the case of slurry polymerization, saturated aliphatic or aromatic hydrocarbons such as hexane, heptane, pentane, cyclohexane, benzene, and toluene are used alone or in mixtures. The polymerization temperature is from room temperature to about 200°C, preferably from 50 to 150°C, and hydrogen can be used as an auxiliary molecular weight regulator at this time. The olefins polymerized with the catalyst system of the present invention have the general formula R-
CH-CH2 (where R is a hydrogen atom or a carbon number of 1 to
10 hydrocarbon residues and may have a branched group. )
It is expressed as Specifically, there are olefins such as ethylene, propylene, butene-1, pentene-1, and hexene-1,4-methylpentene-1. Preferred are ethylene and propylene. In these polymerizations, up to 50% by weight, preferably up to 20% by weight, based on ethylene, of the abovementioned olefins can be copolymerized, and up to 30% by weight, based on propylene, of the abovementioned olefins, especially ethylene. , can be copolymerized with. Copolymerization with other copolymerizable monomers (eg, vinyl acetate, diolefins, etc.) can also be carried out. [Experimental example] Example 1 [Production of component (A)] A thoroughly dried 0.4 liter ball mill that had been purged with nitrogen was filled with 40 stainless steel balls of 12 m + *φ, and 20 g of MgCl2 was added to the ball mill. 15.5 milliliters of dihebutyl phthalate was introduced and milled using a rotary ball mill.
Time crushed. After the pulverization was completed, the mixed pulverized composition was taken out from the mill in a dry box. Subsequently, 8.8 grams of the pulverized composition was introduced into the flask after thorough nitrogen purging, and 25 ml of n-hebutane and TiC14 were added.
25 ml was introduced and the reaction was carried out at 100°C for 3 hours. After the reaction was completed, the mixture was thoroughly washed with rhobutane. When a part of the obtained solid component [component (i)] was taken out and subjected to compositional fracture, T i 6f = 3.011 peaks was 2%. Next, 50 milliliters of sufficiently purified rhohebutane was introduced into a flask that had been sufficiently purged with nitrogen, and 5 grams of component O) obtained above was added to the knead, followed by component (II) (CH) esi (CH3) ( OCH3) 2 to 1
．． 2 ml and Zn (
0.4 g of C2H5)2 was introduced and allowed to contact at 30°C for 2 hours. After the contact was completed, the product was thoroughly washed with n-hebutane to obtain component (A). [Polymerization of propylene] In a 1-5 liter stainless steel autoclave equipped with stirring and temperature control equipment, add 500 milliliters of thoroughly dehydrated and deoxidized rhohebutane and 125 milligrams of triethylaluminum as component (B). , and "-=15 milligrams of self-synthesized catalyst component (A) were introduced. Next, 60 milliliters of H2 was introduced, the temperature and pressure were increased, and polymerization was carried out under the conditions of a polymerization pressure of 5) cg/(7)G1, a polymerization temperature of -75°C, and a polymerization time of -2 hours. After the polymerization was completed, the resulting polymer slurry was separated by filtration, and the polymer was dried. As a result, 88.7 grams of polymer was obtained. ,−
-jj, 0.58 grams of polymer was obtained from the filtrate. From the boiling hebutane extraction test, the overall product quality (hereinafter abbreviated as T-1, I) was 97.2 and 2%. The MFR was 3,9 g/10 minutes, and the polymer bulk specific gravity was 41 g/cc. Example 2 [Production of component (A)] 200 ml of dehydrated and deoxygenated rhohebutane was introduced into a flask that had been sufficiently purged with nitrogen, and then MgC
l2 to 0. 1 mol, 0.2 mol of T i (On C4H9) 4 was introduced,
The reaction was carried out at 95°C for 2 hours. After the reaction was completed, the temperature was lowered to 40°C, then 1-2 ml of methylhydropolysiloxane (20 centistokes) was introduced, and 3
Allowed time to react. The solid components formed were washed with rhohebutane. Next, 50 milliliters of n-hebutane purified in the same manner as above was introduced into a flask that had been sufficiently purged with nitrogen.
0.03 mol of the solid component synthesized above in terms of Mg atoms was introduced through IJ. Next, 25 milliliters of -heptane and 1 ml of S i C140, 05 moles were mixed and heated at 30°C for 30 minutes.
The mixture was introduced into the flask for 0 minutes and reacted at 7 (]°C for 3 hours. After the reaction was completed, it was washed with n-hebutane. Then, phthalic acid chloride 010 was added to 25 ml of rhohebutane.
03 mol were mixed and introduced into a flask at 70°C for 30 minutes, and reacted at 95°C for 1 hour. After the reaction was completed, it was washed with n-hebutane. Then 145 ml of TIC was introduced and 10
The reaction was carried out at 0°C for 6 hours. After the reaction was completed, it was thoroughly washed with n-heptane. The titanium content was 2.45 m2 and 2%. Component (i) for producing solid component (A)
) and 1. Ta. Using this component O), contact was carried out under the same conditions as in Example 1, except that the amount of (CH) C8i (CH3) (OCH3) 2 used in component (II) was changed to 1.6 ml. After the contact was completed, the product was thoroughly washed with rhohebutane to obtain component (A). [Polymerization of propylene] Use of triethylaluminum as component (B) is 150
Polymerization of propy-1-one was carried out under the same conditions as for the polymerization of propy-1-one in Example 1, except that the amount was used in milligrams. As a result, 172 grams of polymer were removed and the MFR
The weight was 2.8 g/10 minutes, the T-1,1-98,5 peak was 2%, and the bulk specific gravity of the polymer was -0.48z/ce. Examples 3 to 6 In the production of solid component (A) of Example 2, component 11
) The catalyst was produced in the same manner as in Example 2, except that the compounds shown in Table 1 were used instead of (CH)C3i(CH3)(OCH3)2, and the polymerization of propylene was also carried out in the same manner as in Example 2. I did the same. The results are shown in Table-1. Examples 7 to 9 Polymerization of propylene in Example 3 was carried out in the same manner as in Example 3, except that the organic aluminum compounds shown in Table 2 were used instead of the organic aluminum of component (B). The results are shown in Table-2. Example 10 [Manufacture of component (A)] Dehydrated and deoxidized n in a flask that was sufficiently purged with nitrogen.
-'＼Introduce 100 ml of butane, then Mg
Cl2 to 0. 1 mol, 0.2 mol of Ti(0-nC4H9)4 was introduced, 95
The reaction was carried out at ℃ for 2 hours. After the reaction was completed, the temperature was lowered to 35°C, and 1. 3. 5. 15 milliliters of 7-titramethylcyclotetrasiloxane was introduced and reacted for 5 hours. The solid component produced was washed with n-hebutane. Next, 50% of n-hebutane was added to the flask which had been sufficiently purged with nitrogen.
Mg is introduced into the solid component synthesized above.
0.03 mol was introduced in terms of atoms. Then SiCl
40.06 mol was introduced at 20°C for 30 minutes, and the temperature was increased to 50°C.
The mixture was allowed to react for 3 hours. After the reaction was completed, it was washed with n-hebutane to obtain a solid component (i) for producing component (A). The titanium content in the solid component was 4.52 weight percent. Next, the sufficiently purified n
- 50 ml of hebutane was introduced, and 5 g of the component (+) obtained above was introduced into it, followed by 1.5 g of Zn(iC4H9)4 as the component (lit), and the mixture was heated at 30°C.
After the contact was completed, the mixture was thoroughly washed with n-hebutane. Next, 4.7 milliliters of (CH3)C3i(CH3)(OCH3)2 as component (i1) was introduced, and the mixture was brought into contact at 40°C for 1 hour. After the contact was completed, the product was thoroughly washed with n-hebutane to obtain component (A). [Polymerization of propylene] Polymerization of propylene was carried out in the same manner as in Example 2, except that the amount of triethylaluminum used as component (B) was 63 mg and the polymerization temperature was 70° C. under the polymerization conditions of Example 2. 109 grams of polymer were obtained, MF
R-8,6 g/10 min, T-1,1-96,2 weight percent, polymer bulk specific gravity -0,46 g/cc. Example 11 Component (A) was produced under the same conditions as in Example 2 except that ethyl benzoate was used instead of phthaloyl chloride. Polymerization of propylene was also carried out in the same manner as in Example 2. As a result, 7
7.8 grams of polymer was obtained, MFR-6.3 g/
10 minutes, T-1,1-93,3 weight percent, polymer bulk specific gravity -0,41 g/cc. Example 12 In the production of component (A) in Example 1, (CH3)3C8i(CH3)(OCH3)2 was used as component (i1) at 1.8
Milliliter, Z n (C2H
5) Production was carried out in exactly the same manner except that 0.47 g of CI was introduced and brought into contact at 50°C for 1 hour, and propylene polymerization was carried out in exactly the same manner. 80.4 grams of polymer was obtained, T-1, l-96,6 weight percent, VF
R-4,3g/10min, polymer bulk specific gravity-0,42g/
It was cc. Examples 13 to 16 In the production of component (A) in Example 2, catalysts were produced in the same manner as in Example 2, except that the compounds shown in Table 3 were used as the silicon compound of component (i1), and the catalyst was produced in the same manner as in Example 2. Polymerization was also carried out in the same manner as in Example 2. The results are shown in Table-3. Comparative Examples 1-2 In the production of component (A) in Examples 1-2, component cim
and (7) except that Zn(C2H5)2 was not used.
Component (A) was produced in exactly the same manner, and propylene was polymerized in exactly the same manner. The results are shown in Table 4. Comparative Example 3 Component (A) was produced using and without using component (i1) and component ciio in the production of component (A) in Example 2, and propylene polymerization was carried out in exactly the same manner. 11
8 grams of polymer were obtained, MFR-30,6g/1
0 minutes, polymer high specific gravity -0, 32y/ee, T-1,
I-68.9ff (51%) Table-4

[Brief explanation of drawings]

FIG. 1 is intended to assist in understanding the technical content of the present invention regarding Ziegler catalysts. Applicant's agent Sato -Yu-y=Zokuinshij] Yusho December 1986 So ■

Claims (1)

[Scope of Claims] An olefin polymerization catalyst comprising the following components (A) and (B). ¥Component (A)¥ Component (i): Solid component containing titanium, magnesium and halogen as essential components, Component (ii): General formula R^1_mX_nSi(OR^2)_4_-_m_-_
n (where R^1 and R^2 are hydrocarbon residues, X is a halogen, m and n are each 0≦m≦
3 and 0≦n≦3, and 0≦m+n≦3. ), a silicon compound represented by component (iii):
A solid catalyst component obtained by contacting an organic zinc compound. ¥Component (B)¥ Organoaluminum compound.