Catalyst for polymerization of olefin monomers

A catalyst for polymerization of olefin monomers, comprising Component (A) which is a solid catalytic compound obtained by subjecting at least the following three compounds to a contact reaction; Sub-component (i) which is a component for Ziegler catalysts comprising titanium, magnesium and a halogen; Sub-component (ii) which is a silicon compound represented by the formula R.sup.1 .sub.4-n SiX.sub.n wherein R.sup.1 is a hydrocarbyl group having 1 to 20 carbon atoms, X is a halogen, and n is a number in the range of 0<n.ltoreq.4, and Sub-component (iii) which is divinylbenzene, the amount of said Sub-component (iii) polymerized in the course of the contact reaction being from 0.01 to 10 g per 1 g of the Sub-component (i), and Component (B) which is an organoaluminum compound. When polymerizing .alpha.-olefin monomers having three or more carbon atoms, the catalyst of this invention does not require a process of preliminary polymerization of the monomers, which process is substantially needed when the monomers are polymerized in the presence of a conventional catalyst.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
This invention relates to a catalyst for polymerization of olefin monomers, 
and more particularly to a catalyst which can give, with high yields, 
polymers having high stereoregularity when used for polymerization of 
olefin monomers having three or more carbon atoms. 
To polymerize olefin monomers having three or more carbon atoms such as 
propylene monomers by using a conventional catalyst, the monomers are, in 
general, subjected to what is called preliminary polymerization before 
conducting main polymerization; otherwise a polymer having high 
stereoregularity would not be obtained in a powder state having good 
properties such as bulk density, particle size distribution. The catalyst 
according to the present invention, however, does not require such a 
process of preliminary polymerization of 
2. Description of the Related Art 
In recent years, there have been proposed various methods for preparing 
polymers having high stereospecificity, in which .alpha.-olefin monomers 
having three or more carbon atoms are subjected to stereospecific 
polymerization in the presence of a solid catalyst component containing as 
requisite components titanium, magnesium and a halogen. In the above 
conventional methods, a process of preliminary polymerization of the 
monomers may be indispensable. In most cases, however, preliminary 
polymerization of the catalyst employed. For this reason, there has been a 
demand for the development of a catalyst suitable for polymerization of 
olefin monomers having three or more carbon atoms, which does not require 
a process of preliminary polymerization of monomers, and can give polymers 
having high stereospecificity. 
SUMMARY OF THE INVENTION 
Accordingly, an object of the present invention is to provide a 
Ziegler-type catalyst for polymerization of capable of overcoming the 
foregoing drawbacks in the art. 
The above object of the invention can be attained by a catalyst for 
polymerization of olefin monomers, comprising Component (A) which is a 
solid catalytic component obtained by subjecting at least the following 
component (i) which is a solid component for Ziegler catalysts comprising 
titanium, magnesium and a halogen, Sub-component (ii) which is a silicon 
compound having the formula R.sup.1.sub.4-n SiX.sub.n wherein R.sup.1 is a 
hydrocarbyl group having 1 to 20 carbon atoms, X is a halogen, and n is a 
number in the range of 0&lt;n.ltoreq.4, and Sub-component (iii) which is 
divinylbenzene, the amount of the Sub-component (iii) polymerized in the 
course of the contact reaction being from 0.01 to 10 g per 1 g of the 
Sub-component (i), and Component (B) which is an organoaluminum compound. 
When olefin monomers are polymerized in the presence of the above catalyst 
of the present invention, polymer yield in a powder state having good 
properties such as bulk density, particle size distribution without 
subjecting the monomers to preliminary polymerization with propylene or 
the like, which is required for polymerization of olefin monomers using a 
conventional catalyst. 
Moreover, when preparing the Component (A), the Sub-component (iii), viz. 
divinylbenzene, can be compound such as an organoaluminum compound which 
has conventionally been required for preliminary polymerization of 
divinylbenzene. In general, a catalyst produced through a process of 
preliminary polymerization using an organometallic compound has the 
shortcomings of low catalytic activity and poor physical characteristics. 
The present invention, therefore, can also eliminate these shortcomings. 
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS 
The catalyst for polymerization of olefin monomers according to the present 
invention comprises specific Components (A) and (B), which will be 
hereinafter explained in detail. The language "comprise" means that the 
components are not restricted only to those indicated, viz. A and B, but 
includes the use of a third component which is compatible with the present 
invention. 
Component (A) 
The Component (A) is a solid catalytic component obtained by subjecting the 
following three components, Sub-components (i), (ii) and (iii), to contact 
with each other. The language "obtained by subjecting the three components 
to contact with each other" means that the components are not restricted 
only to those indicated, viz. (i) to (iii), but include the use of a 
further component which is compatible with the present invention. 
Sub-component (i): 
The Sub-component (i) is a component for Ziegler catalysts comprising as 
essential elements titanium, magnesium, and a halogen. The language 
"comprising as essential elements" means that the elements are not a 
further element which is compatible with the present invention, and that 
these elements concerned can be comprised in the Sub-component (i) in any 
suitable compounds of each of the elements and/or between some of these 
elements. The component for Ziegler catalysts which contains titanium, 
magnesium, and a halogen is known in the art, and those disclosed in 
Japanese Laid-Open Patent Applications Nos. 53-45688, 54-3894, 54-31092, 
54-39483, 54-94591, 54-118484, 54-131589, 55-75411, 55-90510, 55-90511, 
55-127405, 55-147507, 55-155003, 56-18609, 56-70005, 56-72001, 56-86905, 
56-90807, 56-155206, 57-3803, 57-34103, 57-92007, 57-121003, 58-5309, 
58-5310, 58-5311, 58-8706, 58-27732, 58-32604, 58-32605, 58-67703, 
58-117206, 58-127708, 58-183708, 58-183709, 59-149905 and 59-149906 are 
usable in the present invention. 
Examples of a magnesium compound which can be a source of the magnesium in 
the Sub-component (i) include magnesium dihalides, dialkoxymagnesiums, 
alkoxymagnesium halides, magnesium oxyhalides, dialkylmagnesiums, 
magnesium oxide, magnesium hydroxide, and magnesium carboxylates. Of these 
compounds, magnesium dihalides are preferred. 
Examples of a titanium compound which can be a source of the titanium in 
the Sub-component (i) include compounds represented by the formula: 
EQU Ti(OR.sup.3).sub.4-n X.sub.n 
wherein R.sup.3 is a hydrocarbyl group, preferably a hydrocarbyl group 
having approximately 1 to 10 carbon atoms, X is a halogen, and n is a 
number of from 0 to 4. 
Specific examples of the titanium compounds having the above formula 
include TiCl.sub.4, TiBr.sub.4, Ti(OC.sub.2 H.sub.5)Cl.sub.3, Ti(OC.sub.2 
H.sub.5).sub.2 Cl.sub.2, Ti(OC.sub.2 H.sub.5).sub.3 Cl, Ti(O--iC.sub.3 
H.sub.7)Cl.sub.3, Ti(O--nC.sub.4 H.sub.9)Cl.sub.3, Ti(O--nC.sub.4 
H.sub.9).sub.2 Cl.sub.2, Ti(OC.sub.2 H.sub.5)Br.sub.3, Ti(OC.sub.2 
H.sub.5)(OC.sub.4 H.sub.9).sub.2 Cl, Ti(O--nC.sub.4 H.sub.9).sub.3 Cl, 
Ti(O--C.sub.6 H.sub.5)Cl.sub.3, Ti(O--iC.sub.4 H.sub.9).sub.2 Cl.sub.2, 
Ti(OC.sub.5 H.sub.11)Cl.sub.3, Ti(OC.sub.6 H.sub.13)Cl.sub.3, Ti(OC.sub.2 
H.sub.4, Ti(O--nC.sub.3 H.sub.7).sub.4, Ti(O--nC.sub.4 H.sub.9).sub.4, 
Ti(O--iC.sub.4 H.sub.9).sub.4, Ti(O--nC.sub.6 H.sub.13).sub.4, 
Ti(O--nC.sub.8 H.sub.17).sub.4, and Ti[OCH.sub.2 CH(C.sub.2 
H.sub.5)C.sub.4 H.sub.9 ].sub.4. 
A molecular compound obtained by reacting a compound represented by the 
formula TiX'.sub.4, in which X' is a halogen, with an electron donor which 
will be described hereinbelow in more detail can also be used as a source 
of the titanium element. Specific examples of such molecular compounds 
include TiCl.sub.4.CH.sub.3 COC.sub.2 H.sub.5, TiCl.sub.4.CH.sub.3 
CO.sub.2 H.sub.5, TiCl.sub.4.C.sub.6 H.sub.5 NO.sub.2, TiCl.sub.4.CH.sub.3 
COCl, TiCl.sub.4.C.sub.6 H.sub.5 COCl, TiCl.sub.4.C.sub.6 H.sub.5 CO.sub.2 
C.sub.2 H.sub.5, TiCl.sub.4.ClCOC.sub.2 H.sub.5, and TiCl.sub.4.C.sub.4 
H.sub.4 O. 
In addition to the above compounds, titanium compounds such as TiCl.sub.3 
prepared by, for instance, reducing TiCl.sub.4 with H.sub.2, with metallic 
aluminum, or with an organometallic compound, TiBr.sub.3, Ti(OC.sub.2 
H.sub.5)Cl.sub.2, TiCl.sub.2, and dicyclopentadienyltitanium dichloride 
are also employable as sources of the titanium element. 
Among the above-enumerated titanium compounds, TiCl.sub.4, Ti(OC.sub.4 
H.sub.9).sub.4, and Ti(OC.sub.2 H.sub.5)Cl.sub.3 are preferable. 
The halogen to be comprised in the Sub-component (i) is conveniently 
supplied from the above-described halogenated compounds of magnesium 
and/or titanium. However, known halogenating agents such as halogenated 
compounds of aluminum, halogenated compounds of silicon and halogenated 
compounds of phosphorus are also usable as sources of the halogen. 
The halogen comprised in the Sub-component (i) is selected from fluorine, 
chlorine, bromine, iodine, and a mixture thereof. Of these, chlorine is 
preferable in the present invention. 
Besides the above-described essential elements of magnesium, titanium and a 
halogen, the Sub-component (i) can further comprise an additional element 
such as an aluminum compound such as Al(O--iC.sub.3 H.sub.7).sub.3, 
AlCl.sub.3, AlBr.sub.3, Al(OC.sub.2 H.sub.5).sub.3 or Al(OCH.sub.3).sub.2 
Cl, a boron compound such as B(OCH.sub.3).sub.3, B(OC.sub.2 H.sub.5).sub.3 
or B(OC.sub.6 H.sub.5).sub.3, or another metal halide such as WCl.sub.6 or 
MoCl.sub.5. It is acceptable that the elements such as aluminum and boron 
contained in these compounds remain in the Sub-component (i). 
When preparing the Sub-component (i), an electron donor can be used as an 
internal donor. 
Examples of the electron donor (internal donor) usable in the present 
invention include electron donors containing oxygen such as alcohols, 
phenols, ketones, aldehydes, carboxylic acids, esters of an organic acid 
or inorganic acid, ethers, acid amides, acid anhydrides, and electron 
donors containing nitrogen such as ammonia, amines, nitriles and 
isocyanates. 
Specific examples of the electron donors include: 
(a) alcohols having 1 to 18 carbon atoms such as methanol, ethanol, 
propanol, pentanol, hexanol, octanol, dodecanol, octadecyl alcohol, benzyl 
alcohol, phenylethyl alcohol, and isopropylbenzyl alcohol; 
(b) phenols which have 6 to 25 carbon atoms and may or may not contain an 
alkyl substituent, such as phenol, cresol, xylenol, ethylphenol, 
propylphenol, isopropylphenol, nonylphenol and naphthol; 
(c) ketones having 3 to 15 carbon atoms such as acetone, methyl ethyl 
ketone, methyl isobutyl ketone, acetophenone and benzophenone; 
(d) aldehydes having 2 to 15 carbon atoms such as acetaldehyde, 
propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde and 
naphthaldehyde; 
(e) esters of an organic acid having 2 to 20 carbon atoms such as methyl 
formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, 
octyl acetate, cyclohexyl acetate, cellosolve acetate, ethyl propionate, 
methyl butyrate, ethyl valerate, ethyl stearate, methyl chloroacetate, 
ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl 
cyclohexanoate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl 
benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl 
benzoate, cellosolve benzoate, methyl toluate, ethyl toluate, amyl 
toluate, ethyl ethylbenzoate, methyl anisate, ethyl anisate, ethyl 
ethoxybenzoate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate, 
.gamma.-butyrolactone, .alpha.-valerolactone, coumarine, phthalide and 
ethylene carbonate; 
(f) esters of an inorganic acid having a lower alkyl group or a phenyl 
group as the alcohol residue, such as for instance esters of silicic acid 
such as ethyl silicate, butyl silicate and phenyl triethoxy silane; 
(g) acid halides having 2 to 15 carbon atoms such as acetyl chloride, 
benzoyl chloride, toluic acid chloride, anisic acid chloride, phthaloyl 
chloride and isophthaloyl chloride; 
(h) ethers having 2 to 20 carbon atoms such as methyl ether, ethyl ether, 
isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole and 
diphenyl ether; 
(i) acid amides having 1 to 10 carbon atoms, such as acetic acid amide, 
benzoic acid amide and toluic acid amide; 
(j) amines having 1 to 21 carbon atoms, such as methylamine, ethylamine, 
diethylamine, tributylamine, piperidine, tribenzylamine, aniline, 
pyridine, picoline and tetramethylethylenediamine; and 
(k) nitriles having 2 to 10 carbon atoms, such as acetonitrile, 
benzonitrile and tolunitrile. 
The above-enumerated electron donors can be employed either singly or in 
combination. 
Among the above electron donors, esters of an organic acid and acid halides 
are preferred; and phthalates, cellosolve acetate and phthalic acid 
halides are more preferably employed in the present invention. 
The above elements can be incorporated into the Sub-catalyst can exhibit 
the effects of the present invention. However, the following amounts are, 
in general, preferred. 
The amount of the titanium compound is from 1.times.10.sup.-4 to 1000 
times, preferably from 0.01 to 10 times, the amount of the magnesium 
compound on molar basis. In the case where a halogen-containing compound 
is used as a source of a halogen, the amount of such a compound is from 
1.times.10.sup.-2 to 1000 times, preferably from 0.1 to 100 times, the 
amount of the magnesium compound on molar basis whether or not the 
titanium compound and/or magnesium compound contains a halogen. 
In the case where a silicon, aluminum or boron compound is incorporated 
into the Sub-component (i), the amount of such a compound is from 
1.times.10.sup.-3 to 100 times, preferably from 0.01 to 1 times, the 
amount of the magnesium compound on molar basis. 
When the electron donor is employed, the amount thereof is from 
1.times.10.sup.-3 to 10 times, preferably from 0.01 to 5 times, the amount 
of the magnesium compound on molar basis. 
The Sub-component (i) can be prepared, using the above-mentioned titanium 
compound, magnesium compound, halogen-containing compound, and if 
necessary other compounds such as the electron donor, in accordance with 
one of the following preparation methods: 
(1) A method in which a halogenated magnesium and if necessary the electron 
donor are brought into contact with a compound containing titanium. 
(2) A method in which a halogenated magnesium, the electron donor and a 
compound of titanium containing halogen are brought into contact with 
alumina or magnesia which has been treated with a halogenated compound of 
phosphorus in advance. 
(3) A method in which a halogenated compound of titanium and/or halogenated 
compound of silicon is brought into contact with a solid compound prepared 
by subjecting a halogenated magnesium, a titanium tetraalkoxide, and a 
specific polymeric silicon compound to a contact reaction. 
A polymer represented by the following formula is preferably employed in 
this method as the polymeric silicon compound: 
##STR1## 
wherein R is a hydrocarbyl group having approximately 1 to 10 carbon 
atoms, and n is such a number that the polymer has a viscosity of from 1 
to 100 centistokes. 
Specific examples of the polymeric silicon compounds include methylhydrogen 
polysiloxane, ethylhydrogenpolysiloxane, phenylhydrogenpolysiloxane, 
cyclohexylhydrogenpoly siloxane, 1, 3, 5, 7 
-tetramethylcyclotetrasiloxane, and 
1,3,5,7,9-pentamethylcyclopentasiloxane. 
(4) A method in which a titanium compound is brought into contact with a 
solid compound which is a precipitate obtained by dissolving a magnesium 
compound in titanium tetraalkoxide having an alkyl group, preferably a 
lower alkyl group, and an electron donor, followed by precipitation using 
a halogenating agent or a halogenated compound of titanium. 
(5) A method in which an organomagnesium compound such as a Grignard 
reagent is reacted with a halogenating agent or reducing agent, and then, 
if necessary, brought into contact with an electron donor and a titanium 
compound. 
(6) A method in which a halogenating agent and/or titanium compound is 
brought into contact with an alkoxymagnesium compound in the presence or 
absence of an electron donor. 
Of the above methods, methods (3) and (4) are preferable for the 
preparation of the Sub-component (i). 
Sub-component (ii): 
The Sub-component (ii) to be used for preparing the Component (A) of this 
invention is a silicon compound represented by the following formula 
EQU R.sup.1.sub.4-n SiX.sub.n 
wherein R.sup.1 is a hydrocarbyl group having 1 to 20 carbon atoms, X is a 
halogen, and n is a number in the range of 0&lt;n.ltoreq.4. 
Typical examples of R.sup.1 in the above formula are an alkyl group, an 
alkenyl group, a phenyl group, a cyclohexyl group, a phenyl group having 
as a substituent a lower alkyl group having approximately 1 to 15 carbon 
atoms, and a cyclohexyl group having as a substituent a lower alkyl group 
having approximately 1 to 15 carbon atoms. 
Specific examples of the Sub-component (ii) include SiCl.sub.4, SiBr.sub.4, 
CH.sub.3 SiCl.sub.3, C.sub.2 H.sub.5 SiCl.sub.3, C.sub.4 H.sub.9 
SiCl.sub.3, C.sub.6 H.sub.13 SiCl.sub.3, C.sub.10 H.sub.21 SiCl.sub.3, 
(CH.sub.3).sub.2 SiCl.sub.2, (C.sub.2 H.sub.5).sub.2 SiCl.sub.2, (C.sub.3 
H.sub.8).sub.2 SiCl.sub.2, (C.sub.4 H.sub.9).sub.2, 
(CH.sub.2=CH)SiCl.sub.3, C.sub.6 H.sub.11 SiCl.sub.3, C.sub.6 H.sub.5 
SiCl.sub.3, (C.sub.5 H.sub.11) (CH.sub.3)SiCl.sub.2, C.sub.2 H.sub.5 
SiBr.sub.3, C.sub.7 H.sub.11 SiCl.sub.3, (C.sub.5 
H.sub.11)(CH.sub.3)SiCl.sub.2, (phenyl-CH.sub.2)SiCl.sub.3, and C.sub.20 
H.sub.41 SiCl.sub.3. 
Among the silicon compounds having the above formula, those compounds 
having a lower alkyl group having 1 to 3 carbon atoms as R.sup.1, chlorine 
as X, and a number of 3 or 4 as n are preferred. 
Sub-component (iii): 
The Sub-component (iii) to be used for preparing the Component (A) of the 
present invention is divinylbenzene. 
Examples of the divinylbenzene include ortho-divinylbenzene, 
metha-divinylbenzene, para-divinylbenzene, and a mixture thereof. 
Preparation of Component (A): 
No particular limitation is imposed on the conditions for preparing the 
Component (A). It is, however, preferable that the Sub-components (i), 
(ii) and following conditions: 
Namely, it is desirable that the contact reaction be out at a temperature 
of approximately from -50.degree. C. 200.degree. C., preferably from 
0.degree. C. to 100.degree. C., and more preferably from 20.degree. C. to 
50.degree. C. The Sub-components may be mechanically brought into contact 
with each other by medium-stirring pulverizer. Alternatively, they are 
brought into contact with each other by stirring in the presence of an 
inert diluent such as an aliphatic hydrocarbon, a halogenated aliphatic 
hydrocarbon, an aromatic hydrocarbon, a halogenated aromatic hydrocarbon, 
or a polysiloxane. 
When preparing Component (A) of the present invention, it is preferable to 
polymerize the Sub-component (iii) by subjecting the Sub-components (i) 
and (iii) to a contact reaction in the presence of the Sub-component (ii). 
No particular limitation is imposed on the amounts of the Sub-components 
(i), (ii) and (iii) used for the preparation of the Component (A). 
However, in general, the Sub-components (i) and (ii) are used in such a 
proportion that the ratio of the amount of silicon contained in the 
Sub-component (ii) to the amount of titanium contained in the 
Sub-component (i), that is, the atomic ratio of silicon/titanium, falls in 
the range of from 0.01 to 1000, preferably from 0.1 to 100. 
The amount of the Sub-component (iii) which is polymerized is from 0.01 to 
10 times, preferably from 0.1 to 5 times, the amount of the Sub-component 
(i) on weight basis. 
Component (B) 
The Component (B) of the catalyst according to the present invention is an 
organoaluminum compound. 
Examples of the organoaluminum compound usable in the present invention are 
compounds represented by the formula R.sup.4.sub.3-n AlX.sub.n in which 
R.sup.4 is a hydrocarbyl group having approximately 1 to 20 carbon atoms, 
preferably a lower alkyl, or hydrogen atom, X is a halogen, and n is a 
number in the range of 0.ltoreq.n&lt;3, and compounds represented by the 
formula R.sup.5.sub.3-m Al(OR.sup.6).sub.m in which R.sup.5 is a 
hydrocarbyl group having approximately 1 to 20 carbon atoms, preferably a 
lower alkyl, and m is a number in the range of 0&lt;m&lt;3. 
Specific examples of the above organoaluminum compounds include: 
(a) trialkylaluminums such as trimethylaluminum, triethylaluminum, 
triisobutylaluminum, trihexylaluminum, trioctylaluminum and 
tridecylaluminum; 
(b) alkylaluminum halides such as diethylaluminum monochloride, 
diisobutylaluminum monochloride, ethylaluminum sesquichloride and 
ethylaluminum dichloride; 
(c) alkylaluminum hydrides such as diethylaluminum hydride and 
diisobutylaluminum hydride; and 
(d) aluminum alkoxides such as diethylaluminum ethoxide and diethylaluminum 
phenoxide. 
In combination with the above-enumerated organoaluminum compounds (a) to 
(d), alkylaluminum alkoxides represented by the following formula can be 
employed: 
EQU R.sup.7.sub.3-a Al(OR.sup.8).sub.a 
wherein R.sup.7 and R.sup.8, which may be the same or different, each 
represents a hydrocarbyl group having approximately to 20 carbon atoms, 
preferably a lower alkyl, and a is a number of from 1 to 3. 
For instance, the combination use of triethylaluminum and diethylaluminum 
ethoxide, the combination use of diethylaluminum monochloride and 
diethylaluminum ethoxide, the combination use of ethylaluminum dichloride 
and ethylaluminum diethoxide, and the combination use of triethylaluminum, 
diethylaluminum ethoxide and diethylaluminum chloride are acceptable in 
the present invention. 
The weight ratio of the Component (B) to the Component (A) ((B)/(A)) is 
from 0.1 to 1000, preferably from 1 to 100. 
Use of the Catalyst/Polymerization 
The catalyst according to the present invention is applicable not only to 
slurry polymerization but also to liquid-phase/non-solvent polymerization 
which employs substantially no solvent, solution polymerization and gas 
phase polymerization. Furthermore, the catalyst of the invention can also 
be used for continuous polymerization, batch polymerization, and 
polymerization containing a process of prepolymerization. 
Examples of solvents for use in slurry polymerization include saturated 
aliphatic or aromatic hydrocarbons such as hexane, heptane, pentane, 
cyclohexane, benzene and toluene. These solvents are used either singly or 
in combination. The polymerization temperature is from room temperature to 
approximately 200.degree. C., preferably from 50.degree. to 150.degree. 
C.; the polymerization pressure is from atmospheric pressure to 
approximately 300 kg/cm.sup.2, preferably from atmospheric pressure to 50 
kg/cm.sup.2 ; and hydrogen can be optionally used in order to control the 
molecular weight of the resulting polymer. 
An electron donor such as an ester, an ether or an amine can also be 
employed as a third component so as to control the stereospecificity of 
the resulting polymer. 
In the case where the catalyst of this invention is used for slurry 
polymerization, it is preferable that the amount of the Component (A) be 
in the range of from 0.001 g to 0.1 g for 1 liter of a solvent employed. 
By using the catalyst of the present invention, .alpha.-olefins having the 
following formula can be successfully polymerized: 
EQU R--CH=CH.sub.2 
wherein R is hydrogen atom, or a linear or branched hydrocarbyl group 
having 1 to 10 carbon atoms. 
Specific examples of the .alpha.-olefins include olefins such as ethylene, 
propylene, 1-butene, 1-pentene, 1-hexene, and 4-methylpentene. Of these 
olefins, ethylene and propylene are preferred. 
The above olefins can be polymerized either singly or in combination in the 
presence of the catalyst of the present invention. For instance, in the 
case of copolymerization of ethylene and the other olefin, the other 
olefin can be used in an amount of 50% by weight or less, preferably 20% 
by weight or less, of the amount of the ethylene; and in the case of 
copolymerization of propylene and the other olefin, in particular, 
ethylene, the other olefin can be used in an amount of 30% by weight or 
less of the amount of the propylene. Furthermore, the above olefin can be 
copolymerized with other copolymerizable monomer such as vinyl acetate or 
diolefin in the presence of the catalyst of the invention. 
Other features of this invention will become apparent in the course of the 
following description of exemplary embodiments, which are given for 
illustration of this invention and are not intended to be limiting thereof 
.

EXAMPLE 1 
Preparation of Component (A) 
A flask which had been thoroughly purged with nitrogen gas was charged with 
200 ml of dehydrated and deoxygenated n-heptane. 0.4 mol of MgCl.sub.2 and 
0.8 mol of Ti(O--nC.sub.4 H.sub.9).sub.4 were then added to the n-heptane, 
and the resulting mixture was subjected to a reaction at 95.degree. C. for 
two hours. After the reaction was completed, the reaction mixture was 
cooled to a temperature of 40.degree. C, and 48 ml of 
methylhydrogenpolysiloxane having a viscosity of 20 centistokes was added 
thereto, followed by reaction for three hours. A solid product thus 
obtained was washed with n-heptane. 
A flask thoroughly purged with nitrogen gas was charged with 50 ml of 
dehydrated and deoxygenated n-heptane, and 0.24 mol (Mg atom basis) of the 
above-obtained solid product was then added to the n-heptane. To the 
resulting mixture was added a mixture of 25 ml of n-heptane and 0.4 mol of 
SiC14 at 30.degree. C. over a period of 30 minutes, followed by reaction 
at 70.degree. C. for 3 hours. After the reaction was completed, the 
reaction product was washed with n-heptane. A mixture of 25 ml of 
n-heptane and 0.024 mol of phthalic acid chloride was then added to the 
reaction product at 70.degree. C. over a period of 30 minutes, and the 
resulting mixture was then subjected to a reaction at 90.degree. C. for 
one hour. 
After the above reaction was completed, the reaction product was washed 
with n-heptane, thereby to obtain a Sub-component (i). It was found that 
2.18% by weight of titanium was contained in the Sub-component (i). 
A flask which had been thoroughly purged with nitrogen gas was charged with 
50 ml of purified n-heptane. To the n-heptane, 5 g of the Sub-component 
(i), 10 ml of SiCl.sub.4 as a Sub-component (ii), and 7.5 g of 
metha-divinylbenzene as a Sub-component (iii) in the order named, and the 
resulting mixture was subjected to a contact reaction at 50.degree. C for 
two hours. After the reaction was completed, the reaction product was 
thoroughly washed with n-heptane, thereby to obtain a Component (A) of the 
present invention. 
It was found that 0.31 g of the Sub-component (iii) had been polymerized 
per 1 g of the Sub-component (i). 
Polymerization of Propylene Monomers 
In a 1.5 liter autoclave made of stainless steel, equipped with a stirrer 
and a temperature controller were placed 500 ml of thoroughly dehydrated 
and deoxygenated n-heptane, 125 mg of triethylaluminum as a Component (B), 
and 26.8 mg of diphenyldimethoxysilane as an auxiliary component. The 
mixture was heated to a temperature of 75.degree. C., and 60 ml of 
hydrogen was introduced to the autoclave. Thereafter, propylene was 
further introduced to the autoclave to increase the inner pressure to 5 
kg/cm.sup.2 G. The Component (A) containing 15 mg of the Sub-component (i) 
was added to the above reaction mixture with propylene. The resulting 
reaction mixture was then subjected to polymerization, which was carried 
out under the conditions of a pressure of 5 kg/cm.sup.2 G, a temperature 
of 75.degree. C., and a time of two hours. After the polymerization, the 
polymer was obtained from the above-obtained polymer slurry by filtration, 
and then dried. As a result, 165.4 g of polypropylene was obtained. From 
the filtrate, a further crop of 0.45 g of polypropylene was obtained. The 
polymer thus obtained had a total product I.I. (hereinafter referred to as 
T-I.I) of 98.8% by weight, determined by an extraction test carried out 
using boiling heptane, an MFR of 2.2 g/10 minutes, and a bulk density of 
0.43 g/cc. 
EXAMPLE 2 
Preparation of Component (A) 
A flask which had been thoroughly purged with nitrogen gas was charged with 
200 ml of dehydrated and deoxygenated n-heptane. 0.4 mol of MgCl.sub.2 and 
0.8 mol of Ti(O--nC.sub.4 H.sub.9).sub.4 were then added to the n-heptane, 
and the resulting mixture was subjected to a reaction at 95.degree. C. for 
two hours. After the reaction was completed, the reaction mixture was 
cooled to a temperature of 40.degree. C., and 60 ml of 
1,3,5,7,9-pentamethylcyclopentasiloxane was added thereto, followed by 
reaction for three hours. A solid product thus obtained was washed with 
n-heptane. 
A flask thoroughly purged with nitrogen gas was charged with 50 ml of 
dehydrated and deoxygenated n-heptane, and 0.24 mol (Mg atom basis) of the 
above obtained solid product was then added to the n-heptane. To the 
resulting mixture was added a mixture of 25 ml of n-heptane and 0.8 mol of 
SiCl.sub.4 at 30.degree. C. over a period of 30 minutes, followed by 
reaction at 90.degree. C. for 3 hours. After the reaction was completed, 
the reaction product component (i). 
A flask which had been thoroughly purged with nitrogen gas was charged with 
50 ml of purified n-heptane. To the n-heptane, 5 g of the Sub-component 
(i), and 5 ml of SiCl.sub.4 as a Sub-component (ii) were added, and the 
resulting mixture was subjected to a reaction at 70.degree. C. for two 
hours. 10 g of metha-divinylbenzene was then added to the above reaction 
mixture as a Sub-component (iii) to carry out a contact reaction. After 
the reaction was completed, the reaction product was thoroughly washed 
with n-heptane. 1.8 ml of (t--C.sub.4 
H.sub.9)(CH.sub.3)Si(OCH.sub.3).sub.2 was added to the reaction product as 
an auxiliary component, and a contact reaction was carried out at 
30.degree. C. for two hours. After the reaction was completed, the 
reaction product thus obtained was thoroughly washed with n-heptane, 
thereby obtaining a Component (A) of the present invention. 
It was found that 0.36 g of the Sub-component (iii) had been polymerized 
per 1 g of the Sub-component (i). 
Polymerization of Propylene Monomers 
The polymerization procedure in Example 1 was repeated except that the 
diphenyldimethoxysilane used in Example 1 as an auxiliary component was 
not employed. As a result, 108.3 g of polypropylene was obtained. The 
polymer thus obtained was determined to have a T-I.I of 97.8% by weight, 
an MFR of 3.9 g/10 minutes, and a bulk density of 0.42 g/cc. 
EXAMPLE 3 
Preparation of Component (A) 
The procedure for preparing the Component (A) in Example 1 was repeated 
except that 10 ml of SiCl.sub.4 used in Example 1 as the Sub-component 
(ii) and 7.5 g of methadivinylbenzene used in Example 1 as the 
Sub-component (iii) were respectively replaced by 8 ml of 
(CH.sub.3)SiCl.sub.3 and 5 g of ortho-divinylbenzene, thereby obtaining a 
Component (A) of the present invention. 
It was found that 0.21 g of the Sub-component (iii) had been polymerized 
per 1 g of the Sub-component (i). 
Polymerization of Propylene Monomers 
The polymerization procedure in Example 1 was repeated except that the 
polymerization temperature was changed from 75.degree. to 70.degree. C. As 
a result, 141.6 g of polypropylene was obtained. The polymer thus obtained 
was determined to have a T-I.I of 98.9% by weight, an MFR of 2.6 g/10 
minutes, and a bulk density of 0.45 g/cc. 
COMATIVE EXAMPLE 1 
Preparation of Component (A) 
The procedure for preparing the Component (A) in Example 1 was repeated 
except that the methadivinylbenzene used in Example 1 as the Sub-component 
(iii) was not used, thereby to obtain a Comparative Component (A). 
Polymerization of Propylene Monomers 
The polymerization procedure in Example 1 was repeated except that the 
Component (A) used in Example 1 was replaced by the above-obtained 
Comparative Component (A). As a result, 93.6 g of polypropylene was 
obtained. The polymer thus obtained was determined to have a T-I.I of 
97.1% by weight, an MFR of 5.4 g/10 minutes, and a bulk density of 0.33 
g/cc. 
COMATIVE EXAMPLE 2 
Preparation of Component (A) 
The procedure for preparing the Component (A) in Example 2 was repeated 
except that the methadivinylbenzene used in Example 2 as the Sub-component 
(iii) was not used, thereby to obtain a Comparative Component (A). 
POLYMERIZATION OF PROPYLENE MONOMERS 
The polymerization procedure in Example 2 was repeated except that the 
Component (A) used in Example 2 was replaced by the above-obtained 
Comparative Component (A). As a result, 66.1 g of polypropylene was 
obtained. The polymer thus obtained was determined to have a T-I.I of 
94.9% by weight, an MFR of 6.8 g/10 minutes, and a bulk density of 0.35 
g/cc. 
EXAMPLE 4 
Preparation of Component (A) 
The procedure for preparing the Component (A) in Example 1 was repeated 
except that 0.4 mol of SiCl.sub.4 used in Example 1 to obtain the 
Sub-component (i) was replaced by 0.95 g of WCl.sub.6, and 10 ml of 
SiCl.sub.4 used in Example 1 as the Sub-component (ii) was replaced by 15 
ml of (C.sub.10 H.sub.21)SiCl.sub.3, thereby to obtain a Component (A) of 
the present invention. 
It was found that 0.48 g of the Sub-component (iii) had been polymerized 
per 1 g of the Sub-component (i). 
Polymerization of Propylene Monomers 
The polymerization procedure in Example 1 was repeated except that 26.8 mg 
of diphenyldimethoxysilane used in Example 1 was replaced by 50 mg of 
diphenyldimethoxymethane. As a result, 111.6 g of polypropylene was 
obtained. The polymer thus obtained was determined to have a T-I.I. of 
98.1% by weight, an MFR of 3.8 g/10 minutes, and a bulk density of 0.42 
g/cc. 
EXAMPLE 5 
Polymerization of Propylene Monomers 
The polymerization procedure in Example 4 was repeated except that 50 mg of 
diphenyldimethoxymethane used in Example 4 was replaced by 32.5 mg of 
methylcyclohexyldimethoxysilane. As a result, 133.5 g of polypropylene was 
obtained. The polymer thus obtained was determined to have a T-I.I. of 
98.3% by weight, an MFR of 2.4 g/10 minutes, and a bulk density of 0.43 
g/cc. 
EXAMPLE 6 
Polymerization of Propylene Monomers 
The polymerization procedure in Example 4 was d in Example 4 was replaced 
by 19.3 mg of diisopropyldimethoxysilane. As a result, 130.6 g of 
polypropylene was obtained. The polymer thus obtained was determined to 
have a T-I.I. of 98.2% by weight, an MFR of 3.1 g/10 minutes, and a bulk 
density of 0.44 g/cc.