Catalyst component for polymerization of olefins

A catalyst component for the polymerization of olefins which is prepared by contacting (1) a contact reaction product of (a) a metal oxide, (b) a dihydrocarbyl magnesium, and (c) a halogen-containing alcohol held with (d) an electron-donating compound, and (e) a titanium compound.

FIELD OF THE INVENTION 
This invention relates to a catalyst component for the polymerization of 
olefins and, to the catalyst system comprising the catalyst component, and 
to the process of polymerizing olefins, especially olefins having 3 or 
more carbon atoms, in the presence of the catalyst system. 
BACKGROUND OF THE INVENTION 
Concerning Ziegler-Natta type catalysts which are effective in polymerizing 
olefins, catalyst components having transition metals deposited on a 
variety of carriers have been developed for the purpose of improving 
catalyst activity per unit amount of catalyst or decreasing residues 
originating in catalyst and persisting in produced polymer. 
A plurality of catalyst components using silica, alumina, and other similar 
metal oxides as carriers for deposition of transition metals have been 
proposed. Most of them are intended for polymerization of ethylene. A very 
few of them are intended for polymerization of alpha-olefins such as 
propylene. 
As concerns catalyst compositions for the polymerization of propylene, a 
catalyst component comprising a reaction product of a metal oxide and a 
magnesium dialkoxide brought in contact with an electron-donating compound 
and a tetravalent titanium halide (specification of Japanese patent 
application Laid-open No. SHO 58[1973]-162,607) and a catalyst component 
comprising a reaction product of an inorganic oxide and a magnesium 
hydrocarbyl halide compound brought in contact with a Lewis base compound 
and titanium tetrachloride (specification of Japanese patent application 
Laid-open No. SHO 55[1980]-94,909) are known to the art. These catalyst 
components, however, can hardly be called satisfactory in terms of 
activity and stereoregularity. 
Further, a catalyst component obtained by causing a hydrocarbyloxysilane to 
react with a reaction product of a porous carrier such as silica and an 
alkyl magnesium compound and subsequently causing a titanium halide 
compound to react upon the resultant reaction product (specification of 
Japanese patent application Laid-open No. SHO 57[1982]-153,006) and a 
catalyst component obtained by causing an organic metal compound to react 
with a porous carrier, causing a hydrocarbyl alcohol to react with the 
resultant reaction product, and then causing a titanium halide compound to 
react with the reaction product (specification of Japanese patent 
application Laid-open No. SHO 57[1982]-200,408) have been proposed. These 
catalyst components are intended for homopolymerization of ethylene or for 
copolymerization of ethylene with other olefins. They are not suitable for 
polymerization of alpha-olefins such as propylene. 
DISCLOSURE OF THE INVENTION 
Object of the Invention 
It is an object of this invention to provide a catalyst component which 
uses a metal oxide as a carrier and which is used for homopolymerization 
of an olefin exhibiting high activity and high stereoregularity, 
particularly an alpha-olefin such as propylene, and for copolymerization 
of the aforementioned olefin with other olefins. More particularly, in 
accordance with an object of this invention there is provided a catalyst 
component which is prepared by contacting a contact reaction product of a 
metal oxide, a dihydrocarbyl magnesium, and a halogen-containing alcohol 
held in contact with an electron- donating compound and a titanium 
compound fulfills the object of this invention. This discovery has led to 
perfection of this invention. 
SUMMARY OF THE INVENTION 
To be specific, this invention essentially concerns a catalyst component 
for the polymerization of olefins which is prepared by contacting a 
contact reaction product of (1) (a) a metal oxide, (b) a dihydrocarbyl 
magnesium, and (c) a halogen-containing alcohol held with (2) (d) an 
electron-donating compound and (e) a titanium compound. 
Raw materials for Preparation of catalyst component 
(A) Metal Oxide 
The metal oxide to be used in this invention is the oxide of an element 
selected from the class of elements belonging to Groups II through IV in 
the Periodic Table of Elements. Examples of the oxide are B.sub.2 O.sub.3, 
MgO, Al.sub.2 O.sub.3, SiO.sub.2, CaO, TiO.sub.2, ZnO, ZrO.sub.2, 
SnO.sub.2, BaO, and ThO.sub.2. Among other oxides enumerated above, 
B.sub.2 O.sub.3, MgO, Al.sub.2 O.sub.3, SiO.sub.2, TiO.sub.2, and 
ZrO.sub.2 are more desirable selections, and SiO.sub.2 is the most 
desirable selection. Further, composite oxides including these metal 
oxides are also usable. Examples of these composite oxides are SiO.sub.2 
-MgO, SiO.sub.2 -Al.sub.2 O.sub.3, SiO.sub.2 -TiO.sub.2, SiO.sub.2 
-V.sub.2 O.sub.5, SiO.sub.2 -Cr.sub.2 O.sub.3, and SiO.sub.2 -TiO.sub.2 
-MgO. 
The aforementioned metal oxides or composite oxides described above are 
fundamentally desired to be an anhydride. It, however, tolerates inclusion 
of a hydroxide in a very small amount normally entrained in the metal 
oxide of the class under discussion. It also tolerates inclusion therein 
of impurities to an extent incapable of appreciably impairing the nature 
of metal oxide. Examples of the impurities so tolerated are oxides, 
carbonates, sulfates, and nitrates such as sodium oxide, potassium oxide, 
lithium oxide, sodium carbonate, potassium carbonate, calcium carbonate, 
magnesium carbonate, sodium sulfate, aluminum sulfate, barium sulfate, 
potassium nitrate, magnesium nitrate, and aluminum nitrate. 
Generally, the metal oxide of the foregoing description is used in the form 
of powder. The size and shape of the individual particles of this powder 
are desired to be suitably adjusted because they often have bearing on the 
shape of the olefin polymer to be produced. Prior to use, this metal oxide 
is fired at as high a temperature as permissible as for the purpose of 
expelling poisoned substance and then held so as not to be exposed 
directly to the atmosphere. 
(B) Dihydrocarbyl Magnesium 
The dihydrocarbyl magnesium to be used in the present invention 
(hereinafter referred to as "organic Mg") is represented by the general 
formula, RMgR'. In this formula, R and R', which can be the same or 
different, denote an alkyl, cycloalkyl, aryl, or aralkyl group of 1 to 20 
carbon atoms. 
Examples of the organic Mg are dimethyl magnesium (hereinafter "magnesium" 
will be abbreviated "Mg"), diethyl Mg, ethylmethyl Mg, dipropyl Mg, 
diisopropyl Mg, ethylpropyl Mg, dibutyl Mg, diisobutyl Mg, di-sec-butyl 
Mg, di-tert-butyl Mg, butylethyl Mg, butylpropyl Mg, sec-butylethyl Mg, 
tert-butylisopropyl Mg, sec-butyl-tertbutyl Mg, dipentyl Mg, diisopentyl 
Mg, ethylpentyl Mg, isopropylpentyl Mg, sec-butylpentyl Mg, dihexyl Mg, 
ethylhexyl Mg, butylhexyl Mg, tert-butylhexyl Mg, (2-ethylbutyl)ethyl Mg, 
(2,2-diethylbutyl)ethyl Mg, diheptyl Mg, dioctyl Mg, di-2-ethylhexyl Mg, 
didecyl Mg, dicyclohexyl Mg, cyclohexylethyl Mg, butylcyclohexyl Mg, 
di(methylcyclohexyl) Mg, diphenyl Mg, ethylphenyl Mg, butylphenyl Mg, 
sec-butylphenyl Mg, ditolyl Mg, ethyltolyl Mg, dixylyl Mg, dibenzyl Mg, 
benzyl-tert-butyl Mg, diphenethyl Mg, and ethylphenethyl Mg. 
The organic Mg may be a mixture or complex compound with an organic 
compound of other metal. The organic compound of other metal is 
represented by the general formula MRn (wherein M denotes boron, 
beryllium, aluminum, or zinc, R denotes an alkyl, cycloalkyl, aryl, or 
aralkyl group of 1 to 20 carbon atoms, and n denotes the valency of the 
metal M). Concrete examples of the organic compound of other metals are 
triethyl aluminum, tributyl aluminum, triisobutyl aluminum, triphenyl 
aluminum, triethyl boron, tributyl boron, diethyl beryllium, diisobutyl 
beryllium, diethyl zinc, and dibutyl zinc. 
In the aforementioned mixture or complex compound, the ratio of the organic 
Mg to the organic compound of other metal generally is such that the 
amount of the other metal is not more than 5 gram atoms, preferably not 
more than 2 gram atoms, per gram atom of magnesium. 
(C) Halogen-containing Alcohol 
The term "halogen-containing alcohol" as used in this invention means a 
monohydric or polyhydric alcohol possessing one or more hydroxyl groups in 
the molecule thereof and having one or more hydrogen atoms thereof other 
than the aforementioned hydroxyl group substituted with a halogen atom. 
Concrete examples of the halogen atom are chlorine, bromine, iodine, and 
fluorine atom. Among the halogen atoms cited above, the chlorine atom is 
particularly desirable. 
Examples of the halogen-containing alcohol are 2-chloroethanol, 
1-chloro-2-propanol, 3-chloro-1-propanol, 1-chloro-2-methyl-2-propanol, 
4-chloro-1-butanol, 5-chloro-1-pentanol, 6-chloro-1-hexanol, 
3-chloro-1,2-propane diol, 2-chlorocyclohexanol, 4-chlorobenzhydrol, 
(m,o,p)-chlorobenzyl alcohol, 4-chlorocatechol, 4-chloro(m,o)-cresol, 
6-chloro-(m,o)-cresol, 4-chloro-3,5-dimethylphenol, chlorohydroquinone, 
2-benzyl-4-chlorophenol, 4-chloro-1-naphthol, (m,o,p)-chlorophenol, 
p-chloro-alpha-methylbenzyl alcohol, 2-chloro-4-phenylphenol, 
6-chlorothimol, 4-chlororesorcin, 2-bromoethanol, 3-bromo-1-propanol, 
1-bromo-2-propanol, 1-bromo-2-butanol, 2-bromo-p-cresol, 
1-bromo-2-naphthol, 6-bromo-2-naphthol, (m,o,p)-bromophenol, 
4-bromoresorcin, (m,o,p)-fluorophenol, p-iodophenol: 2,2-dichloroethanol, 
2,3-dichloro-1-propanol, 1,3-dichloro-2-propanol, 
3-chloro-1-(alpha-chloromethyl)-1-propanol, 2,3-dibromo-1-propanol, 
1,3-dibromomono-2-propanol, 2,4-dibromophenol, 2,4-dibromo-1-naphthol: 
2,2,2-trichloroethanol, 1,1,1-trichloro-2-propanol, 
.beta.,.beta.,.beta.-trichlorotert-butanol, 2,3,4-trichlorophenol, 
2,4,5-trichlorophenol, 2,4,6-trichlorophenol, 2,4,6-tribromophenol, 
2,3,5-tribromo-2-hydroxy toluene, 2,3,5-tribromo-4-hydroxy toluene, 
2,2,2-trifluoroethanol, alpha,alpha,alpha-trifluoro-m-cresol, 
2,4,6-triiodophenol: 2,3,4,6-tetrachlorophenol, tetrachlorohydroquinone, 
tetrachloro-bis-phenol A, tetrabromo-bis-phenol A, 
2,2,3,3-tetrafluoro-1-propanol, 2,3,5,6-tetrafluorophenol, and 
tetrafluororesorcin. 
(D) Electron-donating Compound 
Examples of the electron-donating compound are carboxylic acids, carboxylic 
anhydrides, carboxylic esters, carboxylic halides, alcohols, ethers, 
ketones, amines, amides, nitriles, aldehydes, alcoholates, phosphorus, 
bismuth, and antimony compounds linked with organic groups through the 
medium of carbon or oxygen atom, phosphamides, thioethers, thioesters, and 
carbonic esters. Among other electron-donating compounds cited above, 
carboxylic acids, carboxylic anhydrides, carboxylic esters, carboxylic 
halides, alcohols and ethers are particularly desirable. 
Concrete examples of the carboxylic acids are aliphatic monocarboxylic 
acids such as formic acid, acetic acid, propionic acid, butyric acid, 
isobutyric acid, valeric acid, caproic acid, pivalic acid, acrylic acid, 
methacrylic acid, and crotonic acid, aliphatic dicarboxylic acids such as 
malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, 
maleic acid, and fumaric acid, aliphatic oxycarboxylic acids such as 
tartaric acid, alicyclic carboxylic acids such as cyclohexane 
monocarboxylic acids, cyclohexene monocarboxylic acids, 
cis-1,2-cyclohexane dicarboxylic acids, and 
cis-4-methylcyclohexane-1,2-dicarboxylic acids, aromatic monocarboxylic 
acids such as benzoic acid, toluic acid, anisic acid, p-tert-butyl-benzoic 
acid, naphtholic acid, and cinnamic acid, and aromatic poly carboxylic 
acids such as phthalic acid, isophthalic acid, terephthalic acid, 
naphthalic acid, trimellitic acid, hemimellitic acid, trimestic acid, 
pyromellitic acid, and mellitic acid. 
Concrete examples of carboxylic anhydrides are the anhydrides of the 
carboxylic acids enumerated above. 
Carboxylic esters are monoesters and polyesters of the carboxylic acids 
enumerated above. Concrete examples of such monoesters and polyesters are 
butyl formate, ethyl acetate, butyl acetate, isobutyl isobutyrate, propyl 
pivalate, isobutyl pivalate, ethyl acrylate, methyl methacrylate, ethyl 
methacrylate, isobutyl methacrylate, diethyl malonate, diisobutyl 
malonate, diethyl succinate, dibutyl succinate, diisobutyl succinate, 
diethyl glutarate, dibutyl glutarate, diisobutyl glutarate, diisobutyl 
adipate, dibutyl sebacate, diisobutyl sebacate, diethyl maleate, dibutyl 
maleate, diisobutyl maleate, monomethyl fumarate, diethyl fumarate, 
diisobutyl fumarate , diethyl tartrate, dibutyl tartrate, diisobutyl 
tartrate, ethyl cyclohexanecarboxylates, methyl benzoate, ethyl benzoate, 
methyl p-toluate, ethyl p-tert butylbenzoate, ethyl p-anisate, ethyl 
alpha-naphthoate, isobutyl alpha-naphthoate, ethyl cinnamate, monomethyl 
phthalate, monobutyl phthalate, dibutyl phthalate, diisobutyl phthalate, 
dihexyl phthalate, dioctyl phthalate, di-2-ethylhexyl phthalate, diallyl 
phthalate, diphenyl phthalate, diethyl isophthalate, diisobutyl 
isophthalate, diethyl terephthalate, dibutyl terephthalate, diethyl 
paphthalate, dibutyl naphthalate, triethyl trimellate, tributyl 
trimellate, tetramethyl pyromellate, tetraethyl pyromellate, and 
tetrabutyl pyromellate. 
Carboxylic halides are halides of the carboxylic acids enumerated above. 
Concrete examples of such halides are acetic acid chloride, acetic acid 
bromide, acetic acid iodide, propionic acid chloride, butyric acid 
chloride, butyric acid bromide, butyric acid iodide, pivalic acid 
chloride, pivalic acid bromide, acrylic acid chloride, acrylic acid 
bromide, acrylic acid iodide, methacrylic acid chloride, methacrylic acid 
bromide, methacrylic acid iodide, crotonic acid chloride, maloic acid 
chloride, maloic acid bromide, succinic acid chloride, succinic acid 
bromide, glutaric acid chloride, glutaric acid bromide, adipic acid 
chloride, adipic acid bromide, sebacic acid chloride, sebacic acid 
bromide, maleic acid chloride, maleic acid bromide, fumaric acid chloride, 
fumaric acid bromide, tartaric acid chloride, tartaric acid bromide, 
cyclohexane-carboxylic acid chloride, cyclohexane-carboxylic acid 
bromides, 1-cyclohexene-carboxylic acid chloride, 
cis-4-methylcyclohexene-carboxylic acid chloride, 
cis-4-methylcyclohexene-carboxylic acid bromide, benzoyl chloride, benzoyl 
bromide, p-toluic acid chloride, p-toluic acid bromide, p-anisic acid 
chloride, p-anisic acid bromide, alpha-naphthoic acid chloride, cinnamic 
acid chloride, cinnamic acid bromide, phthalic acid dichloride, phthalic 
acid dibromide, isophthalic acid dichloride, isophthalic acid dibromide, 
terephthalic acid dichloride, and naphthalic acid dichloride. Further 
monoalkylhalides of dicarboxylic acids such as adipic acid monomethyl 
chloride, maleic acid monoethyl chloride and maleic acid monomethyl 
chloride and phthalic acid butyl chloride are also usable. 
Alcohols are represented by the general formula ROH. In the formula, R 
denotes an alkyl, alkenyl, cycloalkyl, aryl, or aralkyl group of 1 to 12 
carbon atoms. Concrete examples of such alcohols are methanol, ethanol, 
propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, octanol, 
2-ethylhexanol, cyclohexanol, benzyl alcohol, allyl alcohol, phenol, 
cresol, xylenol, ethyl phenol, isopropyl phenol, p-tertiary butyl phenol, 
and n-octyl phenol. Ethers are represented by the general formula ROR'. In 
the formula, R and R' each denote an alkyl, alkenyl, cycloalkyl, aryl, or 
aralkyl group of 1 to 12 carbon atoms, providing that R and R' may be 
equal to or different from each other. Concrete examples of such ethers 
are diethyl ether, diisopropyl ether, dibutyl ether, diisobutyl ether, 
diisoamyl ether, di-2-ethylhexyl ether, diallyl ether, ethylallyl ether, 
butylallyl ether, diphenyl ether, anisol, and ethylphenyl ether. Any of 
the compounds cited above as examples of halogen-containing alcohols is 
also usable. 
(E) Titanium Compound 
Titanium compounds are divalent, trivalent, and tetravalent titanium 
compounds. Concrete examples of such titanium compounds are titanium 
tetrachloride, titanium tetrabromide, trichlorethoxy titanium, 
trichlorobutoxy titanium, dichlorodiethoxy titanium, dichlorodibutoxy 
titanium, dichlorodiphenoxy titanium, chlorotriethoxy titanium, 
chlorotributoxy titanium, tetrabutoxy titanium, and titanium trichloride. 
Among other titanium compounds enumerated above, such tetravalent titanium 
halides such as titanium tetrachloride, trichloroethoxy titanium, 
dichlorodibutoxy titanium, and dichlorodiphenoxy titanium prove desirable 
and titanium tetrachloride proves particularly desirable. 
Method for Preparation of Catalyst Component 
The catalyst component of the present invention is obtained by contacting a 
reaction product comprising (a) a metal oxide (hereinafter referred to as 
"A component"), the organic Mg (hereinafter referred to as "B component"), 
and the halogen-containing alcohol (hereinafter referred to as "C 
component") (b) with an electron-donating compound (hereinafter referred 
to as "D component") and a titanium compound (hereinafter referred to as 
"E component"). 
Contact of A Component, B Component, and C Component 
The contact of A component, B component and C component is effected by (1) 
a procedure of first establishing contact between A component and B 
component and then introducing C component into contact therewith, (2) a 
procedure of first establishing contact between A component and C 
component and then introducing B component into contact thereof, (3) a 
procedure of first establishing contact between B component and C 
component and then introducing A component into contact therewith, or (4) 
a procedure of establishing contact among A component, B component and C 
component all at once. 
The contact mentioned above, for example, is effected by stirring the 
relevant components in the presence or absence of an inactive medium or by 
mechanically comminuting the relevant components jointly. 
Examples of the inactive medium usable in the contact are hydrocarbons such 
as pentane, hexane, heptane, octane, decane, cyclohexane, benzene, 
toluene, and xylene and halides of hydrocarbons such as 
1,2-dichloroethane, 1,2-dichloropropane, carbon tetrachloride, butyl 
chloride, isoamyl chloride, bromobenzene, and chlorotoluene. 
The contact of A component, B component and C component is generally 
carried out at a temperature of -20.degree. C. to +150.degree. C. for a 
period of 0.1 to 100 hours. Where the contact entails evolution of heat, 
there may be adopted a procedure of first mixing the components gradually 
at a low temperature and, after all the components have been wholly mixed, 
elevating the temperature and continuing the contact. Further during the 
course of the contact of the components, the individual components may be 
washed with the aforementioned inactive medium. The proportions in which A 
component, B component, and C component are used in the contact are such 
that the mol ratio B/A falls in the range of 0.01 to 10, that of C/A in 
the range of 0.01 to 10, and that of C/B in the range of 0.1 to 20. 
The solid product obtained by the contact of A component, B component and C 
component (hereinafter referred to as "reaction product I") is subjected 
to the subsequent contact. Optionally, the reaction product I may be 
cleaned with a suitable cleaning agent such as, for example, the 
aforementioned inactive medium. 
Contact with D Component and E Component 
The contact of the reaction product I with an electron-donating (D 
component) and a titanium compound (E component) is effected by (1) a 
procedure of first establishing contact between the reaction product I and 
D component and then introducing E component into contact therewith, (2) a 
procedure of first establishing contact between the reaction product I and 
E component and then introducing D component into contact therewith, or 
(3) a procedure of establishing contact between D component and E 
component used jointly on one part and the reaction product I on the other 
part. 
The contact mentioned above is accomplished by mechanically comminuting the 
relevant components jointly or stirring them in the presence or absence of 
an inactive medium. It is more desirably effected by stirring the relevant 
components in the presence or absence of an inactive medium. As the 
inactive medium, any of the aforementioned compounds can be used 
effectively. 
When the contact of the reaction product I with D component and C component 
is effected by their mechanical joint comminution, it is effected 
generally at a temperature in the range of 0.degree. C. to 200.degree. C. 
for a period of 0.1 to 100 hours. When the contact is carried out by 
stirring, it is effected generally at a temperature of 0.degree. C. to 
200.degree. C. for a period of 0.5 to 20 hours. The amount of D component 
used in this contact is in the range of 0.005 to 10 gram mols, preferably 
0.01 to 1 gram mol, per gram atom of magnesium in the reaction product I. 
The amount of E component used in the contact is above the level of 0.1 
gram mol, preferably in the range of 1 to 50 gram mols, per gram atom of 
magnesium in the reaction product I. 
The contact between the reaction product I and E component may be carried 
out twice or more. This contact can be effected by any of the procedures 
mentioned above. In this case, the product from the former contact may be 
cleaned with an inactive medium and the cleaned product allowed to contact 
with a freshly added portion of E component (in conjunction with the 
aforementioned medium). 
Where the contact with E component is carried out in two or more split 
steps, the reaction mixture under treatment may be allowed to contact with 
an inactive hydrocarbon, halide of hydrocarbon, or metal halide compound 
between the split steps of contact. 
Examples of the inactive hydrocarbon usable for the contact are aliphatic, 
alicyclic, and aromatic hydrocarbons. Concrete examples of such 
hydrocarbons are n-hexane, methyl hexane, dimethyl hexane, ethyl hexane, 
ethylmethyl pentane, n-heptane, methyl heptane, trimethyl pentane, 
dimethyl heptane, ethyl heptane, trimethyl hexane, trimethyl heptane, 
n-octane, methyl octane, dimethyl octane, n-undecane, n-dodecane, 
n-tridecane, n-tetradecane, n-pentadecane, n-hexadecane, n-octadecane, 
n-nonadecane, n-eicosane, cyclopentane, cyclohexane, methyl cyclopentane, 
cycloheptane, dimethyl cyclopentane, methyl cyclohexane, ethyl 
cyclopentane, dimethyl cyclohexane, ethyl cyclohexane, cyclooctane, 
indane, n-butyl cyclohexane, isobutyl cyclohexane, adamantane, benzene, 
toluene, xylene, ethylbenzene, tetramethylbenzne, n-butylbenzene, 
isobutylbenzene, propyl toluene, decalin, and tetralin. 
Examples of the halide of hydrocarbon usable for the contact are mono- and 
poly-halogen substitution products of saturated or unsaturated aliphatic, 
alicyclic, and aromatic hydrocarbons. Concrete examples of such compounds 
are aliphatic compounds such as methyl chloride, methyl bromide, methyl 
iodide, methylene chloride, methylene bromide, methylene iodide, 
chloroform, bromoform, iodoform, carbon tetrachloride, carbon 
tetrabromide, carbon tetraiodide, ethyl chloride, ethyl bromide, ethyl 
iodide, 1,2-dichloroethane, 1,2-dibromo-ethane, 1,2-diiodo-ethane, methyl 
chloroform, methyl bromoform, methyl iodoform, 1,1,2-trichloro-ethylene, 
1,1,2-tribromoethylene, 1,1,2,2-tetrachloro-ethylene, pentachloro-ethane, 
hexachloro-ethane, hexabromo-ethane, n-propyl chloride, 
1,2-dichloropropane, hexachloro-propylene, octachloro-propane, 
decabromobutane, and chlorinated paraffins, alicyclic compounds such as 
chlorocyclopropane, tetrachlorocyclo-pentane, hexachloropentane, and 
hexachlorocyclohexane, and aromatic compounds such as chlorobenzene, 
bromobenzene, o-dichlorobenzene, p-dichlorobenzene, hexachlorobenzene, 
hexabromobenzene, benzotrichloride, and p-chlorobenzo-trichloride. 
These compounds are such that one member of a mixture of two or more 
members selected from the compounds enumerated above may be advantageously 
used. 
The metal halide compound is the halide of one element selected from the 
class of elements of Group IIIa, Group IVa, and Group Va in the Periodic 
Table of Elements (hereinafter referred to as "metal halide"). Examples of 
the metal halide are chlorides, fluorides, bromides, and iodides of B, Al, 
Ga, In, Tl, Si, Ge, Sn, Pb, As, Sb, and Bi. Among other metal halides 
enumerated above, BCl.sub.3, BBr.sub.3, BI.sub.3, AlCl.sub.3, AlBr.sub.3, 
AlI.sub.3, GaCl3, GaBr.sub.3, InCl.sub.3, TlCl.sub.3, SiCl.sub.4, 
SnCl.sub.4, SbCl.sub.5, and SbF.sub.5 prove particularly desirable. 
The contact of the reaction mixture optionally made with the inactive 
hydrocarbon, halide of hydrocarbon, or metal halide (hereinafter referred 
to as "F component") between the two or more split steps of contact made 
by the E component is carried out at a temperature in the range of 
0.degree. to 200.degree. C. for a period of 5 minutes to 20 hours, 
preferably at 20.degree. C. to 150.degree. C. for 10 minutes to 5 hours. 
When the F component is a liquid substance, it is desired to be used in 
such an amount that the reaction product I is obtained in an amount in the 
range of 1 to 1,000 g per liter of the F component. When the F component 
is a solid substance, this solid F component is desired to be used as 
dissolved in another F component capable of dissolving the solid F 
component. The amount of this solid F component is desired to be such that 
the reaction product I is obtained in an amount in the range of 0.01 to 
100 g per g of the F component. 
The mass of contact between the reaction product I with the component E may 
be allowed to contact with the F component. This contact can be carried 
out in the same manner as in the contact optionally made by the use of the 
aforementioned F component. 
The contact reaction product obtained as described above is cleaned, when 
necessary, with hydrocarbon such as hexane, heptane, octane, cyclohexane, 
benzene, toluene, or xylene, and then dried to give birth to the catalyst 
component of the present invention. 
The catalyst component of the present invention is formed of particles 
having a specific surface area in the range of 10 to 1,000 m.sup.2 /g and 
a pore volume in the range of 0.05 to 5 cm.sup.3 /g as measured by the BET 
method at the adsorption temperature of liquefied nitrogen and possessing 
diameters so uniform as to be distributed in a narrow range. As to 
percentage composition, this catalyst component comprises 3 to 90% by 
weight of metal oxide, 1 to 25% by weight of magnesium, 0.5 to 10% by 
weight of titanium, and 4 to 60% by weight of chlorine. 
Catalyst for the Polymerization of Olefins 
The catalyst component of the present invention is used, as combined with 
an organic compound of a metal selected from the class of metals belonging 
to Groups I through III in the Periodic Table of Elements, for catalyzing 
the homopolymerization of an olefin or the copolymerization of the olefin 
with other olefins. 
Organic Compound of Metal of Group I through Group III 
Examples of the organic metal compounds usable in combination with the 
catalyst component are organic compounds of lithium, magnesium, calcium, 
zinc, and aluminum. Among other organic metal compounds just mentioned, 
organic aluminum compounds prove particularly desirable. The organic 
aluminum compounds usable herein are represented by the general formula 
R.sub.n AlX.sub.3-n (wherein R denotes an alkyl group or an aryl group, X 
denotes a halogen atom, an alkoxy group or a hydrogen atom, and n denotes 
a desired number in the range of 1.ltoreq.n.ltoreq.3). Particularly 
desirable examples of the organic aluminum compounds are alkyl aluminum 
compounds such as trialkyl aluminum, dialkyl aluminum monohalide, 
monoalkyl aluminum dihalide, alkyl aluminum sesquihalide, dialkyl aluminum 
monoalkoxide, and dialkyl aluminum monohydride, respectively having 1 to 
18 carbon atoms, preferably 2 to 6 carbon atoms, and mixtures and complex 
compounds thereof. Concrete examples of such organic aluminum compounds 
are trialkyl aluminums such as trimethyl aluminum, triethyl aluminum, 
tripropyl aluminum, triisobutyl aluminum, and trihexyl aluminum, dialkyl 
aluminum monohalides such as dimethyl aluminum chloride, diethyl aluminum 
chloride, diethyl aluminum bromide, diethyl aluminum iodide, and 
diisobutyl aluminum chloride, monoalkyl aluminum dihalides such as methyl 
aluminum dichloride, ethyl aluminum dichloride, methyl aluminum dibromide, 
ethyl aluminum dibromide, ethyl aluminum diiodide, and isobutyl aluminum 
dichloride, alkyl aluminum sesquihalides such as ethyl aluminum 
sesquichloride, dialkyl aluminum monoalkoxides such as dimethyl aluminum 
methoxide, diethyl aluminum ethoxide, diethyl aluminum phenoxide, dipropyl 
aluminum ethoxide, diisobutyl aluminum ethoxide, and diisobutyl aluminum 
phenoxide, and dialkyl aluminum hydrides such as dimethyl aluminum 
hydride, diethyl aluminum hydride, dipropyl aluminum hydride, and 
diisobutyl aluminum hydride. Among other organic aluminum compounds 
enumerated above, trialkyl aluminums, specifically triethyl aluminum, 
triisobutyl aluminum, prove particularly desirable. The trialkyl aluminum 
can be used in combination with other organic aluminum compounds such as 
diethyl aluminum chloride, ethyl aluminum dichloride, ethyl aluminum 
sesquichloride, diethyl aluminum ethoxide, or diethyl aluminum hydride 
which is easily available commercially. These other organic aluminum 
compounds may be used in the form of a mixture or complex compound. 
Further, an organic aluminum compound having two or more aluminum atoms 
linked through the medium of an oxygen atom or nitrogen atom is also 
usable. Concrete examples of this organic aluminum compound are (C.sub.2 
H.sub.5).sub.2 AlOAl(C.sub.2 H.sub.5).sub.2, (C.sub.4 H.sub.9).sub.2 
AlOAl(C.sub.4 H.sub.9).sub.2, and 
##STR1## 
Examples of organic compounds of metals other than aluminum are diethyl 
magnesium, ethyl magnesium chloride, diethyl zinc and such compounds as 
LiAl(C.sub.2 H.sub.5).sub.4 and LiAl(C.sub.7 H.sub.15).sub.4. 
The organic metal compound may be used independently or in combination with 
an electron-donating compound. This electrondonating compound may be any 
of the electron-donating compounds employed in the preparation of the 
catalyst component described above. Besides, organic silicon compounds 
capable of serving as electron-donating compounds and electron-donating 
compounds containing hetero atoms such as nitrogen, sulfur, oxygen, and 
phosphorus atoms are also usable. 
Concrete examples of organic silicon compounds are tetramethoxy silane, 
tetraethoxy silane, tetrabutoxy silane, tetraisobutoxy silane, 
tetraphenoxy silane, tetra(p-methylphenoxy) silane, tetrabenzyloxy silane, 
methyl trimethoxy silane, methyl triethoxy silane, methyl tributoxy 
silane, methyl triphenoxy silane, ethyl triethoxy silane, ethyl 
triisobutoxy silane, ethyl triphenoxy silane, butyl trimethoxy silane, 
butyl triethoxy silane, butyl triphenoxy silane, isobutyl triisobutoxy 
silane, vinyl triethoxy silane, allyl trimethoxy silane, phenyl trimethoxy 
silane, phenyl triethoxy silane, benzyl triphenoxy silane, methyl 
triallyloxy silane, dimethyl dimethoxy silane, dimethyl diethoxy silane, 
dimethyl diisopropoxy silane, dimethyl dibutoxy silane, dimethyl 
dihexyloxy silane, dimethyl diphenoxy silane, diethyl diethoxy silane, 
diethyl diisobutoxy silane, diethyl diphenoxy silane, dibutyl diisopropoxy 
silane, dibutyl dibutoxy silane, dibutyl diphenoxy silane, diisobutyl 
diethoxy silane, diisobutyl diisobutoxy silane, diphenyl dimethoxy silane, 
diphenyl diethoxy silane, diphenyl dibutoxy silane, dibenzyl diethoxy 
silane, divinyl diphenoxy silane, diallyl dipropoxy silane, diphenyl 
diallyloxy silane, methylphenyl dimethoxy silane, and chlorophenyl 
diethoxy silane. 
Concrete examples of the electron-donating compound containing a hetero 
atom are such nitrogen atom-containing compounds as 2,2,6,6-tetramethyl 
piperidine, 2,6-dimethyl piperidine, 2,6-diethyl piperidine, 
2,6-diisopropyl piperidine, 2,2,5,5-tetramethyl pyrrolidine, 2,5-dimethyl 
pyrrolidine, 2,5-diethyl pyrrolidine, 2,5-diisopropyl pyrrolidine, 
2-methyl pyridine, 3-methyl pyridine, 4-methyl pyridine, 1,2,4-trimethyl 
piperidine, 2,5-dimethyl piperidine, methyl nicotinate, ethyl nicotinate, 
nicotinic acid amide, benzoic acid amide, 2-methyl pyrrole, 2,5-dimethyl 
pyrrole, imidazole, toluic acid amide, benzonitrile, acetonitrile, 
aniline, paratoluidine, ortho-toluidine, meta-toluidine, triethyl amine, 
diethyl amine, dibutyl amine, tetramethylene diamine, and tributyl amine, 
such sulfur atom-containing compounds as thiophenol, thiophene, ethyl 
2-thiophene carboxylate, ethyl 3-thiophene carboxylate, 2-methyl 
thiophene, methyl mercaptan, ethyl mercaptan, isopropyl mercaptan, butyl 
mercaptan, diethyl thioether, methyl benzenesulfonate, methyl sulfite, and 
ethyl sulfite, such oxygen atom-containing compounds as tetrahydrofuran, 
2-methyl tetrahydrofuran, 3-methyl tetrahydrofuran, dioxane, dimethyl 
ether, diethyl ether, dibutyl ether, diisoamyl ether, diphenyl ether, 
anisole, acetophenone, acetone, methylethyl ketone, acetyl acetone, ethyl 
2-furalate, isoamyl 2-furalate, methyl 2-furalate, and propyl 2-furalate, 
and such phosphorus atom-containing compounds as triphenyl phosphine, 
tributyl phosphine, triphenyl phosphite, tribenzyl phosphite, diethyl 
phosphate, and diphenyl phosphate. 
These electron-donating compounds are such that two or more members 
selected from the group of compounds enumerated above can be used as a 
mixture. The electron-donating compound may be used at the same time that 
the organic metal compound is used in combination with the catalyst 
component or it may be used after it has been placed in contact with the 
organic metal compound. 
The amount of the organic metal compound to be used relative to the 
catalyst component of the present invention falls generally in the range 
of 1 to 2000 gram mols, preferably 20 ti 500 gram mols, per gram atom of 
titanium present in the catalyst component. 
The proportions of the organic metal compound and the electron-donating 
compound are such that the amount of the organic metal compound falls in 
the range of 0.1 to 40 gram atoms, preferably 1 to 25 gram atoms, per mol 
of the electron-donating compound. 
Polymerization of Olefins 
The catalyst which comprises the catalyst component obtained as described 
above and the organic metal compound (and the electron-donating compound) 
is useful for catalyzing homopolymerization of a monoolefin of 2 to 10 
carbon atoms or copolymerization of the monoolefin in combination with 
other monoolefins or diolefins of 3 to 10 carbon atoms. The catalyst 
exhibits an outstanding function, particularly in catalyzing 
homopolymerization of an alpha-olefin such as, for example, propylene, 
1-butene, 4-methyl-1-pentene, or 1-hexene, copolymerization of two such 
alpha-olefins and/or random and block copolymerization of the alpha-olefin 
with ethylene. 
The polymerization may be carried out in either the gaseous phase or the 
liquid phase. When the polymerization is performed in the liquid phase, it 
can be effected on a liquid monomer in an inactive hydrocarbon such as 
normal butane, iso-butane, normal pentane, iso-pentane, hexane, heptane, 
octane, cyclohexane, benzene, toluene, or xylene. The polymerization 
temperature falls generally in the range of -80.degree. C. to +150.degree. 
C., preferably in the range of 40.degree. C. to 120.degree. C. The 
polymerization pressure is sufficient in the range of 1 to 60 atmospheres. 
Adjustment of the molecular weight of the polymer to be obtained is 
attained by causing the polymerization to proceed in the presence of 
hydrogen or other known molecular weight adjusting agents. The amount of 
the other olefin with which the olefin is copolymerized generally is not 
allowed to exceed 30% by weight and preferably is selected in the range of 
0.3 to 15% by weight. The polymerization by the catalyst system of this 
invention can be carried out continuously or batchwise under those 
conditions which are generally adopted for the purpose of polymerization. 
The copolymerization may be performed in one step or in two or more split 
steps. 
Effect of the Invention 
The catalyst component of the present invention functions effectively as a 
catalyst for the production of a polyolefin, particularly isotactic 
polypropylene, a random copolymer of ethylene and propylene, and a block 
copolymer of ethylene and propylene. 
The polymerization catalyst using the catalyst component of the present 
invention possesses high polymerization activity and high stereoregularity 
and permits the high polymerization activity to be retained long during 
the course of the polymerization. The olefin polymer powder consequently 
obtained has high bulk density. The polymer powder abounds with fluidity.

EXAMPLE 
The present invention will be described more specifically below with 
reference to working examples and applied examples. The examples are for 
purposes of illustrating the invention and should not be interpreted as a 
limitation of the invention. The percents (%) mentioned in the working 
examples and the applied examples are percents by weight unless otherwise 
specified. 
The heptane insolubles content (hereinafter referred to as "HI") which 
shows the proportion of crystalline polymer to the whole of a given 
polymer represents the residue after 6 hours extraction of the polymer 
with boiling n-heptane in an improved version of Soxhlet extracter. The 
melt flow rate (MFR) represents the value determined in accordance with 
ASTM D-1238. The bulk density represents the value determined by the 
method A defined in ASTM D-1895-69. 
EXAMPLE 1 
Contact of Silicon Oxide with n-Butylethyl Magnesium 
A flask having an inner volume of 200 ml and provided with a dropping 
funnel and a stirrer has its interior air displaced with nitrogen gas. In 
the flask, 5 g of silicon oxide (product of Davison Corp. having a 
specific surface area of 302 m.sup.2 /g, a pore volume of 1.54 cm.sup.3 
/g, and an average pore radius of 204.ANG. and marketed under the 
trademark designation of G-952)(hereinafter referred to as "SiO.sub.2 ") 
fired under a flow of nitrogen gas at 200.degree. C. for two hours and 
further at 700.degree. C. for five hours and 20 ml of n-heptane were 
placed. The compounds so placed and 20 ml of a 20% n-heptane solution of 
n-butylethyl magnesium (hereinafter referred to as "BEM") (the solution in 
the amount of 26.8 mmol as BEM) added thereto were stirred at 90.degree. 
C. for two hours. The supernatant consequently formed was removed by 
decantation and the solid was washed with 50 ml of n-heptane at room 
temperature and the supernatant formed again was removed by decantation. 
The washing treatment with n-heptane was repreated four more times. 
Contact with 2,2,2-trichloethanol 
The solid product issuing from the last washing treatment was suspended in 
20 ml of n-heptane. Into the resultant suspension, a solution of 9.6 g (64 
mmols) of 2,2,2-trichloroethanol in 10 ml of n-heptane was added dropwise 
through the dropping funnel at 0.degree. C. over a period of 30 minutes. 
The suspension and the added solution were stirred at 0.degree. C. for one 
hour, heated to 80.degree. C. over a period of one hour and again stirred 
at 80.degree. C. for one hour. After the completion of the reaction, the 
reaction mixture at room temperature was washed twice with 50 ml of 
n-heptane and three times with 50 ml of toluene. The solid consequently 
obtained (solid component I), by analysis, was found to contain 49.5% of 
SiO.sub.2, 3.8% of magnesium, and 33.5% of chlorine. This solid was found 
to have a specific surface area of 255 m.sup.2 /g and a pore volume of 
0.79 cm.sup.2 /g. 
Contact with d-n-butyl phthalate and titanium tetrachloride 
The solid component I obtained in the preceding procedure and 20 ml of 
toluene and 0.6 g of di-n-butyl phthalate added thereto were heated for 
reaction at 50.degree. C. for two hours. Then, the reaction mixture and 30 
ml of titanium tetrachloride added thereto were heated for reaction at 
90.degree. C. for two hours. The solid substance obtained by this reaction 
was washed at room temperature eight times with 50 ml of n-hexane. It was 
then dried under a vacuum at room temperature for one hour. Consequently, 
7.5 g of a catalyst component was obtained. This catalyst component was 
found to have a specific surface area of 285 m.sup.2 /g and a pore volume 
of 0.87 cm.sup.3 /g. This catalyst component was found to contain 55.9% of 
SiO.sub.2, 4.3% of magnesium, 16.3% of chlorine, and 3.1% of titanium. 
EXAMPLE 2 
The solid substance formed after contact with titanium tetrachloride in the 
procedure of Example 1 was separated. This solid substance and 30 ml of 
titanium tetrachloride added thereto were heated for reaction at 
90.degree. C. for two hours. The solid substance consequently formed was 
treated in the same way as in Example 1, to afford a catalyst component 
having a titanium content of 2.8%. 
EXAMPLE 3 
The reaction mixture formed after contact with titanium tetrachloride in 
the procedure of Example 1 was decanted to expel the supernatant. The 
solid substance which remained was cleaned in 50 ml of toluene at 
90.degree. C. for 15 minutes. The washing treatment with toluene was 
repeated. The washed solid substance and 20 ml of toluene and 30 ml of 
titanium tetrachloride added thereto were heated for reaction at 
90.degree. C. for two hours. The resultant reaction mixture was washed 
with n-hexane and dried in the same way as in Example 1, to afford 7.4 g 
of a catalyst component. This catalyst component was found to have a 
specific surface area of 279 m.sup.2 /g and a pore volume of 0.90 m.sup.3 
/g. It was found to contain 56.5% of SiO.sub.2, 4.4 g of magnesium, 15.1% 
of chloride, and 2.4% of titanium. 
EXAMPLE 4 
The procedure of Example 3 was repeated, except that the temperature of 
contact with titanium tetrachloride was changed from 90.degree. C. to 
120.degree. C. Consequently, there was prepared a catalyst component 
having a titanium content of 2.1%. 
EXAMPLE 5 
The procedure of Example 3 was repeated, except that in the contact of 
di-n-butyl phthalate and titanium tetrachloride, these two compounds were 
added at the same time for reaction. Consequently, there was prepared a 
catalyst component having a titanium content of 2.5%. 
EXAMPLE 6 
The procedure of Example 3 was repeated, except that in the contact of 
di-n-butyl phthalate and titanium tetrachloride, 30 ml of titanium 
chloride was added and abruptly heated to 90.degree. C. while under 
stirring, 0.6 g of di-n-butyl phthalate was added subsequently and heated 
for reaction at 90.degree. C. for two hours. Consequently, there was 
prepared a catalyst component having a titanium content of 2.4%. 
EXAMPLE 7 
The solid component I obtained in the procedure of Example 1 and 50 ml of 
titanium tetrachloride added thereto were stirred and heated suddenly to 
90.degree. C. The resultant mixture and 0.6 g of di-n-butyl phthalate 
added thereto were heated for reaction at 90.degree. C. for two hours. 
After completion of the reaction, the supernatant was removed and the 
residue and 50 ml of titanium tetrachloride added thereto were heated for 
reaction at 90.degree. C. for two hours. The resultant reaction mixture 
was washed and dried by following the procedure of Example 1, to afford a 
catalyst component having a titanium content of 3.3%. 
EXAMPLE 8 
In the procedure of Example 7, between the two split steps of contact with 
titanium tetrachloride, the reaction mixture was washed twice with 50 ml 
of titanium tetrachloride at 90.degree. C. for 15 minutes. The reaction 
mixture was washed and dried by following the procedure of Example 1. 
Consequently, there was prepared a catalyst component having a titanium 
content of 3.0%. 
EXAMPLES 9-11 
The procedure of Example 3 was followed, except that in the contact of 
di-n-butyl phthalate and titanium tetrachloride, xylene (Example 9), 
n-heptane (Example 10), and 1,2-dichloroethane (Example 11) were severally 
used as an inactive medium in the place of toluene. Consequently, there 
were prepared catalyst components having titanium contents of 2.2% 
(Example 9), 3.5% (Example 10), and 2.8% (Example 11). 
EXAMPLES 12-14 
During the course of contact with di-n-butyl phthalate and titanium 
tetrachloride in the procedure of Example 3, the reaction mixture 
resulting from the first step of contact with titanium tetrachloride was 
freed of the supernatant. The residue and 50 ml of toluene and 3 g of 
silicon tetrachloride (Example 12), 3 g of aluminum trichloride (Example 
13), or 3 g of hexachloroethane (Example 14) added thereto were heated for 
reaction at 60.degree. C. for one hour. The resultant reaction mixture was 
washed four times with 50 ml of toluene at 60.degree. C. The washed 
reaction mixture was mixed with 20 ml of toluene and 30 ml of titanium 
tetrachloride to undergo the second reaction with titanium tetrachloride. 
The reaction mixture consequently obtained was washed and dried in the 
same way as in Example 1. Consequently, there were produced catalyst 
components having titanium contents of 2.1% (Example 12), 2.7% (Example 
13), and 2.3% (Example 14) respectively. 
EXAMPLES 15 and 16 
A solid substance was obtained by effecting the reaction of the solid 
substance I with titanium tetrachloride and di-n-butyl phthalate in the 
same way as in Example 3. This solid substance was washed eight times with 
n-hexane similarly to Example 1. The washed solid substance was converted 
by addition of n-hexane into a slurry (4.5 g of solid substance and 6.8 g 
of n-hexane). The slurry was held in contact with 1.1 g of 
hexachloroethane and 100 ml of n-hexane (Example 15), 100 ml 
1,2-dichloro-ethane (Example 16) at 50.degree. C. for 30 minutes. The 
solid substance consequently obtained was separated by filtration at 
50.degree. C., washed with 100 ml of n-hexane at room temperature, dried 
under a vacuum for one hour. Consequently, there were prepared catalyst 
components having titanium contents of 1.6% (Example 15) and 1.4% (Example 
16) respectively. 
EXAMPLES 17-20 
Catalyst components having titanium contents shown below in Table I were 
prepared by following the procedure of Example 3, except that varying 
metal oxides indicated below were used in the place of SiO.sub.2. 
TABLE I 
______________________________________ 
Ex- Firing Titanium 
ample Metal Oxide Conditions Content (%) 
______________________________________ 
17 Al.sub.2 O.sub.3 
200.degree. C./2 hours 
3.5 
700.degree. C./5 hours 
18 (MgO).sub.2 (SiO.sub.2).sub.3 
200.degree. C./2 hours 
2.5 
500.degree. C./5 hours 
19 Mixture of 1 kg of SiO.sub.2 
200.degree. C./2 hours 
2.3 
and 100 g of Al.sub.2 O.sub.3 
700.degree. C./5 hours 
20 Mixture of 1 kg of SiO.sub.2 
200.degree. C./2 hours 
1.9 
and 20 g of CrO.sub.3 
700.degree. C./5 hours 
______________________________________ 
EXAMPLES 21-23 
Catalyst components having titanium contents indicated below were prepared 
by following the procedure of Example 3, except that varying magnesium 
compounds indicated below in Table II were used in the place of BEM. 
TABLE II 
______________________________________ 
Ex- Titanium 
am- Content 
ple Organic Mg (%) 
______________________________________ 
21 Di-n-hexyl magnesium (product of Texas Alkyls 
2.5 
Corp., marketed under trademark designation 
of MAGALA .RTM. DNHM) 
22 Di-n-butyl magnesium (0.5 mol)-triethyl 
2.4 
aluminum (1 mol) complex (product of Texas 
Alkyls Corp., marketed under trademark 
designation of MAGALA .RTM. 0.5E) 
23 Di-n-butyl magnesium (7.5 mols)-triethyl 
2.5 
aluminum (1 mol) complex product of Texas 
Alkyls Corp., marketed under trademark 
designation MAGALA .RTM. 7.5E) 
______________________________________ 
EXAMPLE 24-42 
Catalyst components having titanium contents indicated below Table III were 
prepared by following the procedure of Example 3, cept that varying 
hologen-containing alcohols indicated below in ble III were used in the 
place of 2,2,2-trichloroethanol. 
TABLE III 
______________________________________ 
Titanium 
Example Halogen-Containing Alcohol 
Content (%) 
______________________________________ 
24 1,1,1-Trichloro-2-propanol 
2.3 
25 .beta.,.beta.,.beta.-Trichloro-tert-butanol 
2.6 
26 2,2-Dichloroethanol 
2.8 
27 1,3-Dichloro-2-propanol 
2.7 
28 2-Chloroethanol 2.3 
29 4-Chloro-1-butanol 
2.2 
30 6-Chloro-1-hexanol 
2.6 
31 p-Chlorophenol 2.9 
32 4-Chloro-o-cresol 2.7 
33 2,4,6-Trichlorophenol 
2.4 
34 Tetrachlorohydroquinone 
2.2 
35 1-Bromo-2-butanol 2.6 
36 1,3-Dibromo-2-propanol 
2.5 
37 p-Bromophenol 2.3 
38 2,4,6-Tribromophenol 
2.3 
39 p-Iodophenol 2.7 
40 2,4,6-Triiodophenol 
2.5 
41 2,2,2-Trifluoroethanol 
2.9 
42 p-Fluorophenol 2.2 
______________________________________ 
EXAMPLES 43-67 
Catalyst components having titanium contents shown below in Table IV were 
obtained by following the procedure of Example 3, except that varying 
electron-donating compounds indicated below in Table IV were used in the 
place of di-n-butyl phthalate during the contact with the solid component 
I. 
TABLE IV 
______________________________________ 
Titanium 
Example Electron-Donating Compound 
Content (%) 
______________________________________ 
43 Ethyl benzoate 2.3 
44 Diisobutyl phthalate 
2.1 
45 Phthalic anhydride 2.4 
46 Phthalic acid dichloride 
2.7 
47 Phthalic acid n-butyl chloride 
2.5 
48 Mono-n-butyl phthalate 
2.4 
49 Benzoic anhydride 2.2 
50 Benzoyl chloride 2.6 
51 Ethyl cinnamate 2.4 
52 Ethyl cyclohexane carboxylate 
2.5 
53 Tartaric acid 2.8 
54 Di-n-butyl tartrate 
2.4 
55 Isobutyl methacrylate 
2.3 
56 Phthalic acid 2.1 
57 Benzoic acid 3.0 
58 Di-n-butyl maleate 3.2 
59 Diisobutyl sebacate 
2.8 
60 Tri-n-butyl trimellitate 
2.2 
61 Ethanol 2.3 
62 Isobutanol 2.0 
63 2-Ethylhexanol 2.3 
64 p-Cresol 2.1 
65 Diethyl ether 2.0 
66 Di-n-butyl ether 2.2 
67 Diphenyl ether 2.5 
______________________________________ 
EXAMPLE 68 
Contact of Silicon Oxide and 2,2,2-Trichloroethanol 
A flask having an inner volume of 200 ml and provided with a dropping 
funnel and a stirrer had its interior air displaced with nitrogen gas. In 
this flask, 5 g of the same SiO.sub.2 as used in Example 1, 40 ml of 
n-heptane, and 12 g of 2,2,2-trichloroethanol added thereto were stirred 
for contact at 90.degree. C. for two hours. After completion of the 
reaction, the reaction mixture was washed three times with 50 ml of 
n-heptane and decanted at room temperature. 
Contact with n-butylethyl magnesium 
The solid substance obtained in the foregoing procedure was suspended in 20 
ml of n-heptane. To the resultant suspension, 11 ml of the same BEM 
solution as used in Example 1 was added dropwise through the dropping 
funnel at 0.degree. C. over a period of 30 minutes. The resultant mixture 
was stirred at 0.degree. C. for one hour, heated to 80.degree. C. over a 
period of one hour, and stirred at 80.degree. C. for one hour. After 
completion of the reaction, the reaction mixture was washed twice with 50 
ml of n-heptane and three times with 50 ml of toluene. 
Contact with di-n-butyl phthalate and titanium tetrachloride 
By following the procedure of Example 3, except that the solid component 
obtained in the preceding procedure was used instead in the contact with 
the di-n-butyl phthalate and titanium tetrachloride, there was obtained 
7.8 g of a catalyst component having a titanium content of 2.5%. 
EXAMPLE 69 
Contact of Silicon Oxide and 2,2,2-Trichloroethanol 
In a mill pot, 10 g of the same SiO.sub.2 as used in Example 1 and 4.4 g of 
2,2,2-trichloroethanol were subjected to a crushing treatment for 24 
hours. 
Contact with n-Butylethyl Magnesium 
A flask having an inner volume of 200 ml and provided with a dropping 
funnel and a stirrer had its interior air displaced with nitrogen gas. In 
the flask, 6 g of the solid substance obtained in the preceding procedure 
and comminuted and 40 ml of n-heptane were placed. Then, 9 ml of the same 
BEM solution as used in Example 1 was added thereto dropwise through the 
dropping funnel at 0.degree. C. over a period of 30 minutes. The resultant 
reaction mixture was thereafter treated in the same way as in Example 68 
to obtain a solid component. 
Contact with di-n-Butyl Phthalate and Titanium Tetrachloride 
By following the procedure of Example 3, except that the solid component 
obtained in the preceding procedure was used instead in the contact with 
di-n-butyl phthalate and titanium tetrachloride, there was obtained 8.1 g 
of a catalyst component having a titanium content of 2.3%. 
EXAMPLE 70 
Contact of 2,2,2-trichloroethanol and n-butylethyl magnesium 
A flask having an inner volume of 200 ml and provided with a dropping 
funnel and a stirrer had the interior air displaced with nitrogen gas. In 
the flask, 5 g of 2,2,2-trichloroethanol and 40 ml of n-heptanol were kept 
at 0.degree. C. Then, 12.5 ml of the same BEM solution as used in Example 
1 was added dropwise at 0.degree. C. over a period of 30 minutes. The 
contents of the flask were stirred at 0.degree. C. for one hour, then 
heated to 80.degree. C. over a period of one hour, and then stirred at 
80.degree. C. for one hour. After completion of the reaction, the reaction 
mixture was washed three times with 50 ml of n-heptane at room temperature 
and then dried under a vacuum at room temperature for one hour. 
Consequently, there was obtained a solid reaction product. 
Contact with silicon oxide 
In a mill pot, 5 g of the solid reaction product obtained in the preceding 
procedure and 8 g of the same SiO.sub.2 as used in Example 1 were 
subjected to a comminution treatment for 24 hours. 
Contact with di-n-butyl phthalate and titanium tetrachloride 
By following the procedure of Example 3, except that 6 g of the comminuted 
solid substance obtained in the preceding procedure was used instead in 
the contact with di-n-butyl pthalate and titanium tetrachloride, there was 
obtained 6.8 g of a catalyst component having a titanium content of 2.5%. 
EXAMPLE 71 
Contact of Silicon Oxide, n-Butylethyl Magnesium, and 
2,2,2-Trichloroethanol 
A flask having an inner volume of 200 ml and provided with a dropping 
funnel and a stirrer had its interior air displaced with nitrogen gas. In 
the flask, 5 g of the same SiO.sub.2 as used in Example 1 and 20 ml of 
n-heptane were placed. Then 30 ml of the same BEM solution as used in 
Example 1 was added and subsequently 12 g of 2,2,2-trichloroethanol was 
added dropwise thereto at 0.degree. C. over a period of 30 minutes. The 
resultant mixture was stirred at 0.degree. C. for one hour, heated to 
80.degree. C. over a period of one hour, and stirred at 80.degree. C. for 
one hour. After completion of the reaction, the reaction mixture was 
washed twice with 50 ml of n-heptane and three times with 50 ml of toluene 
at room temperature, to obtain a solid component. 
Contact with di-n-butyl phthalate and titanium tetrachloride 
By following the procedure of Example 3, except that the solid component 
obtained in the preceding procedure was used instead in the contact of 
di-n-butyl phthalate and titanium tetrachloride, there was obtained 7.5 g 
of catalyst component having a titanium content of 2.6%. 
APPLIED EXAMPLE 1 
In a stainless steel autoclave having an inner volume of 1.5 liters and 
provided with a stirrer, a reaction mixture obtained by mixing 30.3 mg of 
the catalyst component prepared by the procedure of Example 1, 0.97 ml of 
a solution containing 1 mol of triethyl aluminum (hereinafter referred to 
as "TEAL") per liter of n-heptane, and 0.97 ml of a solution containing 
0.1 mol of phenyl triethoxy silane (hereinafter referred to as "PES") per 
liter of n-heptane and allowing the resultant mixture to stand for five 
minutes was placed under a blanket of nitrogen gas. Then, 0.1 liter of 
hydrogen gas as a molecular weight regulator and 1 liter of liquefied 
propylene were introduced therein under pressure. The reaction system was 
heated to 70.degree. C. to effect polymerization of propylene for one 
hour. After completion of the polymerization, the unaltered propylene was 
purged to produce 105 g of white polypropylene powder having 97.6% of HI, 
4.7 of MFR, and 0.42 g/cm.sup.3 of bulk density [ Kc (amount of produced 
polymer in g per g of catalyst component)=3,500 and Kt (amount of produced 
polymer in kg per g of titanium in catalyst component)=113]. 
APPLIED EXAMPLES 2-71 
Polymerization of propylene was carried out by following the procedure of 
Applied Example 1, except that the catalyst components obtained in 
Examples 2-71 were severally used. The results are shown in Table VI. The 
polypropylene powder obtained in Applied Example 3 was tested for particle 
diameter distribution. The results are shown in Table V below. 
TABLE V 
______________________________________ 
Particle diameter (.mu.m) 
Proportion of distribution (%) 
______________________________________ 
Less than 149 0 
149-250 0.1 
250-350 2.3 
350-420 5.9 
420-590 24.9 
590-840 42.3 
840-1,000 12.8 
1,000-1,680 11.6 
Exceeding 1,680 0.1 
______________________________________ 
TABLE VI 
______________________________________ 
Kc MFR Bulk 
Applied 
Catalyst (g/g Kt HI (g/10 Density 
Example 
Component Cat) (kg/g Ti) 
(%) min) (g/cm.sup.3) 
______________________________________ 
2 Example 2 3,200 114 97.5 4.5 0.42 
3 Example 3 4,300 179 98.1 4.7 0.44 
4 Example 4 3,900 186 98.0 5.1 0.43 
5 Example 5 3,900 156 97.9 4.0 0.43 
6 Example 6 4,300 179 98.4 3.9 0.45 
7 Example 7 3,100 94 97.7 5.5 0.43 
8 Example 8 3,600 120 98.0 5.0 0.44 
9 Example 9 4,000 182 98.0 4.2 0.43 
10 Example 10 
3,600 103 97.9 6.2 0.40 
11 Example 11 
3,700 132 97.5 5.8 0.42 
12 Example 12 
3,600 171 97.8 4.9 0.41 
13 Example 13 
3,900 144 98.2 6.0 0.43 
14 Example 14 
3,700 161 98.0 4.9 0.42 
15 Example 15 
3,200 200 98.2 5.4 0.44 
16 Example 16 
3,400 243 98.3 5.9 0.45 
17 Example 17 
3,100 89 97.8 4.5 0.43 
18 Example 18 
2,800 112 97.3 4.8 0.41 
19 Example 19 
2,600 113 97.2 5.3 0.40 
20 Example 20 
2,900 153 97.6 5.8 0.41 
21 Example 21 
3,900 156 97.8 4.3 0.44 
22 Example 22 
3,600 150 97.6 6.2 0.42 
23 Example 23 
3,500 140 97.5 5.8 0.43 
24 Example 24 
3,900 170 97.9 4.3 0.44 
25 Example 25 
4,100 158 98.0 4.9 0.43 
26 Example 26 
3,600 129 97.7 5.6 0.43 
27 Example 27 
2,900 107 97.5 5.3 0.43 
28 Example 28 
3,200 139 97.6 6.1 0.43 
29 Example 29 
3,200 145 97.4 5.6 0.42 
30 Example 30 
2,900 112 97.3 6.7 0.43 
31 Example 31 
3,600 124 97.7 5.4 0.43 
32 Example 32 
3,300 122 97.8 4.8 0.41 
33 Example 33 
3,700 154 97.6 6.2 0.42 
34 Example 34 
2,700 123 97.6 6.3 0.43 
35 Example 35 
2,500 96 97.4 7.1 0.42 
36 Example 36 
2,800 112 97.2 5.8 0.41 
37 Example 37 
3,100 135 97.1 6.6 0.43 
38 Example 38 
2,900 126 97.3 5.5 0.43 
39 Example 39 
2,600 96 97.0 4.6 0.42 
40 Example 40 
2,500 100 97.4 7.2 0.41 
41 Example 41 
3,100 107 97.3 6.8 0.43 
42 Example 42 
2,600 118 97.3 6.3 0.42 
43 Example 43 
3,000 130 97.9 3.8 0.43 
44 Example 44 
3,800 181 98.2 4.0 0.43 
45 Example 45 
3,200 133 98.0 4.6 0.40 
46 Example 46 
3,500 130 98.1 4.2 0.40 
47 Example 47 
3,100 124 98.0 4.0 0.42 
48 Example 48 
3,300 138 97.9 5.1 0.41 
49 Example 49 
2,900 132 97.9 5.8 0.40 
50 Example 50 
2,900 112 97.8 4.0 0.40 
51 Example 51 
2,700 113 97.6 4.6 0.38 
52 Example 52 
2,900 116 97.8 4.7 0.39 
53 Example 53 
2,800 100 97.5 6.1 0.40 
54 Example 54 
2,900 121 97.6 4.0 0.40 
55 Example 55 
3,100 135 97.6 6.8 0.41 
56 Example 56 
3,000 143 97.8 4.2 0.40 
57 Example 57 
3,000 100 97.5 4.0 0.40 
58 Example 58 
2,900 91 97.6 5.8 0.41 
59 Example 59 
3,000 107 97.9 5.2 0.40 
60 Example 60 
3,200 145 98.1 4.1 0.43 
61 Example 61 
3,000 130 98.0 5.2 0.41 
62 Example 62 
2,900 145 97.9 4.8 0.39 
63 Example 63 
3,000 130 98.0 4.8 0.41 
64 Example 64 
3,100 148 98.0 5.2 0.40 
65 Example 65 
2,800 140 97.4 6.8 0.38 
66 Example 66 
2,900 132 97.6 6.5 0.39 
67 Example 67 
2,900 116 97.6 6.0 0.39 
68 Example 68 
4,000 160 98.1 4.1 0.42 
69 Example 69 
3,900 170 98.0 3.8 0.38 
70 Example 70 
3,900 156 98.2 4.5 0.38 
71 Example 71 
3,800 146 97.9 4.4 0.40 
______________________________________ 
APPLIED EXAMPLE 72 
Gaseous-phase Polymerization of Propylene 
In an autoclave having an inner volume of 5 liters and provided with a 
stirrer, 150 g of polypropylene powder dried in advance under a flow of 
nitrogen gas at 90.degree. C. for four hours was placed. To this 
autoclave, with the stirrer thereof operated at 150 rpm, the same catalyst 
component as prepared in Example 3 was fed at a rate of 50 mg/hr, TEAL at 
a rate of 0.7 mmol/hr, PES at a rate of 0.05 mmol/hr, propylene at a rate 
of 130 g/hr, and hydrogen gas at a rate of 15 ml/hr for continuous 
polymerization of propylene under the conditions of 70.degree. C. of 
temperature and 20 kg/cm.sup.2 of pressure, with the product of 
polymerization continuously withdrawn from the autoclave. Consequently, 
there was obtained polypropylene powder at a rate of 90 g/hr. The polymer 
so produced was found to have an MFR of 5.2 g/10 min and an HI of 96.8%. 
APPLIED EXAMPLE 73 
Block Copolymerization of Propylene 
In an autoclave having an inner volume of 1.5 liters and provided with a 
stirrer, a reaction mixture obtained by mixing 30.0 mg of the catalyst 
component prepared by the procedure of Example 3, 0.75 ml of n-heptane 
solution of TEAL (1 mol/liter), and 0.75 ml of n-heptane solution of PES 
(0.1 mol/liter) and allowing the resultant mixture to stand for five 
minutes was placed under a blanket of nitrogen gas. Then, 100 ml of 
hydrogen gas and 1 liter of liquefied propylene were introduced therein 
under pressure. The reaction system consequently formed was heated to 
70.degree. C. to effect homopolymerization of propylene for one hour. In 
an experiment of polymerization performed parallelly under the same 
conditions, the polypropylene obtained was found to have a HI of 98.1%. 
After completion of the polymerization, the unaltered propylene was purged 
and the interior of the autoclave was displaced with nitrogen gas. Then, a 
mixed gas of ethylene and propylene [ethylene/propylene=1.5 (by mol 
ratio)] was introduced at such a rate as to keep the monomer gas pressure 
at 1.5 atmospheres. Under these conditions, copolymerization was effected 
at 70.degree. C. for three hours. After completion of the polymerization, 
the unaltered mixed gas was discharged. Consequently, there was obtained 
175 g of block copolymer of propylene. 
The proportion of the copolymer fraction calculated based on the consumed 
amount of the mixed gas and the total amount of polymer was found to be 
26.3% and the ethylene content in the total polymer was found by infrared 
spectral analysis to be 12.6%. Thus, the ethylene content in the copolymer 
fraction is found by calculation to have been 48%. The amount of the 
homopolymer of propylene per g of the catalyst component found based on 
the amount of the total polymer and the consumed amount of the mixed gas 
was found to be 4,300 g and the amount of the copolymer fraction formed to 
be 1,530 g. The block copolymer so produced was found to have a MFR of 2.9 
g/10 min and a bulk density of 0.44 g/cm.sup.3. The polymer particles were 
free from cohesion and showed absolutely no sign of fouling in the 
autoclave. 
APPLIED EXAMPLE 74 
Random Copolymerization of Propylene and Ethylene 
During the polymerization of propylene in the procedure of Applied Example 
1, 0.6 g of ethylene was introduced under pressure into the autoclave six 
times at intervals of 10 minutes to effect random copolymerization of 
propylene and ethylene. After completion of the polymerization, the 
unaltered monomers were discharged from the polymerization system. 
Consequently, there was obtained 136 g of a random copolymer of propylene 
and ethylene. The ethylene content in the produced copolymer was found by 
infrared spectral analysis to be 2.7%. The amount of the copolymer formed 
per 1 g of the catalyst component was 4,500 g. The produced copolymer was 
found to have a MFR of 12.4 g/10 min and a bulk density of 0.43 
g/cm.sup.3. 
APPLIED EXAMPLE 75 
Polymerization of 1-Butene 
By following the procedure of Applied Example 1, except using 205 mg of the 
catalyst component obtained in Example 3, 400 ml of isobutane as a medium, 
and 400 ml of 1-butene (liquid) in the place of liquefied propylene and 
carrying out the polymerization under the conditions of 40.degree. C. of 
temperature and five hours of duration, 1-butene was polymerized. 
Consequently, there was obtained 307.3 g of powdery poly-1-butene. The 
value, Kc, was found to be 1,500 g/g of catalyst component. The produced 
polymer was found to have a MFR of 4.1 g/10 min, a bulk density of 0.41 
g/cm.sup.3, and an ether insolubles content (residue after five hours' 
extraction from boiling diethyl ether) of 99.3%. 
APPLIED EXAMPLE 76 
Polymerization of 4-methyl-1-pentene 
By following the procedure of Applied Example 75, except using 230 mg of 
the catalyst component obtained by Example 3 and 400 ml of 
4-methyl-1-pentene in the place of 1-butene, 4-methyl-1-pentene was 
polymerized. Consequently, there was obtained 312.5 g of powdery 
poly-4-methyl-1-pentene. The value, Kc, was found to be 1,360 g/g of 
catalyst component. The produced polymer was found to have a MFR of 3.5 
g/10 min, a bulk density of 0.38 g/cm.sup.3, and an ether insolubles 
content of 98.5%.