Catalyst for polymerizing .alpha.-olefins

Disclosed is a catalyst for polymerizing .alpha.-olefins which comprises PA1 (A) a composition obtained by co-comminuting PA2 (a) a magnesium halide, PA2 (b) an organic acid ester, PA2 (c) a halogenated aliphatic or alicyclic hydrocarbon, PA2 (d) at least one ingredient selected from the group consisting of aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, halogenated aromatic hydrocarbons, liquid propylene oligomers and aromatic ethers, and PA2 (e) an aluminum halide optionally added thereto and then heat-treating the resulting mixture together with titanium tetrachloride; PA1 (B) an organic aluminum compound; and PA1 (C) an organic acid ester or a complex thereof with an aluminum halide.

BACKGROUND OF THE INVENTION 
(1) Field of the Invention 
The present invention relates to a catalyst for polymerizing 
.alpha.-olefins with which poly-.alpha.-olefins having a high degree of 
stereoregularity are produced with the aid of the catalyst comprising a 
titanium component of the so-called carrier type and an organic aluminum 
compound. 
(2) Description of the Prior Art 
Recently, a method for improving the activity of a Ziegler-Natta catalyst 
by supporting its titanium component on a carrier has been developed. One 
example of the prior art concerned therewith is proposed in Japanese 
Laid-Open Patent Publication No. 9342/72 which discloses a method for 
improving the stereoregularity of the resulting polymer by adding an 
electron donative compound as the third component to a combination of a 
carrier type titanium component (composed of a titanium compound supported 
on a magnesium halide) and an organic aluminum compound. 
However, if propylene is polymerized in the presence of such a conventional 
two-component catalyst comprising a carrier type titanium component and an 
organic aluminum compound, the crystallinity of the resulting polymer is 
extremely low despite the high polymerization activity of the catalyst. 
Although the crystallinity of the resulting polymer is improved by adding 
an electron donative compound to the catalyst, the polymerization activity 
of the catalyst is remarkably lowered. Moreover, the effect of improving 
the crystallinity of the resulting polymer is not satisfactory because it 
is difficult to produce crystalline polypropylene which is equal in 
quality to that obtained with the aid of a catalyst (for example, a 
titanium trichloridediethylaluminum monochloride catalyst) in current use 
for industrial purposes. 
In the process disclosed in Japanese Laid-Open Patent Publication No. 
126590/75, there is proposed a catalyst composed of a composition obtained 
by reacting a co-comminuted mixture of a magnesium halide and an organic 
acid ester with titanium tetrachloride; an organic aluminum compound; and 
an organic acid ester. However, this catalyst is unsatisfactory from the 
viewpoints of both its polymerization activity and the crystallinity of 
the resulting polymer. 
SUMMARY OF THE INVENTION 
The present invention is directed to improvements in the performance of 
such carrier type catalysts. First of all, it has been found that the use 
of a composition obtained by co-comminuting a magnesium halide, an organic 
acid ester and a halogenated aliphatic or alicyclic hydrocarbon and then 
heat-treating the resulting mixture together with titanium tetrachloride 
brings about a marked increase in polymerization activity as compared with 
the use of the composition of Japanese Laid-Open Patent Publication No. 
126590/75 as the titanium component. In spite of the increased 
polymerization activity, the performance of catalysts so prepared is not 
satisfactory for the polymerization of .alpha.-olefins because the 
crystallinity and bulk density of the resulting polymer are low. Thus, we 
have made a study of such catalysts with a view to enhancing the 
crystallinity and bulk density of the resulting polymer, and have found 
that these parameters are greatly improved by carrying out the aforesaid 
co-comminuting operation in the presence of various organic compounds. The 
present invention has been completed on the basis of this discovery. 
The catalysts so prepared are desirable because both their polymerization 
activity and the crystallinity of the resulting polymer are high. However, 
it may happen that the co-comminuted mixture agglomerates to form a mass 
if large amounts of raw materials are charged into a pulverizer and that 
coarse particle in the resulting polymer increases. In order to overcome 
these difficulties, an aluminum halide may optionally be added to the 
co-comminuted mixture of a magnesium halide and other ingredients. 
Thus, the present invention provides a catalyst having outstandingly high 
performance in the polymerization of .alpha.-olefins, the catalyst being 
composed of 
(A) a composition obtained by co-comminuting 
(a) a magnesium halide, 
(b) an organic acid ester, 
(c) a halogenated aliphatic or alicyclic hydrocarbon, 
(d) at least one ingredient selected from the group consisting of aliphatic 
hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, halogenated 
aromatic hydrocarbons, liquid propylene oligomers and aromatic ethers, and 
(e) an aluminum halide optionally added thereto and then heat-treating the 
resulting mixture together with titanium tetrachloride; 
(B) an organic aluminum compound; and 
(C) an organic acid ester or a complex thereof with an aluminum halide. 
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS 
The magnesium halide used as the ingredient (a) in the preparation of the 
component (A) of the present catalyst may be any magnesium halide that is 
in a substantially anhydrous state. Among others, anhydrous magnesium 
chloride is preferred. 
The organic acid ester used as the ingredient (b) is an aromatic, aliphatic 
or alicyclic carboxylic acid ester of the formula 
EQU R.sup.2 COOR.sup.1 
wherein R.sup.1 is an aromatic, aliphatic or alicyclic hydrocarbon radical 
of 1 to 12 carbon atoms and R.sup.2 is the same as R.sup.1 or 
##STR1## 
Specific examples thereof include methyl benzoate, ethyl benzoate, propyl 
benzoate, phenyl benzoate, ethyl toluate, ethyl anisate, ethyl naphthoate, 
ethyl acetate, n-butyl acetate, ethyl methacrylate, ethyl 
hexahydrobenzoate and the like. 
The halogenated aliphatic or alicyclic hydrocarbon used as the ingredient 
(c) is a saturated or unsaturated hydrocarbon having one or more halogen 
substituents. Specific examples thereof include methylene chloride, 
chloroform, carbon tetrachloride, ethylene dichloride, n-butyl chloride, 
propenyl chloride, 1,2-dichloropropane, 1,2-dichloroethylene, 
hexachloroethane, tetrachloroethylene, tetrabromoethane, chlorinated 
paraffin and the like. 
The organic compound used as the ingredient (d) is selected from any of the 
following three groups: 
(1) Saturated aliphatic hydrocarbons such as n-hexane, n-heptane, n-octane, 
isooctane, etc.; unsaturated aliphatic hydrocarbons such as pentene-1, 
hexene-1, octene-1, etc.; aromatic hydrocarbons such as benzene, toluene, 
ethylbenzene, o-xylene, m-xylene, p-xylene, etc.; alicyclic hydrocarbons 
such as cyclohexane, cyclopentane, etc.; and halogenated aromatic 
hydrocarbons such as monochlorobenzene, o-dichlorobenzene, 
m-dichlorobenzene, etc. 
(2) Somewhat viscous liquid propylene oligomers having a molecular weight 
of the order of 100 to 1500 and preferably 200 to 1000. Such propylene 
oligomers can be prepared by any conventional procedure (for example, by 
polymerizing propylene with the aid of a catalyst such as aluminum 
chloride or the like). 
(3) Aromatic ethers such as methyl phenyl ether, ethyl phenyl ether, allyl 
phenyl ether, diphenyl ether, ditolyl ether, etc. 
Among the foregoing compounds, those belonging to the group (3) are 
particularly preferred from the viewpoint of the crystallinity and bulk 
density of the resulting polymer. 
The aluminum halide used as the ingredient (e) may be any aluminum halide 
that is in a substantially anhydrous state. Among others, aluminum 
chloride and aluminum bromide are preferred. 
In the preparation of the component (A), the ingredients (a), (b), (c), (d) 
and optionally (e) are first co-comminuted according to any well-known 
method that is commonly used in the preparation of the titanium component 
of a Ziegler-Natta catalyst. For example, the co-comminuting operation is 
carried out at a temperature of 0.degree. to 80.degree. C. for a period of 
1 to 100 hours in a vacuum or in an inert atmosphere. This should be done 
in a state where moisture, oxygen and the like are almost completely 
removed. 
On the occasion of the co-comminution, the ingredient (a) is used in an 
amount of 50 to 95 wt.%, preferably 55 to 90 wt.% and more preferably 60 
to 80 wt.%; the ingredient (b) in an amount of 1 to 40 wt.%, preferably 2 
to 30 wt.% and more preferably 3 to 20 wt.%; the ingredient (c) in an 
amount of 1 to 40 wt.%, preferably 2 to 30 wt.% and more preferably 3 to 
20 wt.%; the ingredient (d) in an amount of 1 to 40 wt.%, preferably 2 to 
30 wt.% and more preferably 3 to 25 wt.%; and the ingredient (e) in an 
amount of 0.1 to 10 wt.%, preferably 0.2 to 5 wt.% and more preferably 0.3 
to 3 wt.%. 
The resulting co-comminuted mixture is then heat-treated together with 
titanium tetrachloride. Preferably, the above co-comminuted mixture is 
suspended in titanium tetrachloride or a solution thereof in an inert 
solvent and then heat-treated at a temperature of 40.degree. to 
135.degree. C. Thereafer, the resulting composition is washed with an 
inert solvent to remove the free titanium tetrachloride or dried, if 
necessary, under reduced pressure. 
On the occasion of the heat treatment, it is preferable to use a solution 
of titanium tetrachloride in an inert solvent because the bulk density of 
the resulting polymer is higher and the particle size distribution thereof 
is narrower. The concentration of titanium tetrachloride in this solution 
is not less than 0.1 vol.%, preferably 0.3 to 30 vol.% and more preferably 
1 to 20 vol.%. The inert solvent used for this purpose is selected from 
aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons 
as well as halogenated derivatives of the foregoing. Specific examples 
thereof include hexane, heptane, benzene, toluene, chlorobenzene, 
cyclohexane and the like. 
The component (A) obtained as a result of the heat treatment preferably 
contains from 0.1 to 10 wt.% of titanium. 
The organic aluminum compound used as the component (B) of the present 
catalyst is a trialkylaluminum of the formula 
EQU AlR.sub.3.sup.3 
wherein R.sup.3 is an alkyl radical of 1 to 12 carbon atoms. Specific 
examples thereof include trimethylaluminum, triethylaluminum, 
tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, 
tri-n-hexylaluminum and the like. 
In order to further improve the polymerization activity of the resulting 
catalyst, an alkylaluminum halide of the formula 
EQU AlR.sub.n.sup.4 X.sub.3-n 
wherein R.sup.4 is an alkyl radical of 1 to 12 carbon atoms, X is a halogen 
atom, and n is a number of 1 to 2, may preferably be added to the 
component (B). Specific examples thereof include diethylaluminum 
monochloride, ethylaluminum sesquichloride, ethylaluminum dichloride, 
diethylaluminum monobromide, diethylaluminum monoiodide, diethylaluminum 
monofluoride, di-n-propylaaluminum monochloride, diisobutylaluminum 
monochloride, di-n-hexylaluminum monochloride and the like. 
In the present catalyst, the ratio of the component (A) to the component 
(B) can vary widely. However, the trialkylaluminum is generally used in an 
amount of 1 to 500 mmoles, preferably 3 to 100 mmoles and more preferably 
5 to 50 mmoles per milligram atom of the titanium contained in the 
component (A). Similarly, the alkylaluminum halide is generally used in an 
amount of 0.05 to 100 moles, preferably 0.1 to 30 moles and more 
preferably 0.3 to 5 moles per mole of the trialkylaluminum. The 
trialkylaluminum is preferably added in small portions at suitable 
intervals of time during the polymerization, instead of being charged in 
bulk at the start of the polymerization. This is because such stepwise 
addition creates a good balance between the polymerization activity of the 
catalyst and the crystallinity of the resulting polymer and prevents the 
polymerization rate from changing with time. 
The component (C) used in the present catalyst is an organic acid ester or 
a complex thereof with an aluminum halide. The organic acid ester may be 
the same as that used in the preparation of the component (A) and specific 
examples thereof have been mentioned previously. The complex of an organic 
acid ester with an aluminum halide can be prepared, for example, by mixing 
the the organic acid ester with the aluminum halide (preferably, aluminum 
chloride or aluminum bromide) or by heating such a mixture. For this 
purpose, the organic acid ester and the aluminum halide is preferably used 
in a molar ratio of 1:1. 
The amount of component (C) used depends on the amount of component (B) 
used, the amount and titanium content of component (A) used, and 
polymerization conditions such as polymerization temperature and the like. 
However, the component (C) is generally used in an amount of not more than 
5 moles, preferably 0.001 to 1.5 moles and more preferably 0.1 to 1 mole 
per mole of the trialkylaluminum used as the component (B). 
The catalyst of the present invention can be applied to the 
homopolymerization of .alpha.-olefins having the formula 
EQU R--CH.dbd.CH.sub.2 
wherein R is an alkyl radical of 1 to 10 carbon atoms. It can also be 
applied to the copolymerization of such .alpha.-olefins and to the block 
or random copolymerization of such .alpha.-olefins and ehtylene. Specific 
examples of the above .alpha.-olefins include propylene, 1-butene, 
1-hexene, 4-methyl-1-pentene and the like. 
Polymerization reactions using the catalyst of the present invention can be 
carried out by the use of procedures and conditions conventionally known 
in this field of art. Specifically, the polymerization temperature is in 
the range of 20.degree. to 100.degree. C. and preferably 40.degree. to 
90.degree. C., and the polymerization pressure is in the range of 1 to 60 
kg/cm.sup.2 abs. and preferably 1 to 50 kg/cm.sup.2 abs. Generally, such 
polymerization reactions can be carried out in a solvent comprising at 
least one compound selected from aliphatic, alicyclic and aromatic 
hydrocarbons. Specific examples thereof include propane, butane, pentane, 
hexane, heptane, cyclohexane, benzene and the like as well as mixtures of 
the foregoing. 
The catalyst of the present invention can also be applied to the bulk 
polymerization in which a liquid monomer per se is used as the solvent and 
to the so-called gas phase polymerization in which a gaseous monomer is 
contacted with a catalyst in a substantial absence of solvent. 
In the process of the present invention, the molecular weight of the 
resulting polymer varies according to the mode of polymerization, the type 
of catalyst, and polymerization conditions. If desired, the molecular 
weight of the resulting polymer can further be controlled, for example, by 
adding hydrogen, an alkyl halide, a dialkylzinc or the like to the 
reactor. 
The process of the present invention is characterized in that the 
polymerization activity of the catalyst is outstandingly high and, 
moreover, in that the content in the resulting polymer of the residual 
polymer obtainable after extraction with boiling n-heptane is as high as 
95-97 wt.%. Thus, a polymer having satisfactorily good properties can be 
obtained even if the extraction or removal of non-crystalline polymer is 
omitted. This enables simplification of the production system. 
Furthermore, in the process of the present invention, the additional use of 
an aluminum halide as the ingredient (e) in the preparation of the 
component (A) prevents the co-comminuted mixture from agglomerating to 
form a mass and, therefore, permits large amounts of raw materials to be 
charged into a pulverizer. In addition, the coarse particle content of the 
resulting polymer is so low that a slurry thereof can be easily handled 
without any trouble.

The present invention is further illustrated by way of the following 
examples. 
EXAMPLE 1 
(1) Preparation of Component (A) 
A vibration mill equipped with a 600-ml pulverizing pot containing 80 steel 
balls of 12-mm diameter was provided. Into this pot were charged 20 g of 
anhydrous magnesium chloride, 2.1 g of ethyl benzoate, 2.3 g of chloroform 
and 3.4 g of diphenyl ether in an atmosphere of nitrogen. Then, these 
ingredients were co-comminuted for 20 hours. 
Into a 300-ml round bottom flask were charged 10 g of the above 
co-comminuted mixture, 100 ml of n-heptane and 1.5 ml of titanium 
tetrachloride in an atmosphere of nitrogen, and the contents were stirred 
at 80.degree. C. for 2 hours. Thereafter, the supernatant liquid was 
removed by decantation. Then, 200 ml of n-heptane was added to the flask 
and the contents were stirred at room temperature for 30 minutes. 
Thereafter, the supernatant liquid was removed by decantation. This 
washing operation was repeated 5 times. 
Subsequently, 200 ml of n-heptane was further added to form a slurry of the 
composition (the component (A) of the present catalyst) obtained by 
supporting the titanium compound on the co-comminuted mixture. A sample of 
this slurry was taken and analyzed after the evaporation of n-heptane. 
Thus, the above composition was found to have a titanium content of 1.30 
wt.%. 
(2) Polymerization 
A catalyst within the scope of the present invention was prepared as 
follows: Into a 2-liter autoclave made of SUS-32 (a stainless steel 
designated according to the Japanese Industrial Standards) were charged 1 
liter of n-heptane, 0.20 g of the aforesaid component (A) (0.054 milligram 
atom at titanium), 0.4 ml (1.59 mmoles) of triisobutylaluminum and 0.10 ml 
(0.7 mmole) of ethyl benzoate in an atmosphere of nitrogen. 
After the nitrogen present in the autoclave was evacuated by means of a 
vacuum pump, hydrogen was introduced thereinto up to a gas phase partial 
pressure of 0.3 kg/cm.sup.2 abs., and propylene was then introduced to 
make the gas phase pressure 2 kg/cm.sup.2 gauge. The contents of the 
autoclave were heated in such a manner that the internal temperature rose 
to 70.degree. C. after 5 minutes, and the polymerization was continued for 
2 hours while propylene was supplied so as to maintain the polymerization 
pressure of 5 kg/cm.sup.2 gauge at 70.degree. C. After being cooled, the 
autoclave was purged to expel unreacted propylene. Then, the contents were 
removed from the autoclave and filtered to obtain 230 g of a white 
polypropylene powder. 
The content in this polypropylene powder of the residual polymer 
(crystalline polypropylene) obtainable after extraction with boiling 
n-heptane (hereinafter referred to as "powder I.I.") was 96.3 wt.%. The 
bulk density of the polypropylene powder was 0.48 g/ml and the intrinsic 
viscosity thereof was 1.61 dl/g (when measured in tetralin at 135.degree. 
C.). 
On the other hand, 3 g of an n-heptane-soluble polymer (non-crystalline 
polypropylene) was obtained by concentrating the filtrate. 
When determined by a boiling n-heptane extraction test, the content of the 
residual polymer in the total polypropylene thus obtained (hereinafter 
referred to as "total I.I.") was 95.1 wt.%. 
The polymerization activity of the catalyst used in this polymerization 
reaction was 552 g/g-(A)/hr. or 45 kg/g-Ti/hr. and the amount of 
polypropylene obtained was 1165 g/g-(A) or 90 kg/g-Ti. 
Controls 1-3 
In the preparation of the same co-comminuted mixture as used in the 
component (A) of Example 1, the addition of one or two of ethyl benzoate, 
chloroform and diphenyl ether was omitted to obtain a total of three 
different co-comminuted mixtures as shown in Table 1. Thereafter, these 
co-comminuted mixtures were heat-treated together with titanium 
tetrachloride in the same manner as described in Example 1-(1). 
Polymerization was carried out in the same manner as described in Example 
1, except that each of the compositions prepared as above was used as the 
component (A). The results thus obtained are shown in Table 2. As can be 
seen from the results of Table 2, the polymerization activity of the 
catalyst and the total I.I. and bulk density of the resulting polymer were 
all low when the co-comminuted mixture was composed solely of magnesium 
chloride and ethyl benzoate. However, the addition of chloroform raised 
the polymerization activity and the addition of diphenyl ether enhanced 
the polymerization activity, the total I.I. and the bulk density. This 
indicates that a catalyst prepared according to the present invention 
shows a great improvement in performance. 
TABLE 1 
______________________________________ 
PREATION OF CARRIER TYPE TITANIUM 
COMPONENT 
Titanium 
Co-comminuted Mixture Content of Carrier 
Magnes- Ethyl Di- Type Titanium 
De- ium Benzo- Chloro- 
phenyl 
Component after 
sign- 
Chloride ate Form Ether Heat Treatment 
ation 
(g) (g) (g) (g) with TiCl.sub.4 (wt. 
______________________________________ 
%) 
Cat. 20 2.1 -- -- 1.20 
Cat. 20 2.1 2.3 -- 1.42 
b 
Cat. 20 2.1 -- 3.4 1.08 
c 
______________________________________ 
TABLE 2 
__________________________________________________________________________ 
EXPERIMENTAL RESULTS 
Yield 
Designation 
Polypro- 
Non-crystal- Polymerization 
of pylene 
line Poly- 
Powder 
Total 
Activity Amount of Intrinsic 
Bulk 
Component Powder 
propylene 
I.I. I.I. g/g-(A)/ 
kg/g-Ti/ 
Polymer Obtained 
Viscosity 
Density 
Run No. 
(A) (g) (g) (wt. %) 
(wt. %) 
hr. hr. g/g-(A) 
kg/g-Ti 
(dl/g) 
(g/ml) 
__________________________________________________________________________ 
Control 
1 Cat. a 
96 6 93.5 88.0 265 22 510 43 1.60 0.30 
Control 
2 Cat. b 
183 6 93.3 90.3 473 33 945 66 1.73 0.29 
Control 
3 Cat. c 
93 6 94.4 88.7 248 23 495 46 1.68 0.31 
__________________________________________________________________________ 
EXAMPLE 2 
In this example, 0.20 g of the component (A) prepared in Example 1-(1) 
(0.054 milligram atom as titanium), 0.12 ml (0.97 mmole) of 
diethylaluminum monochloride, 0.10 ml (0.07 mmole) of ethyl benzoate and 
0.4 ml (1.59 mmoles) of triisobutylaluminum were used as catalyst 
components. Among these components, the triisobutylaluminum was divided 
into six portions and introduced into the autoclave under pressure at 
intervals of 20 minutes. Polymerization was carried out in the same manner 
as described in Example 1, except that the aforesaid catalyst was used and 
the polymerization time was 2.5 hours. The results thus obtained are shown 
in Table 3. 
EXAMPLES 3 AND 4 
Polymerization was carried out in the same manner as described in Example 
2, except that the diethylaluminum monochloride was replaced by an 
equimolar amount of ethylaluminum sesquichloride or ethylaluminum 
dichloride. The results thus obtained are shown in Table 3. 
Control 4 
Polymerization was carried out in the same manner as described in Example 
2, except that the component (A) used in Example 2 was replaced by the 
component (A) of Control 1 designated as "Cat. a". The results thus 
obtained are shown in Table 3. 
TABLE 3 
__________________________________________________________________________ 
EXPERIMENTAL RESULTS 
Yield 
Type of Polypro- 
Non-crystal- 
Total 
Polymerization 
Alkyl- pylene 
line Poly- 
Powder 
I.I. 
Activity Amount of Intrinsic 
Bulk 
aluminum Powder 
propylene 
I.I. (wt. 
g/g-(A)/ 
kg/g-Ti/ 
Polymer Obtained 
Viscosity 
Density 
Run No. 
Halide (g) (g) (wt. %) 
%) hr. hr. g/g-(A) 
kg/g-Ti 
(dl/g) 
(g/ml) 
__________________________________________________________________________ 
Example 
AlEt.sub.2 Cl 
517 5 98.2 97.3 
1044 80 2610 201 1.65 0.49 
Example 
AlEt.sub.3/2 Cl.sub.3/2 
492 4 97.9 97.1 
992 76 2480 191 1.62 0.48 
3 
Example 
AlEtCl.sub.2 
488 4 97.8 97.0 
984 76 2460 189 1.78 0.49 
4 
Control 
AlEt.sub.2 Cl 
153 7 93.1 89.0 
320 27 800 67 1.53 0.31 
4 
__________________________________________________________________________ 
EXAMPLES 5-12 
In the preparation of the same component (A) as described in Example 1-(1), 
the chloroform used as the ingredient (c) was replaced by various 
halogenated hydrocarbons to obtain a total of eight different 
compositions. 
Polymerization was carried out in the same manner as described in Example 
2, except that each of the above compositions was used as the component 
(A). The results thus obtained are shown in Table 4. 
TABLE 4 
__________________________________________________________________________ 
EXPERIMENTAL RESULTS 
Yield 
Non- 
crystal- 
Component (A) line Amount of 
Tita- 
Polypro- 
Poly- Polymerization 
Polymer 
Type of nium pylene 
pro- 
Powder 
Total 
Activity Obtained 
Intrinsic 
Bulk 
Ingredi- 
Content 
Powder 
pylene 
I.I. I.I. g/g-(A)/ 
kg/g-Ti/ 
g/g- 
kg/g- 
Viscosity 
Density 
Run No. 
ent (c) 
(wt. %) 
(g) (g) (wt. %) 
(wt. %) 
hr. hr. (A) 
Ti (dl/g) 
(g/ml) 
__________________________________________________________________________ 
Example 
Methylene 
1.25 510 4 97.7 96.9 1028 82 2570 
206 1.69 0.48 
5 chloride 
Example 
Carbon tetra- 
1.30 486 4 97.7 96.9 980 75 2450 
188 1.77 0.49 
6 chloride 
Example 
n-Butyl 
1.31 507 4 98.1 97.3 1022 78 2555 
195 1.89 0.48 
7 chloride 
Example 
1,2-Dichloro- 
1.31 504 4 97.8 97.0 1016 76 2540 
194 1.79 0.48 
8 ethane 
Example 
Hexachloro- 
1.29 490 5 98.3 97.3 990 77 2475 
192 1.67 0.49 
9 ethane 
Example 
Propenyl 
1.33 513 5 97.7 96.8 1036 78 2590 
195 1.85 0.49 
10 chloride 
Example 
Tetrabromo- 
1.37 488 4 97.8 97.0 984 72 2460 
180 1.86 0.48 
11 ethane 
Example 
Chlorinated 
1.35 491 5 98.2 97.2 992 73 2480 
184 1.66 0.48 
12 paraffin 
(having a Cl 
content of 
70 wt.%) 
__________________________________________________________________________ 
EXAMPLE 13-23 
In the preparation of the same component (A) as described in Example 1-(1), 
the diphenyl ether used as the ingredient (d) was replaced by various 
compounds to obtain a total of eleven different compositions. 
Polymerization was carried out in the same manner as described in Example 
2, except that each of the above compositions was used as the component 
(A). The results thus obtained are shown in Table 5. 
TABLE 5 
__________________________________________________________________________ 
EXPERIMENTAL RESULTS 
Polymeri- 
Yield zation Amount of 
Component (A) Polypro- 
Non-crystal- Activity 
Polymer Bulk 
Type of Titanium 
pylene 
line Poly- 
Powder 
Total 
g/g- 
kg/g- 
Obtained 
Intrinsic 
Den- 
Run Ingredi- 
Content 
Powder 
propylene 
I.I. I.I. (A)/ 
Ti/ g/g- 
kg/g- 
Viscosity 
sity 
No. ent (d) (wt. %) 
(g) (g) (wt. %) 
(wt. %) 
hr. 
hr. (A) 
Ti (dl/g) 
(g/ml) 
__________________________________________________________________________ 
Example 
n-Heptane 
1.37 485 6 96.3 95.1 982 
72 2455 
179 1.63 0.40 
13 
Example 
n-Octane 
1.30 517 7 96.3 95.0 1028 
79 2570 
197 1.65 0.41 
14 
Example 
1-Octane 
1.31 494 6 96.2 95.1 1000 
76 2500 
191 1.67 0.40 
15 
Example 
Toluene 1.40 484 6 95.9 94.7 980 
70 2450 
176 1.84 0.39 
16 
Example 
Cyclohexane 
1.29 488 7 96.3 94.9 990 
77 2475 
192 1.64 0.39 
17 
Example 
Monochloro- 
1.35 518 6 96.3 95.2 1048 
77 2620 
194 1.78 0.41 
18 benzene 
Example 
Propylene 
1.30 513 5 96.7 95.8 1036 
80 2590 
199 1.65 0.45 
19 oligomer 
(mol.wt.400) 
Example 
Propylene 
1.26 508 5 97.0 95.1 1026 
81 2565 
204 1.68 0.45 
20 oligomer 
(mol.wt.730) 
Example 
Methyl phenyl 
1.32 485 5 98.0 97.0 980 
74 2450 
186 1.67 0.49 
21 ether 
Example 
Ethyl phenyl 
1.39 485 4 97.7 96.9 978 
70 2445 
176 1.69 0.48 
22 ether 
Example 
Ditolyl 1.39 507 4 98.0 97.2 1022 
74 2555 
184 1.67 0.48 
23 ether 
__________________________________________________________________________ 
EXAMPLES 24-27 
Polymerization was carried out in the same manner as described in Example 
2, except that the ethyl benzoate used as the component (C) was replaced 
by an equimolar amount of various organic acid esters. The results thus 
obtained are shown in Table 6. 
TABLE 6 
__________________________________________________________________________ 
EXPERIMENTAL RESULTS 
Yield 
Polypro- 
Non-crystal- Polymerization Bulk 
Type of pylene 
line Poly- 
Powder 
Total 
Activity Amount of Intrinsic 
Den- 
Compo- Powder 
propylene 
I.I. I.I. g/g-(A)/ 
kg/g-Ti/ 
Polymer Obtained 
Viscosity 
sity 
Run No. 
nent (C) 
(g) (g) (wt. %) 
(wt. %) 
hr. hr. g/g-(A) 
kg/g-Ti 
(dl/g) 
(g/ml) 
__________________________________________________________________________ 
Example 
Methylben- 
517 4 98.0 97.2 1042 80 2605 200 1.71 0.49 
24 zoate 
Example 
Isobutyl 
489 4 97.8 97.0 985 76 2465 190 1.77 0.49 
25 benzoate 
Example 
Isoamyl 
507 5 97.8 96.8 1024 79 2560 197 1.66 0.48 
26 benzoate 
Example 
Ethyl 495 4 98.1 97.3 998 77 2495 192 1.79 0.48 
27 anisate 
__________________________________________________________________________ 
EXAMPLES 28-32 
Polymerization was carried out in the same manner as described in Example 
2, except that the amounts of the component (A), diethylaluminum 
monochloride, ethyl benzoate and triisobutylaluminum used were varied. The 
results thus obtained are shown in Table 7. 
EXAMPLE 33 
Polymerization was carried out in the same manner as described in Example 
2, except that the triisobutylaluminum was replaced by an equimolar amount 
of triethylaluminum. The results thus obtained are shown in Table 7. 
TABLE 7 
__________________________________________________________________________ 
EXPERIMENTAL RESULTS 
Yield 
Catalyst Components Non- 
Diethyl crystal- Polymeri- 
Triiso- 
Alumi- Poly- 
line 
Pow- zation Amount of 
butyl- 
num Ethyl 
propyl- 
Poly- 
der Total 
Activity 
Polymer Bulk 
Compo- alumi- 
Mono- 
Benzo- 
ene propyl- 
I.I. 
I.I. 
g/g- 
kg/g- 
Obtained 
Intrinsic 
Den- 
Run nent(A) 
num chloride 
ate Powder 
ene (wt. 
(wt. 
(A)/ 
Ti/ g/g- 
kg/g- 
Viscosity 
sity 
No. (g) (ml) 
(ml) 
(ml) (g) (g) %) %) hr. 
hr. (A) 
Ti (dl/g) 
(g/ml) 
__________________________________________________________________________ 
Example 
0.2 0.4 0.24 
0.12 505 4 98.1 
97.3 
1018 
78 2545 
196 1.69 0.48 
28 
Example 
0.2 0.3 0.24 
0.10 505 3 98.1 
97.5 
1018 
78 2545 
196 1.67 0.49 
29 
Example 
0.15 0.4 0.12 
0.10 381 5 98.0 
96.7 
1029 
79 2575 
198 1.73 0.47 
30 
Example 
0.15 0.4 0.24 
0.10 486 5 97.6 
96.6 
1309 
101 3273 
252 1.64 0.48 
31 
Example 
0.2 0.4 0.12 
0.12 374 3 98.3 
97.5 
746 
57 1865 
143 1.78 0.48 
32 
Example 
0.2 0.22* 
0.24 
0.10 483 5 97.9 
96.9 
976 
76 2440 
188 1.65 0.49 
33 
__________________________________________________________________________ 
*Triethylaluminum- 
EXAMPLES 34-39 
In the preparation of the same component (A) as described in Example 1-(1), 
the chemical makeup of the co-comminuted mixture composed of magnesium 
chloride, ethyl benozate, chloroform and diphenyl ether was modified as 
shown in Table 8 to obtain a total of six different compositions. 
Polymerization was carried out in the same manner as described in Example 
1, except that each of the above compositions was used as the component 
(A). The results thus obtained are shown in Table 8. 
TABLE 8 
__________________________________________________________________________ 
EXPERIMENTAL RESULTS 
Component (A) Yield 
Co-comminuted Mixture Non- 
Mag- Titan- 
Poly- 
crystal- Polymeri- 
nes- ium propyl- 
line 
Pow- zation Amount of 
Intrin- 
ium Ethyl 
Chlo- 
Di- Con- 
ene Poly- 
der Total 
Activity 
Polymer 
sic Bulk 
Chloro- Benzo- 
ro- phenyl 
tent 
Pow- 
propyl- 
I.I. 
I.I. 
g/g- 
kg/g- 
Obtained 
Viscos- 
Den- 
Run ide ate form 
Ether 
(wt. 
der ene (wt. 
(wt. 
(A)/ 
Ti/ g/g- 
kg/g- 
ity sity 
No. (g) (g) (g) (g) %) (g) (g) %) %) hr. 
hr. (A) 
Ti (dl/g) 
(g/ml) 
__________________________________________________________________________ 
Example 
20 2.1 2.3 1.7 1.44 
225 4 96.8 
95.1 
573 
40 1145 
80 1.66 
0.48 
34 
Example 
20 2.1 2.3 6.8 1.18 
217 3 96.7 
95.4 
550 
47 1100 
93 1.65 
0.48 
35 
Example 
20 1.1 2.3 3.4 1.38 
258 4 96.2 
94.7 
655 
47 1310 
93 1.66 
0.48 
36 
Example 
20 4.2 2.3 3.4 1.27 
197 4 96.9 
95.0 
503 
40 1005 
79 1.71 
0.49 
37 
Example 
20 2.1 1.2 3.4 1.11 
181 4 96.6 
94.5 
463 
42 925 
83 1.78 
0.49 
38 
Example 
20 2.1 4.6 3.4 1.68 
283 4 96.2 
94.9 
718 
43 1435 
85 1.77 
0.48 
39 
__________________________________________________________________________ 
EXAMPLE 40 
Polymerization was carried out in the same manner as described in Example 
2, except that the ethyl benzoate used during the polymerization was 
replaced by 0.193 g of a 1:1 complex of ethyl benzoate with aluminum 
chloride and the component (A) was used in an amount of 0.15 g. The 
results thus obtained are shown in Table 9. 
TABLE 9 
__________________________________________________________________________ 
EXPERIMENTAL RESULTS 
Yield Amount of 
Polypro- 
Non-crystal- Polymerization 
Polymer Bulk 
Type of pylene 
line Poly- 
Powder 
Total 
Activity Obtained 
Intrinsic 
Den- 
Run Compo- Powder 
propylene 
I.I. I.I. g/g-(A)/ 
kg/g-Ti/ 
g/g- 
kg/g- 
Viscosity 
sity 
No. nent (C) (g) (g) (wt. %) 
(wt. %) 
hr. hr. (A) Ti (dl/g) 
(g/ml) 
__________________________________________________________________________ 
Example 
PhCOOEt .multidot. AlCl.sub.3 
485 4 97.7 96.9 1304 100 3260 
251 1.77 0.48 
40 
__________________________________________________________________________ 
EXAMPLE 41 
Polymerization was carried out in the same manner as described in Example 
2, except that the propylene used as the monomer was replaced by a mixed 
gas of propylene and ethylene having an ethylene concentration of 1.0 
wt.%. The polymerization was continued for 2.15 hours to obtain 484 g of 
polypropylene powder and 6 g of non-crystalline polypropylene. 
The powder I.I. of this polypropylene powder was 96.3 wt.%, the intrinsic 
viscosity thereof was 1.72 dl/g, the bulk density thereof was 0.47 g/ml, 
and the ethylene content thereof was 0.6 wt.%. The total I.I. of the 
resulting polymer was 95.1 wt.%. 
The polymerization activity of the catalyst used in this polymerization 
reaction was 1139 g/g-(A)/hr, or 88 kg/g-Ti/hr. and the amount of polymer 
obtained was 2450 g/g-(A) or 189 kg/g-Ti. 
EXAMPLE 42 
Polymerization was carried out in the same manner as described in Example 
2. The polymerization was continued for 1.7 hours until about 400 g of 
propylene was polymerized. After the autoclave was cooled, the propylene 
present therein was replaced by ethylene, and 0.1 ml of 
triisobutylaluminum was introduced thereinto. Using a hydrogen partial 
pressure of 1.5 kg/cm.sup.2 abs., a polymerization pressure of 5 
kg/cm.sup.2 gauge and a polymerization temperature of 70.degree. C., the 
polymerization was further continued for 0.6 hour to obtain 513 g of 
polymer powder and 6 g of non-crystalline polymer. 
The powder I.I. of this polymer powder was 97.5 wt.%, the intrinsic 
viscosity thereof was 1.73 dl/g, the bulk density thereof was 0.48 g/ml, 
and the ethylene content thereof was 19.3 wt.%. The total I.I. of the 
resulting polymer was 96.4 wt.%. 
The polymerization activity of the catalyst used in this polymerization 
reaction was 1128 g/g-(A)hr. or 87 kg/g-Ti/hr. and the amount of polymer 
obtained was 2695 g/g-(A) or 200 kg/g-Ti. 
The following Examples 43-76 illustrate the use of an aluminum halide as 
the optional ingredient (e) in the preparation of the component (A) of the 
present catalyst. 
EXAMPLE 43 
(1) Preparation of Component (A) 
A vibration mill equipped with a 600-ml pulverizing pot containing 80 steel 
balls of 12-mm diameter was provided. Into this pot were charged 30 g of 
anhydrous magnesium chloride, 3.15 g of ethyl benzoate, 3.45 g of 
chloroform, 5.1 g of diphenyl ether and 0.38 g of aluminum chloride in an 
atmosphere of nitrogen. Then, these ingredients were co-comminuted for 20 
hours. When the pot was opened, it was found that the co-comminuted 
mixture neither had agglomerated to form a mass nor stuck to the inner 
walls of the pot or the steel balls. 
Into a 300-ml round bottom flask were charged 10 g of the above 
co-comminuted mixture, 100 ml of n-heptane and 1.5 ml of titanium 
tetrachloride in an atmosphere of nitrogen, and the contents were stirred 
at 80.degree. C. for 2 hours. Thereafter, the supernatant liquid was 
removed by decantation. Then, 200 ml of n-heptane was added to the flask 
and the contents were stirred at room temperature for 30 minutes. 
Thereafter, the supernatant liquid was removed by decantation. This 
washing operation was repeated 5 times. 
Subsequently, 200 ml of n-heptane was further added to form a slurry of the 
composition (the component (A) of the present catalyst) obtained by 
supporting the titanium compound on the co-comminuted mixture. A sample of 
this slurry was taken and analyzed after the evaporation of n-heptane. 
Thus the above composition was found to have a titanium content of 1.12 
wt.%. 
(2) Polymerization 
A catalyst within the scope of the present invention was prepared as 
follows: Into a 2-liter autoclave made of SUS-32 were charged 1 liter of 
n-heptane, 0.15 g of the aforesaid component (A) (0.035 milligram atom as 
titanium), 0.4 ml (1.59 mmoles) of triisobutylaluminum and 0.10 ml (0.7 
mmole) of ethyl benzoate in an atomsphere of nitrogen. 
After the nitrogen present in the autoclave was evacuated by means of a 
vacuum pump, hydrogen was introduced thereinto up to a gas phase partial 
pressure of 0.3 kg/cm.sup.2 abs., and propylene was then introduced to 
make the gas phase pressure 2 kg/cm.sup.2 gauge. The contents of the 
autoclave were heated in such a manner that the internal temperature rose 
to 70.degree. C. after 5 minutes, and the polymerization was continued for 
2 hours while propylene was supplied so as to maintain the polymerization 
pressure of 5 kg/cm.sup.2 gauge at 70.degree. C. After being cooled, the 
autoclave was purged to expel unreacted propylene. Then, the contents were 
removed from the autoclave and filtered to obtain 230 g of a white 
polypropylene powder. 
The powder I.I. of this polypropylene powder was 96.4 wt.%, the bulk 
density thereof was 0.48 g/ml, and the intrinsic viscosity thereof was 
1.64 dl/g (when measured in tetralin at 135.degree. C.). 
On the other hand, 3 g of an n-heptane-soluble polymer (non-crystalline 
polypropylene) was obtained by concentrating the filtrate. 
The total I.I. of the resulting polymer was 95.2 wt.%. 
The polymerization activity of the catalyst used in this polymerization 
reaction was 803 g/g-(A)/hr. or 72 kg/g-Ti/hr. and the amount of 
polypropylene obtained was 1606 g/g-(A) or 143 kg/g-Ti. The above 
polypropylene powder was sifted to examine its particle size distribution. 
This revealed that the content of the particles not passed by a 10-mesh 
screen (hereinafter referred to as "coarse particles") was 1.0 wt.% and 
the content of the particles passed by a 200-mesh screen (hereinafter 
referred to as "fine particles") was 8.3 wt.%. 
REFERENCE EXAMPLE 1 
(1) Preparation of Component (A) 
In the preparation of the same co-comminuted mixture as described in 
Example 43-(1), the addition of aluminum chloride was omitted. When the 
pot was opened, about 5 g of the resulting co-comminuted mixture was found 
to stick to the inner walls of the pot and the steel balls. 
In the same manner as described in Example 43-(1), the above co-comminuted 
mixture was heat-treated together with titanium tetrachloride and then 
washed with n-heptane to form a slurry of the composition obtained by 
supporting the titanium compound on the co-comminuted mixture. This 
composition had a titanium content of 1.32 wt.%. 
(2) Polymerization 
Polymerization was carried out in the same manner as described in Example 
43, except that 0.20 g of the aforesaid composition (0.055 milligram atom 
as titanium) was used as the component (A). Thus, 232 g of polypropylene 
powder was obtained. 
The powder I.I. of this polypropylene powder was 96.1 wt.%, the bulk 
density thereof was 0.48 g/dl, and the intrinsic viscosity thereof was 
1.63 dl/g. 
On the other hand, 3 g of non-crystalline polypropylene was obtained by 
concentrating the filtrate. 
The total I.I. of the resulting polymer was 94.9 wt.%. 
The polymerization activity of the catalyst used in this polymerization 
reaction was 588 g/g-(A)/hr. or 45 kg/g-Ti/hr. and the amount of 
polypropylene obtained was 1175 g/g-(A) or 89 kg/g-Ti. 
The above polypropylene powder was sifted to examine its particle size 
distribution. This revealed that its coarse particle content was 7.0 wt.% 
and its fine particle content was 10.8 wt.%. 
EXAMPLE 44 
In this example, 0.15 g of the component (A) prepared in Example 43-(1) 
(0.035 milligram atom as titanium), 0.12 ml (0.97 mmole) of 
diethylaluminum monochloride, 0.10 ml (0.07 mmole) of ethyl benzoate and 
0.4 ml (1.59 mmoles) of triisobutylaluminum were used as catalyst 
components. Among these components, the triisobutylaluminum was divided 
into six portions and introduced into the autoclave under pressure at 
intervals of 20 minutes. Polymerization was carried out in the same manner 
as described in Example 43, except that the aforesaid catalyst was used 
and the polymerization time was 2.5 hours. The results thus obtained are 
shown in Table 10. 
EXAMPLES 45 AND 46 
Polymerization was carried out in the same manner as described in Example 
44, except that the diethylaluminum monochloride was replaced by an 
equimolar amount of ethylaluminum sesquichloride or ethylaluminum 
dichloride. The results thus obtained are shown in Table 10. 
TABLE 10 
__________________________________________________________________________ 
EXPERIMENTAL RESULTS 
Yield Polymeri- 
Non-crys- 
Pow- zation Amount of 
Intrin- Coarse 
Fine 
Type Polypro- 
talline 
der Total 
Activity 
Polymer 
sic Bulk 
Parti- 
Parti- 
Alkyl- pylene 
Polypro- 
I.I. 
I.I. 
g/g- 
kg/g- 
Obtained 
Viscos- 
Den- 
cle cle 
Run aluminum 
Powder 
pylene 
(wt. 
(wt. 
(A)/ 
Ti/ g/g- 
kg/g- 
ity sity 
Content 
Content 
No. Halide (g) (g) %) %) hr. 
hr. (A) 
Ti (dl/g) 
(g/ml) 
(wt. 
(wt. 
__________________________________________________________________________ 
%) 
Example 
AlEt.sub.2 Cl 
508 5 98.1 
97.1 
1368 
122 3420 
305 1.70 
0.49 
1.5 6.5 
44 
Example 
AlEt.sub.3/2 Cl.sub.3/2 
535 5 97.7 
96.8 
1440 
129 3600 
321 1.81 
0.48 
0.9 5.3 
45 
Example 
AlEtCl.sub.2 
521 4 97.9 
97.2 
1400 
125 3500 
313 1.69 
0.48 
1.8 6.1 
46 
__________________________________________________________________________ 
EXAMPLE 47-54 
In the preparation of the same component (A) as described in Example 
43-(1), the chloroform used as the ingredient (c) was replaced by various 
halogenated hydrocarbons to obtain a total of eight different 
compositions. 
Polymerization was carried out in the same manner as described in Example 
44, except that each of the above composition was used as the component 
(A). The results thus obtained are shown in Table 11. 
TABLE 11 
__________________________________________________________________________ 
EXPERIMENTAL RESULTS 
Coarse 
Component (A) 
Yield Coarse 
Fine 
Particle 
Tita- 
Poly- 
Non- Polymeri- Parti- 
Parti- 
Content 
nium 
propyl- 
crys- 
Pow- zation Amount of 
Intrin- cle cle Observed 
Con- 
ene talline 
der 
Total 
Activity 
Polymer 
sic Bulk 
Con- 
Con- 
Without 
Type of tent 
Pow- 
Poly- 
I.I. 
I.I. 
g/g- 
kg/g- 
Obtained 
Viscos- 
Den- 
tent 
tent 
Addition 
Run 
Ingredi- 
(wt. 
der propyl- 
(wt. 
(wt. 
(A)/ 
Ti/ g/g- 
kg/g- 
ity sity 
(wt. 
(wt. 
of AlCl.sub.3 
No. 
ent (c) 
%) (g) ene (g) 
%) %) hr. 
hr. (A) 
Ti (dl/g) 
(g/ml) 
%) %) (wt. 
__________________________________________________________________________ 
%) 
Ex. 
Methylene 
1.18 
525 5 97.7 
96.8 
1413 
120 3533 
299 1.69 
0.49 
1.1 6.1 6.8 
47 chloride 
Ex. 
Carbon 
1.17 
535 4 97.7 
97.0 
1437 
123 3593 
307 1.68 
0.49 
1.5 5.3 7.2 
48 tetra- 
chloride 
Ex. 
n-Butyl 
1.18 
523 5 98.1 
97.2 
1407 
119 3520 
298 1.71 
0.48 
1.2 5.7 6.8 
49 chloride 
Ex. 
1,2-Di- 
1.13 
502 5 97.8 
96.8 
1352 
120 3380 
299 1.73 
0.48 
1.5 5.8 6.9 
50 chloro- 
ethane 
Ex. 
Hexa- 1.17 
491 4 97.8 
97.0 
1320 
113 3300 
282 1.66 
0.48 
1.4 6.1 6.9 
51 chloro- 
ethane 
Ex. 
Propenyl 
1.15 
533 4 97.7 
97.0 
1432 
125 3580 
311 1.69 
0.48 
1.6 6.1 7.0 
52 chloride 
Ex. 
Tetra- 
1.15 
501 4 97.9 
97.1 
1346 
117 3367 
293 1.62 
0.48 
1.1 5.8 7.1 
53 bromo- 
ethane 
Ex. 
Chlorinated 
1.12 
522 4 98.1 
97.4 
1403 
125 3507 
313 1.70 
0.49 
1.3 5.9 7.1 
54 paraffin 
(having a 
Cl content 
of 70 wt. %) 
__________________________________________________________________________ 
EXAMPLES 55-65 
In the preparation of the same component (A) as described in Example 
43-(1), the diphenyl ether used as the ingredient (d) was replaced by 
various components to obtain a total of eleven different compositions. 
Polymerization was carried out in the same manner as described in Example 
44, except that each of the above compositions was used as the component 
(A). The results thus obtained are shown in Table 12. 
TABLE 12 
__________________________________________________________________________ 
EXPERIMENTAL RESULTS 
Coarse 
Component (A) 
Yield Coarse 
Fine 
Particle 
Tita- Non- Polymeri- Parti- 
Parti- 
Content 
nium 
Poly- 
crys- 
Pow- zation Amount of 
Intrin- cle cle Observed 
Con- 
propyl- 
talline 
der 
Total 
Activity 
Polymer 
sic Bulk 
Con- 
Con- 
Without 
Type of tent 
ene Poly- 
I.I. 
I.I. 
g/g- 
kg/g- 
Obtained 
Viscos- 
Den- 
tent 
tent 
Addition 
Run 
Ingredi- 
(wt. 
Pow- 
propyl- 
(wt. 
(wt. 
(A)/ 
Ti/ g/g- 
kg/g- 
ity sity 
(wt. 
(wt. 
of AlCl.sub.3 
No. 
ent (d) 
%) der (g) 
ene (g) 
%) %) hr. 
hr. (A) 
Ti (dl/g) 
(g/ml) 
%) %) (wt. 
__________________________________________________________________________ 
%) 
Ex. 
n-Heptane 
1.19 
501 6 96.2 
95.1 
1352 
114 3380 
284 1.65 
0.40 
1.1 5.7 7.2 
55 
Ex. 
n-Octane 
1.16 
521 7 96.3 
95.0 
1408 
121 3520 
303 1.67 
0.39 
0.9 6.1 7.2 
56 
Ex. 
1-Octene 
1.20 
513 7 96.1 
94.8 
1387 
115 3467 
289 1.66 
0.40 
1.4 6.2 6.8 
57 
Ex. 
Toluene 
1.15 
521 6 95.9 
94.8 
1406 
122 3513 
306 1.60 
0.41 
1.1 6.5 7.6 
58 
Ex. 
Cyclo- 
1.18 
503 6 96.3 
95.2 
1357 
115 3393 
288 1.58 
0.41 
1.0 6.2 6.9 
59 hexane 
Ex. 
Mono- 1.16 
522 7 96.0 
94.7 
1411 
122 3527 
304 1.62 
0.40 
1.4 5.7 7.4 
60 chloro- 
benzene 
Ex. 
Propylene 
1.19 
524 5 96.8 
95.9 
1411 
119 3527 
296 1.73 
0.45 
1.2 6.1 6.3 
61 oligomer 
(mol.wt. 
400) 
Ex. 
Propylene 
1.18 
516 5 97.1 
96.2 
1389 
117 3473 
294 1.67 
0.45 
1.1 6.4 6.7 
62 oligomer 
(mol.wt. 
730) 
Ex. 
Methyl 
1.18 
514 4 97.8 
97.0 
1381 
117 3453 
293 1.59 
0.48 
1.7 6.4 6.3 
63 phenyl 
ether 
Ex. 
Ethyl 1.17 
504 4 97.7 
96.9 
1355 
116 3387 
289 1.73 
0.49 
1.1 6.4 6.9 
64 phenyl 
ether 
Ex. 
Ditolyl 
1.22 
525 4 97.9 
97.2 
1410 
116 3527 
289 1.70 
0.49 
1.3 6.5 7.2 
65 ether 
__________________________________________________________________________ 
EXAMPLES 66-73 
In the preparation of the same component (A) as described in Example 
43-(1), the chemical makeup of the co-communited mixture composed of 
magnesium chloride, ethyl benzoate, chloroform, diphenyl ether and 
aluminum chloride was modified as shown in Table 13 to obtain a total of 
eight different compositions. 
Polymerization was carried out in the same manner as described in Example 
43, except that each of the above compositions was used as the component 
(A). The results thus obtained are shown in Table 13. 
TABLE 13 
__________________________________________________________________________ 
EXPERIMENTAL RESULTS 
__________________________________________________________________________ 
Component (A) Yield 
Co-comminuted Mixture Polypro- 
Non-crystal- 
Magnesium 
Ethyl Diphenyl 
Aluminum 
Titanium 
pylene 
line Poly- 
Powder 
Total 
Chloride 
Benzoate 
Chloroform 
Ether Chloride 
Content 
Powder 
propylene 
I.I. I.I. 
Run No. 
(g) (g) (g) (g) (g) (wt. %) 
(g) (g) (wt. 
(wt. 
__________________________________________________________________________ 
%) 
Example 
30 3.15 3.45 5.1 0.15 1.21 233 3 96.3 95.1 
66 
Example 
30 3.15 3.45 5.1 0.60 1.16 238 3 95.9 94.7 
67 
Example 
30 3.15 3.45 2.55 0.38 1.17 229 4 96.6 94.9 
68 
Example 
30 3.15 3.45 10.2 0.38 1.18 223 4 96.6 94.9 
69 
Example 
30 1.65 3.45 5.1 0.38 1.15 244 3 95.7 94.2 
70 
Example 
30 6.3 3.45 5.1 0.38 1.20 195 3 96.8 95.3 
71 
Example 
30 3.15 1.8 5.1 0.38 1.18 183 4 96.6 94.5 
72 
Example 
30 3.15 6.9 5.1 0.38 1.16 289 4 96.0 94.7 
73 
__________________________________________________________________________ 
Polymerization Coarse 
Fine Coarse Particle 
Activity Amount of Intrinsic 
Bulk Particle 
Particle 
Content Observed 
g/g-(A)/ 
kg/g-Ti/ 
Polymer Obtained 
Viscosity 
Density 
Content 
Content 
Without Addition 
Run No. 
hr. hr. g/g-(A) 
kg/g-Ti 
(dl/g) 
(g/ml) 
(wt. %) 
(wt. %) 
of AlCl.sub.3 (wt. 
%) 
__________________________________________________________________________ 
Example 
787 65 1573 130 1.65 0.48 0.9 6.1 6.7 
66 
Example 
804 69 1607 139 1.67 0.49 1.3 6.3 6.4 
67 
Example 
743 64 1486 127 1.62 0.49 1.6 7.1 7.3 
68 
Example 
757 64 1515 128 1.69 0.49 1.0 6.5 6.5 
69 
Example 
824 72 1647 143 1.67 0.48 1.3 6.3 6.2 
70 
Example 
660 55 1320 110 1.66 0.49 1.1 6.7 6.6 
71 
Example 
624 53 1247 106 1.63 0.49 1.3 7.1 6.3 
72 
Example 
977 65 1953 130 1.62 0.48 1.2 6.4 6.5 
73 
__________________________________________________________________________ 
EXAMPLE 74 
Polymerization was carried out in the same manner as described in Example 
44, except that the ethyl benzoate used during the polymerization was 
replaced by 0.198 g of a 1:1 complex of ethyl benzoate with aluminum 
chloride and the polymerization time was 2 hours. The results thus 
obtained are shown in Table 14. 
TABLE 14 
__________________________________________________________________________ 
EXPERIMENTAL RESULTS 
Coarse 
Yield Particle 
Non- Polymeri- Content 
Poly- 
crys- 
Pow- zation Amount of Obtained 
propyl- 
talline 
der 
Total 
Activity 
Polymer Coarse 
Fine Without 
Type of ene Poly- 
I.I. 
I.I. 
g/g- 
kg/g- 
Obtained 
Intrinsic 
Bulk Particle 
Particle 
Addition 
Run 
Compo- 
Pow- 
propyl- 
(wt. 
(wt. 
(A)/ 
Ti/ g/g- 
kg/g- 
Viscosity 
Density 
Content 
Content 
of AlCl.sub.3 
No. 
nent (C) 
der (g) 
ene (g) 
%) %) hr. 
hr. (A) 
Ti (dl/g) 
(g/ml) 
(wt. %) 
(wt. 
(wt. 
__________________________________________________________________________ 
%) 
Ex. 
PhCOOEt .multidot. 
500 4 97.8 
97.0 
1680 
150 3360 
300 1.69 0.48 1.3 6.8 7.0 
74 AlCl.sub.3 
__________________________________________________________________________ 
EXAMPLE 75 
Polymerization was carried out in the same manner as described in Example 
44, except that the propylene used as the monomer was replaced by a mixed 
gas of propylene and ethylene having an ethylene concentration of 1.0 
wt.%. The polymerization was continued for 2.15 hours to obtain 503 g of 
polypropylene powder and 7 g of non-crystalline polypropylene. 
The powder I.I. of this polypropylene powder was 96.0 wt.%, the intrinsic 
viscosity thereof was 1.70 dl/g, the bulk density thereof was 0.47 g/ml, 
and the ethylene content thereof was 0.6 wt.%. The total I.I. of the 
resulting polymer was 94.7 wt.%. 
The polymerization activity of the catalyst used in this polymerization 
reaction was 1581 g/g-(A)/hr. or 141 kg/g-Ti/hr. and the amount of polymer 
obtained was 3400 g/g-(A) or 304 kg/g-Ti. 
EXAMPLE 76 
Polymerization was carried out in the same manner as described in Example 
44. The polymerization was continued for 1.7 hours until about 400 g of 
propylene was polymerized. After the autoclave was cooled, the propylene 
present therein was replaced by ethylene, and 0.1 ml of 
triisobutylaluminum was introduced thereinto. Using a hydrogen partial 
pressure of 1.5 kg/cm.sup.2 abs., a polymerization pressure of 5 
kg/cm.sup.2 gauge and a polymerization temperature of 70.degree. C., the 
polymerization was further continued for 0.6 hour to obtain 518 g of 
polymer powder and 7 g of non-crystalline polymer. 
The powder I.I. of this polymer powder was 97.0 wt.%, the intrinsic 
viscosity thereof was 1.83 dl/g, the bulk density thereof was 0.48 g/ml, 
and the ethylene content thereof was 18.3 wt.%. The total I.I. of the 
resulting polymer was 95.7 wt.%. 
The polymerization activity of the catalyst used in this polymerization 
reaction was 1527 g/g-(A)/hr. or 136 kg/g-Ti/hr. and the amount of polymer 
obtained was 3500 g/g-(A) or 312 kg/g-Ti.