Process for polymerizing alpha-olefins and catalyst therefor

A process for polymerizing or copolymerizing .alpha.-olefins in the presence of a catalyst composed of (A) a mechanically pulverized solid titanium-containing catalyst component and (B) an organometallic compound of a metal of Groups I to III of the periodic table, wherein said titanium-containing component is a solid halogen-containing titanium catalyst component obtained by reacting a mechanically copulverized solid product in the absence of mechanical pulverization with a titanium compound which is liquid under the reaction conditions, said mechanically copulverized product being derived from (1) a magnesium compound, (2) an organic acid ester, and (3) an active hydrogen-containing compound selected from the group of alcohols and phenols; and a catalyst composition used therefor.

This invention relates to a process for polymerizing .alpha.-olefins and a 
catalyst suitable for use in the process. More specifically, the invention 
relates to a process for producing highly stereoregular .alpha.-olefin 
polymers or copolymers in improved yields with a superior polymer output 
per unit weight of a solid titanium compound used as a catalyst component, 
and per unit weight of halogen containing the solid titanium compound 
while greatly inhibiting the formation of a fine powdery polymer which is 
detrimental to the separation of the resulting desired polymer. The 
catalyst used has a superior activity in terms of the number of grams of 
the polymer formed per millimole of titanium atom per hour. Furthermore, 
the time required for mechanical copulverization in catalyst preparation 
can be shortened. 
The present invention provides a process for polymerizing or copolymerizing 
.alpha.-olefins in the presence of a catalyst composed of (A) a 
mechanically pulverized solid titanium-containing catalyst component and 
(B) an organometallic compound of a metal of Groups I to III of the 
periodic table, wherein said titanium-containing catalyst component is a 
solid halogen-containing titanium component obtained by reacting a 
mechanically copulverized solid product in the absence of mechanical 
pulverization with a titanium compound which is liquid under the reaction 
conditions, said mechanically copulverized solid product being derived 
from (1) a magnesium compound (2) an organic acid ester, and (3) an active 
hydrogen-containing compound selected from the group of alcohols and 
phenols; and a catalyst composition suitable for use in the practice of 
this process. 
Methods have heretofore been suggested for polymerizing or copolymerizing 
.alpha.-olefins in the presence of a catalyst composed of (A) a solid 
titanium compound mechanically pulverized in the presence or absence of 
another compound, and (B) an organometallic compound of a metal of Groups 
I to III of the periodic table. One example of the titanium catalyst 
component of this type is the highly active titanium catalyst component 
disclosed in Japanese Laid-Open Patent Publication No. 126590/75 (laid 
open on Oct. 4, 1975) which is obtained by contacting a halogen-containing 
magnesium compound with an aromatic carboxylic acid ester by a 
mechanically pulverizing means, and reacting the resulting mixture with a 
titanium compound. This Patent Publication does not at all give a 
description about pulverization in the presence of the active 
hydrogen-containing compound (3). Highly stereoregular .alpha.-olefin 
polymers or copolymers can be prepared with superior activity using the 
solid titanium compound suggested in this Publication. On further 
investigations, it was found that a further improvement is desired in the 
output of polymer or copolymer per unit weight of halogen which is likely 
to be contained in the resulting polymer or copolymer, and cause rust to 
fabricating molds and other metallic materials at the time of, say, 
molding, and that the formation of a fine powdery polymer detrimental to 
the separation of the resulting polymer cannot be ignored, and it is 
desired to inhibit the formation of such a fine powdery polymer. Moreover, 
it is desired to further shorten the time required for mechanical 
copulverization in catalyst preparation. 
Another suggestion was made in Japanese Laid-Open Patent Publication No. 
16986/73 laid open on Mar. 3, 1973 (corresponding to West German OLS No. 
2,230,672, and to French Pat. No. 2,143,347). Example 13 of this patent 
discloses a solid titanium compound used as a catalyst component which was 
prepared by dissolving anhydrous magnesium chloride in anhydrous ethanol, 
evaporating the ethanol rapidly, drying the residue at 300.degree. C. and 
0.1 mmHg, and mechanically copulverizing the resulting product together 
with a complex of TiCl.sub.4 and ethyl benzoate. This patent fails to 
disclose anything about a solid titanium catalyst component which is 
obtained by reacting the aforesaid titanium compound with a liquid 
titanium compound in the absence of mechanical pulverization. The amount 
of polymer yielded in Example 13 is as low as 1340 g/Ti millimole. The 
stereospecificity (I.I. - - - - the boiling n-heptane extraction residue) 
is as low as 74.3%. 
The present inventors furthered their investigations in order to overcome 
the disadvantages of the prior art methods mentioned above. These 
investigations led to the discovery that the use of a solid 
halogen-containing titanium compound obtained by reacting a mechanically 
copulverized solid product derived from (1) a magnesium compound, (2) an 
organic acid ester, and (3) an active hydrogen-containing compound 
selected from the group of alcohols and phenols, with titanium compound 
liquid under the reaction conditions in the absence of mechanical 
pulverization can increase the output of polymer per gram of the halogen 
which becomes a cause of rust formation in the first-mentioned prior 
patent, and inhibit the undersirable formation of a fine powdery polymer 
in the aforementioned patent. It was also found that the low yield and the 
low stereoregularity of polymer in the second prior patent mentioned above 
can be obviated. 
It was confirmed as shown in Comparative Examples 1 and 2 to be given 
hereinbelow that when the mechanically copulverized solid product derived 
from the compounds (1), (2) and (3) is used without reaction with the 
specified titanium compound in the absence of mechanical pulverization, or 
the reaction of the solid product with the titanium compound is carried 
out in the presence of mechanical pulverization, the improvement 
contemplated by the present invention cannot be achieved. 
It is an object of this invention therefore to provide a process for 
polymerizing olefins, which can overcome the disadvantages of the 
conventional processes for polymerizing or copolymerizing .alpha.-olefins 
in the presence of a catalyst composed of (A) a mechanically pulverized 
solid titanium catalyst component, and (B) an organometallic compound of a 
metal of Groups I to III of the periodic table. 
Another object of this invention is to provide a catalyst composition for 
polymerization or copolymerization of .alpha.-olefins which is used in 
performing the aforesaid improved process of this invention. 
The above and other objects of the invention along with its advantages will 
become more apparent from the following description. 
The solid halogen-containing titanium catalyst component used in the 
process of this invention is obtained by reacting a mechanically 
pulverized solid product derived from (1) a magnesium compound, (2) an 
organic acid ester, and (3) an active hydrogen-containing compound 
selected from alcohols and phenols, with a titanium compound liquid under 
the reaction conditions in the absence of mechanical pulverization. 
The magnesium compound (1) used in this invention is preferably a compound 
containing a halogen or both a halogen and an organic group (including a 
member selected from hydrocarbon groups, alkoxy groups, aryloxy groups and 
acyloxy groups) which may further contain another metal such as aluminum, 
tin, silicon or germanium. The magnesium compound may be prepared by any 
method, and may also be a mixture of two or more such compounds. Examples 
of the magnesium compound are decomposition products of organic Mg 
compounds such as Grignard reagents. There can also be used complex 
compounds obtained by dissolving halogen-containing magnesium compounds 
with or without other compounds soluble in acetone and ether, such as 
Al(OR).sub.n X.sub.3-n (in which R is a hydrocarbon group, X is a halogen 
atom, and 0.ltoreq.n.ltoreq.3) or GeCl.sub.4, in the aforesaid solvent, 
and then evaporating the solvent. Of the exemplified compounds, magnesium 
dihalides and their complex compounds are preferred. Examples of 
especially preferred magnesium compounds (1) used in this invention are 
compounds of the formula MgX.sup.1 X.sup.2 wherein X.sup.1 is halogen and 
X.sup.2 represents a member selected from halogen atoms, and the groups 
OR" in which R" is a group selected from the group consisting of alkyl 
groups, preferably alkyl groups containing 1 to 10 carbon atoms, 
cycloalkyl groups, preferably cycloalkyl groups containing 6 to 12 carbon 
atoms, and aryl groups, preferably, a phenyl group optionally substituted 
by an alkyl group containing 1 to 4 carbon atoms. Specific examples 
include MgCl.sub.2, MgBr.sub.2, MgI.sub.2, MgF.sub.2, Mg(OCH.sub.3)Cl, 
Mg(OC.sub.2 H.sub.5)Cl, Mg(O n-C.sub.4 H.sub.9)Cl, 
##STR1## 
Preferably, the magnesium compound (1) is as anhydrous as possible. It is 
permissible however for the magnesium compound to contain moisture in an 
amount which does not substantially affect the performance of the 
catalyst. For the convenience of use, it is advantageous to use the 
magnesium compound as a powder having an average particle diameter of 
about 1 to about 50 microns. Since a mechanical pulverization step is 
essential in the preparation of the titanium catalyst component, larger 
partice sizes are also feasible. 
Examples of the organic acid ester (2) used in this invention are (i) 
aliphatic carboxylic acid esters containing 2 to 40 carbon atoms, (ii) 
alicyclic carboxylic acid esters containing 7 to 20 carbon atoms, (iii) 
aromatic carboxylic acid esters containing 8 to 40 carbon atoms, and (iv) 
lactones containing 4 to 10 carbon atoms. More specifically, the organic 
acid esters include the following. 
i. Esters formed between a member selected from saturated or unsaturated 
aliphatic carboxylic acids containing 1 to 18 carbon atoms, preferably 1 
to 4 carbon atoms, and halogen-substitution products of the above 
carboxylic acids, and a member selected from the group consisting of 
saturated or unsaturated aliphatic primary alcohols containing 1 to 18, 
preferably 1 to 4, carbon atoms, saturated or unsaturated cycloaliphatic 
alcohols containing 3 to 8, preferably 5 to 6, carbon atoms, phenols 
containing 6 to 10, preferably 6 to 8, carbon atoms, saturated or 
unsaturated primary alcohols containing 1 to 4 carbon atoms and bonded to 
an aliphatic ring with 3 to 10 carbon atoms, and saturated or unsaturated 
primary alcohols containing 1 to 4 carbon atoms and bonded to an aromatic 
ring with 6 to 10 carbon atoms; 
ii. Esters formed between alicyclic carboxylic acids containing 6 to 12, 
preferably 6 to 8, carbon atoms and saturated or unsaturated primary 
alcohols containing 1 to 8, preferably 1 to 4, carbon atoms; 
iii. Esters formed between aromatic carboxylic acids containing 7 to 18 
carbon atoms, preferably 7 to 12 carbon atoms, and a member selected from 
the group consisting of saturated or unsaturated aliphatic primary 
alcohols containing 1 to 18, preferably 1 to 4, carbon atoms, saturated or 
unsaturated cycloaliphatic alcohols containing 3 to 8, preferably 5 to 8, 
carbon atoms, phenols containing 6 to 10, preferably 6 to 8, carbon atoms, 
saturated or unsaturated primary alcohols containing 1 to 4 carbon atoms 
and bonded to an aliphatic ring with 3 to 10 carbon atoms, and saturated 
or unsaturated primary alcohols containing 1 to 4 carbon atoms and bonded 
to an aromatic ring with 6 to 10 carbon atoms; and 
iv. 5- or 6- membered cyclic lactones containing 4 to 10 carbon atoms. 
Specific examples of the esters (i) are primary alkyl esters of saturated 
fatty acids such as methyl formate, ethyl acetate, n-amyl acetate, 
2-ethylhexyl acetate, n-butyl formate, ethyl butyrate, and ethyl valerate; 
alkenyl esters of saturated fatty acids such as vinyl acetate or allyl 
acetate; primary alkyl esters of unsaturated fatty acids such as methyl 
acrylate, methyl methacrylate or n-butyl crotonate; and halogenated 
aliphatic monocarboxylic acid esters such as methyl chloroacetate or ethyl 
dichloroacetate. 
Specific examples of the esters (ii) are methyl cyclohexanecarboxylate, 
ethyl cyclohexanecarboxylate, methyl methylcyclohexanecarboxylate, and 
ethyl methylcyclohexanecarboxylate. 
Specific examples of the esters (iii) are alkyl benzoates in which the 
alkyl group is a saturated or unsaturated hydrocarbon group usually 
containing 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, such as 
methyl benzoate, ethyl benzoate, n- or i-propyl benzoate, n-, i-, sec- or 
tert-butyl benzoate, n- or i-amyl benzoate, n-hexyl benzoate, n-octyl 
benzoate, 2-ethylhexyl benzoate, vinyl benzoate, and allyl benzoate 
(preferably methyl benzoate and ethyl benzoate); cycloalkyl benzoates in 
which the cycloalkyl group is a non-aromatic cyclic hydrocarbon group 
usually containing 3 to 8 carbon atoms, preferably 5 to 6 carbon atoms, 
such as cyclopentyl benzoate and cyclohexyl benzoate; aryl benzoates in 
which the aryl group is a hydrocarbon group usually containing 6 to 10 
carbon atoms, preferably 6 to 8 carbon atoms in which halogen and/or an 
alkyl group with 1 to 4 carbon atoms may be bonded to the ring, such as 
phenyl benzoate, 4-tolyl benzoate, benzyl benzoate, styryl benzoate, 
2-chlorophenyl benzoate, and 4-chlorobenzyl benzoate; aromatic 
monocarboxylic acid esters in which an electron-donating substituent, such 
as a member selected from halogens, alkoxy groups and alkyl groups, may be 
bonded to the aromatic ring; alkoxy benzoates in which the alkyl group 
constituting the alkoxy group is an alkyl group usually containing 1 to 4 
carbon atoms, preferably methyl or ethyl, and the alkyl and aryl groups in 
the ester are the same as described hereinabove, such as methyl anisate, 
ethyl anisate, i-propyl anisate, i-butyl anisate, phenyl anisate, benzyl 
anisate, ethyl o-methoxybenzoate, methyl p-ethoxybenzoate, ethyl 
p-ethoxybenzoate, n-butyl p-ethoxybenzoate, ethyl-p-allyloxybenzoate, 
phenyl p-ethoxybenzoate, methyl o-ethoxybenzoate, ethyl veratrate, and 
ethyl asym-guaiacolcarboxylate; alkylbenzoic acid esters in which the 
alkyl group attached to the aromatic ring of benzoic acid is a saturated 
or unsaturated hydrocarbon group usually containing 1 to 8 carbon atoms, 
and the alkyl and aryl groups of the ester are the same as mentioned 
hereinabove, such as methyl p-toluate, ethyl p-toluate, i-propyl 
p-toluate, n- or i-amyl toluate, allyl p-toluate, phenyl p-toluate, 
2-tolyl p-toluate, ethyl o-toluate, ethyl m-toluate, methyl 
p-ethylbenzoate, ethyl p-ethylbenzoate, sec-butyl p-ethylbenzoate, 
i-propyl o-ethylbenzoate, n-butyl m-ethylbenzoate, ethyl 
3,5-xylenecarboxylate, and ethyl p-styrenecarboxylate; halogen-substituted 
benzoic acid esters (in which the halogen is chlorine, bromine, or iodine, 
preferably chlorine), such as methyl chlorobenzoate, ethyl chlorobenzoate, 
n-butyl chlorobenzoate, and benzyl chlorobenzoate. 
Examples of the lactones (iv) are .gamma.-butyrolactone, 
.delta.-valerolactone, coumarin, and phthalide. 
Of these, the benzoic acid, alkylbenzoic acid, and alkoxybenzoic acid 
esters are preferred. Alkyl esters with 1 to 4 carbon atoms, especially 
methyl or ethyl esters, of benzoic acid, o- or p-toluic acid, and p-anisic 
acid are especially preferred. 
These esters are usually employed as such, but may be fed to the reaction 
system in such a form which will form an ester during the formation of the 
mechanically pulverized solid product derived from the compounds (1), (2) 
and (3). For example, when an alkoxy-magnesium compound is used as the 
magnesium compound, the organic acid ester may be supplied in the form of 
a carboxylic acid halide. 
The active hydrogen-containing compound (3) used in this invention 
includes, for example, aliphatic acohols containing 1 to 12 carbon atoms, 
preferably 3 to 12 carbon atoms, more preferably 6 to 12 carbon atoms; 
alicyclic alcohols containing 3 to 12 carbon atoms, preferably 6 to 12 
carbon atoms, aromatic alcohols containing 7 to 12 carbon atoms, and 
phenols containing 6 to 18 carbon atoms. 
Specific examples of these compounds include alcohols such as methanol, 
ethanol, n- or iso-propanol, n-, iso-, sec- or tert-butanol, n-pentanol, 
2-methyl butanol, hexanol, 2-ethylhexanol, ethyleneglycohol 
monomethylether, mono-n-butylether or monophenylether, cyclopentyl 
alcohol, cyclohexanol, 2,6-dimethylhexanol, menthol, benzyl alcohol, 
phenethyl alcohol, and cumyl alcohol; and phenols such as phenol, cresol, 
xylenol, butyl phenol, octyl phenol, nonyl phenol, dibutyl phenol, 
naphthol, and cumyl phenol. Of the alcohols, alcohols containing at least 
3 carbon atoms, such as n-butanol and aromatic alcohols are preferred, and 
monohydric alkylphenols are the preferred phenols. 
The organic acid ester (2) and the active hydrogen-containing compound (3) 
may be used in the form of a complex with the magnesium compound (1). 
Suitable titanium compounds used to prepare the solid titanium compound (A) 
in this invention are tetravalent titanium compounds of the following 
formula 
EQU Ti(OR).sub.g X.sub.4-g 
wherein R is a hydrocarbon group selected from the group consisting of 
alkyl groups, preferably containing 1 to 4 carbon atoms, cycloalkyl 
groups, preferably containing 6 to 12 carbon atoms, and aryl groups, 
preferably containing 6 to 10 carbon atoms; X is halogen; and 
0.ltoreq.g.ltoreq.4. Examples of such titanium compounds are titanium 
tetrahalides such as TiCl.sub.4, TiBr.sub.4 and TiI.sub.4 ; alkoxytitanium 
trihalides such as Ti(OCH.sub.3)Cl.sub.3, Ti(OC.sub.2 H.sub.5)Cl.sub.3, 
Ti(O n-C.sub.4 H.sub.9)Cl.sub.3, Ti(OC.sub.2 H.sub.5)Br.sub.3, Ti(O 
iso-C.sub.4 H.sub.9)Br.sub.3 and Ti(O cyclo-C.sub.6 H.sub.12)Cl.sub.3 ; 
aryloxy titanium trihalides such as Ti(OC.sub.6 H.sub.5)Cl.sub.3, 
##STR2## 
alkoxytitanium dihalides such as Ti(OCH.sub.3).sub.2 Cl.sub.2, Ti(OC.sub.2 
H.sub.5).sub.2 Cl.sub.2, Ti(O n-C.sub.4 H.sub.9).sub.2 Cl.sub.2, and 
Ti(OC.sub.2 H.sub.5).sub.2 Br.sub.2 ; trialkoxytitanium monohalides such 
as Ti(OCH.sub.3).sub.3 Cl, Ti(OC.sub.2 H.sub.5).sub.3 Cl, Ti(O n-C.sub.4 
H.sub.9).sub.3 Cl, and Ti(OC.sub.2 H.sub.5).sub.3 Br; and tetraalkoxy 
titaniums such as Ti(OCH.sub.3).sub.4, Ti(OC.sub.2 H.sub.5).sub.4, and 
Ti(O n-C.sub.4 H.sub.9).sub.4. Of these, the titanium tetrahalides are 
preferred, and titanium tetrachloride is most preferred. 
The magnesium compound (1) and the titanium compound are used preferably as 
halides. When they are used in other forms, it is necessary to include 
halogen in the final solid titanium catalyst component by using a suitable 
halogenating agent. 
The solid halogen-containing titanium catalyst component (A) used in this 
invention is prepared by reacting the mechanically pulverized solid 
product derived from the compounds (1), (2) and (3), with the titanium 
compound liquid under the reaction conditions in the absence of mechanical 
pulverization. In the copulverization process, the compounds (1), (2) and 
(3) may be pulverized together. Or it is possible to copulverize any two 
compounds, then add the remaining compound, and further pulverize them 
together. The order of addition, and the method of addition (for example, 
whether to add a particular compound at a time or portionwise) can be 
properly chosen. 
The copulverization may be carried out in the copresence of an inorganic or 
organic filler such as LiCl, CaCO.sub.3, CaCL.sub.2, SrCl.sub.2, 
BaCl.sub.2, Na.sub.2 SO.sub.4, Na.sub.2 CO.sub.3, TiO.sub.2, NaB.sub.4 
O.sub.7, Ca.sub.3 (PO.sub.4).sub.2, CaSO.sub.4, BaCO.sub.3, Al.sub.2 
(SO.sub.4).sub.3, B.sub.2 O.sub.3, Al.sub.2 O.sub.3, SiO.sub.2, 
polyethylene, polypropylene or polystyrene. 
The mechanical copulverization is carried out using a ball mill, a 
vibratory mill, or impact mill or the like preferably in the substantial 
absence of oxygen or water. 
The "mechanical copulverization", as used in this application, denotes 
pulverization which imparts a violent pulverizing effect to a material, 
and excludes such means as mere mechanical stirring. 
The ratio between the magnesium compound (1) and the organic acid ester (2) 
in copulverization is such that the latter is used in an about of about 
0.01 to about 10 moles, preferably about 0.01 to about 5 moles, especially 
preferably about 0.01 to about 1 mole, per atom of magnesium in the 
former. The amount of the active hydrogen-containing compound (3), when it 
contains at least 3 carbon atoms; is about 0.001 to about 10 moles, 
preferably about 0.01 to about 1 mole, especially preferably about 0.01 to 
about 0.5 mole, per atom of magnesium in the magnesium compound (1). When 
it contains 2 or less carbon atoms, the amount is preferably about 0.001 
to about 10 moles, more preferably about 0.01 to about 5 moles, especially 
preferably about 0.01 to about 3 moles. 
The pulverization conditions should preferably be chosen according to the 
types of the materials or the pulverizing apparatus used. Generally, the 
pulverization time is about 1 hour to 10 days. The pulverization can be 
carried out at room temperature, and it is not especially necessary to 
cool or heat the pulverization system. Usually, however, temperatures of 
about 0.degree. to 100.degree. C. can be employed. 
Where the organic acid ester or the active hydrogen-containing compound is 
solid, especially strong pulverization is desired. For example, when 
pulverization is to be performed in a vibratory ball mill, the strength of 
pulverization is desirably such that 20 to 40 g of materials to be treated 
are placed in an inner cylinder (100 mm in inside diameter) of an 800 ml. 
stainless steel (SUS 32) vibratory ball mill which accommodates therein 
2.8 kg of stainless steel (SUS 32) balls each with a diameter of 15 mm, 
and pulverized at an impact acceleration of 7G for at least 3 hours, 
preferably at least 6 hours, especially preferably at least 24 hours. 
The mechanically copulverized solid product so produced from the compounds 
(1), (2) and (3) is then reacted in the absence of mechanical 
pulverization with a titanium compound which is liquid under the reaction 
conditions. 
The term "in the absence of mechanical pulverization", as used in the 
present application, means that the violent mechanical copulverizing 
action used at the time of forming the solid product from the compounds 
(1), (2) and (3) is absent, but such an operation as mere stirring is 
permissible. 
It is preferred that the above reaction be performed while suspending the 
mechanically copulverized solid product in a normally liquid titanium 
compound such as titanium tetrachloride, or a solution of it in an inert 
solvent such as hexane, heptane or kerosene, or a solution of a normally 
solid titanium compound in the inert solvent. This procedure undergoes 
little effects of traces of impurities generated in the copulverizing 
step, and makes it possible to vary the proportions of the raw materials 
within a broad range. 
The amount of the titanium compound varies according to the amounts of the 
organic acid ester (2) and the active hydrogen-containing compound (3), 
but is desirably such that about 0.001 to about 1000, preferably at least 
about 0.05, titanium atoms are used per atom of magnesium. 
There is no special restriction on the temperature at which the solid 
copulverization product is reacted with the titanium compound in the 
liquid phase. Usually, it is convenient to perform the reaction at about 
20.degree. to about 200.degree. C. for at least 0.5 hour. Preferably, the 
solid halogen-containing titanium compound is isolated after the reaction, 
and washed well with an inert solvent before it is used for 
polymerization. 
A typical example of the composition of the solid halogen-containing 
titanium catalyst component which is suitable for polymerization 
catalysts, although varying according to the conditions for catalyst 
preparation, is: 2.0-5.0% by weight of titanium, 16.0-25.0% by weight of 
magnesium, 55.0-65.0% by weight of halogen, and 5.0-15.0% by weight of the 
organic acid ester. The composition does not substantially change by 
washing with hexane at room temperature. 
Usually, the resulting solid halogen-containing titanium compound has a 
surface area of at least 10 m.sup.2 /g, preferably at least 50 m.sup.2 /g, 
especially preferably at least 100 m.sup.2 /g. 
The organometallic compound (B) of a metal of Groups I to III of the 
periodic table to be used in conjunction with the titanium catalyst 
component (A) is a compound having a hydrocarbon group directly bonded to 
a metal. Examples of the organometallic compound (B) are alkylaluminum 
compounds, alkylaluminum alkoxides, alkylaluminum hydrides, alkylaluminum 
halides, dialkyl zincs, and dialkyl magnesiums. Of these, the 
organoaluminum compounds are especially suitable. Examples of the 
organoaluminum compounds are trialkyl or trialkenyl aluminums such as 
Al(C.sub.2 H.sub.5).sub.3, Al(CH.sub.3).sub.3, Al(C.sub.3 H.sub.7), 
Al(C.sub.4 H.sub.9), or Al(C.sub.12 H.sub.25).sub.3 ; alkylaluminum 
compounds in which a number of aluminum atoms are connected through an 
oxygen or nitrogen atom, such as (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), or 
##STR3## 
dialkylaluminum hydrides such as (C.sub.2 H.sub.5).sub.2 AlH or (C.sub.4 
H.sub.9).sub.2 AlH; dialkylaluminum halides such as (C.sub.2 
H.sub.5).sub.2 AlCl, (C.sub.2 H.sub.5).sub.2 AlI, or (C.sub.4 
H.sub.9).sub.2 AlCl; and dialkylaluminum alkoxides or phenoxides such as 
(C.sub.2 H.sub.5).sub.2 Al(OC.sub.2 H.sub.5) or (C.sub.2 H.sub.5).sub.2 
AL(OC.sub.6 H.sub.5). The trialkylaluminums are most preferred. 
Examples of the olefins used for polymerization are ethylene, propylene, 
1-butene, and 4-methyl-1-pentene. The olefins can be homopolymerized, 
random-copolymerized and block-copolymerized. In copolymerization, a 
polyunsaturated compound such as a conjugated or nonconjugated diene can 
be used as a comonomer. Examples of the dienes are 
5-ethylidene-2-norbornene, 1,7-octadiene, vinyl cyclohexene, 
1,4-hexadiene, and dicyclopentadiene. 
Highly stereoregular polymers can be obtained in high yields especially 
when the process of this invention is applied to the polymerization of 
.alpha.-olefins having at least 3 carbon atoms, the copolymerization of 
these olefins with the dienes, and the copolymerization of the 
.alpha.-olefins having at least 3 carbon atoms with a minor amount of 
ethylene. 
The polymerization can be carried out either in the liquid or gaseous 
phase. When it is carried out in the liquid phase, an inert organic 
solvent such as hexane, heptane or kerosene can be used as a reaction 
medium, or the olefin itself can be used as the reaction medium. In the 
liquid-phase polymerization, it is preferred that the concentration of the 
solid halogen-containing titanium catalyst component (A) be adjusted to 
about 0.001 to about 0.5 millimoles calculated as titanium atom, and the 
concentration of the organometallic compound (B) to about 0.1 to about 50 
millimoles, both per liter of liquid phase. 
A molecular weight regulator such as hydrogen may be used during the 
polymerization. It is also possible to perform the polymerization in the 
copresence of an ether, ethylene glycol derivative such as ethylene glycol 
monomethylether, a ketone, an amine, a sulfur-containing compound, a 
nitrile, or an ester in order to control the stereoregularity of the 
polymer. An organic acid ester, especially an aromatic carboxylic acid 
ester, is preferred as such a controlling agent. The species of the 
aromatic carboxylic acid esters which are exemplified hereinabove with 
regard to the preparation of the solid halogen-containing titanium 
compound can be chosen for this purpose. Especially suitable species are 
benzoic acid esters and ring-substituted benzoic acid esters, such as 
toluates, anisates, phthalate diesters, terephthalate diesters, 
hydroxybenzoates, and aminobenzoates. The lower alkyl toluates, such as 
methyl p-toluate or ethyl p-toluate are most preferred. 
Such a controlling agent may be used in the form of an adduct with the 
organometallic compound (B). The effective amount of the controller is 
usually about 0.001 to about 10 moles, preferably about 0.01 to about 2 
moles, especially preferably about 0.1 to about 1 mole, per mole of the 
organometallic compound (B). 
The polymerization temperature for olefins is about 20.degree. to about 
200.degree. C., preferably about 50.degree. to about 180.degree. C. The 
polymerization pressure is from atmospheric pressure to about 50 
kg/cm.sup.2, preferably about 2 to about 20 kg/cm.sup.2. 
The polymerization can be carried out by any of batchwise, semi-continuous 
and continuous methods. It is also possible to perform the polymerization 
in two or more stages under different reaction conditions. 
The following examples illustrate the present invention more specifically.

EXAMPLE 1 AND COMATIVE EXAMPLES 1 AND 2 
Preparation of the catalyst component (A) 
Commercially available magnesium chloride (20 g), 6.30 g of ethyl benzoate 
and 14.49 g of ethanol were placed in an 800 ml. stainless steel (SUS-32) 
ball mill cylinder having an inside diameter of 100 mm and accomodating 
therein 2.8 kg of stainless steel (SUS-32) balls with a diameter of 15 mm 
under an atomosphere of nitrogen and contacted with one another at an 
impact acceleration of 7G. Ten grams of the resulting solid product was 
suspended in 100 ml. of titanium tetrachloride, and the suspension was 
stirred at 110.degree. C. for 2 hours. It was again suspended in 100 ml of 
TiCl.sub.4, and reacted at 110.degree. C. for 2 hours. The solid component 
was collected by filtration, and washed with refined hexane until free 
titanium tetrachloride was no longer detected in the wash liquid. The 
washed product was dried to afford a titanium-containing solid catalyst 
component containing 3.0% by weight of titanium and 58.5% by weight of 
chlorine. 
Polymerization 
A 2-liter autoclave was purged with propylene, and charged with 750 ml of 
hexane thoroughly deprived of oxygen and water, 0.744 g (3.75 millimoles) 
of triisobutyl aluminum, 0.188 g (1.25 millimoles) of methyl p-toluate, 
and 0.0359 g (0.0225 millimole calculated as titanium atom) of the solid 
catalyst component (A) prepared by the procedure of the preceding section. 
The autoclave was sealed, and 0.3 Nl of hydrogen was introduced. The 
temperature was raised. When the temperature of the polymerization system 
reached 60.degree. C., propylene was introduced, and its polymerization 
was started at a total pressure of 8 kg/cm.sup.2. After polymerizing at 
60.degree. C. for 4 hours, the introduction of propylene was stopped. The 
inside of the autoclave was cooled to room temperature, and the resulting 
solid was collected by filtration, and dried to afford 209.5 g of 
polypropylene as a white powder, which had a boiling n-heptane extraction 
residue of 96.1%, an apparent density of 0.36 g/ml, and a melt index (MI) 
of 1.70. On the other hand, concentration of the liquid phase afforded 5.8 
g of a solvent-soluble polymer. A very fine polymer having a particle size 
of less than 105 microns was formed in an amount of 8% by weight. 
For comparison, the following two runs were performed. 
In the preparation of the catalyst component (A) on Example 1, anhydrous 
magnesium chloride was dissolved in ethanol, and then the ethanol was 
evaporated rapidly. The residue was dried under reduced pressure. The 
resulting product and a complex of ethyl benzoate and titanium 
tetrachloride were copulverized in the same way as in Example 1 to afford 
a solid product. Without treating the product with titanium tetrachloride, 
it was directly used in the polymerization of propylene under the same 
conditions as in Example 1. (Comparative Example 1) 
Propylene was polymerized under the same conditions as in Example 1 except 
using a catalyst component (A) which was prepared by placing 20 g of the 
copulverized solid product and 1.9 g of titanium tetrachloride in an 800 
ml pot including 100 balls with a diameter of 15 mm, and rotating the pot 
at 67 rpm for 100 hours (Comparative Example 2). 
The results of Example 1 and Comparative Examples 1 and 2 are shown in 
Table 1. 
Table 1 
______________________________________ 
Yield of Activity t-I.T. 
poly- Yield of poly- 
(boiling 
propylene propylene n-heptane 
(g/millimole (g/milli- extraction 
Melt 
of Ti) mole of Ti.atm.hr) 
residue) index 
______________________________________ 
Example 1 
9600 300 93.9 1.7 
Com- 
parative 
Example 1 
2100 53 87.1 1.2 
Com- 
parative 
Example 2 
1500 47 85.2 1.3 
______________________________________ 
EXAMPLE 2 
A titanium catalyst component containing 2.30% by weight of titanium and 
61.95% by weight of chlorine was prepared by the same procedure as in 
Example 1 except that 7.76 g of n-butanol was used instead of the ethanol, 
and the reaction of the copulverized product with titanium tetrachloride 
was performed at 100.degree. C. 
The same polymerization as in Example 1 was performed using the resulting 
catalyst component (A), thereby to afford 341.4 g of polypropylene as a 
white powder which had a boiling n-heptane extraction residue of 95.1%, an 
apparent density of 0.33 g/ml and a melt index of 0.8. On the other hand, 
concentration of the liquid phase afforded 9.6 g of a solvent-soluble 
polymer. 
A fine powdery polymer having a particle size of less than 105 microns was 
formed in an amount of 8% by weight. 
EXAMPLE 3 
A catalyst component (A) containing 3.35% by weight of titanium and 53.70% 
by weight of chlorine was prepared in the same way as in Example 2 except 
that the amount of the n-butanol was changed to 31.06. 
The same polymerization as in Example 1 was performed except that this 
catalyst component (A) was used, and the polymerization pressure was 
changed to 10 kg/cm.sup.2. Thus, 200.8 g of a white powdery polymer was 
obtained. The polymer had a boiling n-heptane extraction residue of 96.5%, 
an apparent density of 0.37 g/ml and a melt index of 0.5. Concentration of 
the liquid phase afforded 4.2 g of a solvent-soluble polymer. A fine 
powdery polymer having a particle diameter of less than 105 microns was 
formed in an amount of 13% by weight. 
EXAMPLE 4 
Preparation of catalyst component (A) 
Commercially available anhydrous magnesium chloride (20 g), 5.74 g of ethyl 
o-toluate and 2.27 g of o-cresol were placed in the same ball mill 
cylinder as set forth in Example 1 under an atmosphere of nitrogen, and 
contacted with one another at an impact acceleration of 7G for 24 hours. 
Ten grams of the resulting solid product was suspended in 100 ml of 
titanium tetrachloride, and the mixture was stirred at 80.degree. C. for 2 
hours. The solid component was collected by filtration, and washed with 
refined hexane until free titanium tetrachloride was no longer detected in 
the wash liquid. The product was then dried to afford a 
titanium-containing solid catalyst component (A) containing 4.2% by weight 
of titanium and 60.0% by weight of chlorine. 
Polymerization 
A 2-liter autoclave was purged with propylene, and then charged with 750 ml 
of hexane thoroughly deprived of oxygen and water, 0.428 g (3.75 
millimoles) of triethyl aluminum, 0.205 g (1.25 millimoles) of ethyl 
p-toluate, and 0.026 g (0.0225 millimole calculated as titanium atom) of 
the solid catalyst component (A) obtained by the procedure of the previous 
section. The autoclave was sealed, and 0.5 Nl of hydrogen was introduced. 
The temperature was raised, and when the temperature of the polymerization 
system reached 60.degree. C., propylene was introduced and its 
polymerization was started at a total pressure of 8 kg/cm.sup.2. After 
polymerization at 60.degree. C. for 4 hours, the introduction of propylene 
was stopped, and the inside of the autoclave was cooled to room 
temperature. The resulting solid was collected by filtration, and dried to 
afford 380.4 g of polypropylene as a white powder which had a boiling 
n-heptan extraction residue of 95.3%, an apparent density of 0.31 g/ml, 
and a melt index of 3.55. On the other hand, concentration of the liquid 
phase afforded 12.1 g of a solvent-soluble polymer. 
A fine powdery polymer having a particle size diameter of less than 105 
microns was formed in an amount of 12.6% by weight. The yield of the 
polymer (g/Cl g) was 25,000. 
EXAMPLE 5 
Preparation of the catalyst component (A) 
Anhydrous magnesium chloride (20 g) was suspended in 200 ml of kerosene 
containing 7.5 ml of ethyl benzoate, and with stirring, they were reacted 
at 150.degree. C. for 2 hours. The solid component was collected by 
filtration, washed thoroughly with hexane, and dried to afford 26.7 g of a 
white powdery solid which was considered to be a complex having an average 
composition: MgCl.sub.2 0.22 
##STR4## 
The resulting powdery solid (26 g) and 2.85 g of cumyl alcohol were placed 
in the same ball mill cylinder as set forth in Example 1, and contacted 
with one another at an impact acceleration of 7G for 24 hours. The 
resulting solid product was suspended in 150 ml of titanium tetrachloride, 
and stirred at 80.degree. C. for 2 hours. The solid component was 
collected by filtration, and washed with refined hexane until free 
titanium tetrachloride was no longer detected in the wash liquid. The 
resulting titanium-containing catalyst component contained 3.2% by weight 
of titanium and 58.0% by weight of chlorine. 
Polymerization 
Propylene was polymerized under the same conditions as in Example 4 using 
0.034 g of the resulting solid catalyst component (A), 0.428 g of triethyl 
aluminum and 0.743 g of triisobutyl aluminum. As a result, 263 g of 
polypropylene as a white powder and 9.8 g of a solvent-soluble polymer 
were obtained. The powdery polypropylene obtained has a boiling n-heptane 
extraction residue of 95.6%, an apparent density of 0.30 g/ml and a melt 
index of 3.86. 
A fine powdery polymer having a particle diameter of less than 105 microns 
was formed in an amount of 12.1% by weight. The yield of the polymer (g/Cl 
g) was 14,000. 
Comparative Example 3 
A titanium catalyst component (A) containing 3.8% by weight of titanium and 
59.0% by weight of chlorine was prepared in the same way as in Example 4 
except that o-cresol was not used. 
Propylene was polymerized under the same conditions as in Example 4 using 
0.028 g of the resulting titanium catalyst component (A). As a result, 
138.5 g of a powdery solid polymer and 5.6 g of a solvent-soluble polymer 
were obtained. The powdery solid polymer had a boiling n-heptane 
extraction residue of 94.9%, and apparent density of 0.32 g/ml and a melt 
index of 5.08. 
A fine powdery polymer having a particle diameter of less than 105 microns 
was formed in an amount of 25.0% by weight. The yield of the polymer (g/Cl 
g) was 8,600. 
EXAMPLES 6 TO 8 
A solid titanium catalyst component (A) was prepared in the same way as in 
Example 4 except that each of the active hydrogen-containing compounds 
shown in Table 2 was used in the amounts indicated instead of the 
o-cresol. 
Propylene was polymerized in the same way as in Example 4 using the 
resulting titanium catalyst component (A) in an amount of 0.032 g (Example 
6), 0.030 g (Example 7), and 0.028 g (Example 8), respectively. 
The results are shown in Table 2. 
Table 
__________________________________________________________________________ 
Results of polymerization 
Amount 
of a 
fine 
Amount 
Ex- powdery 
Catalyst component Amount 
of traction polymer 
Active hydrogen of solvent- 
residue Melt (less 
containing compound 
Composition 
powdery 
soluble 
of the 
Apparent 
index 
Polymer 
than 
Ex- Amount 
Ti Cl solid 
polymer 
powder 
density 
(g/10 
yield 
105 .mu.) 
ample 
Type (g) wt. % 
wt. % 
(g) (g) (%) (g/ml) 
min.) 
(g/Cl g) 
(wt. 
__________________________________________________________________________ 
%) 
6 .alpha.-Naphthol 
3.0 3.4 57.0 
252.9 
8.9 95.1 0.32 12.9 
14,000 
12.0 
7 2,6-Di-t- 
butyl-4- 
methylphenol 
4.6 3.6 58.0 
224.6 
8.0 95.4 0.28 6.07 
13,000 
12.1 
8 2- 
Ethylhexanol 
2.7 3.9 57.0 
213.8 
6.2 94.8 0.32 5.92 
14,000 
8.5 
__________________________________________________________________________ 
EXAMPLES 9 TO 14 
Propylene was polymerized under the same conditions as in Example 4 using 
the same solid catalyst component (A) as used in Example 4 and each of the 
organic acid esters indicated in Table 3 in the amounts indicated. The 
results are also shown in Table 3. 
Table 3 
__________________________________________________________________________ 
Results of polymerization 
Amount of 
a fine 
Amount of 
Amount of 
Extrac- powdery 
powdery 
solvent- 
tion Melt polymer 
Organic acid ester 
solid soluble 
residue 
Apparent 
index (less than 
Ex- Amount 
polymer 
polymer 
of the 
density 
(g/10 
Polymer 
105 .mu.) 
ample 
Type (g) (g) (g) powder 
(g/ml) 
min.) 
(g/Cl g) 
(wt.%) 
__________________________________________________________________________ 
9 Ethyl 0.205 
370.6 14.5 95.4 0.30 3.65 
25,000 
11.0 
p-anisate 
10 Methyl 0.188 
360.6 13.8 95.1 0.30 4.21 
24,000 
11.2 
p-toluate 
11 Ethyl p-t- 
butylbenzoate 
0.258 
396.5 14.2 95.5 0.20 4.85 
27,000 
10.3 
Ethyl p- 
12 amino- 0.206 
380.3 15.9 94.5 0.30 3.21 
26,000 
10.4 
benzoate 
Ethyl 
13 p-hydroxy- 
0.208 
350.6 16.1 94.5 0.30 2.86 
24,000 
10.9 
benzoate 
Dimethyl 
14 tere- 0.245 
230.5 10.8 95.9 0.30 3.55 
16,000 
12.5 
phthalate 
__________________________________________________________________________ 
EXAMPLE 15 
Preparation of the catalyst component (A) 
A catalyst component (A) containing 4.3% by weight of titanium and 57.0% by 
weight of chlorine was prepared under the same conditions as in Example 4 
except that a compound of the following formula 
##STR5## 
prepared in a conventional manner was used instead of the anhydrous 
magnesium chloride, and 2 85 g of cumyl alcohol was used instead of 2.27 g 
of o-cresol. 
Polymerization 
Propylene was polymerized under the same conditions as in Example 4 except 
that 0.025 g of the catalyst component (A) obtained by the procedure set 
forth in the previous section was used. As a result, 208.5 g of 
polypropylene as a white powder and 10.8 g of a solvent-soluble polymer 
were obtained. The powdery polymer had an extraction residue of 94.2%, an 
apparent density of 0.29 g/ml, and an melt index of 4.86. 
The yield of the polymer (g/Cl g) was 15,000 and the amount of a very fine 
powdery polymer having a particle diameter of less than 105 microns was 
5.0% by weight. 
EXAMPLE 16 
Preparation of the catalyst component (A) 
Commercially available anhydrous magnesium chloride (20 g), 12.4 g of a 
complex having an average composition TiCl.sub.4 -(ethyl p-toluate), and 
2.85 g of cumyl alcohol were copulverized under the conditions set forth 
in Example 4, and treated with titanium tetrachloride. The resulting solid 
catalyst component (A) contained 4.5% by weight of titanium and 58.0% by 
weight of chlorine. 
Polymerization 
Propylene was polymerized under the same conditions as in Example 4 using 
0.024 g of the titanium catalyst component (A) obtained by the procedure 
set forth in the previous section. As a result, 300.6 g of a white powdery 
solid polymer and 13.1 g of a solvent-soluble polymer were obtained. The 
powdery solid had an extraction residue of 94.9%, an apparent density of 
0.30 g/ml, and a melt index of 4.21. 
The yield of the polymer (g/Cl g) was 23,000 and the amount of a very fine 
polymer having a particle diameter of less than 105 microns was 10.1% by 
weight . 
EXAMPLE 17 
Anhydrous magnesium chloride (10 g), 2.87 g of ethyl o-toluate, and 1.43 g 
of cumyl alcohol were pulverized in a vibratory mill under the same 
conditions as in Example 4. Ten grams of the resulting solid product was 
suspended in titanium tetrachloride, and stirred at 80.degree. C. for 2 
hours. The solid component was collected by filtration, and washed with 
refined hexane until free titanium tetrachloride was no longer detected in 
the wash liquid. The washed product was dried to afford a 
titanium-containing catalyst component (A) containing 2.2% by weight of 
titanium and 31.0% by weight of chlorine. 
Propylene was polymerized under the same conditions as in Example 4 using 
0.049 g of the solid titanium catalyst component (A) obtained by the 
procedure set forth above. As a result, 224.6 g of a powdery solid and 
12.6 g of a solvent-soluble polymer were obtained. The powdery solid had 
an extraction residue of 93.9%, an apparent density of 0.26 g/ml, and a 
melt index of 8.83. 
The yield of the polymer (g/Cl g) was 8,800 and the amount of a very fine 
polymer having a particle diameter of less than 105 microns was 9.5% by 
weight.