Process for producing olefin polymers and catalyst composition therefor

In a process for producing olefin polymers or copolymers which comprises polymerizing olefins or copolymerizing olefins with each other or with dienes in the presence of [A] a solid titanium catalyst component containing magnesium, titanium and halogen as essential ingredients and [B] an organometallic compound of a metal selected from the group consisting of metals of Groups I to III of the periodic table; the improvement wherein said catalyst component [A] is obtained by contacting (i) a magnesium compound in the liquid state with (ii) a titanium compound in the liquid state to form a solid product or first preparing a liquid mixture of the magnesium compound (i) and the titanium compound (ii) and then forming a solid product therefrom, said reaction of forming the solid product being carried out in the presence of at least one electron donor (iii) selected from the group consisting of aliphatic carboxylic acids with 1 to 6 carbon atoms, aryloxy group-containing alcohols, alkylene glycol diethers, aluminum trialkoxides and aluminum triaryloxides, said solid product being not contacted, during or after its formation, with an ester selected from the group consisting of esters of polycarboxylic acids and esters of polyhydroxy compounds.

This invention relates to a process for procuding olefin polymers 
(sometimes used to denote both homopolymers and copolymers of olefins) by 
the polymerization (sometimes used to denote both homopolymerization and 
copolymerization) of olefins. Particularly, this invention relates to a 
process for producing olefin polymers which when applied to slurry 
polymerization or vapor-phase polymerization of olefins, for example, 
enables the polymerization operation and the aftertreating operation to be 
carried out smoothly and efficiently, and can give with a high catalytic 
efficiency olefin polymers having a desirable size and shape and a narrow 
particle size distribution with a reduced amount of a fine powdery 
polymer. This invention also relates to a new type of a solid titanium 
catalyst component for use in the above improved process. 
More specifically, this invention relates to a process for producing olefin 
polymers or copolymers which comprises polymerizing olefins or 
copolymerizing olefins with each other or with dienes in the presence of 
[A] a solid titanium catalyst component containing magnesium, titanium and 
halogen as essential ingredient and [B] an organometallic compound of a 
metal selected from the group consisting of metals of Groups I to III of 
the periodic table; characterized in that said catalyst component [A] is 
obtained by contacting (i) a magnesium compound in the liquid state with 
(ii) a titanium compound in the liquid state to form a solid product or 
first preparing a liquid mixture of the magnesium compound (i) and the 
titanium compound (ii) and then forming a solid product therefrom, said 
reaction of forming the solid product being carried out in the presence of 
at least one electron donor (iii) selected from the group consisting of 
aliphatic carboxylic acids with 1 to 6 carbon atoms, aryloxy 
group-containing alcohols, alkylene glycol diethers, aluminum trialkoxides 
and aluminum triaryloxides, said solid product being not contacted, during 
or after its formation, with an ester selected from the group consisting 
of esters of polycarboxylic acids and esters of polyhydroxy compounds. 
Many proposals have already been made on methods of producing a solid 
catalyst component containing magnesium, titanium and halogen as essential 
ingredients which is useful as a titanium catalyst component for 
polymerization of olefins. It is also known that or catalyst formed from 
this solid catalyst component and an organometallic compound of a metal of 
Groups I to III of the periodic table is suitable for polymerizing olefins 
with high activity. Many of these proposals, however, are still desired to 
be improved in regard to polymerization activity or the properties of the 
resulting powdery polymer. 
For example, to obtain an olefin polymer of high quality which does not 
require a catalyst removing operation after polymerization, it is desired 
that the yield of the polymer per unit amount of titanium or halogen 
should be sufficiently high. 
Furthermore, in slurry polymerization or vapor-phase polymerization, the 
polymer should desirably has an excellent particle size distribution, 
excellent flowability, a high bulk density and good breakage resistance. 
Furthermore in order that the polymer in its powder form as produced may be 
acceptable to the market without performing pelletization which is usually 
carried out, it is desired that the polymer should have a small proportion 
of a fine powder and consist of particles having a large particle diameter 
with a uniform shape or particle size distribution. 
No process for producing olefin polymers has yet been provided which can 
fully meet the various requirements. 
The present inventors have long been engaged in a research and development 
work on a process for producing olefin polymers which can meet the 
aforesaid requirements. Previously, they proposed the following process in 
Japanese Laid-Open Patent Publication No. 83006/1983 laid-open on May 18, 
1983 (corresponding to West German OLS No. 3,241,999; and U.S. patent 
application Ser. No. 428,140, filed Sept. 29, 1982, now abandoned). 
A process for producing olefin polymers or copolymers which comprises 
polymerizing olefins or copolymerizing olefins with each other or with 
dienes, preferably, polymerizing or copolymerizing alpha-olefins having at 
least 3 carbon atoms or copolymerizing at least one such olefin with up to 
10 mole% of ethylene and/or diene in the presence of a catalyst system 
composed of the following components (A), (B) and (C): 
(A) a solid titanium catalyst component containing magnesium, titanium, 
halogen and an ester selected from the group consisting of esters of 
polycarboxylic acids and esters of polyhydroxy compounds, said catalyst 
component being obtained by contacting a liquid hydrocarbon solution of 
(i) a magnesium compound with (ii) a titanium compound in the liquid state 
to form a solid product or first preparing a liquid hydrocarbon solution 
of the magnesium compound (i) and the titanium compound (ii) and then 
forming a solid product therefrom, said reaction of forming the solid 
product being carried out in the presence of (D) at least one electron 
donor selected from the group consisting of monocarboxylic acid esters, 
aliphatic carboxylic acids, carboxylic acid anhydrides, ketones, aliphatic 
ethers, aliphatic carbonates, alkoxy group-containing alcohols, aryloxy 
group-containing alcohols, organic silicon compounds having an Si--O--C 
bond and organic phosphorus compounds having a P--O--C bond, and during or 
after the formation of the solid product, contacting the solid product 
with (E) an ester selected from the group consisting of esters of 
polycarboxylic acids and esters of polyhydroxy compounds, 
(B) an organometallic compound of a metal selected from the group 
consisting of metals of Groups I to III of the periodic table, and 
(C) an organic silicon compound having an Si--O--C bond or Si--N--C bond. 
On further investigations, the present inventors have found that a process 
for producing olefin polymers which can meet the aforesaid requirements 
can be provided which comprises polymerizing or copolymerizing olefins, 
preferably polymerizing ethylene or copolymerizing ethylene with a minor 
amount (for example, not more than 10 mole %) of an alpha-olefin having at 
least 3 carbon atoms and/or a diene in the presence of a catalyst composed 
of [A] a solid titanium catalyst component and [B] an organometallic 
compound specified as above in the process of this invention by completely 
omitting the treatment of supporting the ester (E) which is essential in 
the process of the above Japanese Laid-Open Patent Publication No. 
83006/1983 and without the need for the organic silicon compound (C) which 
is essential in the process of the above Japanese patent document. It has 
thus been found that when the process is applied to slurry polymerization 
or vapor-phase polymerization of olefins for example, the process enables 
the polymerization operation and the after-treating operation to be 
carried out smoothly and efficiently, and can give with a high catalytic 
efficiency olefin polymers having a desirable size and shape and a narrow 
particle size distribution with a reduced amount of a fine powdery 
polymer. 
It is an object of this invention therefore to provide an improved process 
for producing olefin polymers. 
Another object of this invention is to provide a new polymerization 
catalyst, particularly a titanium catalyst component, suitable for 
practicing the improved process of the invention. 
The above and other objects and advantages will become more apparent from 
the following description. 
The solid titanium catalyst component [A] in the present invention can be 
obtained by contacting (i) a magnesium compound in the liquid state with 
(ii) a titanium compound in the liquid state to form a solid product or 
first preparing a liquid mixture of the magnesium compound (i) and the 
titanium compound (ii) and then forming a solid product therefrom. The 
reaction of forming the solid product is carried out in the presence of at 
least one electron donor (iii) selected from the group consisting of 
aliphatic carboxylic acids having 1 to 6 carbon atoms, aryloxy 
group-containing alcohols, alkylene glycol diethers, aluminum trialkoxides 
and aluminium triaryloxides. The solid product is not contacted, during or 
after its formation, with an ester selected from the group consisting of 
esters of polycarboxylic acids and esters of polyhydroxy compounds. 
The magnesium compound (i) used in the preparation of the solid titanium 
catalyst component (A) in this invention is preferably a magnesium 
compound having no reducing ability, i.e. a magnesium compound free from a 
magnesium-carbon bond or magnesium-hydrogen bond. Such a magnesium 
compound may be derived from a magnesium compound having reducing ability. 
Illustrative of the magnesium compound having no reducing ability are 
magnesium halides such as magnesium chloride, magnesium bromide, magnesium 
iodide and magnesium fluoride; alkoxy magnesium halides, for example 
C.sub.1 -C.sub.10 alkoxy magnesium halides such as methoxy magnesium 
chloride, ethoxy magnesium chloride, isopropoxy magnesium chloride, butoxy 
magnesium chloride and octoxy magnesium chloride; aryloxy magnesium 
halides, for example phenoxy magnesium halides which may optionally be 
substituted by lower alkyl groups, such as phenoxy magnesium chloride and 
methylphenoxy magnesium chloride; alkoxy magnesiums, for example C.sub.1 
-C.sub.10 alkoxy magnesiums such as ethoxy magnesium, isopropoxy 
magnesium, butoxy magnesium, n-octoxy magnesium and 2-ethylhexoxy 
magnesium; aryloxy magnesiums, for example phenoxy magnesiums which may 
optionally be substituted by lower alkyl groups such as phenoxy magnesium 
and dimethylphenoxy magnesium; and magnesium salts of carboxylic acids, 
for example magnesium salts of aliphatic carboxylic acids having 1 to 20 
carbon atoms, such as magnesium laurate and magnesium stearate. 
The magnesium compounds may be in the form of complexes or mixtures with 
other metals. The halogen-containing magnesium compounds, above all 
magnesium chloride, alkoxy magnesium chlorides and aryloxy magnesium 
chlorides, are preferred among these magnesium compounds. 
The magnesium compounds (i) may be in the form of a solution of such an 
exemplified magnesium compound in a solvent. 
In preparing the magnesium compound (i) in the liquid state, various 
solvents can be used. Examples include aliphatic hydrocarbons such as 
pentane, hexane, heptane, octane, decane, dodecane, tetradecane and 
kerosene; alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, 
cyclohexane, methylcyclohexane, cyclooctane and cyclohexene; aromatic 
hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene and 
cymene; and halogenated hydrocarbons such as dichloroethane, 
dichloropropane, trichloroethylene, carbon tetrachloride and 
chlorobenzene. 
The solution may be prepared by various methods chosen depending upon the 
types of the magnesium compound and the solvent, for example by simply 
mixing the two; mixing the two and heating the mixture; or mixing the 
magnesium compound with the above solvent in the presence of, or after 
being treated with, an electron donor capable of solubilizing the 
magnesium compound, such as an alcohol, an aldehyde, a carboxylic acid, an 
amine, an ether or a mixture thereof, or a mixture thereof with another 
electron donor, and as required, heating the mixture. 
For example, in the case of dissolving a halogen-containing magnesium 
compound (i) in the hydrocarbon solvent with the aid of an alcohol, the 
alcohol may be used in an amount of at least about 1 mole, preferably at 
least about 1.5 mole, especially preferably more than 2 moles, per mole of 
the halogen-containing magnesium compound although the molar ratio of 
these may be varied properly depending upon the type and amount of the 
hydrocarbon solvent and the type of the magnesium compound. There is no 
particular upper limit to the amount of the alcohol, but economically, it 
is desirable not to use it in too large an amount. For example, the amount 
of the alcohol is up to about 40 moles, preferably up to about 20 moles, 
especially preferably up to about 10 moles, per mole of the magnesium 
compound (i). 
When an aliphatic or alicyclic hydrocarbon is used as the solvent, alcohols 
are used in the above-mentioned proportion, and among them, alcohols 
having at least 6 carbon atoms are used in an amount of at least about 1 
mole, preferably at least about 1.5 moles, per mole of the 
halogen-containing magnesium compound. This is preferred since the 
halogen-containing magnesium compound can be solubilized with the use of 
alcohols in a small total amount and a catalyst component having high 
activity can be prepared. If in this case only alcohols having not more 
than 5 carbon atoms are used, their amount should be at least about 15 
moles per mole of the halogen-containing magnesium compound, and the 
resulting catalyst component has lower catalytic activity than that 
obtained as described above. On the other hand, when an aromatic 
hydrocarbon is used as the solvent, the halogen-containing magnesium 
compound can be solubilized by using alcohols in the aforesaid amounts 
irrespective of the types of the alcohols. Furthermore, if, for example, a 
tetraalkoxy titanium is caused to be present together as the titanium 
compound (ii) in solubilizing the halogen-containing magnesium compound, 
the use of a small amount of alcohols makes it possible to solubilize the 
halogen-containing magnesium compound. 
Preferably, the contacting of the halogen-containing magnesium compound 
with the alcohols is carried out in a hydrocarbon medium usually at room 
temperature or a higher temperature, and depending upon the types of these 
compounds, at more than about 65.degree. C., preferably about 80.degree. 
to about 300.degree. C., more preferably at about 100.degree. to about 
200.degree. C. The contact time can also be properly selected. For 
example, it is about 15 minutes to about 5 hours, preferably about 30 
minutes to about 2 hours. Illustrative of suitable alcohols having at 
least 6 carbon atoms are C.sub.6 -C.sub.20 aliphatic alcohols such as 
2-methylpentanol, 2-ethylbutanol, n-heptanol, n-octanol, 2-ethylhexanol, 
decanol, dodecanol, tetradecyl alcohol, undecenol, oleyl alcohol and 
stearyl alcohol; C.sub.6 -C.sub.20 alicyclic alcohols such as cyclohexanol 
and methylcyclohexanol; C.sub.7 -C.sub.20 aromatic alcohols such as benzyl 
alcohol, methylbenzyl alcohol, isopropylbenzyl alcohol, alpha-methylbenzyl 
alcohol and alpha,alpha-dimethylbenzyl alcohol; and C.sub.6 -C.sub.20 
aliphatic alcohols containing an alkoxy group, such as n-butyl Cellosolve 
(=ethylene glycol mono-n-butyl ether) and 1-butoxy-2-propanol. Examples of 
other alcohols are alcohols having not more than 5 carbon atoms such as 
methanol, ethanol, propanol, butanol, ethylene glycol and methyl carbitol. 
When the magnesium compound (i) is to be dissolved in the hydrocarbon 
solvent by using a carboxylic acid, organic carboxylic acids having at 
least 7 carbon atoms are preferred. Examples include organic carboxylic 
acids having 7 to 20 carbon atoms, such as caprylic acid, 2-ethylhexanoic 
acid, undecylenic acid, undecanoic acid, nonylic acid and octanoic acid. 
When the magnesium compound (i) is to be dissolved in the hydrocarbon 
solvent by using an aldehyde, aldehydes having at least 7 carbon atoms are 
preferred. Examples are aldehydes having 7 to 18 carbon atoms, such as 
capric aldehyde, 2-ethylhexyl aldehyde, capryl aldehyde and undecylic 
aldehyde. 
Suitable amines are those having at least 6 carbon atoms. Examples include 
amines having 6 to 18 carbon atoms, such as heptylamine, octylamine, 
nonylamine, decylamine, laurylamine, undecylamine and 2-ethylhexylamine. 
Illustrative of the ether is tetrahydrofuran. 
The preferred amounts of these carboxylic acids, aldehydes, amines and 
ethers and the preferred temperatures at which they are used are much the 
same as described hereinabove. 
The solution of the magnesium compound (i) may also be formed by using 
magnesium metal or another magnesium compound capable of being converted 
to the magnesium compound (i), and dissolving it in the solvent while 
converting it to the magnesium compound (i). For example, this can be 
achieved by dissolving or suspending a magnesium compound having an alkyl, 
alkoxy, aryloxy, acyl, amino or hydroxyl group, magnesium oxide, or 
metallic magnesium in a solvent having the alcohol, amine, aldehyde, 
carboxylic acid, ether, etc. dissolved therein, and forming a 
halogen-containing magnesium compound (i) having no reducing ability while 
halogenating it with a halogenating agent (which, however, is not always 
necessary when a halogenated hydrocarbon is used as the solvent) such as a 
hydrogen halide, a halogenated hydrocarbon, a halogen-containing silicon 
compound, halogen, a halogen-containing aluminum compound, a 
halogen-containing lithium compound or a halogen-containing sulfur 
compound. Alternatively, it is possible to treat a Grignard reagent, a 
dialkyl magnesium, magnesium hydride or a complex of such a magnesium 
compound with another organometalic compound, for example a magnesium 
compound having reducing ability represented by the formula M.sub..alpha. 
Mg.sub..beta. R.sup.1.sub.p R.sup.2.sub.q X.sub.r Y.sub.s wherein M 
represents aluminum, zinc, boron or beryllium, R.sup.1 and R.sup.2 
represents a hydrocarbon group, X and Y represent a group of the formula 
OR.sup.3, OSiR.sup.4 R.sup.5 R.sup.6, NR.sup.7 R.sup.8 or SR.sup.9, 
R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 represent a 
hydrogen atom or a hydrocarbon group, R.sup.9 represents a hydrocarbon 
group, .alpha. and .beta. are greater than zero, p, q, r and s are a 
number of at least 0, m represents the atomic valence of M, 
.beta./.alpha..gtoreq.0.5, p+q+r+s=m.alpha.+2.beta., and 
0.ltoreq.(r+s)/(.alpha.+.beta.)&lt;1.0 with a compound capable of destroying 
reducing ability, such as an alcohol, a ketone, an ester, an ether, an 
acid halide, a silanol, a siloxane, oxygen, water, an acetal, or an alkoxy 
or aryloxy compound of silicon or aluminum, and dissolving the resulting 
magnesium compound (i) having no reducing ability in the solvent. In the 
above formula, examples of the hydrocarbon groups are C.sub.1 to C.sub. 20 
alkyl groups such as an ethyl group, propyl group, butyl group, amyl 
group, hexyl group, octyl group and dodecyl group, and C.sub.6 to C.sub.20 
aryl groups such as a phenyl group and tolyl group. 
Various titanium compounds can be used as the titanium compound (ii) in the 
preparation of the solid titanium catalyst component [A]. Preferred are 
tetravalent titanium compounds of the formula 
EQU Ti(OR).sub.g X.sub.4-g 
wherein R represents a hydrocarbon group, X represents a halogen atom and g 
is a number represented by 0.ltoreq.g.ltoreq.4. In the above formula, 
examples of the hydrocarbon group are C.sub.1 -C.sub.10 alkyl groups, and 
a phenyl group which may have a substituent such as a lower alkyl group, 
for example C.sub.1 to C.sub.4 alkyl group, and a halogen atom. 
Specific examples of the titanium compound (ii) include titanium 
tetrahalides such as TiCl.sub.4, TiBr.sub.4 and TiI.sub.4 ; alkoxy 
titanium trihalides such as Ti(OCH.sub.3)Cl.sub.3, Ti(OC.sub.2 
H.sub.5)Cl.sub.3, Ti(On--C.sub.4 H.sub.9)Cl.sub.3, Ti(OC.sub.2 
H.sub.5)Br.sub.3 and Ti(Oiso--C.sub.4 H.sub.9)Br.sub.3 ; alkoxy titanium 
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(On--C.sub.4 H.sub.9).sub.2 Cl.sub.2 and Ti(OC.sub.2 
H.sub.5).sub.2 Br.sub.2 ; trialkoxy titanium monohalides such as 
Ti(OCH.sub.3).sub.3 Cl, Ti(OC.sub.2 H.sub.5).sub.3 Cl, Ti(On--C.sub.4 
H.sub.9).sub.3 Cl and Ti(OC.sub.2 H.sub.5).sub.3 Br; tetraalkoxy titaniums 
such as Ti(OCH.sub.3).sub.4, Ti(OC.sub.2 H.sub.5).sub.4 and Ti(On--C.sub.4 
H.sub.9).sub.4 ; aryloxy titanium halides such as Ti(OC.sub.6 
H.sub.6)Cl.sub.3 ; aryloxy titanium such as Ti(OC.sub.6 H.sub.6).sub.4 ; 
mixtures of these; and mixtures of these with hydrogen halides, halogens, 
other metallic compounds such as aluminum compounds or silicon compounds, 
or sulfur compounds. Of these, halogen-containing titanium compounds are 
preferred. Titanium tetrahalides, above all titanium tetrachloride, are 
especially preferred. 
The titanium compound (ii) in the liquid state may be one, or a mixture, of 
titanium compounds which are liquid themselves, or may be a solution of 
the titanium compound in a solvent such as hydrocarbons. 
In the present invention, the solid titanium catalyst component (A) 
containing magnesium, titanium and halogen, as essential components, can 
be prepared in the following manner. 
A liquid solution of the magnesium compound (i) is contacted with the 
titanium compound (ii) in the liquid state to form a solid product [to be 
sometimes referred to as method (a) hereinafter]. Or a liquid solution of 
a mixture of the magnesium compound (i) and the titanium compound (ii) is 
first prepared, and then a solid product is formed from it [to be 
sometimes referred to as method (b) hereinafter]. 
The reaction of forming the solid product is carried out in the presence of 
at least one electron donor (iii) selected from the group consisting of 
aliphatic carboxylic acids with 1 to 6 carbon atoms, aryloxy 
group-containing alcohols, alkylene glycol diethers, aluminum trialkoxides 
and aluminum triaryloxides. Thus, there can be easily obtained a solid 
titanium catalyst component [A] which has excellent activity, an excellent 
particle shape, a large particle diameter and a narrow particle size 
distribution. 
Specific examples of the aliphatic carboxylic acids with 1 to 6 carbon 
atoms are formic acid, acetic acid, propionic acid, butyric acid and 
valeric acid. Specific examples of the aryloxy group-containing alcohols 
are C.sub.6 -C.sub.12 aryloxy-group containing alcohols such as ethylene 
glycol monophenyl ether and propylene glycol monophenyl ether. Specific 
examples of the alkylene glycol diethers include C.sub.1 -C.sub.6 alkylene 
glycol diethers such as ethylene glycol dimethyl ether, ethylene glycol 
diethyl ether, ethylene glycol diisobutyl ether, ethylene glycol 
di-tert-butyl ether, ethylene glycol diphenyl ether, propylene glycol 
dibutyl ether and propylene glycol diethyl ether. Specific examples of 
aluminum trialkoxides include aluminum tri(C.sub.1 -C.sub.12) alkoxides 
such as aluminum trimethoxide, aluminum triethoxide, aluminum 
triisopropoxide, aluminum tri-tert-butoxide, aluminum tri-n-octoxide and 
aluminum tri-2-ethylhexoxide. Specific examples of the aluminum 
triaryloxides are tri(C.sub.6 -C.sub.12) aryloxides such as aluminum 
triphenoxide, aluminum trimethylphenoxide and aluminum 
tri(dimethylphenoxide). 
The preferred amount of the electron donor (iii) used varies depending upon 
its type or the conditions of forming the solid product [A] and can be 
properly selected. For example, it is about 0.01 to about 1 mole, 
preferably about 0.05 to about 0.5 mole, per mole of the magnesium 
compound (i). By adjusting the amount of the electron donor (iii), the 
particle diameter of the solid product [A] can be adjusted. 
The liquid mixture in the method (b) can be prepared, for example, by 
dissolving a magnesium halide, an alkoxy magnesium halide, a dialkoxy 
magnesium, etc. in a tetraalkoxy titanium in the presence or absence of a 
suitable diluent, or by dissolving titanium tetrachloride and a magnesium 
halide in tetrahydrofuran. 
In the technique of forming a solid product containing magnesium and 
titanium by contacting the magnesium compound (i) in the liquid state with 
the titanium compound (ii) in the liquid state in accordance with method 
(a), it is preferred, for example, to react a magnesium halide in the 
liquid state containing a solubilizing agent such as the aforesaid alcohol 
for solubilization of magnesium compounds with a liquid of a titanium 
compound such as a liquid titanium halide, or to react a magnesium 
compound in the liquid state having good solubility, such as an 
alkoxymagnesium compound, with a liquid of a titanium compound such as a 
titanium halide. 
The amount of the titanium compound (ii) used varies depending upon its 
type, the contacting conditions or the amount of the electron donor used, 
etc. and can be properly chosen. Preferably, it is at least about 1 mole, 
for example about 2 to about 200 moles such as about 2 to about 100 moles, 
particularly about 3 to about 100 moles, per mole of the magnesium 
compound (i). 
If the solid product is difficult to form by the mere contacting of the 
magnesium compound (i) in the liquid state with the titanium compound (ii) 
in the liquid state, or if the solid product is difficult to form by 
simply leaving the solution of the compounds (i) and (ii) to stand, an 
additional amount of the titanium compound (ii), preferably a 
halogen-containing titanium compound (ii), may be added, or another 
precipitating agent may be added, so as to form the solid product. 
Illustrative of such precipitating agent are halogenating agents such as 
halogens, halogenated hydrocarbons, halogen-containing silicon compounds, 
halogen-containing aluminum compounds, halogen-containing lithium 
compounds, halogen-containing sulfur compounds and halogen-containing 
antimony compounds. Specific examples are chlorine, bromine, hydrogen 
chloride, hydrochloric acid, phosphorus pentachloride, thionyl chloride, 
thionyl bromide, sulfuryl chloride, phosgene, and nitrosyl chloride. 
The solid product differs in shape or size depending upon the conditions 
for its formation. In order to obtain a solid product having a uniform 
shape and a uniform particle size, it is preferred to avoid its rapid 
formation. For example, when the solid product is to be formed by mixing 
the compounds (i) and (ii) in the liquid state and reacting them with each 
other, it is advisable to mix them at a sufficiently low temperature which 
does not cause rapid formation of a solid product, and then to elevate the 
temperature gradually. According to this method, there can easily be 
obtained a granular or spherical solid product having a relatively large 
particle diameter and a narrow particle size distribution. 
When slurry polymerization or vapor phase polymerization is carried out by 
using the granular or spherical solid catalyst component [A] having a good 
particle size distribution which can be obtained as above, the resulting 
polymer is granular or spherical and has a narrow particle size 
distribution, a high bulk density and good flowability. The term 
"granular", as used herein denotes particles which look like an assembly 
of fine powders when examined by an enlarged scale photograph. Particles 
ranging from those having many uneven parts to those close to a true 
sphere can be obtained as the granular product depending upon the method 
of preparing the solid catalyst component. 
The contacting of the liquid hydrocarbon solution of the magnesium compound 
(i) in the liquid state with the titanium compound (ii) in the liquid 
state may be effected, for example, at a temperature of about -70.degree. 
C. to about +200.degree. C. The temperature of the two liquids to be 
contacted may be different from each other. Generally, it is frequently 
preferred to employ a contacting method not involving too high a 
temperature, in order to obtain a solid catalyst component having a 
desirable granular or spherical shape and high performance. For example, 
temperatures of about -70.degree. to about +50.degree. C. are preferred. 
If the contacting temperature is too low, precipitation of a solid product 
may sometimes be not observed. In such a case, it is desirable to elevate 
the temperature to about 50.degree. to about 150.degree. C. for example, 
or continue the contacting for a longer period of time until precipitation 
of the solid product occurs. 
In the present invention, the formation of the solid product may be carried 
out in the presence of a porous inorganic and/or organic compound, whereby 
the solid product is deposited on the surface of such a porous compound. 
In employing this method, the porous compound may be preliminarily 
contacted with the magnesium compound in the liquid state, and then with 
the titanium compound in the liquid state while it contains the liquid 
magnesium compound. Illustrative of such a porous compound are silica, 
alumina, polyolefins and products obtained by treating these compounds 
with halogen-containing compounds. 
The solid titanium catalyst component [A] used in this invention consists 
basically of the solid product obtained as above and contains magnesium, 
titanium and halogen as essential ingredients. It may be a product 
obtained by simply washing the aforesaid solid product with an inert 
solvent such as a hydrocarbon. Preferably, it may be a product obtained by 
washing the solid product at least once at a temperature of about 
20.degree. to about 150.degree. C. with an excessive amount of a liquid 
titanium compound or a liquid halogenated hydrocarbon, more preferably 
with titanium tetrachloride, 1,2-dichloroethane, chlorobenzene, methyl 
chloride, or hexachloroethane. 
The solid titanium catalyst component [A] used in this invention may be one 
obtained by the aforesaid embodiment (a) or (b), with or without further 
washing with a titanium compound, a hydrocarbon, etc. 
Preferably, the solid titanium catalyst component [A] which can be obtained 
by any of the above-described embodiments is used for polymerization after 
it is well washed with a hydrocarbon. The resulting solid titanium 
catalyst component [A] preferably has such a composition that the 
magnesium/titanium atomic ratio is, for example, from about 2 to about 
100, preferably from about 4 to about 50, more preferably from about 5 to 
about 30, the halogen/titanium atomic ratio is, for example, from about 4 
to about 100, preferably from about 5 to about 90, more preferably from 
about 8 to about 50. As stated hereinabove, the shape of the catalyst 
component [A] is, in many cases, granualr or nearly spherical. Usually, it 
has a specific surface area of, for example, at least about 10 m.sup.2 /g, 
preferably about 100 to about 1000 m.sup.2 /g, and a particle diameter in 
the range of, for example, about 1 to about 100 microns. Its particle size 
distribution is narrow. 
According to this invention, olefins are polymerized by using a catalyst 
system composed of the solid titanium catalyst component [A] prepared as 
above and the organometallic compound (B) of the metal of Groups I to III 
of the periodic table. 
As examples of the organometallic compound (B), the following compounds may 
be cited. 
(1) Organoaluminum compounds having at least one Al--C bond in the 
molecule, for example organoaluminum compounds of the general formula 
EQU R.sup.1.sub.m Al(OR.sup.2).sub.n H.sub.p X.sub.q 
wherein R.sup.1 and R.sup.2 are identical or different and each represents 
a hydrocarbon group, for example a hydrocarbon group having 1 to 15 carbon 
atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, m is a 
number represented by 0&lt;m.ltoreq.3, n is a number represented by 
0.ltoreq.n&lt;3, p is a number represented by 0.ltoreq.p&lt;3, q is a number 
represented by 0.ltoreq.q&lt;3, and m+n+p+q=3. 
(2) Complex alkylated products of aluminum and a Group I metal represented 
by the general formula 
EQU M.sup.1 AlR.sup.1.sub.4 
wherein M.sup.1 represents Li, Na or K, and R.sup.1 is as defined above. 
(3) Dialkyl compounds of a Group II metal represented by the general 
formula 
EQU R.sup.1 R.sup.2 M.sup.2 
wherein R.sup.1 and R.sup.2 are as defined above, and M.sup.2 is Mg, Zn or 
Cd. 
In the above formulae, examples of the hydrocarbon group for R.sup.1 and 
R.sup.2 are alkyl groups and aryl groups. 
Examples of the organoaluminum compounds (1) are shown below. 
Compounds of the general formula R.sup.1.sub.m Al(OR.sup.2).sub.3-m wherein 
R.sup.1 and R.sup.2 are as defined above, m is preferably a number 
represented by 1.5.ltoreq.m.ltoreq.3; 
compounds of the general formula R.sup.1.sub.m AlX.sub.3-m wherein R.sup.1 
is as defined above, X is halogen, and m is preferably a number 
represented by 0&lt;m&lt;3; 
compounds represented by the general formula R.sup.1.sub.m AlH.sub.3-m 
wherein R.sup.1 is as defined above, and m is preferably a number 
represented by 2.ltoreq.m&lt;3, and 
compounds represented by the general formula R.sup.1.sub.m 
Al(OR.sup.2).sub.n X.sub.q wherein R.sup.1 and R.sup.2 are as defined 
above, X represents halogen, 0&lt;m.ltoreq.3, 0.ltoreq.n&lt;3, 0.ltoreq.q&lt;3, and 
m+n+q=3. 
Specific examples of the organoaluminum compounds of formula (1) are 
trialkyl aluminums such as triethyl aluminum and tributyl aluminum; 
trialkenyl aluminums such as triisoprenyl aluminum; partially alkoxylated 
alkyl aluminums, for example, dialkyl aluminum alkoxides such as diethyl 
aluminum ethoxide and dibutyl aluminum butoxide; alkyl aluminum 
sesquialkoxides such as ethyl aluminum sesquiethoxide and butyl aluminum 
sesquibutoxide; compounds having an average composition expressed by 
R.sup.1.sub.2.5 Al(OR.sup.2).sub.0.5 ; partially halogenated alkyl 
aluminums, for example, dialkyl aluminum halide such as diethyl aluminum 
chloride, dibutyl aluminum chloride and diethyl aluminum bromide; alkyl 
aluminum sesquihalides such as ethyl aluminum sesquichloride, butyl 
aluminum sesquichloride and ethyl aluminum sesquibromide; alkyl aluminum 
dihalides such as ethyl aluminum dichloride, propyl aluminum dichloride 
and butyl aluminum dibromide; partially hydrogenated alkyl aluminums, for 
example, dialkyl aluminum hydroxides such as diethyl aluminum hydride and 
dibutyl aluminum hydride, alkyl aluminum dihydrides such as ethyl aluminum 
dihydride and propyl aluminum dihydride; and partially alcoholated and 
halogenated alkyl aluminums, for example, alkyl aluminum alkoxyhalides 
such as ethyl aluminum ethoxychloride, butyl aluminum butoxychloride and 
ethyl aluminum ethoxybromide. 
Examples of the compounds mentioned in (2) above are LiAl(C.sub.2 
H.sub.5).sub.4 and LiAl(C.sub.7 H.sub.15).sub.4. 
Examples of the compounds mentioned in (3) above are diethyl zinc and 
diethyl magnesium. Alkyl magnesium halides such as ethyl magnesium 
chloride may also be used. 
Organoaluminum compounds in which two or more aluminum atoms are bonded 
through an oxygen or nitrogen atom, similar to the compounds (1), may also 
be used. Examples of such aluminum compounds are (C.sub.2 H.sub.5).sub.2 
AlOAl(C.sub.2 H.sub.5).sub.2, (C.sub.4 H.sub.9).sub.2 AlOAl(C.sub.4 
H.sub.9).sub.2 and 
##STR1## 
Among the above organoaluminum compounds, trialkyl aluminums and alkyl 
aluminums in which two or more aluminums are bonded are preferred. 
According to this invention, there is provided a process for producing 
olefin polymers or copolymers which comprises polymerizing or 
copolymerizing olefins or copolymerizing at least one olefin with a minor 
amount, for example up to 10 mole%, of a diene in the presence of a 
catalyst system composed of the solid titanium catalyst component [A] and 
the organometallic compound [B]. 
Illustrative of olefins which can be used are olefins having 2 to 10 carbon 
atoms such as ethylene, propylene, 1-butene, 4-methyl-1-pentene and 
1-octene. They may be homopolymerized or random-copolymerized or 
block-copolymerized. The diene may be a polyunsaturated compound such as 
conjugated dienes or nonconjugated dienes. Specific examples include 
butadiene, isoprene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 
1,4-hexadiene, ethylidene norbornene, vinyl nobornene and 1,7-octadiene. 
The catalyst system of this invention can be advantageously used in the 
polymerization or copolymerization of ethylene, specifically in the 
polymerization of ethylene or copolymerization of ethylene with at least 
one alpha-olefin having at least 3 carbon atoms such as alpha-olefins 
having 3 to 10 carbon atoms and/or a diene. For example, copolymerization 
of ethylene with up to 10 mole% of at least one such alpha-olefin and/or a 
diene. 
The polymerization can be carried out either in the liquid or vapor phase. 
When the liquid-phase polymerization is carried out, inert solvents such 
as hexane, heptane and kerosene may be used as a reaction medium. If 
desired, the olefin itself may be used as the reaction medium. The amount 
of the catalyst can be properly selected. For example, in a preferred 
embodiment, per liter of the reaction solvent in the case of the 
liquid-phase reaction or per liter of the volume of the reaction zone in 
the case of the vapor-phase reaction, the component [A] is used in an 
amount of 0.0001 to 1 millimole as the titanium atom; the component [B] is 
used in such a proportion that the amount of the metal atom in the 
component [B] is 1 to 2,000 moles, preferably 5 to 500 moles, per mole of 
the titanium atom in the component [A]. 
In performing the polymerization, hydrogen, a halogenated hydrocarbon, and 
an electron donor may be added to the polymerization system in order, for 
example, to increase the activity of the catalyst, and control the 
molecular weight, molecular weight distribution or composition 
distribution of the polymer. 
The polymerization temperature is preferably about 20.degree. to about 
200.degree. C., more preferably about 50.degree. to about 180.degree. C. 
The pressure is from atmospheric pressure to about 100 kg/cm.sup.2, 
preferably from about 2 to about 50 kg/cm.sup.2. The polymerization can be 
carried out batchwise, semicontinuously, or continuously. Or the 
polymerization may also be carried out in two or more stages having 
different reaction conditions. 
In the present invention, an olefin polymer can be produced with a high 
catalytic efficiency. In particular, when the process of this invention is 
applied to slurry polymerization or vapor-phase polymerization, there can 
be formed a granular or nearly spherical polymer having a high bulk 
density and a narrow particle size distribution, which looks as if it 
consisted of flocculated fine particles. Such a granular or spherical 
polymer has good flowability and in some application, can be used without 
pelletization.

The following Examples illustrate the present invention in more detail. 
EXAMPLES 1 TO 5 
Preparation of the catalyst component 
Anhydrous magnesium chloride (4.76 g; 50 mmoles), 25 ml of decane and 23.2 
ml (150 mmoles) of 2-ethylhexyl alcohol were heated at 130.degree. C. for 
2 hours to form a uniform solution. Each of the electron donor compounds 
(iii) shown in Table 1 was added in the amount indicated and the mixture 
was stirred under heat to form a uniform solution of magnesium containing 
the electron donor (iii). The solution was then added dropwise over about 
1 hour to 200 ml of TiCl.sub.4 kept at -20.degree. C. with stirring. Then, 
the temperature was raised to 90.degree. C. over the course of about 2 
hours, and the reaction was carried out at this temperature for 2 hours. 
After the reaction, the solid material in the reaction mixture was 
collected by hot filtration, and fully washed with hot decane and hexane 
at room temperature until no free titanium compound was detected in the 
washings. Thus, a solid catalyst component [A] was obtained. Its 
composition is shown in Table 1. 
Polymerization 
A 2-liter autoclave was charged with 1000 ml of purified hexane, and under 
nitrogen atmosphere at room temperature, 1.0 mmole of triethyl aluminum 
and 0.02 mmole, calculated as titanium atom, of the catalyst component [A] 
were fed. The autoclave was then sealed up and heated to 70.degree. C. 
During temperature elevation, hydrogen was introduced at 60.degree. C. 
until the internal pressure of the autoclave reached 4.0 kg/cm.sup.2.G. 
Ethylene was further introduced, and the total pressure of the autoclave 
was adjusted to 8.0 kg/cm.sup.2.G. After the lapse of 2 hours from the 
introduction of ethylene, the autoclave was cooled, and the pressure was 
then released. After the polymerization, the slurry containing the 
resulting polymer was filtered to collect a powdery white polymer and 
dried. The results of the polymerization are shown in Table 2. 
EXAMPLES 6 TO 9 
Preparation of catalyst component [A] 
Anhydrous magnesium chloride (4.76 g; 50 mmoles), 25 ml of decane and 23.2 
ml (150 mmoles) of 2-ethylhexyl alcohol were heated at 130.degree. C. for 
2 hours to form a uniform solution. Then, each of the electron donor 
compounds (iii) shown in Table 1 was added, and mixed with stirring under 
heat to prepare a uniform solution of magnesium containing the electron 
donor (iii). Then, the uniform solution was added dropwise over the course 
of about 1 hour to 200 ml of TiCl.sub.4 kept at -20.degree. C. with 
stirring. The temperature was raised to 130.degree. C. over the course of 
about 3 hours, and the reaction was carried out at this temperature for 2 
hours. After the reaction, the solid material in the reaction mixture was 
collected by hot filtration. It was again suspended in 200 ml of 
TiCl.sub.4, and reacted at 130.degree. C. for 2 hours. The solid material 
was collected by hot filtration, and washed fully with hot decane and 
hexane at room temperature until no free titanium compound was detected in 
the washings. Thus, a solid catalyst component [A] was obtained. The 
composition of this component [A] is shown in Table 1. 
Polymerization 
A 2-liter autoclave was charged with 1000 ml of purified hexane, and under 
nitrogen atomosphere at room temperature, 1.0 mmole of triethyl aluminum 
(in Example 6, triisobutyl aluminum was used) and 0.02 mmole, calculated 
as titanium atom, of the catalyst component [A] were fed. The autoclave 
was sealed up, and then heated to 70.degree. C. During the temperature 
elevation, hydrogen was introduced at 60.degree. C. until the internal 
pressure of the autoclave reached 4.0 kg/cm.sup.2.G. Further, ethylene was 
introduced, and the total pressure of the autoclave was adjusted to 8.0 
kg/cm.sup.2.G. During the polymerization, the autoclave was maintained for 
2 hours at a temperature of 70.degree. C. and a pressure of 8.0 
kg/cm.sup.2.G. After the lapse of 2 hours from the introduction of 
ethylene, the autoclave was cooled and then the pressure was released. 
After the polymerization, the slurry containing the resulting polymer was 
filtered, and a white powdery polymer was collected and then dried. The 
results of the polymerization are shown in Table 2. 
TABLE 1 
______________________________________ 
Electron donor (iii) Catalyst 
Ex- (iii)/Mg composition (%) 
ample Compound Mole ratio 
Ti Cl Mg 
______________________________________ 
1 Acetic acid 0.20 4.4 65 24 
2 Propionic acic 0.25 5.2 64 17 
3 Ethylene glycol 0.20 4.1 60 18 
dibutyl ether 
4 Ethylene glycol 0.20 4.1 63 18 
diethyl ether 
5 Triisopropoxy aluminum 
0.20 4.5 64 18 
6 Acetic acic 0.25 3.6 69 21 
7 Propionic acid 0.25 4.0 63 18 
8 Triethoxy aluminum 
0.20 5.7 64 17 
9 Phenyl Cellosolve 
0.20 4.1 63 19 
______________________________________ 
TABLE 2 
__________________________________________________________________________ 
Organo- 
metallic Activity 
compound g-PE/ 
kg-PE/g-solid 
MI BD Particle size distribution (wt. 
%)* 
Example 
[B] mmole-Ti 
catalyst [A] 
(190.degree. C./10 min.) 
(g/ml) 
.about.20 
20.about.32 
32.about.60 
60.about.150 
150.about.350 
350.about. 
__________________________________________________________________________ 
1 Triethyl 
19700 
18.1 3.6 0.40 0 7 78 15 0 0 
aluminum 
2 Triethyl 
21600 
23.4 2.5 0.36 0 5 73 22 0 0 
aluminum 
3 Triethyl 
10500 
8.9 2.4 0.37 0 0 66 33 1 0 
aluminum 
4 Triethyl 
18400 
15.7 4.3 0.37 0 1 50 48 1 0 
aluminum 
5 Triethyl 
17200 
16.2 1.9 0.35 0 0 22 77 1 0 
aluminum 
6 TIBA 19000 
14.3 0.6 0.39 0 8 68 24 0 0 
7 TIBA 22000 
18.4 1.0 0.32 0 1 12 85 2 0 
8 TIBA 15600 
18.6 0.2 0.35 0 1 28 69 2 0 
9 TIBA 17300 
14.8 0.9 0.34 0 1 34 63 2 0 
__________________________________________________________________________ 
*Determined by a sieving method. The particle site distribution numbers 
show the meshes of sieves. 
EXAMPLE 10 
Acetic acid (0.75 ml) was added to a uniform solution obtained by reacting 
83.6 ml of a decane solution containing 50 mmoles of ethyl butyl magnesium 
with 15.4 ml of 2-ethylhexanol at 80.degree. C. for 2 hours. The mixture 
was fully stirred, and added dropwise over the course of 1 hour to 200 ml 
of titanium tetrachloride kept at -20.degree. C. with stirring. 
Thereafter, the same procedure as in Example 1 was repeated to synthesize 
a catalyst component [A]. Using the catalyst component [A], ethylene was 
polymerized in the same way as in Example 1. 
The results of the polymerization are shown in Table 3. 
EXAMPLE 11 
Metallic magnesium (1.2 g), 5.0 ml of methanol and 23.3 ml of 
2-ethylhexanol and then 0.75 ml of acetic acid and 50 ml of decane were 
reacted at 65.degree. C. for 4 hours in the presence of hydrogen chloride 
to form a decane solution containing magnesium. Using the resulting decane 
solution, a catalyst component [A] was prepared in the same way as in 
Example 1, and ethylene was polymerized in the same way as in Example 1. 
The results of the polymerization are shown in Table 3. 
EXAMPLE 12 
A solid substance (formed by the reaction of 50 mmoles of butyl magnesium 
chloride with silicon tetrachloride), 25 ml of decane and 23.4 ml of 
2-ethylhexyl alcohol were reacted at 120.degree. C. for 2 hours to obtain 
a decane solution containing magnesium. Acetic acid (0.75 ml) was added to 
the decane solution, and mixed with stirring. 
Subsequently, by the same procedure as in Example 1, a catalyst component 
[A] was prepared, and ethylene was polymerized in the same way as in 
Example 1. 
The results of the polymerization are shown in Table 3. 
EXAMPLE 13 
Diethoxy magnesium (5.7 g), 23.4 ml of 2-ethylhexyl alcohol and 50 ml of 
decane were reacted at 130.degree. C. for 3 hours in the presence of 
hydrogen chloride to form a decane solution containing magnesium. Acetic 
acid (0.75 ml) was added to the decane solution, and mixed with stirring. 
Subsequently, by the same procedure as in Example 1, a catalyst component 
[A] was prepared, and ethylene was polymerized in the same way as in 
Example 1. 
The results of the polymerization are shown in Table 3. 
EXAMPLE 14 
Anhydrous magnesium chloride (4.76 g; 50 mmoles), 25 ml of decane and 26.2 
ml of ethylene glycol dibutyl ether were reacted at 130.degree. C. for 2 
hours to form a decane solution containing magnesium. Acetic acid (0.75 
ml) was added to the decane solution and mixed with stirring. 
Subsequently, by the same procedure as in Example 1, a catalyst component 
[A] was prepared, and ethylene was polymerized in the same way as in 
Example 1. 
The results of the polymerization are shown in Table 3. 
EXAMPLE 15 
Anhydrous magnesium chloride (4.76 g; 50 mmoles), 25 ml of decane and 23.2 
ml (150 mmoles) of 2-ethylhexyl alcohol were reacted at 130.degree. C. for 
2 hours to form a uniform solution. Acetic acid (0.6 g; 10 mmoles) was 
added, and the mixture was stirred under heating to prepare a uniform 
solution of magnesium containing the electron donor (iii). To this 
solution was added 1.1 ml (10 mmoles) of titanium chloride, and mixed with 
stirring (at this time, no precipitation of particles occurred, and the 
mixture was a uniform solution). By using the resulting solution, a solid 
catalyst component [A] was prepared by the same procedure as in Example 1. 
Ethylene was then polymerized by using the solid catalyst component [A] in 
the same way as in Example 1. 
The results of the polymerization are shown in Table 3. 
EXAMPLE 16 
A Ti-containing solid catalyst component [A] was prepared in the same way 
as in Example 15 except that instead of titanium tetrachloride, 6.1 ml (10 
mmoles) of tetra-2-ethylhexoxy titanium was used. Using the solid catalyst 
component [A], ethylene was polymerized. 
The results of the polymerization are shown in Table 3. 
COMATIVE EXAMPLE 1 
Preparation of catalyst component [A] 
Anhydrous magnesium chloride (4.76 g; 50 mmoles), 25 ml of decane and 23.2 
ml (150 mmoles) of 2-ethylhexyl alcohol were reacted at 130.degree. C. for 
2 hours to prepare a uniform solution of magnesium. The uniform solution 
was added dropwise over the course of about 1 hour to 200 ml of TiCl.sub.4 
kept at -20.degree. C. with stirring. The temperature was elevated to 
90.degree. C. over the course of about 2 hours, and the reaction was 
carried out at this temperature for 2 hours. After the reaction, the 
reaction mixture was filtered in an attempt to remove the solid material. 
But the solid material blocked up the meshes of the filter (G-3 filter), 
and its separation by filtration was extremely difficult. On the other 
hand, solid-liquid separation was attempted by decantation, but the speed 
of sedimentation of the solid portion was very slow. The solid substance 
obtained by filtering the reaction mixture for about 5 hours was washed 
with hot decane and hexane at room temperature by the same procedure as in 
Example 1 to form a solid catalyst component [A]. Examination by an 
optical microscope showed that the solid material had a particle diameter 
of less than about 1 microns. 
Polymerization 
Using the solid catalyst component [A] obtained above, ethylene was 
polymerized by the same procedure as in Example 1. The results of the 
polymerization are shown in Table 3. 
TABLE 3 
__________________________________________________________________________ 
Catalyst 
composition Activity 
(wt. %) g-PE/ 
kg-PE/g-solid 
MI BD Particle size distribution (wt. %) 
Example 
Ti Cl 
Mg mmole-Ti 
catalyst [A] 
(190.degree. C./10 min.) 
(g/ml) 
.about.20 
20.about.32 
32.about.60 
60.about.150 
150.about.350 
350.about. 
__________________________________________________________________________ 
10 4.1 
64 
23 20300 
17.4 1.9 0.39 
1 2 69 28 0 0 
11 3.8 
60 
19 16700 
13.2 3.3 0.36 
0 1 49 50 0 0 
12 4.0 
60 
18 18300 
13.9 2.9 0.38 
0 7 76 17 0 0 
13 4.0 
61 
19 16200 
13.5 2.9 0.37 
0 0 70 29 1 0 
14 4.7 
64 
18 10300 
10.1 6.1 0.33 
0 1 50 48 1 0 
15 5.6 
53 
15 11300 
13.2 36 0.38 
0 5 79 16 0 0 
16 5.0 
55 
16 13200 
13.8 4.1 0.38 
0 3 80 17 0 0 
Compar- 
13.0 
63 
8 5300 
14.4 2.3 0.13 
2 5 18 36 29 10 
ative 
Example 
__________________________________________________________________________