Process for producing polyethylenes

A process for producing polyethylene is disclosed in which ethylene is polymerized in the presence of a composite catalyst. The catalyst is made up of a solid catalyst component typified by a selected chromium compound, a modified aluminum compound typified by a trialkylaluminum and an R.sub.n.sup.1 Al(OR.sup.2).sub.3-n compound wherein R.sup.1 and R.sup.2 are represented by selected hydrocarbon groups and n by 0.ltoreq.n.ltoreq.3. The polymer has improved melt index, flow parameter and melt tension characteristics.

BACKGROUND OF THE INVENTION 
1. Technical Field 
This invention relates to a process for the production of ethylene 
homopolymers or copolymers of improved moldability characteristics with 
the use of a composite catalyst of specified compositions. 
2. Prior Art 
It is known that ethylene can be homo- or co-polymerized in the presence of 
Phillips type catalysts having chromium oxide supported on silica or the 
like. In general, this type of catalyst is subject to activation only 
under elevated temperature and pressure conditions and also susceptible to 
malfunction even on contact with a limited amount of impurities which will 
be present in ethylene monomers, .alpha.-olefin comonomers or solvents 
used. The Phillips catalyst has a further drawback in that it involves 
prolonged induction period and hence reduced production rate. 
To cope with the above problems, a certain process of polymerization has 
been proposed in which a chromium oxide catalyst supported is employed in 
combination with a small amount of a reaction product of an organoaluminum 
compound with water as disclosed in Japanese Patent Publication No. 
49-7341. Given a minimum induction period, however, this process is 
required to be effected in the presence of a chromium oxide catalyst 
calcined at high temperature and at a polymerization temperature not lower 
than 100.degree. C. so as to produce polyethylenes of great melt indices. 
To regulate the molecular weight of a polymer to be formed, the 
last-mentioned process is necessarily dependent upon the temperature of 
reaction rather than the feed of hydrogen. This mode of molecular weight 
control is difficult to accomplish with reliability. Such prior process is 
not wholly satisfactory in respect of the efficiency of operation. 
A keen demand has been voiced for polyethylenes of superior melting and 
molding properties particularly in an industrial sector in which bottles 
of small dimensions are blow-molded for instance for daily use detergents. 
SUMMARY OF THE INVENTION 
The present invention seeks to provide an improved process for producing 
ethylene homopolymers or copolymers which will exhibit increased catalytic 
activity, minimized induction period and simplified molecular weight 
regulation and further have freedom from residual catalyst removal. 
Polymers obtainable by the invention are wide in molecular weight 
distribution and superior in melt index and melt tension and thus highly 
moldable by blowing or by injection. 
As will become better understood from the following description, the 
invention provides a process for producing ethylene homopolymers or 
copolymers which comprises homopolymerizing ethylene or copolymerizing the 
same with an .alpha.-olefin of from 3 to 12 carbon atoms in the presence 
of a composite catalyst comprising (I) a solid catalyst component 
containing a chromium oxide or a chromium compound capable of partially 
forming a chromium oxide upon calcination and supported on an inorganic 
oxide carrier and subsequently calcined, (II) a modified aluminum compound 
resulting from reaction of an organoaluminum compound with water and 
having one or more Al-O-Al bonds in the molecule and (III) a compound of 
the formula R.sub.n.sup.1 Al(OR.sup.2).sub.3-n where R.sup.1 and R.sup.2 
each are hydrocarbon groups of from 1 to 18 carbon atoms, R.sup.1 and 
R.sup.2 being the same or different, and n is 0.ltoreq.n.ltoreq.3. 
DETAILED DESCRIPTION OF THE INVENTION 
Composite catalysts used for purposes of the present invention are 
comprised essentially of a solid catalyst component (component I), a 
modified organoaluminum compound (component II) and a compound of the 
formula R.sub.n.sup.1 Al(OR.sup.2).sub.3-n. 
Component I may be obtained by supporting on an inorganic oxide carrier a 
chromium oxide or a chromium compound which, when calcined, is converted 
partially to a chromium oxide. Chromium compounds may be selected from 
chromium halides, chromium oxyhalides, chromium nitrate salts, chromium 
acetate salts, chromium sulfate salts, chromium alcoholates and the like. 
In specific examples of component I are included chromium trioxide, 
chromyl chloride, potassium bichromate, ammonium chromate, chromium 
nitrate, chromium acetate, chromium acetylacetate, di-tert-butyl chromate 
and the like. 
Carriers include for example silica, alumina, silica-alumina, titania, 
silica-titania, zirconia and tria and mixtures thereof. Silica, 
silica-alumina and silica-titania are particularly preferred. The carrier 
should preferably have a surface area of 50 to 1,000 m.sup.2 /g and a pore 
volume of 0.5 to 2.5 cm.sup.2 /g. 
As means for supporting component I on the carrier, there may be utilized 
impregnation, solvent distillation, sublimation or the like commonly 
accepted in the art. Component I should be supported in an amount of 0.1 
to 10% by weight in terms of Cr, preferably 0.3 to 5%, more preferably 0.5 
to 3%, based on the weight of the carrier. 
Component I is calcined to activate generally in a moisture-free, 
non-reductive atmosphere for example in an oxygen stream, in an inert gas 
stream or in vacuo. Fully dried air may conveniently be used to this end 
in a fluidized state. Calcination conditions are at a temperature higher 
than 400.degree. C., preferably between 500.degree. and 900.degree. C., 
and for a length of time from several minutes to tens of hours, preferably 
30 minutes to 10 hours. Component I may if necessary be adjusted in its 
catalytic activity in conventional fashion by the addition of a titanate 
or a fluorine-containing salt at the time of support or calcination. 
Component II includes reaction products resulting from reacting an 
organoaluminum component with water and having in the molecule an 
Al--O--Al bond in the number of 1 to 100, preferably 1 to 50. Reaction may 
be performed usually in an inert hydrocarbon selected from an aliphatic 
hydrocarbon such as pentane, hexane, heptane or the like, an alicyclic 
hydrocarbon such as cyclohexane, methylcyclohexane or the like, or an 
aromatic hydrocarbon such as benzene, toluene, xylene or the like. 
Preferred among these hydrocarbons are aliphatic and alicyclic types. 
Organoaluminum compounds used herein are represented by the formula R.sub.n 
AlX.sub.3-n where R is a hydrocarbon group of a carbon number of 1 to 18, 
preferably 1 to 12, such as an alkyl, alkenyl, aryl, aralkyl or similar 
group, X is a hydrogen or halogen atom, and n is 0&lt;n.ltoreq.3. 
Trialkylaluminums are particularly preferred in which the alkyl group may 
be chosen from methyl, ethyl, propyl, iso-propyl, butyl, iso-butyl, 
pentyl, hexyl, octyl, decyl, dodecyl or the like among which an iso-butyl 
group is typified. 
The molar ratio of water to organoaluminum compound should be in the range 
of 0.25:1 to 1.2:1 in terms of H.sub.2 O:Al, preferably 0.5:1 to 1:1. 
Reaction conditions are at a temperature of -70.degree. to 100.degree. C., 
preferably -70.degree. to 20.degree. C., and for a length of time of 5 to 
100 minutes, preferably 10 to 30 minutes. 
Component III is one compound of the formula R.sub.n.sup.1 
(OR.sup.2).sub.3-n where R.sup.1 and R.sup.2 each are hydrocarbon groups 
of a carbon number of 1 to 18, preferably 1 to 12, R.sup.1 and R.sup.2 
being the same or different, and n is 0.ltoreq.n.ltoreq.3, preferably 
0&lt;n&lt;3. Hydrocarbon groups may be selected from alkyl, alkenyl, aryl, 
aralkyl, alicyclic and similar groups in which are included methyl, ethyl, 
n-propyl, iso-propyl, iso-butyl, hexyl, 2-methylpentyl, octyl, decyl, 
dodecyl, cyclohexyl, cyclohexylmethyl, phenyl, naphthyl, benzyl and the 
like. Particularly preferred are iso-propyl, iso-butyl and 2-ethylhexyl 
groups. 
Specific examples of component III include (C.sub.2 H.sub.5).sub.2 
AlOC.sub.2 H.sub.5, C.sub.2 H.sub.5 Al(OC.sub.2 H.sub.5).sub.2, 
Al(OC.sub.2 H.sub.5).sub.3, (C.sub.2 H.sub.5).sub.2 AlO-iso-C.sub.3 
H.sub.7, C.sub.2 H.sub.5 Al(O-iso-C.sub.3 H.sub.7).sub.2 m 
Al(O-iso-C.sub.3 H.sub.7).sub.3, (iso-C.sub.4 H.sub.9).sub.2 AlOC.sub.2 
H.sub.5, (iso-C.sub.4 H.sub.9).sub.2 AlO-iso-C.sub.3 H.sub.7, iso-C.sub.4 
H.sub.9 Al(OC.sub.2 H.sub.5).sub.2, iso-C.sub.4 H.sub.9 Al(O-iso-C.sub.3 
H.sub.7).sub.2, (n-C.sub.6 H.sub.11).sub.2 AlOC.sub.2 H.sub.5, (n-C.sub.6 
H.sub.11).sub.2 AlO-iso-C.sub.3 H.sub.7, n-C.sub.6 H.sub.11 Al(OC.sub.2 
H.sub.5).sub.2, (n-C.sub.6 H.sub.11).sub.2 AlO-iso-C.sub.4 H.sub.7, 
Al(O-sec-C.sub.4 H.sub.9).sub.3, (C.sub.2 H.sub.5).sub.2 Al(OC.sub.6 
H.sub.5) and the like. Most typically chosen are (iso-C.sub.4 
H.sub.9).sub.2 AlO-iso-C.sub.3 H.sub.7 and (iso-C.sub.4 H.sub.9).sub.2 
AlO-n-C.sub.4 H.sub.9 compounds. 
Component III may be synthesized in known manner for instance by reacting 
an organoaluminum compound with an R.sup.2 OH compound, or by reacting two 
different organoaluminum compounds of R.sub.3.sup.1 Al and 
Al(OR.sup.2).sub.3 where R.sup.1 and R.sup.2 are as defined above. The 
first-mentioned reaction may more preferably be employed in which 
R.sub.3.sup.1 Al and R.sup.2 OH compounds are reacted, and in this 
instance an iso-butyl group is preferred as R.sup.1 and an iso-propyl or 
2-ethylhexyl group as R.sup.2. Reaction is effected usually in an inert 
hydrocarbon selected from an aliphatic hydrocarbon such as pentane, 
hexane, heptane or the like, an alicyclic hydrocarbon such as cyclohexane, 
methylcyclohexane or the like, or an aromatic hydrocarbon such as benzene, 
toluene, xylene or the like, and preferably in an aliphatic or alicyclic 
hydrocarbon. The molar ratio of R.sup.2 OH compound to organoaluminum 
compound should be in the range of 0.25:1 to 3:1 in terms of R.sup.2 
OH:Al, preferably 0.5:1 to 2:1, the reaction temperature in the range of 
-70.degree. to 100.degree. C., preferably -20.degree. to 50.degree. C., 
and the reaction time in the range of 5 to 100 minutes, preferably 10 to 
60 minutes. 
The atomic ratio of component I to components II and III should range from 
0.01 to 1,000 in terms of Al:Cr, preferably 0.1 to 500, more preferably 1 
to 100, and the molar ratio of component II to component III from 0.01 to 
100, preferably 1 to 20. Departures from the above specified ratios would 
make the finished catalyst less active, resulting in a polymer of 
deteriorated quality. 
The higher temperature while in calcination of component I, the greater 
melt index the resulting polymer has. The catalyst according to the 
invention has now been found highly capable, on calcination of component I 
even at a relatively low temperature, say about 500.degree. C., of 
producing polymers of sufficient melt indices. This is interpreted to mean 
that such catalyst is distinguished in nature from the Phillips catalysts 
noted above. 
In the practice of the process contemplated under the invention, the 
catalyst may be incorporated into the reaction system by either one of the 
following sequences. 
a) Separate addition of individual components I, II and III. 
b) Contact of components II and III and subsequent addition independently 
of component I. 
c) Contact of components I and II and subsequent addition independently of 
component III. 
d) Contact of components I and III and subsequent addition independently of 
component II. 
e) Admixing components II and III and subsequent contact with component I 
prior to addition. 
The last sequence e) is most preferred. In all the cases components II and 
III are dissolved in an aliphatic, alicyclic or aromatic hydrocarbon 
solvent such as pentane, hexane, heptane, cyclohexane, methylcyclohexane, 
benzene, toluene, xylene or the like. Typified is an aliphatic or 
alicyclic hydrocarbon solvent. 
According to the process of the invention, ethylene is homopolymerized or 
copolymerized with a given comonomer. In examples of suitable comonomers 
are included .alpha.-olefins of a carbon number of 3 to 12, preferably 3 
to 6, such as propylene, 1-butene, 1-pentene, 4-metylpentene-1, 1-hexene 
and the like. The content of a polyolefin other than polyethylene should 
not exceed 10% by mol in the final copolymer. 
The process of the invention is designed to suit slurry, solution and gas 
phase polymerizations among which slurry and gas phase modes of reaction 
are typified. Gas phase polymerization is particularly preferred which is 
accomplished in a substantially oxygen-free, water-free state and in the 
presence of or in the absence of an inert solvent. Suitable solvents may 
be chosen from aliphatic hydrocarbons such as hexane, heptane and the 
like, alicyclic hydrocarbons such as cyclohexane, methylcyclohexane and 
like and aromatic hydrocarbons such as benzene, toluene, xylene and the 
like. Polymerization conditions are at a temperature of 20.degree. to 
200.degree. C., preferably 50.degree. to 100.degree. C., at a pressure of 
atmospheric to 70 kg/cm.sup.2 G, preferably atmospheric to 20 kg/cm.sup.2 
G, and for a length of time of 5 minutes to 10 hours, preferably 5 minutes 
to 5 hours. These conditions should strictly be observed to preclude 
prolonged time of reaction and increased polymer of low molecular weight. 
The molecular weight of a polymer to be formed may be controlled by feeding 
a predetermined amount of hydrogen into the reaction system. With 
efficiency and accuracy in view, it is more preferable to use hydrogen 
than varying the polymerization temperature or catalyst proportion. It has 
also been found that the catalyst according to the invention is 
acceleratively activable on contact with the hydrogen charged, whereby 
molecular weight regulation and catalytic activity buildup are 
concurrently attainable. The catalyst may be pretreated with hydrogen, 
where desired, at from 25.degree. to 100.degree. C. and at from 0.5 to 10 
kg/cm2G for from 10 to 60 minutes.

The invention will be further described by way of the following examples 
which are provided for purposes of illustration only. 
TEST METHODS 
Different polyethylenes provided in the examples were examined for melt 
index, flow parameter and melt tension under the conditions given below 
and with the results tabulated below. 
Melt Index (MI) 
ASTM D-1238-57T was followed with temperature: 190.degree. C. and loads: 
2.16 kg, MI.sup.2.16, and 21.6 kg, MI.sup.21.6. 
Flow Parameter (FP) 
Flowability was determined from the equation, log MI.sup.21.6 /MI2.16. The 
larger numerical value, the wider the molecualr weight distribution. 
Melt Tension (MT) 
On a melt tension tester (Toyo Seki Co.) the polymer melted at 190.degree. 
C. in a cylinder (inside diameter: 9.55 mm) was extruded into a stranded 
form at a piston descent speed of 20 mm/min through an orifice (aperture: 
2.10 mm, length 8.00 mm), followed by take-up on to a roll (outside 
diameter: 5.0 cm). Melt tension was expressed by the stress (g) required 
for the strand to be rolled at 100 rpm. In the case of scission prior to 
arrival at 100 rpm, the stress was determined at that time. 
Preparation of Catalyst Components 
Catalyst Component A 
Twenty (20) grams of silica (Grade 952, Fuji-Davison Co.) was vacuum-dried 
at 300.degree. C. for 3 hours and then immersed in a solution of 0.8 g of 
chromium trioxide in 100 ml of pure water. The mixture was stirred at room 
temperature for one hour, followed by removal of water at 120.degree. C. 
in a nitrogen atmosphere and by vacuum drying at 120.degree. C. for 10 
hours. Calcination was effected at 500.degree. C. for 5 hours in a 
fluidized bed and in an oxygen stream after which a catalyst component was 
provided. The component was stored in a nitrogen atmosphere. 
Catalyst Component B 
The method for Catalyst Component A was followed except that the 
calcination temperature was elevated to 800.degree. C. 
Catalyst Component C 
The method for Catalyst Component A was followed except that 1.9 g of 
chromium acetate was used in place of chromium trioxide and that 
calcination was done at 600.degree. C. 
Catalyst Component D 
The same amount of the same silica as in Catalyst Component A was 
vacuum-dried at 300.degree. C. for 3 hours and put into a 300-ml 
three-neck flask, followed by addition of 150 ml of anhydrous hexane and 
then 0.9 g of tert-butyl chromate. The mixture was stirred at room 
temperature for one hour, and excess hexane was removed at 80.degree. C. 
in a nitrogen atmosphere. Vacuum drying was thereafter done at 80.degree. 
C. and calcination at 600.degree. C. for 5 hours in a fluidized bed with 
dry air being streamed. The resulting catalyst component was stored in a 
nitrogen atmosphere. 
Preparation of Modified Aluminum Compound 
To 50 ml of a solution of tri-iso-butylaluminum (1 mmol/ml) in hexane was 
added with ice cooling a total ot 0.9 ml of nitrogen-blown, oxygen-purged, 
purified water (H.sub.2 O:Al=1:1), every 20 .mu.l, over 10 minutes. The 
resulting solution was reacted at room temperature for 30 minutes to 
thereby give a transparent, homogeneous hexane solution. 
Preparation of R.sub.n.sup.1 Al(OR.sup.2).sub.3-n Compound 
An (iso-C.sub.4 H.sub.9).sub.2 AlO-iso-C.sub.3 H.sub.7 compound was 
prepared in modified form. To 50 ml of a solution of tri-isobutylaluminum 
(1 mmol/ml) in hexane was added with ice cooling a total of 3.8 ml of 
anhydrous iso-propanol (iso-C.sub.4 H.sub.9 :Al=1:1), every 20 .mu.l, over 
20 minutes. Subsequent reaction at room temperature for 30 minutes gave a 
transparent, homogeneous hexane solution. 
EXAMPLE 1 
A 3-liter stainless steel autoclave equipped with a stirrer was replaced 
with nitrogen and charged with 1,500 ml of hexane, 80 mg of Catalyst 
Component A, 1 mmol of a modified aluminum compound and 0.5 mmol of an 
R.sub.n.sup.1 Al(OR.sup.2).sub.3-n compound, the latter two compounds 
having been prepared above. The mixture was heated with stirring at 
80.degree. C. so that the reaction system was raised to 1.5 kg/cm.sup.2 G 
with the vapor pressures of nitrogen and hexane. Hydrogen was fed at 4.3 
kg/cm.sup.2 G and ethylene at a total pressure of 10 kg/cm.sup.2 G. 
Polymerization was initiated and continued for one hour with the total 
pressure maintained at 10 kg/cm.sup.2 G by a successive feed of ethylene. 
The reaction mixture after being purged of excess monomer was cooled and 
dried to obtain 171 g of polyethylene. 
The polymer showed an MI of 0.36 g/10 min, an FP of 2.1 and an MT of 16 g. 
EXAMPLES 2 and 3 
The procedure of Example 1 was followed except that the amount of 
(iso-C.sub.4 H.sub.9).sub.2 AlO-iso-C.sub.3 H.sub.7 was varied. 
EXAMPLES 4 and 5 
The procedure of Example 1 was followed except that hydrogen was charged in 
varied concentrations. 
EXAMPLE 6 
The procedure of Example 1 was followed except that Catalyst Component B 
was substituted for Catalyst Component A. 
EXAMPLE 7 
The procedure of Example 1 was followed except that Catalyst Component C 
was used. 
EXAMPLE 8 
The procedure of Example 1 was followed except that Catalyst Component D 
was used. 
EXAMPLE 9 
The procedure of Example 1 was followed except that Catalyst Component C 
was used and that the modified aluminum compound and (iso-C.sub.4 
H.sub.7).sub.2 AlO-iso-C.sub.3 H.sub.7 were added in varied amounts. 
EXAMPLE 10 
The procedure of Example 1 was followed except that the polymerization 
temperature was elevated to 90.degree. C. 
EXAMPLE 11 
The procedure of Example 1 was followed except that (iso-C.sub.4 
H.sub.9).sub.2 AlO-iso-C.sub.3 H.sub.7 was replaced with a reaction 
product of Al(C.sub.2 H.sub.5).sub.2 and Al(O-sec-C.sub.4 H.sub.9).sub.3. 
EXAMPLE 12 
The procedure of Example 1 was followed except that (C.sub.2 H.sub.5).sub.2 
AlOC.sub.2 H.sub.5 was used in place of (iso-C.sub.4 H.sub.9).sub.2 
AlO-iso-C.sub.3 H.sub.7. 
EXAMPLE 13 
The procedure of Example 1 was followed except that a reaction product of 
Al(iso-C.sub.4 H.sub.9).sub.3 and tert-C.sub.4 H.sub.9 OH, (iso-C.sub.4 
H.sub.9).sub.2 AlO-tert-C.sub.4 H.sub.9, was substituted for (iso-C.sub.4 
H.sub.9).sub.2 AlO-iso-C.sub.3 H.sub.7. 
EXAMPLE 14 
The procedure of Example 1 was followed except that diethyl 
mono-2-ethylhexyloxyaluminum obtained by reacting Al(C.sub.2 
H.sub.5).sub.2 with 2-ethylhexanol was used in place of (iso-C.sub.4 
H.sub.9).sub.2 AlO-iso-C.sub.3 H.sub.7. 
EXAMPLE 15 
The procedure of Example 1 was followed except that (iso-C.sub.4 
H.sub.9).sub.2 AlO-iso-C.sub.3 H.sub.7 was replaced with (C.sub.2 
H.sub.5).sub.2 Al(OC.sub.6 H.sub.5) derived by reacting Al(C.sub.2 
H.sub.5).sub.3 with phenol. 
COMATIVE EXAMPLE 1 
The procedure of Example 1 was followed except that the modified aluminum 
compound was omitted. Because the resulting polymer was negligibly small 
in MI, the FP quality was not determinable. 
COMATIVE EXAMPLE 2 
The procedure of Example 1 was followed except that the R.sub.n.sup.1 
Al(OR.sup.2).sub.3-n compound was omitted. 
COMATIVE EXAMPLE 3 
The procedure of Example 1 was followed except that unmodified 
Al(iso-C.sub.4 H.sub.9).sub.3 was used and that the amount of (iso-C.sub.4 
H.sub.9).sub.2 AlO-iso-C.sub.3 H.sub.7 was halved. The polymer obtained 
was found too high in MI and hence impossible of MT measurement. 
EXAMPLE 16 
Catalyst Component A was contacted with (iso-C.sub.4 H.sub.9).sub.2 
Al(AlO-iso-C.sub.3 H.sub.7)at room temperature, followed by charge into 
the reaction system independently of the modified aluminum compound. 
Polymerization was carried out as was in Example 1, the details as regards 
the catalyst composition and polymer quality being tabulated. 
EXAMPLE 17 
Catalyst Component A was contacted with the modified aluminum compound at 
room temperature and then added to the system separately of (iso-C.sub.4 
H.sub.9).sub.2 AlO-iso-C.sub.3 H.sub.7. 
EXAMPLE 18 
The modified aluminum compound was admixed with the (iso-C.sub.4 
H.sub.9).sub.2 AlO-iso-C.sub.3 H.sub.7 compound at room temperature to 
thereby give a mixed solution with which Catalyst Component A was then 
contacted. The catalyst thus pretreated was charged into the system. 
Example 19 
The procedure of Example 18 was followed except that the amount of 
(iso-C.sub.4 H.sub.9).sub.2 AlO-iso-C.sub.3 H.sub.7 was varied and that 
Catalyst Component D was substituted for Catalyst Component A. 
TABLE 
__________________________________________________________________________ 
Catalyst component (I) 
modified 
calcina- organo- R.sub.n.sup.1 Al(OR.sup.2).sub.3-n 
II/III 
Cr tion temp 
amount 
aluminum (II) 
(III) (mol 
run type 
(wt %) 
(.degree.C.) 
(mg) 
(mmol) (mmol) ratio) 
__________________________________________________________________________ 
Example 
1 
A 2 500 80 1 0.5 2 
2 
A 2 500 80 1 0.25 4 
3 
A 2 500 80 1 1 1 
4 
A 2 500 80 1 0.5 2 
5 
A 2 500 80 1 0.5 2 
6 
B 2 800 80 1 0.5 2 
7 
C 2 600 80 1 0.5 2 
8 
D 1 600 80 1 0.5 2 
9 
C 2 600 80 2 1 2 
10 
A 2 500 80 1 0.5 2 
11 
A 2 500 80 1 0.5 2 
12 
A 2 500 80 1 0.5 2 
13 
A 2 500 80 1 0.5 2 
14 
A 2 500 80 1 0.5 2 
15 
A 2 500 80 1 0.5 2 
Comparative 
Example 
1 
A 2 500 80 1 -- -- 
2 
A 2 500 80 1 1 -- 
3 
A 2 500 80 1 (unmodified) 
0.25 4 
Example 
16 
A 2 500 80 1 1 1 
17 
A 2 500 80 1 1 1 
18 
A 2 500 80 1 1 1 
19 
D 1 600 80 1 0.5 2 
__________________________________________________________________________ 
Al/Cr 
polymerization 
activity 
(atomic 
temp 
H.sub.2 
time 
yield 
(g/g .multidot. catalyst .multidot. 
MI MT 
run ratio) 
(.degree.C.) 
(vol %) 
(hr) 
(g) 
hr .multidot. pressure) 
(g/10 min) 
FP (g) 
__________________________________________________________________________ 
Example 
1 
49 80 50 1 103 
300 0.36 2.1 
16 
2 
41 80 50 1 114 
330 0.31 2.1 
16 
3 
65 80 50 1 110 
320 0.29 2.1 
18 
4 
49 80 10 1 233 
380 0.11 2.3 
25 
5 
49 80 25 1 184 
360 0.20 2.2 
19 
6 
49 80 50 1 100 
290 0.68 2.4 
10 
7 
49 80 50 1 120 
350 0.53 2.2 
12 
8 
49 80 50 1 124 
360 0.50 2.2 
13 
9 
98 80 50 1 127 
370 0.50 2.2 
13 
10 
49 90 50 1 120 
350 0.72 2.0 
10 
11 
49 80 50 1 86 
250 0.40 2.3 
14 
12 
49 80 50 1 68 
200 0.31 2.5 
16 
13 
49 80 50 1 103 
300 0.29 2.2 
18 
14 
49 80 50 1 96 
280 0.32 2.2 
16 
15 
49 80 50 1 82 
240 1.43 2.2 
14 
Comparative 
Example 
1 
49 80 50 1 93 
270 0.001 -- 70 
2 
49 80 50 1 21 
60 0.10 2.4 
20 
3 
41 80 50 1 30 
75 10 2.6 
-- 
Example 
16 
65 80 50 1 50 
150 0.51 2.0 
13 
17 
65 80 50 1 60 
180 0.05 2.4 
35 
18 
65 80 50 1 131 
390 0.30 2.2 
18 
19 
49 80 50 1 134 
400 0.48 2.2 
13 
__________________________________________________________________________