Catalysts effective for the polymerization of olefins at high productivity formed upon mixing (1) a solution of titanium tetrahydrocarbyloxide or a zirconium tetrahydrocarbyloxide and an organoaluminum halide with (2) a dihydrocarbylmagnesium compound alone or admixed with a minor amount of a trialkylaluminum and (3) combining the product obtained in (2) with a metal halide selected from a silicon tetrahalide and a titanium tetrahalide. The catalyst component thus produced can be combined with an organoaluminum compound as a cocatalyst component.

BACKGROUND OF THE INVENTION 
The invention relates to a composition of matter, a method of preparing 
same, catalyst, a method of producing a catalyst and a process of using 
the catalyst. In another aspect, this invention relates to a particularly 
effective ethylene polymerization catalyst and process. 
In the production of polyolefins such as, for example, polyethylene, 
polypropylene, ethylene-butene copolymers, etc., an important aspect of 
the various processes and catalysts used to produce such polymers is the 
productivity. By productivity is meant the amount or yield of solid 
polymer that is obtained by employing a given quantity of catalyst. If the 
productivity is high enough, then the amount of catalyst residues 
contained in the polymer is low enough that the presence of the catalyst 
residues does not significantly affect the properties of the polymer and 
the polymer either does not require additional processing or less 
processing is needed to remove the catalyst residues. As those skilled in 
the art are aware, removal of catalyst residues from polymer is an 
expensive process and it is very desirable to employ a catalyst which 
provides sufficient productivity so that catalyst residue removal is not 
necessary or at least substantially reduced. 
In addition, high productivities are desirable in order to minimize 
catalyst costs. Therefore, it is desirable to develop new and improved 
catalysts and polymerization processes which provide improved polymer 
productivities. 
Accordingly, the object of the invention is to provide a catalyst. 
Another object of the invention is to provide a polymerization process for 
using a catalyst capable of providing improved polymer productivities as 
compared to prior art catalysts. 
Other objects, aspects, and the several advantages of this invention will 
be apparent to those skilled in the art upon a study of this disclosure 
and the appended claims. 
SUMMARY OF THE INVENTION 
In accordance with the invention, an active catalyst effective for the 
polymerization of olefin monomers at high productivity is formed upon 
mixing (1) a solution of a titanium tetrahydrocarbyloxide or a zirconium 
tetrahydrocarbyloxide and an organoaluminum halide with (2) a 
dihydrocarbylmagnesium compound, alone or admixed with a minor amount of a 
trialkylaluminum, and (3) combining the product obtained in (2) with a 
metal halide selected from among a silicon tetrahalide and a titanium 
tetrahalide. 
In accordance with one embodiment, a polymerization catalyst is prepared by 
(1) forming a solution of an alkyl aluminum chloride and a titanium 
alkoxide or a zirconium alkoxide, 
(2) treating (1) with a dialkylmagnesium compound alone or admixed with a 
minor amount of a trialkylaluminum compound, and 
(3) treating (2) with titanium tetrachloride or silicon tetrachloride. The 
catalyst (3) is used with aluminum alkyls to polymerize ethylene. 
Further, in accordance with the invention, a method for producing the above 
compositions is provided. 
Further, in accordance with the invention, a catalyst is provided which 
forms on mixing the above composition of matter and an organoaluminum 
compound as a co-catalyst component. 
Further, in accordance with the invention, aliphatic monoolefins are 
homopolymerized or copolymerized with other 1-olefins, conjugated 
diolefins, monovinylaromatic compounds and the like under polymerization 
conditions employing the catalysts described above. 
Further, in accordance with the invention, the above-described catalyst is 
prepared by mixing together a titanium tetrahydrocarbyloxide compound or a 
zirconium tetrahydrocarbyloxide compound and an organoaluminum halide 
compound in a suitable solvent to produce a first catalyst component 
solution; a second catalyst component comprising a dihydrocarbylmagnesium 
compound is added under suitable conditions to the above-described first 
catalyst component solution in a manner so as to avoid a significant 
temperature rise in the solution to produce a solid composition in a form 
of a slurry with the solvent; the composition thus formed is then treated 
with a silicon tetrahalide or titanium tetrahalide; and excess titanium or 
silicon tetrahalide compound is removed from the resulting composition, 
for example, washed with a hydrocarbon compound and dried to form an 
active catalyst component which can then be combined with a co-catalyst 
component comprising an organoaluminum compound. 
DETAILED DESCRIPTION OF THE INVENTION 
Suitable titanium tetrahydrocarbyloxide compounds employed in step (1) 
include those expressed by the general formula 
EQU Ti(OR).sub.4 
wherein each R is a hydrocarbyl radical individually selected from an 
alkyl, cycloalkyl, aryl, alkaryl, and aralkyl hydrocarbon radical 
containing from about 1 to about 20 carbon atoms per radical and each R 
can be the same or different. Titanium tetrahydrocarbyloxides in which the 
hydrocarbyl group contains from about 1 to about 10 carbon atoms per 
radical are most often employed because they are more readily available. 
Suitable titanium tetrahydrocarbyloxides include, for example, titanium 
tetramethoxide, titanium tetraethoxide, titanium tetra-n-butoxide, 
titanium tetrahexyloxide, titanium tetradecyloxide, titanium 
tetraeicosyloxide, titanium tetracyclohexyloxide, titanium 
tetrabenzyloxide, titanium tetra-p-tolyloxide, titanium tetraisopropoxide 
and titanium tetraphenoxide and mixtures thereof. Titanium tetraethoxide 
or titanium tetraisopropoxide is presently preferred because of especial 
efficacy in the process. 
Catalysts derived from titanium tetraethoxide are very active and yield 
polymer at high productivity rates having a narrow molecular weight 
distribution. Catalysts derived from titanium tetraiisopropoxide are less 
active but produce polymers exhibiting a broad molecular weight 
distribution. 
Suitable zirconium tetrahydrocarbyloxide compounds include those 
represented by the formula 
EQU Zr(OR).sub.4.nR.sup.4 OH 
wherein R is as defined before, n is in the range of 0 to 2 and R.sup.4 OH 
represents an alcohol, preferably an alkanol having 1-10 carbon atoms. 
Generally, the radicals R and R.sup.4 are the same in the alcohol solvated 
tetrahydrocarbyloxides. Examples of suitable zirconium compounds are 
zirconium tetramethoxide, zirconium tetraethoxide, zirconium 
tetraisopropoxide isopropanol 1:1 molar complex, zirconium 
tetradecyloxide, zirconium tetraeicosyloxide, zirconium 
tetracyclohexyloxide, zirconium tetrabenzyloxide, zirconium 
tetra-p-tolyloxide and zirconium tetraphenoxide and mixtures thereof. 
The titanium alkoxide can be employed in a form complexed with an alcohol, 
i.e., in the form Ti(OR).sub.4.nR.sup.4 OH, wherein R.sup.4 OH again is an 
alcohol, preferably an alkanol with 1-10 carbon atoms. 
Ti(OR).sub.4 and Zr(OR).sub.4 alkoxides can be made by reacting the 
corresponding tetrachloride, e.g., TiCl.sub.4, with an alcohol, e.g., an 
alkanol having 1-10 carbon atoms, in the presence of a HCl acceptor such 
as NH.sub.3 as shown below; e.g.: 
EQU TiCl.sub.4 +4EtOH+4NH.sub.3 --Ti(OEt).sub.4 +4NH.sub.4 Cl 
EQU ZrCl4+4BuOH+4NH.sub.3 --Zr(OBu).sub.4 +4NH.sub.4 Cl 
EQU (Et=--C.sub.2 H.sub.5, Bu=--n--C.sub.4 H.sub.9) 
If an excess of the alcohol is present, then the product alkoxide can be 
solvated with the alcohol. The alcohol is easier to remove from the 
solvated Ti(OR).sub.4 than the solvated Zr(OR).sub.4. Thus, in complexes 
containing alcohols, it is desirable or essential that the alcohol 
complexed is the same used in preparing the alkoxide as shown above. 
The lower Ti alkoxides such as titanium tetraisopropoxide, Ti(O-i-C.sub.3 
H.sub.7).sub.4, can react with a higher alcohol to form the corresponding 
alkoxide, e.g., Ti(O-i C.sub.3 H.sub.7).sub.4 +4BuOH--Ti(OBu.sub.4 
+4i-C.sub.3 H.sub.7 OH. If the zirconium alkoxides react similarly, then 
the alcohol solvated complexes must be tied to the alcohol used in their 
preparation as shown in the two equations above. 
Mixtures of the hydrocarbyloxides of titanium and zirconium can also be 
employed. However, no advantage in productivity appears to be gained from 
doing this. It is presently preferred to use either the titanium or the 
zirconium compound alone in preparing the catalyst and most preferably a 
titanium compound because of its cheaper cost and efficacy in the catalyst 
system. 
A second catalyst component used in step (1) is generally an organoaluminum 
halide compound which includes, for example, dihydrocarbylaluminum 
monohalides of the formula R.sub.2 AlX, monohydroxycarbylaluminum 
dihalides of the formula RAlX.sub.2, and hydrocarbylaluminum sesquihalides 
of the formula R.sub.3 Al.sub.2 X.sub.3 wherein each R in the above 
formulas is as defined before and each X is a halogen atom and can be the 
same or different. Some suitable organoaluminum halide compounds include, 
for example, methylaluminum dibromide, ethylaluminum dichloride, 
ethylaluminum diiodide, isobutylaluminum dichloride, dodecylaluminum 
dibromide, dimethylaluminum bromide, diethylaluminum chloride, 
diisopropylaluminum chloride, methyl-n-propylaluminum bromide, 
di-n-octylaluminum bromide, diphenylaluminum chloride, 
dicyclohexylaluminum bromide, dieicosylaluminum chloride, methylaluminum 
sesquibromide, ethylaluminum sesquichloride, ethylaluminum sesquiiodide, 
and the like. Polyhalided compounds are preferred. 
The molar ratio of the titanium tetrahydrocarbyloxide compound or zirconium 
tetrahydrocarbyloxide compound to the organoaluminum halide compound can 
be selected over a relatively broad range. Generally, the molar ratio is 
within the range of about 1:5 to about 5:1. The preferred molar ratios are 
within the range of about 1:2 to about 2:1. 
A titanium tetrahydrocarbyloxide compound or zirconium 
tetrahydrocarbyloxide compound and organoaluminum halide compound are 
normally mixed together in a suitable solvent or diluent which is 
essentially inert to these compounds and the product produced. By the term 
"inert" is meant that the solvent does not chemically react with the 
dissolved components such as to interfere with the formation of the 
product or the stability of the product once it is formed. Such solvents 
or diluents include hydrocarbons, for example, paraffinic hydrocarbons 
such as n-pentane, h-hexane, n-heptane, cyclohexane, and the like and 
monocyclic and alkyl-substituted monocyclic aromatic hydrocarbons such as 
benzene, toluene, the xylenes, and the like. Polymers produced with 
catalysts prepared from an aromatic solvent and titanium 
tetraiisopropoxide show broader molecular weight distributions, based on 
higher HLMI/MI values, than polymers made with an aromatic 
solvent-titanium tetraiisopropoxide-titanium tetraethoxide system. The 
tetraiisopropoxide is more soluble in an aromatic solvent than a paraffin, 
hence such a solvent is preferred in producing that invention catalyst. 
The nature of the solvent employed is, therefore, related to the type of 
metal hydrocarbyloxide employed. Generally, the amount of solvent or 
diluent employed can be selected over a broad range. Usually the amount of 
solvent or diluent is within the range of about 10 to about 30 g per gram 
of titanium tetrahydrocarbyloxide. 
The temperature employed during the formation of the solution of the two 
components of step (1) can be selected over a broad range. Normally a 
temperature within the range of about 0.degree. C. to about 100.degree. C. 
is used when solution is formed at atmospheric pressure. Obviously, 
temperatures employed can be higher if the pressure employed is above 
atmospheric pressure. The pressure employed during the solution-forming 
step is not a significant parameter. At atmospheric pressure good results 
are obtained from about 20.degree.-30.degree. C. and are presently 
preferred. 
The solution of titanium compound or zirconium compound and organoaluminum 
halide compound formed in step (1) is then contacted with a 
dihydrocarbylmagnesium compound alone or admixed with a minor amount of a 
trialkylaluminum. The organomagnesium compound can be expressed as 
MgR".sub.2 in which R" can be the same or different and each is a 
hydrocarbyl group such as alkyl, cycloalkyl, aryl, aralkyl, and alkaryl 
containing from one to about 12 carbon atoms wherein presently preferred 
compounds are dialkylmagnesium compounds in which alkyl group contains 
from 1 to about 6 carbon atoms. Specific examples of suitable compounds 
include dimethylmagnesium, diethylmagnesium, and 
n-butyl-sec-butylmagnesium, di-n-pentylmagnesium, didodecylmagnesium, 
diphenylmagnesium, dibenzylmagnesium, dicyclohexylmagnesium and the like 
and mixtures thereof. 
The molar ratio of tetravalent titanium compound employed in step (1) to 
organomagnesium compound used in step (2) can range from about 5:1 to 
about 1:2, preferably, from about 3:1 to about 1:1. 
The trialkylaluminum compound can be expressed as AlR'.sub.3 in which R' is 
an alkyl group containing from one to about 12 carbon atoms. Specific 
examples of suitable compounds include trimethylaluminum, 
triethylaluminum, tri-n-butylaluminum, tridodecylaluminum, and the like 
and mixtures thereof. By a minor amount in association with the 
dihydrocarbylmagnesium compound is meant from about 1 to about 25 mole 
percent trialkylaluminum. 
The product formed after addition of organomagnesium compound in step (2) 
is treated with a metal halide selected from silicon tetrahalide or 
titanium tetrahalide, preferably, titanium tetrachloride. 
In step (3) the molar ratio of titanium tetrahalide to the combined moles 
of components of step (2) products can range from about 10:1 to about 
0.5:1, preferably, from about 2:1 to about 1:1. 
After addition of titanium tetrahalide to the other catalyst components the 
product formed can be recovered by filtration, decantation, and the like. 
The product is preferably washed with a suitable material such as a 
hydrocarbon, for example, n-pentane, n-heptane, cyclohexane, benzene, 
xylenes, and the like to remove soluble material and excess titanium 
compound which may be present. Product can then be dried and stored under 
any inert atmosphere. The products formed in this manner can be designated 
as catalyst A which can subsequently be combined with a co-catalyst B. 
Co-catalyst component B is a metallic hydride or organometallic compound 
wherein said metal is selected from Periodic Groups IA, IIA, IIIA of the 
Mendeleev Periodic Table. The preferred compound to be used as component B 
is an organoaluminum compound which can be represented by the formula 
AlY.sub.b R"'.sub.3-b in which R'" is the same or different and is a 
hydrocarbon radical selected from such groups as alkyl, cycloalkyl, aryl, 
alkaryl, aralkyl, alkenyl and the like having from 1 to about 12 carbon 
atoms per molecule, Y is a monovalent radical selected from among the 
halogens and hydrogen, and b is an integer of 0 to 3. Specific examples of 
organoaluminum compounds include trimethylaluminum, triethylaluminum, 
triisobutylaluminum, tridodecylaluminum, tricyclohexylaluminum, 
triphenylaluminum, tribenzylaluminum, triisopropenylaluminum, 
diethylaluminum chloride, diisobutylaluminum hydride, ethylaluminum 
dibromide, and the like. 
The amount of cocatalyst (component B) employed with the catalyst 
(component A) during polymerization can vary rather widely from about 0.02 
mmole per liter reactor contents to about 10 mmole per liter reactor 
contents. However, particularly good results are obtained at a more 
preferred range of about 0.07 mmole per liter reactor contents to about 
2.5 mmole per liter reactor contents. 
The polymerization process can be effected in a batchwise or in a 
continuous fashion by employing any conventional mode of contact between 
the catalyst system and the monomer or monomers. Thus the monomer can be 
polymerized by contact with the catalyst system in solution, in 
suspension, or in gaseous phase at temperatures ranging from about 
20.degree.-200.degree. C. and pressures ranging from about atmospheric to 
about 1,000 psia (6.9 MPa). The polymerization process can be conducted 
batchwise such as in a stirred reactor or continuously such as in a loop 
reactor under turbulent flow conditions sufficient to maintain the 
catalyst in suspension. A variety of polymerizable compounds are suitable 
for use in the process of the present invention. Olefins which can be 
polymerized or copolymerized with the invention catalyst include aliphatic 
mono-1-olefins. While the invention would appear to be suitable for use 
with any aliphatic monoolefin, olefins having 2 to 8 carbon atoms are most 
often used and ethylene is particularly preferred. 
The ethylene polymers produced are normally solid ethylene homopolymers or 
polymers prepared by copolymerizing ethylene alone or in combination with 
at least one aliphatic 1-olefin containing from 3 to about 10 carbon atoms 
or a conjugated acyclic diolefin containing 4 or 5 carbon atoms. In such 
polymers, the ethylene can range from about 80 to 100 mole percent. The 
polymers can be converted into various useful items including films, 
fibers, pipe, containers, and the like by employing conventional plastics 
fabrication equipment. 
It is especially convenient when producing ethylene polymers to conduct the 
polymerization in the presence of a dry hydrocarbon diluent inert in the 
process such as isobutane, n-heptane, methylcyclohexane, benzene, and the 
like at a reactor temperature ranging from about 60.degree. C. to about 
110.degree. C. and a reactor pressure ranging from about 250 to about 600 
psia (1.7-4.1 MPa). In such a process, particle form polymerization, the 
polymer is produced as discrete solid particles suspended in the reaction 
medium. The polymer can be recovered, can be treated to deactivate and/or 
remove catalyst residues, can be stabilized with an antioxidant system, 
and can be dried, all as known in the art to obtain the final product. 
Also, molecular weight controls such as hydrogen can be employed in the 
reactor as is known in the art to adjust the molecular weight of the 
product, if desired.

EXAMPLE I 
Catalyst Preparation 
Generally, each catalyst was prepared by charging to a stirred 500 mL round 
bottom flask equipped for refluxing, when used, about 300 mL of n-hexane, 
0.035 mole of titanium tetraethoxide [Ti(OEt).sub.4 ] or titanium 
tetraisopropoxide [Ti(O-i-Pr).sub.4 ] and 0.035 mole of ethylaluminum 
dichloride (EADC) as a 25 wt. % solution in n-heptane, all at room 
temperature (23.degree. C.). The solution was stirred and then to it was 
added 0.019 mole of n-butyl-sec-butylmagnesium (MgBu.sub.2) as a 0.637 
molar solution in n-heptane over about a 20 minute period resulting in the 
formation of a slurry. Titanium tetrachloride, 0.192 mole, the halide 
treating agent in this series, was added neat to the slurry and the 
mixture stirred for one hour at room temperature or refluxed at 68.degree. 
C. for one hour as indicated. The catalyst was recovered by allowing the 
slurry to settle, decanting a mother liquor and washing the slurry twice 
with portions of n-hexane and twice with portions of n-pentane. The 
product was dried over a warm water bath and stored in an inert atmosphere 
in a dry box until ready for use. 
EXAMPLE II 
Ethylene polymerization was conducted for 1 hour at 80.degree. C. in a 3.8 
liter stirred, stainless steel reactor in the presence of isobutane 
diluent and 0.92 mole of triethylaluminum (TEA) as cocatalyst. Charge 
order was cocatalyst, catalyst and 2 liters diluent. Ethylene partial 
pressure was 0.69 MPa and total reactor pressure was 2.0 MPa. Ethylene was 
supplied on demand from a pressurized reservoir as required during each 
run. Polymerization was terminated by venting ethylene and diluent. The 
polymer was recovered, dried and weighed to determine yields. Catalyst 
productivity is calculated by dividing polymer weight in grams by catalyst 
weight in grams and is conveniently expressed as kg polymer per g catalyst 
per hour (kg/g/hr). 
The titanium alkoxide used, halide treating temperature employed, mole 
ratios used and results obtained are given in Table 1. 
TABLE 1 
__________________________________________________________________________ 
Halide 
Mole Ratios 
No.Run 
UsedTi(OR).sub.4 
.degree.C.Temp.Treating 
##STR1## 
##STR2## 
##STR3## mgWt.Cat. 
gWt.Polymer 
kg/g/hrProductivityCalculate 
d 
__________________________________________________________________________ 
1.sup.(a) 
Ti(OEt).sub.4 
68 1:1 1.8:1 2:1 0.4 
120 300 
2.sup.(a) 
" " " " " 0.8 
158.sup.(b) 
198 
3 " " " " " 2.7 
434 161 
4.sup.(a) 
" " " " " 0.6 
101 168 
5 " 23 " " " 1.4 
283 202 
6 Ti(O--i-Pr).sub.4 
" " " " 6.4 
44 6.8 
7.sup.(c) 
Ti(OEt).sub.4 
" " " " 1.2 
253 211 
8.sup.(d) 
" " " " " 1.7 
302 178 
__________________________________________________________________________ 
notes: 
.sup.(a) Mixed organometal compounds at 0.degree. C., warmed mixture to 
23.degree. C. and added TiCl.sub.4. 
.sup.(b) Repeated polymerization with a second portion of run 1 catalyst. 
.sup.(c) Mixed organometal compounds at 23.degree. C., allowed solids to 
settle washed them twice with nhexane, added TiCl.sub.4 to washed slurry. 
.sup.(d) Mixed Ti(OR).sub.4 and EADC at 23.degree. C. Heated to 68.degree 
C., added Mg Bu.sub.2, then cooled to 23.degree. C. and added TiCl.sub.4. 
The data show with Ti(OEt).sub.4 -derived catalysts that variations in 
mixing conditions may alter catalyst activity somewhat but that generally 
considerable latitude in said conditions can be tolerated. Thus, 
calculated catalyst productivities of about 200 kg/g/hr in the absence of 
hydrogen at 80.degree. C. is considered to be normal for the invention 
catalyst. 
Poor results are noted with the Ti(O-i-Pr).sub.4 -derived catalyst based on 
one test only and may represent an anomalous result. 
EXAMPLE III 
Control 
A catalyst was prepared in the manner employed for the "standard" catalyst 
of run 5 except that TiCl.sub.4 was omitted from the recipe. Ethylene 
polymerization was conducted at conditions identical to those of Example 
II with a 3.2 mg portion of the catalyst. Only a polymer trace resulted. 
Thus, the presence of a halide treating agent as exemplified by TiCl.sub.4 
is shown to be essential in the catalyst preparation. 
EXAMPLE IV 
Catalysts were prepared using the process employed for the standard 
catalyst except that in one instance ethylaluminum sesquichloride (EASC) 
was used in place of EADC and in the other instance diethylaluminum 
chloride (DEAC) was used in place of EADC. Ethylene polymerization was 
conducted with a portion of each catalyst as before. The results are given 
in Table 2. 
TABLE 2 
__________________________________________________________________________ 
Mole Ratios 
No.Run 
HalideOrganoaluminum 
##STR4## 
##STR5## 
##STR6## mgWt.Cat. 
gWt.Polymer 
kg/g/hrProductivityCal 
culated 
__________________________________________________________________________ 
1 EASC 1.8:1 1:1 2.5:1 1.2 
209 174 
2 DEAC 1.7:1 1.1:1 2.4:1 5.5 
286 52 
__________________________________________________________________________ 
The results show that ethylaluminum sesquichloride is about equivalent to 
ethylaluminum dichloride in preparing the invention catalyst based on the 
calculated productivity but diethylaluminum chloride is not as efficient 
under these conditions as the polyhalide aluminum compounds. Thus, the 
DEAC-derived catalyst only exhibited about 0.3, the activity of the 
EASC-derived catalyst under the same polymerization conditions. 
EXAMPLE V 
A series of catalysts was prepared using the process employed for the 
standard catalyst except that the level of EADC was varied. Ethylene 
polymerization was conducted with a portion of each catalyst as before. 
The results are presented in Table 3. 
TABLE 3 
__________________________________________________________________________ 
Mole Ratios Cat. 
Polymer 
Calculated 
No.Run 
EADCmmoles 
##STR7## 
##STR8## 
##STR9## mg.Wt. 
gWt. 
kg/g/hrProductivity 
__________________________________________________________________________ 
1 0 0 0 3.4:1 1.6 
140 87.5 
2 0.017 
2:1 1:1 2.6:1 4.1 
318 77.6 
3 0.027 
1.3:1 
1.4:1 2.2:1 2.8 
210 75.0 
4* 0.035 
1:1 1.8:1 2:1 1.4 
283 202 
5 0.042 
0.83:1 
2.2:1 1.9:1 5.1 
655 128 
__________________________________________________________________________ 
*same as run 5, Table 1 (standard catalyst) 
The results show that relatively active catalyst results even in the 
absence of EADC (run 1). Runs 2, 3 suggest that catalysts prepared with 
EADC levels below that of the standard catalyst of run 4 are about 
equivalent or slightly poorer in activity than a catalyst prepared in the 
absence of EADC. When the EADC level is increased to about 11/4 times that 
employed in preparing the standard catalyst of run 4 then a catalyst is 
made having about 0.63 times the activity of the standard but still about 
1.5 times better than when no EADC is used. 
EXAMPLE VI 
A catalyst was prepared using the process employed for the standard 
catalyst except that 18 mL of commercial preparation (Magala.sup.R), 
containing dibutylmagnesium (1.026 mg Mg/mL) and TEA (0.173 mmoles Al/mL) 
in hydrocarbon was employed in place of MgBu.sub.2. Ethylene 
polymerization was conducted with a 2.0 mg portion of catalyst as before 
yielding 339 g polyethylene. A calculated catalyst productivity of 169 
kg/g/hr resulted. Thus, an active catalyst is produced having about 0.84 
times the activity of the standard catalyst. This indicates that about 
15-20 mole percent of an organoaluminum compound can be substituted for 
the organomagnesium compound to yield compositions which can be employed 
in preparing active catalysts. 
EXAMPLE VII 
A catalyst was prepared using the process employed for the standard 
catalyst except that 1/2 the level of MgBu.sub.2 was used (0.0095 mmoles 
vs 0.019 mmoles for the standard catalyst) and the halide treatment 
occurred at 68.degree. C. Ethylene polymerization was conducted with a 2.2 
mg portion of the catalyst as before yielding 138 g polyethylene giving a 
calculated catalyst productivity of 62.7 kg/g/hr. The calculated mole 
ratios are: Ti(OEt).sub.4 :EADC=1:1, EADC/MgBu.sub.2 =3.7:1 and TiCl.sub.4 
:combined organometal compounds=2.4:1. Thus, decreasing the level of 
MgBu.sub.2 to 1/2 that normally used decreases catalyst activity to about 
0.3 that of the standard catalyst. 
EXAMPLE VIII 
Several catalysts were prepared using the general process employed for the 
standard catalyst except that the halide agent employed was SiCl.sub.4, 
0.175 moles in one instance and 0.349 moles in the other, instead of the 
0.182 moles of TiCl.sub.4 used in the standard catalyst. Ethylene 
polymerization was conducted as before. The results are given in Table 4. 
TABLE 4 
__________________________________________________________________________ 
Calculated 
Mole Ratios Cat. 
Polymer 
Catalyst 
No.Run 
##STR10## 
##STR11## 
##STR12## mg.Wt. 
gWt. 
kg/g/hrProductivity 
__________________________________________________________________________ 
1 1:1 1.8:1 2.0:1 1.2 
44 36.7 
2 1:1 1.8:1 3.9:1 2.2 
150 68.2 
__________________________________________________________________________ 
The results indicate that catalysts prepared with SiCl.sub.4 instead of 
TiCl.sub.4 do not yield catalysts as active in ethylene polymerization. 
Compared to the results employed with the standard catalyst (run 5, Table 
1), run 1 catalyst shows about 0.2 the activity of the standard catalyst 
and run 2 catalyst shows about 0.3 the activity of the standard catalyst. 
In the following series, ethylene polymerization was conducted in the 3.8 
liter reactor employing a reactor temperature of 100.degree. C., an 
ethylene partial pressure of 1.38 MPa, a hydrogen partial pressure of 
0.345 MPa (unless indicated otherwise), 0.92 mmole of TEA as cocatalyst as 
before (unless indicated otherwise) and 2 liters of isobutane diluent. 
EXAMPLE IX 
A standard catalyst was prepared as described in run 5, Table 1. A 7.0 mg 
portion of it was employed in ethylene polymerization with 0.345 MPa 
hydrogen partial pressure and 3.83 MPa total reactor pressure. A second 
4.8 mg portion of the catalyst was employed in ethylene polymerization 
with 0.827 MPa hydrogen partial pressure and 4.38 MPa total reactor 
pressure. 
A second catalyst was prepared in a variation of the standard catalyst as 
described in run 7, Table 1. A 7.6 mg portion of it was employed in 
ethylene polymerization with 0.414 MPa hydrogen partial pressure and 3.69 
MPa total reactor pressure. 
The results with melt index (MI), high load melt index (HLMI) and HLMI/MI 
ratios are given in Table 5. 
TABLE 5 
______________________________________ 
Calculated 
Catalyst Polymer Properties 
Produc- Bulk 
No.Run 
kg/g/hrtivity 
##STR13## 
MI HLMI 
##STR14## 
g/ccDensity 
______________________________________ 
1 60.3 0.46 0.51 16.5 32 not made 
2 51.5 " 11. 273 25 not made 
3 41.1 0.92 3.0 80.3 27 0.32 
______________________________________ 
MI -- ASTM D 123873, condition E; g/10 minutes, 2160 g total load 
HLMI -- ASTM D 123873, condition F; g/10 minutes, 21,600 g total load 
HLMI/MI -- A ratio which indicates the molecular weight distribution. The 
higher the ratio, the broader the molecular weight distribution and 
greater the shear response of the polymer. 
The results show the invention catalyst to be responsive to hydrogen as the 
melt index values of the polymers show. The polymer bulk density shown in 
run 3 indicates that the polymer "fluff" (as made polymer) can be 
processed in conventional equipment and that commercially useful polymer 
can be made. The HLMI/MI ratios shown are considered to be normal for 
titanium-based catalysts and are relatively narrow molecular weight 
distribution polymers. 
The effect of the hydrogen is to reduce catalyst productivity and decrease 
polymer molecular weight as the hydrogen concentration increases. These 
effects are normal for the titanium-based catalysts. 
EXAMPLE X 
Several catalysts were prepared in this series. One was made by mixing 
about 300 mL of n-hexane, 0.035 mole of Ti(OEt).sub.4 and 18 mL of 
Magala.RTM. at about 23.degree. C. as described in Example VI. To the 
stirred mixture was added 0.211 mole of VOCl.sub.3 and the slurry stirred 
for 1 more hour at about 23.degree. C. The catalyst was recovered as 
before. A 71.5 mg portion was used in ethylene polymerization (run 1, 
Table 6). 
A portion of the catalyst used in run 1, Table 4 was employed as the second 
catalyst. A 15.7 mg portion of it was employed in ethylene polymerization 
(run 2, Table 6). 
In each run, the hydrogen partial pressure was 0.414 MPa and 0.92 mmole TEA 
was used as cocatalyst. The results are shown in Table 6. 
TABLE 6 
______________________________________ 
Calculated 
Catalyst Polymer Property 
No.Run kg/g/hrProductivity 
MI HLMI 
##STR15## 
______________________________________ 
1 1.10 1.05 45 43 
2 28.6 1.9 48 25 
______________________________________ 
The results demonstrate in run 1 that VOCL.sub.3 is not an effective 
substitute for TiCl.sub.4 in preparing active catalysts in this invention 
as the low productivity value obtained clearly shows. On the other hand, 
in this instance, SiCl.sub.4 is seen to give a moderately active catalyst. 
EXAMPLE XI 
Three catalysts were prepared in this series. In (1) about 300 mL of mixed 
xylenes (as commercially sold), 0.035 mole of Ti(O-i-Pr).sub.4 and 0.035 
mole of EADC were mixed together at about 23.degree. C. (room 
temperature). To the stirred mixture at room temperature was added 0.019 
mole of MgBu.sub.2 as before. Finally, 0.182 mole of TiCl.sub.4 was added, 
the mixture was stirred and the catalyst was recovered as before. In (2), 
a mixture containing about 200 mL of mixed xylenes, 5 g (0.011 mole) of a 
1:1 molar complex of Zr(O-i-Pr).sub.4.i-C.sub.3 H.sub.7 OH and 0.017 mole 
of EADC as before. Finally, 0.182 mole of TiCl.sub.4 was added, the 
mixture was stirred and the catalyst was recovered as before. In (3) the 
same procedure was followed as in (2) except that 2.5 g (0.0064 mole) of 
the Zr(O-i-Pr).sub.4.i-C.sub.3 H.sub.7 OH complex and 0.0064 mole of 
Ti(O-i-Pr).sub.4 were employed in place of the complex. 
Ethylene polymerization was conducted as before with a hydrogen partial 
pressure of 0.345 MPa and 0.46 mmole TEA as cocatalyst. A 32.8 mg portion 
of catalyst was used in run 1, 14.3 mg of catalyst 2 used in run 2 and 
12.4 mg of catalyst 3 used in run 3. 
The results are given in Table 7. 
TABLE 7 
______________________________________ 
Calculated Catalyst 
Polymer Productivity 
No.Run 
kg/g/hrProductivity 
MI HLMI 
##STR16## 
______________________________________ 
1 25.3 0.21 9.8 47 
2 8.88 0.13 8.4 65 
3 11.9 0.31 15 48 
______________________________________ 
The results in run 1 suggest that moderately active catalysts can be 
derived from Ti(O-i-Pr).sub.4 when the hydrocarbon reaction medium in 
catalyst preparation in xylene rather than n-hexane as employed for the 
otherwise identical catalyst of run 6, Table 1. In that run, a 
productivity of only about 7 kg/g/hr was obtained compared to about 200 
kg/g/hr for the standard catalyst. In this series the Ti(O-i-Pr).sub.4 
-derived catalyst gave 25.3 kg/g/hr which can be compared with the results 
under identical conditions for the standard catalyst in run 1, Table 5 of 
60.3 kg/g/hr. 
The results in runs 2, 3 indicate that only fairly active catalysts can be 
derived from the zirconium alkoxide-isopropanol complex or the complex 
admixed with an equimolar amount of Ti(O-i-Pr).sub.4. However, in run 2 
with the catalyst derived from the zirconium alkoxide-alkanol complex, the 
polymer produced therewith had a HLMI/MI value of 65, indicative of a 
polymer with a broad molecular weight distribution. 
EXAMPLE XII 
Two catalysts previously described, one in Example VI and the other of run 
1, Table 7, renumbered 1 and 4, respectively in this series, and two new 
catalysts are employed in this series. Catalysts 2, 3 were prepared in the 
general manner described for catalyst 4 in which a mixed xylenes reaction 
medium is used. 
Catalyst 2 was prepared by mixing about 250 mL of mixed xylenes, 0.023 mole 
of Ti(OEt).sub.4, 0.012 mole of Ti(O-i-Pr).sub.4, 0.035 mole of EADC, 
0.019 mole of MgBu.sub.2 and 0.182 mole of TiCl.sub.4. Catalyst 3 was 
prepared by mixing about 250 mL of mixed xylenes, 0.012 mole of 
Ti(OEt).sub.4, 0.023 mole of Ti(O-i-Pr).sub.4, 0.019 mole of MgBu.sub.2 
and 0.182 mole of TiCl.sub.4. 
Ethylene polymerization was conducted as before with a portion of each 
catalyst for 1 hour at 100.degree. C. and 1.38 MPa ethylene partial 
pressure in 2 liters of isobutane and the indicated hydrogen partial 
pressure. In one series, 0.5 mmole TEA was used as cocatalyst along with 
0.34 MPa hydrogen partial pressure. In a second series, 0.4 mmole of 
triisobutylaluminum (TIBA) was used as cocatalyst along with 0.34 MPa 
hydrogen partial pressure. In a third series, DEAC of the indicated 
concentration, was used as cocatalyst along with 0.69 MPa hydrogen partial 
pressure. The results are given in Table 8. 
TABLE 8 
__________________________________________________________________________ 
Titanium Alkoxide Source 
2/3 Ti(OEt).sub.4 
1/3 Ti(OEt).sub.4 
Ti(OEt).sub.4 
1/3 Ti(O--i-Pr).sub.4 
2/3 Ti(O--i-Pr.sub.4) 
Ti(O--i-Pr).sub.4 
__________________________________________________________________________ 
Run No. 1A 1B 1C 1D 
__________________________________________________________________________ 
Cocatalyst 
TEA (0.46) 
TEA (0.46) 
TEA (0.46) 
TEA (0.46) 
(mmole) 
Catalyst (mg) 
5.5 7.3 11.1 7.0 
Productivity 
64.7 41.8 21.4 25.3 
(kg/g/hr) 
MI 1.2 0.53 2.2 0.21 
HLMI/MI 30 29 34 47 
__________________________________________________________________________ 
Run No. 2A 2B 2C 2D 
__________________________________________________________________________ 
Cocatalyst 
TIBA (0.4) 
TIBA (0.4) 
TIBA (0.4) 
TIBA (0.4) 
(mmole) 
Catalyst (mg) 
4.3 7.3 10.5 6.5 
Productivity 
67.9 47.1 71.6 34.6 
(kg/g/hr) 
MI 1.2 1.2 1.1 0.39 
HLMI/MI 28 33 34 53 
__________________________________________________________________________ 
Run No. 3A 3B 3C 3D 
__________________________________________________________________________ 
Cocatalyst 
DEAC (1.3) 
DEAC (2.1) 
DEAC (2.1) 
DEAC (4.2) 
(mmole) 
Catalyst (mg) 
3.5 6.5 13.9 16.9 
Productivity 
61.1 34.6 19.1 3.49 
(kg/g/hr) 
MI 0.21 0.47 0.59 0.98 
HLMI/MI 29 38 54 95 
__________________________________________________________________________ 
The results show that the nature of the titanium alkoxide used in preparing 
the catalyst can profoundly affect the activity of the catalyst as well as 
the molecular weight distribution of the polymer made with the catalyst. 
Thus, titanium tetraiisopropoxide is favored in producing broad molecular 
weight distribution polymers and titanium tetraethoxide is preferred when 
high productivity and narrow molecular weight distribution polymers are 
described.