In accordance with the present invention, there is provided a solid organoaluminoxy product prepared by reacting an organoaluminoxane with an oxygen-containing compound selected from the group consisting of organic peroxide, alkylene oxide, or organic carbonate. Further there is provided olefin polymerization catalyst systems comprising the solid organoaluminoxy product and a transition metal-containing catalyst. Still further there is provided processes for the polymerization of olefins using the catalyst systems.

The present invention relates to solid organoaluminoxy products. The term 
organoaluminoxy as used herein refers to organic compounds having a 
plurality of aluminum atoms each bound to at least two oxygen atoms. In 
another aspect, the present invention relates to a method of modifying 
organoaluminoxanes to make them suitable for use in particle form 
polymerization. In still another aspect, the present invention relates to 
a catalyst system comprising a transition metal-containing catalyst and a 
solid organoaluminoxy product. In still another aspect, the present 
invention relates to a process for polymerizing olefins employing such 
catalyst systems. 
BACKGROUND OF THE INVENTION 
Organoaluminoxanes are known in the art and can be produced by the partial 
hydrolysis of hydrocarbyl aluminum compounds. Such aluminoxanes have been 
found useful in a variety of chemical reactions, including utility as 
cocatalyst components for polymerization catalysts, especially in high 
activity metallocene catalyst systems. Such metallocene catalysts have 
been used in homogeneous solution polymerization. Since such homogeneous 
catalyst systems are soluble in the polymerization medium it is generally 
observed that the resulting polymer has low bulk density. 
Attempts to use metallocene/organoaluminoxane catalyst systems in a slurry 
or particle form type polymerization have not heretofore been found to be 
commercially feasible. It has been observed that when such particle form 
polymerizations are carried out in the presence of a soluble 
metallocene/organoaluminoxane catalyst system, large amounts of polymeric 
material are formed on the surfaces of the polymerization vessel. This 
fouling produces an adverse effect on the heat transfer and also results 
in the need for periodic, if not continuous, cleaning of the reactor. It 
is therefore necessary to have a catalyst system which will not cause 
significant amounts of reactor fouling. 
It is known that a solid form of organoaluminoxane can be obtained by 
treating a commercial organoaluminoxane solution with a countersolvent; 
however, such solids have been found to cause reactor fouling in slurry 
polymerizations. Reactor fouling is still a problem in slurry 
polymerization even when a countersolvent is used to precipitate the 
organoaluminoxane onto an insoluble particulate carrier. 
It would therefore be desirable to produce an economical solid 
organoaluminoxy product useful as a cocatalyst in a polymerization process 
free of reactor fouling. 
SUMMARY OF THE INVENTION 
An object of the present invention is to provide a solid organoaluminoxy 
product useful as a cocatalyst which does not produce significant reactor 
fouling in a particle form polymerization process. 
Another object of the present invention is to provide an efficient and 
economical process for preparing a solid organoaluminoxy product. 
Still another object of the present invention is to provide a 
polymerization catalyst system comprising a transition metal-containing 
catalyst and a solid organoaluminoxy product for use in a particle form 
polymerization process. 
Still another object of the present invention is to provide a 
polymerization process free of significant reactor fouling, especially in 
a particle form polymerization. 
In accordance with the present invention, a process for preparing a solid 
organoaluminoxy product is provided comprising contacting an 
organoaluminoxane and an oxygen-containing compound selected form the 
group consisting of organic peroxides, alkylene oxides, and organic 
carbonates. Other aspects of the present invention include the solid 
organoaluminoxy product thus produced, a catalyst system comprising a 
transition metal-containing catalyst and the solid organoaluminoxy 
product, and a polymerization process employing such catalyst system.

DETAILED DESCRIPTION OF THE INVENTION 
Various techniques are known for making organoaluminoxanes. One technique 
involves the controlled addition of water to a trialkylaluminum. Another 
technique involves combining a trialkylaluminum and a hydrocarbon with a 
compound containing water of adsorption or a salt containing water of 
crystallization. The present invention is considered applicable to any of 
the commercially available organoaluminoxanes. 
Typically the organoaluminoxanes comprise oligomeric, linear and/or cyclic 
hydrocarbyl aluminoxanes having repeating units of the formula 
##STR1## 
Typically the linear aluminoxanes are represented by the formula: 
##STR2## 
The oligomeric, cyclic aluminoxanes can be represented by the formula: 
##STR3## 
wherein each R is a hydrocarbyl radical, preferably an alkyl radical 
containing 1-8 carbon atoms, n is 2 to 50, preferably 4 to 40, m is 3 to 
50, preferably 4 to 40. Generally the aluminoxanes are more active when m 
and n are greater than 4, more preferably 10 to 40. Typically R is 
predominantly methyl or ethyl. Preferably at least about 30 mole percent 
of the repeating groups have an R which is methyl, more preferably at 
least 50 mole percent, and still more preferably at least 70 mole percent. 
Generally in the preparation of an organoaluminoxane, a mixture of linear 
and cyclic compounds is obtained. 
Organoaluminoxanes are commercially available in the form of hydrocarbon 
solutions, generally aromatic hydrocarbon solutions. Typically such 
organoaluminoxane solutions contain trialkylaluminum compounds as well as 
the oligomeric organoaluminoxane. The trialkylaluminum compounds generally 
include those in which the alkyl radicals contain 1 to 8 carbon atoms, 
preferably 1 to 2 carbon atoms. 
Peroxides useful in the invention are represented by the formula 
R.sub.2 OOR.sub.3, 
wherein R.sub.2 and R.sub.3 are individually selected from hydrogen, 
hydrocarbyl, and hydrocarbonyl radicals selected from the group consisting 
of alkyl, cycloalkyl, aryl, alkenyl, and alkynyl radicals containing 1 to 
24 carbon atoms, preferably 1 to 18 carbon atoms and more preferably 1 to 
12 carbon atoms, with the proviso that at least one of R.sub.2 and R.sub.3 
is a hydrocarbyl or hydrocarbonyl radical. Preferably both R.sub.2 and 
R.sub.3 are individually hydrocarbyl radicals. 
Examples of suitable peroxides include diethyl peroxide, diacetyl peroxide, 
tert-butyl hydroperoxide, di-tert-butyl peroxide, 
2,5-dimethyl-(2,5-di(tert-butylperoxy) hexane, tert-amyl hydroperoxide, 
di-tert-amyl peroxide, dibenzoyl peroxide, dicrotonyl peroxide, 
bis(1-methyl-1-phenylethyl) peroxide, dilauryl peroxide, peroxybenzoic 
acid, peroxyacetic acid, tert-butyl perbenzoate, tert-amyl perbenzoate, 
peroxybutyric acid, peroxycinnamic acid, tert-butyl peracetate, and the 
like and mixtures thereof. Excellent results have been obtained with 
di-tert-butyl peroxide and it is preferred. 
Suitable alkylene oxides are represented by the formulas 
##STR4## 
wherein R.sub.4 and R.sub.5 are individually selected from the group 
consisting of hydrogen and alkyl radicals containing 1 to 12 carbon atoms, 
x is 0 to 12, preferably 0 to 8. Examples of suitable alkyl radicals 
include methyl, ethyl, propyl, isobutyl, isoamyl, octyl and decyl. 
Examples of alkylene oxides which are useful include ethylene oxide, 
propylene oxide, 2,2-dimethyloxirane, 1,2-dimethyloxirane, 
1,2-diethyloxirane, cyclohexene oxide, 1-methylcyclohexene oxide, and 
mixtures thereof. 
Other suitable alkylene oxides include glycidyl ethers having the formula 
R'(G).sub.y wherein R' is a hydrocarbyl radical having 2 to 12 carbon 
atoms, y is 1 or 2, and G is the glycidyl group, 
##STR5## 
Examples of suitable glycidyl ethers include glycidyl isopropyl n-butyl 
ether, glycidyl tert-butyl ether, 2,2-dimethyl-1,3-propanediol diglycidyl 
ether, and 1,4-butanediol diglycidyl ether. Alkylene oxides containing a 
total of 2 to 16 carbon atoms are preferred, more preferably 2 to 12 
carbon atoms. Propylene oxide is especially preferred. 
Organic carbonates useful in carrying out the invention are represented by 
the formulas 
##STR6## 
wherein R.sub.6 and R.sub.7 are individually selected from the group 
consisting of hydrogen and alkyl radicals containing 1 to 10 carbon atoms 
and R.sub.8 is a hydrocarbyl radical selected from the group consisting of 
alkyl, cycloalkyl, aryl, aralkyl, and alkaryl radicals having 1 to 12 
carbon atoms. The alkyl radical can be straight chain or branched. 
Examples of suitable alkyl radicals include methyl, ethyl, propyl, 
isobutyl, isoamyl, octyl and decyl. Examples of suitable organic 
carbonates include 1,3-dioxolan-2-one (commonly named ethylene carbonate), 
4-methyl-1,3-dioxolan-2-one (commonly named propylene carbonate), 
4,5-dimethyl-1,3-dioxolan-2-one, 4-(1-butyl)-1,3-dioxolan-2-one, 
4,5-di(1-propyl)-1,3-dioxolan-2-one dimethyl carbonate, diethyl carbonate, 
bis(2-methylallyl) carbonate, dibenzyl carbonate, and diphenyl carbonate, 
and mixtures thereof. Preferred organic carbonates are those wherein the 
carbonyldioxy radical is attached to a terminal carbon atom and the carbon 
adjacent thereto. Propylene carbonate is especially preferred. 
The amount of oxygen-containing compound employed relative to the 
organoaluminoxane is the amount sufficient to produce a solid 
organoaluminoxy product from an aromatic hydrocarbon solution and can vary 
over a wide range depending upon the particular compounds employed and the 
results desired. The molarity of an organoaluminoxane solution can be 
approximated by vacuum stripping the solvent from a known volume of 
aluminoxane solution, weighing the recovered solid, and multiplying the 
weight of the solid in grams per milliliter by 1000 and dividing by the 
average molecular weight of the aluminoxy units, (i.e. 58 for 
methylaluminoxane). It is presumed that the vacuum stripping removes a 
substantial portion of any free trialkylaluminum compound. 
Generally the amount of organoaluminoxane is in the range of from about one 
mole to about 1000 moles per mole of oxygen-containing compound, 
preferably about 2 moles to about 500 moles, and more preferably from 5 
moles to 200 moles per mole of oxygen-containing compound. When employing 
propylene carbonate as the oxygen-containing compound, a particularly 
preferred range is from about 20 moles to about 200 moles of 
organoaluminoxane per mole of propylene carbonate. 
The conditions for contacting the oxygen-containing compound and the 
organoaluminoxane are those sufficient to produce a solid product and can 
vary widely depending upon the particular compounds employed. Generally 
the temperature will be in the range of from about 0.degree. C. to about 
100.degree. C., preferably from about 10.degree. C. to about 100.degree. 
C., and more preferably from 10.degree. C. to 75.degree. C. Generally the 
pressure will be in the range of from about 0 psig to about 100 psig, 
preferable about 0 psig to about 50 psig. The time of reaction will 
generally be in the range of from about 1 minute to about 72 hours, 
preferably about 5 minutes to about 30 hours. 
The reaction of the oxygen-containing compound and the organoaluminoxane 
can be carried out in any suitable manner. Typically the reactants will be 
contacted in a suitable liquid diluent. A preferred technique involves 
contacting a hydrocarbon solution of the aluminoxane with a countersolvent 
to produce a slurry comprising soluble aluminoxane and insoluble 
aluminoxane and then contacting the resulting slurry with a solution of 
the oxygen-containing compound. One example is to mix a toluene solution 
of methylaluminoxane with hexane to form a slurry and then contacting the 
oxygen-containing compound and the slurry. 
It is also within the scope of the present invention to carry out the 
reaction of the oxygen-containing compound and the aluminoxane in the 
presence of a particulate diluent so that the insoluble product becomes 
deposited upon the particulate diluent. Typical particulate diluents 
include such inorganic materials as silica, alumina, aluminum phosphate, 
silica-alumina, titania, kaolin, fumed silica, and the like. 
It is also within the scope of the present invention to prepare the 
inventive solid organoaluminoxy product and then combine it with a 
solution of a trialkylaluminum compound, i.e. trimethylaluminum or others 
of the type mentioned above, and then to contact the resulting slurry with 
additional amount of the oxygen-containing compound. It is believed that 
this process may provide a method for further increasing the molecular 
weight of the solid organoaluminoxy product. The process can be repeated 
several times to obtain the desired level of molecular weight, particle 
size, bulk density, or other characteristic that is desired for a 
particular application. 
In view of the demonstrated activity of the solid organoaluminoxy products 
of the present invention, it is considered that such solid products will 
be suitable as replacements for soluble aluminoxy products in 
polymerization reactions. Accordingly, the inventive solid 
organoaluminoxane products should be suitable as catalyst components with 
any number of the transition metal-containing olefin polymerization 
catalysts that have in the past been employed with soluble aluminoxanes. 
Suitable transition-metal containing catalysts are represented by the 
formula ML.sub.x, wherein M is a Group IVB or VB transition metal, x is 
the valence of the transition metal, and each L is individually selected 
from the group consisting of cyclopentadienyl-type radicals containing 5 
to 20 carbon atoms, hydrocarbyl radicals containing 1 to 12 carbon atoms, 
alkoxy radicals containing 1 to 12 carbon atoms, aryloxy radicals 
containing 6 to 12 carbon atoms, halogen and hydrogen. 
Some examples of such transition metal-containing olefin polymerization 
catalysts are disclosed in U.S. Pat. No. 3,242,099, the disclosure of 
which is incorporated herein by reference. Examples of such transition 
metal-containing catalysts include titanium trichloride, titanium 
tetrachloride, titanium tetrabromide, titanium tetraethoxide, titanium 
tetrabutoxide, titanium tetraiodide, vanadium trichloride, vanadium 
tetrachloride, zirconium trichloride, zirconium tetrachloride, zirconium 
tetraethoxide, zirconium tetrabutoxide, and the like and mixtures thereof. 
In a particular preferred embodiment the transition metal-containing 
catalyst component is a metallocene. Suitable metallocene compounds that 
can be employed include any metallocene compounds known in the art. 
Examples of suitable metallocene compounds, their preparation, and their 
use in polymerization processes are described in detail in U.S. Pat. No. 
5,091,352; 5,057,475; 5,124,418; and EP 524,624 published Jan. 27, 1993, 
the disclosures of which are herein incorporated by reference. 
Metallocene compounds, as used herein, are represented by the formula 
above, ML.sub.x, wherein at least one L is a cyclopentadienyl-type 
radical. Cyclopentadienyl-type radicals, as used herein, include 
unsubstituted cyclopentadienyl, substituted cyclopentadienyl, 
unsubstituted indenyl, substituted indenyl, unsubstituted fluorenyl, and 
substituted fluorenyl. The substituents can be, for example hydrocarbyl 
radicals containing 1 to 12 carbon atoms, alkoxy radicals containing 1 to 
12 carbon atoms, or halogen. Typical hydrocarbyl radicals include methyl, 
ethyl, propyl, butyl, amyl, isoamyl, hexyl, isobutyl, heptyl, octyl, 
nonyl, decyl, cetyl, 2-ethylhexyl, and phenyl, preferably the hydrocarbyl 
radicals are alkyl radicals containing 1 to 10 carbon atoms, and more 
preferably 1 to 6 carbon atoms. The metallocene can contain one, two, 
three or four cyclopentadienyl-type radicals, preferably two. The metal is 
selected from Group IVB or VB transition metals, preferably titanium, 
zirconium, hafnium, and vanadium, and more preferably zirconium. 
It is also within the scope of the present invention to have two of the L 
radicals be cyclopentadienyl-type radicals which are bonded together by a 
suitable bridging radical such as carbon, silicon, germanium, and tin. 
Some examples of such bridged ligands include 
(9-fluorenyl)(cyclopentadienyl) methane, (9-fluorenyl) (cyclopentadienyl) 
dimethyl methane, 1,2-bisindenyl ethane, and the like. 
Metallocenes also include those containing two cyclopentadienyl-type 
radicals where only one of such radicals is bonded to the transition 
metal. An example would be (9-fluorenyl)(cyclopentadienyl) methane 
zirconium trichloride. 
Examples of suitable metallocene compounds include bis(cyclopentadienyl) 
zirconium dichloride, bis(cyclopentadienyl) zirconium dibromide, 
bis(cyclopentadienyl) zirconium diiodide, bis(methylcyclopentadienyl) 
zirconium dichloride, bis(n-butylcyclopentadienyl) zirconium dichloride, 
bis(cyclopentadienyl) hafnium dichloride, bis(cyclopentadienyl) hafnium 
dibromide, bis(cyclopentadienyl) hafnium diiodide, 
bis(methylcyclopentadienyl) hafnium dichloride, 
bis(n-butylcyclopentadienyl) hafnium dichloride, bis(cyclopentadienyl) 
titanium dichloride, bis(methylcyclopentadienyl) titanium dichloride, 
bis(n-butylcyclopentadienyl) titanium dichloride, bis(cyclopentadienyl) 
zirconium methyl chloride, bis(methylcyclopentadienyl) zirconium ethyl 
chloride, bis(n-butylcyclopentadienyl) zirconium phenyl chloride, 
bis(cyclopentadienyl) hafnium methyl chloride, bis(methylcyclopentadienyl) 
hafnium ethyl chloride, bis(n-butylcyclopentadienyl) hafnium phenyl 
chloride, bis(cyclopentadienyl) titanium methyl chloride, 
bis(methylcyclopentadienyl) titanium ethyl chloride, 
bis(n-butylcyclopentadienyl) titanium phenyl chloride, 
bis(cyclopentadienyl) zirconium dimethyl, bis(methylcyclopentadienyl) 
zirconium dimethyl, bis(n-butylcyclopentadienyl) zirconium dimethyl, 
bis(cyclopentadienyl) hafnium dimethyl, bis(methylcyclopentadienyl) 
hafnium dimethyl, bis(n-butylcyclopentadienyl) hafnium dimethyl, 
bis(cyclopentadienyl) titanium dimethyl, bis(methylcyclopentadienyl) 
titanium dimethyl, bis(n-butylcyclopentadienyl) titanium dimethyl, 
pentamethylcyclopentadienyl titanium trichloride, 
pentaethylcyclopentadienyl zirconium trichloride, 
pentaethylcyclopentadienyl hafnium trichloride, 
bis(pentamethylcyclopentadienyl) titanium diphenyl, 
(9-fluorenyl)(cyclopentadienyl) methane zirconium dichloride, 
(9-fluorenyl)(cyclopentadienyl) dimethyl methane zirconium dichloride, 
bis(indenyl) hafnium dichloride, bis(indenyl) titanium diphenyl, 
bis(indenyl) zirconium dichloride, (9-fluorenyl)(cyclopentadienyl) methane 
zirconium trichloride, and the like. 
The amount of solid organoaluminoxy product relative to the transition 
metal-containing catalyst can vary broadly depending upon the particular 
catalyst selected and the results desired. Typically, the solid 
organoaluminoxy product will be present in the amount of about 1 mole to 
about 5000 moles per mole of transition metal-containing catalyst, 
preferably about 10 moles to about 1000 moles, and more preferably 100 
moles to 1000 moles. 
A variety of olefin compounds are suitable for use a monomers in the 
polymerization process of the present invention. Olefins which can be 
employed include aliphatic mono-1-olefins. While the invention would 
appear to be suitable for use with any aliphatic mono-1-olefin, those 
olefins having 2 to 18 carbon atoms are most often used. Ethylene is 
especially preferred. Often a second mono-1-olefin (comonomer) having from 
2 to 12 carbon atoms, preferably from 4 to 10 carbon atoms can be 
employed. Preferred comonomers include 1-butene, 1-pentene, 
4-methyl-l-pentene, 1-hexene, and 1-heptene. Of these 1-hexene is most 
preferred. 
The reaction conditions for contacting the olefin and the catalyst system 
can vary broadly depending on the olefin employed, and are those 
sufficient to polymerize the mono-1-olefins. Generally the temperature is 
in the range of about 20.degree. C. to about 200.degree. C., preferably in 
the range of 50.degree. C. to 150.degree. C. The pressure is generally in 
the range of from about 0.5 MPa to about 5.0 MPa (70-725 psi). 
The polymerization processes according to the present invention can be 
performed either batchwise or continuously. The olefin, transition 
metal-containing catalyst, and solid organoaluminoxy product can be 
contacted in any order. In a batch process, for example, a stirred 
autoclave is prepared by first purging with nitrogen and then with a 
suitable compound, such as isobutane for example. Either the transition 
metal-containing catalyst or the solid organoaluminoxy product cocatalyst 
can be charged to the reactor first or the catalyst and the cocatalyst can 
be charged simultaneously. It is preferred that the transition 
metal-containing catalyst and the solid organoaluminoxy product are 
contacted prior to contacting with the olefin. After closing the entry 
port, a diluent such as isobutane is added to the reactor. The reactor is 
heated to the desired reaction temperature and olefin, such as ethylene, 
is then admitted and maintained at a partial pressure within a range of 
from about 0.5 MPa to about 5.0 MPa (70-725 psi) for best results. At the 
end of the designated reaction period, the polymerization reaction is 
terminated and the unreacted olefin and diluent can be vented. The reactor 
can be opened and the polymer can be collected as a free-flowing white 
solid and dried to obtain the product. 
The present invention is particularly useful in a slurry type 
polymerization. A particularly preferred type slurry polymerization 
involves a continuous loop reactor which is continuously charged with 
suitable quantities of diluent, catalyst, cocatalyst, and polymerizable 
compounds in any desirable order. Typically the polymerization will 
include a higher alpha-olefin comonomer and optionally hydrogen. Generally 
the slurry polymerization would be conducted at a temperature in the range 
of about 60.degree. C. to about 100.degree. C., although higher and lower 
temperatures can be used. The employment of hydrogen in such a continuous 
loop polymerization using the inventive cocatalyst can in some cases 
provide broad molecular weight distribution. Polyethylenes of varying 
molecular weight distribution can be produced by varying the amount of 
hydrogen. The reaction product can be continuously withdrawn and the 
polymer recovered as appropriate, generally by flashing the diluent and 
unreacted monomers and drying the resulting polymer. 
It is also within the scope of this invention to apply prepolymer to 
catalyst and cocatalyst to control particle form. 
The following examples will serve to show the present invention in detail 
by way of illustration and not by way of limitation. 
EXAMPLE 1 
Example 1 demonstrates the effectiveness of various oxygen-containing 
compounds for preparing solid methylaluminoxane (MAO). 
MAO was obtained from Ethyl Corporation as 10 weight percent MAO in toluene 
solution. The MAO was precipitated by adding a solution containing a 
predetermined amount of various oxygen-containing compounds dropwise to a 
slurry of MAO in about 50 to 75 mL hexane. The resulting slurry was 
stirred at a predetermined temperature for about 2 to 18 hours. The slurry 
was then filtered. The thus produced MAO solid product was then dried in a 
dry box. The results are tabulated in Table 1. In the table below, MAO is 
the amount MAO in millimoles. Oxygen-Containing Compound is the amount of 
oxygen-containing compound in millimoles. T is temperature in .degree.C. 
Yield is grams of the solid MAO product produced. 
TABLE 1 
______________________________________ 
MAO Oxygen-Containing T Yield 
Run (mmol) Compound (mmol) (.degree.C.) 
(g) 
______________________________________ 
101 17 None 25 0.17 
102 17 None 66 0.24 
103 34 None 25 0.56 
2.2 di-t-butyl peroxide 
25 0.21 
104 17 
105 17 2.2 di-t-butyl peroxide 
66 0.71 
106 17 2.1 propylene oxide 
25 0.70 
107 17 1.7 propylene carbonate 
25 1.06 
108 34 2.1 propylene carbonate 
25 1.88 
109 34 1.4 propylene carbonate 
25 1.40 
110 34 1.0 propylene carbonate 
25 0.95 
______________________________________ 
Table 1 demonstrates the effectiveness of organic peroxides, alkylene 
oxides, and organic carbonates in precipitating MAO. 
EXAMPLE 2 
Example 2 demonstrates the effectiveness of the inventive catalyst system 
in polymerizing ethylene. The catalyst system was prepared employing solid 
organoaluminoxy product (MAO) from Example 1 and a metallocene, 
bis(n-butylcyclopentadienyl) zirconium dichloride, available from Ethyl 
Corporation. 
A predetermined amount of solid MAO product was slurried in 20-30 mL 
hexane. A solution containing the amount of metallocene indicated in Table 
2 was added and the mixture was stirred at room temperature for 1 to 28 
hours. The thus produced solid MAO product/metallocene catalyst system was 
collected on a filter and dried to constant weight in a dry box. 
Polymerizations were conducted in a 1-gallon stirred autoclave reactor 
under particle form conditions. The polymerizations were conducted at 
about 70.degree. C. in 2 liters isobutane in the presence of hydrogen for 
about one hour, except Run 207 where the polymerization run was 23 
minutes. The total pressure was about 340 psig and the partial pressure of 
the isobutane and hydrogen was about 152 psig. After the polymerization 
was complete, the isobutane was removed and the polymer collected as a dry 
fluff. The results are tabulated in Table 2. 
In the table below, OC/Run is the oxygen-containing compound and the Run 
number from Example 1 of the solid MAO product employed in the catalyst 
system. MAO/OC is the ratio of moles of MAO per mole of oxygen-containing 
compound employed in preparing the solid organoaluminoxy product. DTBP is 
di-tert-butyl peroxide. PO is propylene oxide. PC is propylene carbonate. 
MAO is the millimoles of solid MAO product combined with the metallocene 
to form the catalyst system. Metallocene is the millimoles of 
bis(n-butylcyclopentadienyl) zirconium dichloride combined with the solid 
MAO product to form the catalyst system. Catalyst is the grams of solid 
MAO/Metallocene catalyst system employed in the polymerization. Yield is 
the grams of polyethylene produced. 
TABLE 2 
______________________________________ 
Metal- Cat- 
MAO/ MAO locene alyst Yield 
Run OC/Run OC (mmols) 
(mmols) 
(g) (g PE) 
______________________________________ 
201 DTBP/105 8 4.3 0.0086 0.0414 
95 
202 PO/106 8 4.3 0.0074 0.0446 
19 
203 PO/106 8 4.3 0.0074 0.0972 
100 
204 PC/107 10 3.4 0.0035 0.0979 
4 
205 PC/108 16 3.4 0.0140 0.0802 
* 
206 PC/109 24 3.4 0.0070 0.0854 
307 
207 PC/110 34 3.4 0.0140 0.0923 
351** 
______________________________________ 
*Light dusting of polymer inside reactor 
**Polymerization time was 23 minutes 
Table 2 demonstrates the effectiveness of employing a catalyst comprising a 
metallocene and a solid MAO product reacted with various oxygen-containing 
compounds. It is noted that solid MAO product prepared at an MAO/OC ratio 
of greater than 20, produces an especially active catalyst.