Polymerization catalyst systems, their production and use

This invention is generally directed toward a supported catalyst system useful for polymerizing olefins. The method for supporting the catalyst of the invention provides for a supported mixed metallocene/non-metallocene catalyst useful in a process for polymerizing olefins.

FIELD OF THE INVENTION 
This invention relates to catalysts, catalyst systems and to methods for 
their production and use in olefin polymerization. The invention 
particularly relates to a process for preparing a supported mixed 
metallocene/non-metallocene catalyst for use in the gas phase, slurry 
phase or liquid/solution phase. 
BACKGROUND OF THE INVENTION 
It is widely known that olefin polymerization processes utilizing 
metallocene catalysts have been used to produce a wide range of new 
polymers for use in a variety of applications and products. Mixed 
metallocene and non-metallocene catalyst systems for broadening a 
polymer's molecular weight distribution are known in the art. U.S. Pat. 
Nos. 4,701,432, 5,077,255, 5,124,418 and 5,183,867 all discuss methods for 
producing olefin polymerization supported catalysts of a metallocene and a 
non-metallocene. These U.S. patents describe adding a metallocene and a 
non-metallocene catalyst component to a support material followed by the 
addition of an alumoxane activator compound. Other non-limiting examples 
of publications discussing mixed metallocene and non-metallocenes 
catalysts can be found in PCT patent publication WO 94/03508 published 
Feb. 17, 1994, which discusses a process for making a non-metallocene 
titanium compound with a metallocene hafnium and or zirconium compound. 
This publication describes forming a solid, hydrocarbon-insoluble catalyst 
by dissolving a magnesium containing compound in a liquid and reacting the 
solution with carbon dioxide or sulfur dioxide, precipitating out solid 
particles with a titanium containing non-metallocene and treating the 
particles with an electron donor and adding a zirconium or hafnium 
containing metallocene, no alumoxane is used. U.S. Pat. No. 5,082,817 and 
related EP-A-318 048 published May 31, 1989 describe an olefin 
polymerization catalyst obtained by reacting a transition metal compound 
containing at least one metal-halogen linkage, an active magnesium halide 
as a support material with a titanium, zirconium or hafnium containing at 
least one metal-carbon linkage, no alumoxane is used. EP-A-447 071 
describes forming a metallocene and an alumoxane solution, adding the 
solution to a magnesium dichloride support and then adding a 
non-metallocene, for example titanium tetrachloride. EP-A-447 070 
discusses a similar procedure where the magnesium chloride support is 
treated with an electron donor. EP-A-586 168 discloses forming an olefin 
polymerization catalyst of a homogenous metallocene/alumoxane catalyst and 
a traditional Ziegler-Natta catalyst, a non-metallocene, on a support. The 
two catalyst systems enter the reactor as separate components. U.S. Pat. 
No. 5,332,706 discusses treating a support with a magnesium containing 
compound adding a non-metallocene compound and a metallocene/alumoxane 
mixture. 
While all these supported catalysts are useful it would be desirable to 
have an improved olefin polymerization catalyst system that is very active 
and simple to make. 
SUMMARY OF THE INVENTION 
This invention is generally directed towards a new polymerization catalyst 
system, to methods for its manufacture and to its use in a polymerization 
process. 
In one embodiment a method is provided to produce a supported catalyst 
system by contacting a water containing support material with an 
organometallic compound capable of forming an activator, adding at least 
one metallocene catalyst component and a non-metallocene catalyst 
component. 
In another embodiment of the invention, there is provided a process for 
producing polyolefins by contacting olefin monomer, optionally with at 
least one comonomer in the presence of the catalyst system described 
above. 
DETAILED DESCRIPTION OF THE INVENTION 
Introduction 
This invention is generally directed toward a supported catalyst system 
useful for polymerizing olefins. The method for forming the catalyst 
system of the invention involves supporting a metallocene catalyst 
component, a non-metallocene catalyst component and an activator or 
cocatalyst, which is produced by contacting a water containing support 
material with an organometallic compound. 
The method for forming the mixed catalyst system of the invention provides 
for a commercially useful supported catalyst system with improved 
activity. 
Metallocene Catalyst Components of the Invention 
Metallocene catalysts, for example, are typically those bulky ligand 
transition metal compounds which corresponds to the formula: 
EQU [L].sub.m M[A].sub.n 
where L is a bulky ligand; A is leaving group, M is a transition metal and 
m and n are such that the total ligand valency corresponds to the 
transition metal valency. Preferably the catalyst is four co-ordinate such 
that the compound is ionizable to a 1.sup.+ charge state. 
The ligands L and A may be bridged to each other, and if two ligands L 
and/or A are present, they may be bridged. The metallocene compound may be 
full-sandwich compounds having two or more ligands L, which may be 
cyclopentadienyl ligands or cyclopentadiene derived ligands, or 
half-sandwich compounds having one ligand L, which is a cyclopentadienyl 
ligand or derived ligand. 
In one embodiment, at least one ligand L has a multiplicity of bonded 
atoms, preferably carbon atoms, that typically is a cyclic structure such 
as, for example, a cyclopentadienyl ligand, substituted or unsubstituted, 
or cyclopentadienyl derived ligand or any other ligand capable of .eta.-5 
bonding to the transition metal atom. One or more bulky ligands may be 
.pi.-bonded to the transition metal atom. The transition metal atom may be 
a Group 4, 5 or 6 transition metal and/or a metal from the lanthanide and 
actinide series. Other ligands may be bonded to the transition metal, such 
as a leaving group, such as but not limited to hydrocarbyl, hydrogen or 
any other univalent anionic ligand. Non-limiting examples of metallocene 
catalysts and catalyst systems are discussed in for example, U.S. Pat. 
Nos. 4,530,914, 4,871,705, 4,937,299, 4,952,716, 5,124,418, 5,017,714, 
5,120,867, 5,278,264, 5,278,119, 5,304,614, 5,324,800 all of which are 
herein fully incorporated by reference. Also, the disclosures of EP-A-0 
591 756, EP-A-0 520 732, EP-A-0 420 436, WO 91/04257 WO 92/00333, WO 
93/08221, and WO 93/08199 are all fully incorporated herein by reference. 
Further, the metallocene catalyst component of the invention can be a 
monocyclopentadienyl heteroatom containing compound. This heteroatom is 
activated by either an alumoxane, an ionizing activator, a Lewis acid or a 
combination thereof to form an active polymerization catalyst system. 
These types of catalyst systems are described in, for example, PCT 
International Publication WO 92/00333, WO 94/07928, and WO 91/04257, WO 
94/03506, U.S. Pat. Nos. 5,057,475, 5,096,867, 5,055,438, 5,198,401, 
5,227,440 and 5,264,405 and EP-A-0 420 436, all of which are fully 
incorporated herein by reference. In addition, the metallocene catalysts 
useful in this invention can include non-cyclopentadienyl catalyst 
components, or ancillary ligands such as boroles or carbollides in 
combination with a transition metal. Additionally it is within the scope 
of this invention that the metallocene catalysts and catalyst systems may 
be those described in U.S. Pat. Nos. 5,064,802, 5,145,819, 5,149,819, 
5,243,001, 5,239,022, 5,276,208, 5,296,434, 5,321,106, 5,329,031 and 
5,304,614, PCT publications WO 93/08221 and WO 93/08199 and EP-A- 0 578 
838 all of which are herein incorporated by reference. 
The preferred transition metal component of the catalyst of the invention 
are those of Group 4, particularly, zirconium, titanium and hafnium. The 
transition metal may be in any oxidation state, preferably +3 or +4 or a 
mixture thereof. 
For the purposes of this patent specification and appended claims the term 
"metallocene catalyst" is defined to contain at least one metallocene 
catalyst component containing one or more cyclopentadienyl moiety in 
combination with a transition metal. In one embodiment the metallocene 
catalyst component is represented by the general formula (C.sub.p).sub.m 
MR.sub.n R'.sub.p wherein at least one C.sub.p is an unsubstituted or, 
preferably, at least one Cp is a substituted cyclopentadienyl ring, 
symmetrical or unsymetrically substituted; M is a Group 4, 5 or 6 
transition metal; R and R' are independently selected halogen, hydrocarbyl 
group, or hydrocarboxyl groups having 1-20 carbon atoms or combinations 
thereof, m=1-3, n=0-3, p=0-3, and the sum of m+n+p equals the oxidation 
state of M, preferably m=2, n=1 and p=1. 
In another embodiment the metallocene catalyst component is represented by 
one of the formulas: 
EQU (C.sub.5 R'.sub.m).sub.p R".sub.s (C.sub.5 R'.sub.m)MQ.sub.3-p-x and 
EQU R".sub.s (C.sub.5 R'.sub.m).sub.2 M.sub.Q ' 
wherein M is a Group 4, 5, 6 transition metal, at least one C.sub.5 
R'.sub.m is a substituted cyclopentadienyl, each R', which can be the same 
or different is hydrogen, alkyl, alkenyl, aryl, alkylaryl or arylalkyl 
radical having from 1 to 20 carbon atoms or two carbon atoms joined 
together to form a part of a substituted or unsubstituted ring or ring 
system having 4 to 20 carbon atoms, R" is one or more of or a combination 
of a carbon, a germanium, a silicon, a phosphorous or a nitrogen atom 
containing radical bridging two (C.sub.5 R'.sub.m) rings, or bridging one 
(C.sub.5 R'.sub.m) ring to M, when p=0 and x=1 otherwise "x" is always 
equal to 0, each Q which can be the same or different is an aryl, alkyl, 
alkenyl, alkylaryl, or arylalkyl radical having from 1 to 20 carbon atoms, 
halogen, or alkoxides, Q' is an alkylidene radical having from 1-20 carbon 
atoms, s is 0 or 1 and when s is 0, m is 5 and p is 0, 1 or 2 and when s 
is 1, m is 4 and p is 1. 
For the purposes of this patent specification, the terms "cocatalysts" and 
"activators" are used interchangeably and are defined to be any compound 
or component which can activate or convert a neutral bulky ligand 
transition metal compound or a metallocene as defined above to a compound 
which operates as a catalyst. It is within the scope of this invention to 
use alumoxane as an activator, and/or to also use ionizing activators, 
neutral or ionic, or compounds such as tri (n-butyl) ammonium 
tetra(pentaflurophenyl) boron or trisperfluoro phenyl boron metalloid 
precursor, which ionize the neutral metallocene compound. 
There are a variety of methods for preparing alumoxane, non-limiting 
examples of which are described in U.S. Pat. Nos. 4,665,208, 4,952,540, 
5,091,352, 5,206,199, 5,204,419, 4,874,734, 4,924,018, 4,908,463, 
4,968,827, 5,308,815, 5,329,032, 5,248,801, 5,235,081, 5,157,137, 
5,103,031 and EP-A-0 561 476, EP-B1-0 279 586, EP-A-0 594-218 and WO 
94/10180, all of which incorporated herein by reference. 
Ionizing compounds may contain an active proton, or some other cation 
associated with but not coordinated or only loosely coordinated to the 
remaining ion of the ionizing compound. Such compounds and the like are 
described in EP-A-0 570 982, EP-A-0 520 732, EP-A-0 495 375, EP-A-0 426 
637, EP-A-500 944, EP-A-0 277 003 and EP-A-0 277 004, and U.S. Pat. Nos. 
5,153,157, 5,198,401, 5,066,741, 5,206,197 and 5,241,025 and U.S. patent 
application Ser. No. 08/285,380, filed Aug. 3, 1994 are all herein fully 
incorporated by reference. Combinations of activators are contemplated by 
the invention, for example, alumoxane and ionizing activators in 
combinations, see for example, WO 94/07928. 
In another embodiment of the invention two or more metallocene catalyst 
components can be combined in the catalyst system of the invention. For 
example, those mixed catalysts described in U.S. Pat. No. 5,281,679 and 
U.S. application Ser. No. 138,818 filed Oct. 14, 1993 both of which are 
incorporated herein by reference. 
Non-Metallocene Catalyst Components of the Invention 
For the purposes of this patent specification and appended claims a 
non-metallocene catalyst components is a coordination compound of Group 
3-7 and 9 metals, excluding cyclopentadienyl derivatives. Non-limiting 
examples of non-metallocene catalyst components are those halide, 
alkoxide, oxyhalide and hydride derivative compounds of the transition 
metals of Groups 3-7 and 9. Typical non-metallocene catalyst compounds are 
generally represented by the formulas: TrX'.sub.4-q (OR').sub.q, 
TrX'.sub.4-q R.sub.q.sup.2, VOX').sub.3, and VO(OR').sub.3, wherein Tr is 
a Group 4, 5, or 6 metal, preferably a Group 4 or 5 metal and preferably 
titanium, vanadium or zirconium, q is 0 or a number equal to or less than 
4, X' is a halogen and R' is an alkyl group, aryl group or cycloalkyl 
group having from 1 to 20 carbon atoms, and R.sup.2 is an alkyl group, 
aryl group, aralkyl group, substituted aralkyl group, and the like. The 
aryl, aralkyls, and substituted aralkyls contain from 1 to 20 carbon atoms 
preferably 1 to 10 carbon atoms. When the transition metal compound 
contains a hydrocarbyl group, R.sup.2, being an alkyl, cycloalkyl aryl, or 
aralkyl group, the hydrocarbyl group will preferably not contain an H atom 
in the position beta to the metalcarbon bond. Illustrative, but 
non-limiting examples of alkyl groups are methyl, neopentyl, 
2,2-dimethylbutyl, 2,2-dimethylhexyl; aryl groups such as phenyl, 
naphthyl; aralkyl groups such as benzyl; cycloalkyl groups such as 
1-norbornyl. Mixtures these transition metal compounds can be employed if 
desired. 
Illustrative examples of the transition metal compounds include TiCl.sub.4, 
TiBr.sub.4, Ti(OC.sub.2 H.sub.5).sub.3 Cl, Ti(OC.sub.2 H.sub.5)Cl.sub.3, 
Ti(OC.sub.4 H.sub.9).sub.3 Cl,, Ti(OC.sub.3 H.sub.7).sub.2 Cl.sub.2, 
Ti(OC.sub.6 H.sub.13).sub.2 Cl.sub.2, Ti(OC.sub.8 H.sub.17).sub.2 
Br.sub.2, and Ti(OC.sub.12 H.sub.25)C.sub.13. Illustrative examples of 
vanadium compounds include VCl.sub.4, VOCl.sub.3, VO(OC.sub.2 HS).sub.3, 
and VO(OC.sub.4 H.sub.9).sub.3. Illustrative examples of zirconium 
compounds include ZrCl.sub.4, ZrCl.sub.3 (OC.sub.2 H.sub.5), ZrCl(OC.sub.2 
H.sub.5).sub.2, ZrCl.sub.2 (OC.sub.2 H.sub.5).sub.2, Zr(OC.sub.2 
H.sub.5).sub.4, ZrCl.sub.3 (OC.sub.4 H.sub.9), ZrCl.sub.2 (OC.sub.4 
H.sub.9).sub.2, and ZrCl(OC.sub.4 H.sub.9).sub.3. 
Non-limiting examples of non-metallocene catalyst compounds can also be 
found in U.S. Pat. Nos. 2,825,721, 4,302,565, 4,302,566, 3,242,099, 
3,231,550, 3,642,749, 4,124,532, 4,302,565, 3,302,566, 5,317,076 and 
5,077,255 which are fully incorporated herein by reference. 
Non-metallocene catalyst components also include chromium catalysts, for 
example (Cp).sub.2 Cr, where Cp are cyclopentadienyl ring which can be 
substituted. Other chromium catalyst include for example disubstituted 
chromates CrO.sub.2 (OR).sub.2 where R is triphenylsilane or tertiary 
polyalicyclic alkyls. 
Other Compounds of the Invention 
In one embodiment, a halogenating agent is used in the method of the 
invention to enhance catalyst performance. Non-limiting examples of 
halogenating agents can be represented by the formula MR.sub.n X.sub.4-n 
where M is a Group 14 element and n is a integer from 0 to 3 and R is 
hydrogen or a linear or branched hydrocarbyl radical having from 1 to 20 
carbon atoms and X is a halogen, chlorinating agents being preferred where 
X is chlorine. Other non-limiting examples of halogenating agents can be 
represented by the formula MR.sub.n X.sub.3-n where M is a Group 13 
element and n is a integer from 0 to 2 and R is hydrogen or a linear or 
branched hydrocarbyl radical having from 1 to 20 carbon atoms and X is a 
halogen, chlorinating agents being preferred where X is chlorine. 
Representative compounds of these formulas include chloroform, 
methylenechloride, chloromethane, tetrachlorosilane, trichlorosilane and 
boronchloride and the like. 
In another embodiment a magnesium containing compound is used in the method 
of the invention. Non-limiting examples of magnesium compounds are 
represented by the formula X.sub.n MgR.sub.2-n wherein n is a number 
satisfying the condition of 0.ltoreq.n&lt;2; R is hydrogen, branch, a 
straight chain or cyclic alkyl group of 1-20 carbon atoms, an aryl group 
or a cycloalkyl group or an alkoxide or aryloxide having from 4 to 20 
carbon atoms; when n is 0, two of R may be the same or different from each 
other; and X is halogen. 
Non-limiting examples of the organomagnesium compounds include: 
dialkylmagnesium compounds such as dimethylmagnesium, diethylmagnesium, 
dipropylmagnesium, dibutylmagnesium, diamylmagnesium, dihexylmagnesium, 
didecylmagnesium, octylbutylmagnesium and ethylbutylmagnesium; 
alkymagnesium halides such as ethylmagnesium chloride, propylmagnesium 
chloride, butylmagnesium chloride, hexylmagnesium chloride and 
amylmagnesium chloride; alkylmagnesium alkoxides such as 
butylethoxymagnesium, ethylbutoxymagnesium and octylbutoxymagnesium; 
butylmagnesium hydride; magnesium halides such as magnesium chloride, 
magnesium bromide, magnesium iodide and magnesium fluoride; 
alkoxymagnesium halides such as methoxymagnesium chloride, ethoxymagnesium 
chloride, isopropoxymagnesium chloride, butoxymagnesium chloride and 
octoxymagnesium chloride; aryloxymagnesium halides such as 
ethoxymagnesium, isopropoxymagnesium, butoxymagnesium, n-octoxymagnesium 
and 2-ethylhexoxymagnesium; aryloxymagnesiums such as phenoxymagnesium and 
dimethylphenoxymagnesium; and carboxylic acid salts of magnesium such as 
magnesium laurate and magnesium stearate. Also employable as the magnesium 
containing compound are other magnesium metals and hydrogenated magnesium 
compounds. 
While magnesium containing compounds are preferred other Group 2 containing 
compounds can be used. For example, dialkylcalcium compounds such as 
ethylcalciumchloride and the like. 
Carrier Components of the Invention 
For purposes of this patent specification and appended claims the term 
"carrier" or "support" are interchangeable and can be any support 
material, preferably a porous support material, capable of containing 
water, absorbed or adsorbed, such as for example, clay, inorganic oxides, 
inorganic chlorides such as magnesium dichloride, and resinous support 
materials such as polystyrene or polystyrene divinyl benzene polyolefins 
or polymeric compounds or any other organic support material and the like, 
or mixtures thereof. 
The preferred support materials are inorganic oxide materials, which 
include those of Groups 2, 3, 4, 5, 13 or 14 metal oxides. In a preferred 
embodiment, the catalyst support materials include silica, alumina, 
silica-alumina, and mixtures thereof. Other inorganic oxides that may be 
employed either alone or in combination with the silica, alumina or 
silica-alumina are magnesia, titania, zirconia, and the like. 
In accordance with this invention the support material preferably has a 
water content in the range of from about 3 weight percent to about 27 
weight percent based on the total weight of the support material and water 
contained therein, preferably in the range of from about 7 weight percent 
to about 15 weight percent, and most preferably in the range of from about 
9 weight percent to about 14 weight percent. The amount of water contained 
within the support material can be measured by techniques well known in 
the art. For the purposes of this patent specification and the appended 
claims the weight percent water is measured by determining the weight loss 
of the support material which has been heated and held at a temperature of 
about 1000.degree. C. for about 16 hours. This procedure is known as "Loss 
on Ignition" (LOI) and is measured in weight percent. 
The support material of the invention may be formed by adding or removing 
the desired quantity of water from, for example, commercially available 
silica (Davison 948 available from Davison Chemical Company, a division of 
W. R. Grace, Baltimore, Md.). 
It is preferred that the carrier of the catalyst of this invention has a 
surface area in the range of from about 10 to about 700 m.sup.2 /g, pore 
volume in the range of from about 0.1 to about 4.0 cc/g and average 
particle size in the range of from about 10 to about 500 .mu.m. More 
preferably, the surface area is in the range of from about 50 to about 500 
m.sup.2 /g, pore volume of from about 0.5 to about 3.5 cc/g and average 
particle size of from about 10 to about 200 .mu.m. Most preferably the 
surface area range is from about 100 to about 400 m.sup.2 /g, pore volume 
from about 0.8 to about 3.0 cc/g and average particle size is from about 
10 to about 100 .mu.m. The pore size of the carrier of the invention 
typically is in the range of from 10 to 1000 .ANG., preferably 50 to about 
800 .ANG., and most preferably 75 to about 500 .ANG.. 
Method of Producing the Supported Activator of the Invention 
In the method of making the catalyst system of the invention the support 
material is first contacted with an organometallic compound capable of 
forming an activator, particularly for the metallocene catalyst component. 
In one embodiment, the preferred organometallic compound of Group 1, 2, 3 
and 4 organometallic alkyls, alkoxides, and halides. The preferred 
organometallic compounds are lithium alkyls, magnesium alkyls, magnesium 
alkyl halides, aluminum alkyls, silicon alkyl, silicon alkoxides and 
silicon alkyl halides. The more preferred organometallic compounds are 
aluminum alkyls and magnesium alkyls. The most preferred organometallic 
compounds are aluminum alkyls, for example, triethylaluminum (TEAL), 
trimethylaluminum (TMAL), tri-isobutylaluminum (TIBAL) and 
tri-n-hexylaluminum (TNHAL) and the like. 
The most preferred organometallic compounds are those that when contacted 
with the water containing support material of the invention form an 
oxy-containing organometallic compound represented by the following 
general formula: 
EQU (R--Al--O).sub.n 
which is a cyclic compound and 
EQU R(R--Al--O).sub.n AlR.sub.2 
which is a linear or non-cyclic compound and mixtures thereof including 
multidimensional structures. In the general formula R is a C.sub.1 to 
C.sub.12 linear or branched alkyl group such as for example methyl, ethyl, 
propyl, butyl, pentyl, hexyl, octyl, nonyl and n is an integer from about 
1 to 20. The most preferred oxy containing organometallic compounds are 
alumoxanes, for example methyl alumoxane and/or ethylalumoxane. 
In another embodiment an oxy-containing organometallic compound such as 
alumoxane can be combined with the water containing support material 
resulting in the further hydrolysis of the oxy-containing organometallic 
compound. 
In an alternative embodiment an oxy-containing organometallic compound such 
as alumoxane and derivatives thereof can be combined with a support 
material free from water. For the purpose of this patent specification and 
appended claims "free" means that the support material has been dehydrated 
physically or chemically such that it is essentially dry. 
In the preferred embodiment the support material is introduced to a 
solution of an organometallic compound such that the temperature of the 
solution containing the organometallic compound remains substantially 
constant throughout the introduction of the support material such that the 
temperature is always within the temperature ranges described below. 
The temperature range for this step in the process of the invention is from 
about 150.degree. C. to about -45.degree. C., preferably from about 
120.degree. C. to about -30.degree. C., even more preferably from about 
80.degree. C. to -20.degree. C., and most preferably from about 50.degree. 
C. to about -20.degree. C. 
In another embodiment the temperature of the solution containing the 
organometallic compound is maintained in the range of from about 
80.degree. C. to about -20.degree. C., preferably in the range of 
50.degree. C. to about -15.degree. C. and most preferably in the range of 
40.degree. C. to about -10.degree. C. 
While it is preferred that the temperature remain substantially constant, 
the temperature depends on the quantity of the catalyst system of the 
invention being produced in a single batch. It is known in the art that 
formation of alumoxane by contacting for example TMAL with water is 
exothermic, thus, the larger the batch the more difficult it is to 
maintain a constant temperature. 
The amount of organometallic compound and water containing support material 
is such that the mole ratio of metal of the organometallic to the water 
content of the support material, for example TMAL/H.sub.2 O, is preferably 
in the range of from 0.7 to 1.5, preferably about 0.8 to 1.3, and even 
more preferably in the range of 0.9 to less than 1.3. 
In another embodiment the mole ratio of the metal of the organometallic to 
water content of the support material is greater than 0.7, preferably in 
the range of greater than 0.8 to about 1 and most preferably greater than 
about 0.9 to less than about 1.0. 
In a preferred embodiment, the alumoxane formed has a high weight average 
molecular weight, typically greater than about 500, preferably greater 
than about 800 to about 2000, more preferably from about 800 to about 
1000. The pore diameter of a preferred support material has a majority 
distribution of pore diameters of about 200 .ANG.. 
Method of Producing the Catalyst System of the Invention 
Once the support material containing water is contacted with the 
organoaluminum compound to form the supported activator of the invention, 
the metallocene catalyst component and the non-metallocene catalyst 
component are then added. Optionally added components can include a 
halogenating or chlorinating agent and/or a magnesium containing compound. 
The supported activator can be dried before introducing the metallocene 
and non-metallocene catalyst components. The optional components can be 
then added. 
In an embodiment, the supported activator is first contacted with a 
metallocene catalyst component followed by introduction of the 
non-metallocene catalyst component. In a preferred embodiment the 
supported activator is first contacted with the metallocene catalyst 
component followed by introduction of the non-metallocene catalyst 
components which has been contacted with at least one chlorinating agent. 
In another embodiment the supported activator is contacted with a mixture 
of a metallocene and non-metallocene catalyst components; optionally 
included in the mixture, or separately, a halogenating agent and/or a 
magnesium containing compound is introduced to the supported activator. 
In another embodiment the supported activator is contacted with a 
metallocene catalyst component first, then a magnesium containing compound 
is added followed by the addition of the non-metallocene component, with 
or without a halogenating agent. 
In a preferred embodiment the magnesium compound is mixed with the 
halogenating agent. In another preferred embodiment the mixture of the 
magnesium compound and the halogenating agent are added after the 
metallocene catalyst component has been contacted with the supported 
activator. 
In the most preferred embodiment a halogenating agent is introduced to the 
supported activator, preferably after the metallocene catalyst component 
has been added. In one embodiment the halogenating agent is added such 
that the mole ratio of the halogenating agent (the halogen) to the 
magnesium containing compound (the magnesium) is in the range of from 
about 1:1 to about 1:100, preferably from about 1:1 to about 1:10 and most 
preferably of from about 1:1 to about 1:5. 
In an alternative embodiment of the invention the mole ratio of the support 
material to the halogenating agent is in the range of from about 5:1 to 
about 1000:1, preferably from about 10:1 to 500:1, more preferably from 
about 20:1 to about 250:1, and most preferably about 20:1 to about 50:1. 
In any of the embodiments discussed above, at any stage in the preparation 
of the catalyst system, the forming catalyst system can be used without 
washing or drying or washed and dried or washed, dried and reslurried or 
even just dried and reslurried in a suitable compatible liquid. 
In one embodiment the catalyst system components including the metallocene 
component, non-metallocene component and any other component including a 
halogenating agent or a magnesium containing compound or an antistatic 
agent or the like typically in solutions are added to the supported 
activator, which has preferably been dried such that the total volume of 
the solutions is less than four times the pore volume of the porous 
support, more preferably less than three times, even more preferably less 
than two times, and most preferably less than 1 times the remaining pore 
volume of the carrier used to form the supported activator. In another 
preferred embodiment the range of the total volume of the solutions 
containing the catalyst system components added to the supported activator 
is between about 1 to 3 times, preferably greater than 1 times to about 
2.5 times the remaining pore volume of the carrier used to form the 
supported activator. In an alternative preferred embodiment the range of 
the total volume of solutions containing the catalyst system components 
added to the supported activator is in the range of from 1.1 to about 2.5 
times, preferably about 1.2 to about 2.5 times, and most preferably from 
about 1.5 to about 2.4 times the pore volume of the carrier used to form 
the catalyst. 
In another embodiment, the metallocene, non-metallocene, optionally the 
halogenating agent and/or magnesium containing compound components are 
added to the supported activator such that the total volume of these 
components is less than four times the pore volume of the porous support, 
more preferably less than three times, even more preferably less than two 
times, and most preferably less than 1 times the pore volume of the 
carrier used to form the supported activator. 
The procedure for measuring the total pore volume of a porous support is 
well known in the art. Details of one of these procedures is discussed in 
Volume 1, Experimental Methods m Catalytic Research (Academic Press, 1968) 
(specifically see pages 67-96). This preferred procedure involves the use 
of a classical BET apparatus for nitrogen absorption. Another method well 
know in the art is described in Innes, Total porosity and Particle Density 
of Fluid Catalysts By Liquid Titration, Vol. 28, No. 3, Analytical 
Chemistry 332-334 (March, 1956). 
The catalyst system components are typically slurried in a liquid to form a 
solution. The liquid can be any compatible solvent or other liquid capable 
of forming a solution or the like with at least the metallocene catalyst 
component. In a preferred embodiment the liquid is an aliphatic or 
aromatic hydrocarbon. It is within the scope of this invention that the 
different components can be slurried in different liquids, for instance 
those in which the non-metallocene component is insoluble. It is preferred 
that at least two of the components are added to the supported activator 
in the same solution, for example the metallocene and non-metallocene 
components or the magnesium compound and the chlorinating agent. 
In an embodiment, when all the catalyst system components have been added 
to the supported activator the catalyst system of the invention is ready 
for its introduction into a reactor. In another embodiment, the catalyst 
system is dried to a free flowing powder, particularly for use in a gas 
phase polymerization processes. Drying the catalyst system makes it easily 
transportable and particularly useful in a gas phase polymerization 
process. In a further embodiment, the catalyst system is dried to a free 
flowing powder and re-slurried for use, particularly in a slurry 
polymerization process. 
Polymerization Process of the Invention 
The catalyst system of this invention is suited for the polymerization of 
monomers, optionally with at least one comonomer in any polymerization or 
prepolymerization process, gas, slurry or solution phase or a high 
pressure autoclave process. In the preferred embodiment a gas phase or 
slurry phase process is utilized. 
In a preferred embodiment the invention is directed toward the gas or 
slurry phase polymerization reactions involving the polymerization of one 
or more of the monomers including ethylene and/or alpha-olefin monomers 
having from 3 to 20 carbon atoms, preferably 3-12 carbon atoms. The 
invention is particularly well suited to the copolymerization reactions 
involving the polymerization of one or more of the monomers, for example 
alpha-olefin monomers of ethylene, propylene, butene-1, pentene-1, 
4-methylpentene-1, hexene-1, octene-1, decene-1, and cyclic olefins such 
as cyclopentene, and styrene or a combination thereof. Other monomers can 
include polar vinyl, diolefins such as dienes, polyenes, norbornene, 
norbornadiene, acetylene and aldehyde monomers. Preferably a copolymer of 
ethylene or propylene is produced. Preferably the comonomer is an 
alpha-olefin having from 3 to 15 carbon atoms, preferably 4 to 12 carbon 
atoms and most preferably 4 to 10 carbon atoms. 
In another embodiment ethylene or propylene is polymerized with at least 
two different comonomers to form a terpolymer and the like, the preferred 
comonomers are a combination of alpha-olefin monomers having 3 to 10 
carbon atoms, more preferably 3 to 8 carbon atoms. 
Typically in a gas phase polymerization process a continuous cycle is 
employed where in one part of the cycle of a reactor, a cycling gas 
stream, otherwise known as a recycle stream or fluidizing medium, is 
heated in the reactor by the heat of polymerization. The recycle stream 
usually contains one or more monomers continuously cycled through a 
fluidized bed in the presence of a catalyst under reactive conditions. 
This heat is removed in another part of the cycle by a cooling system 
external to the reactor. The recycle stream is withdrawn from the 
fluidized bed and recycled back into the reactor. Simultaneously, polymer 
product is withdrawn from the reactor and new or fresh monomer is added to 
replace the polymerized monomer. See for example U.S. Pat. Nos. 4,543,399, 
4,588,790, 5,028,670 and 5,352,749 and U.S. Application Serial No. 
216,520, filed Mar. 22, 1994, U.S. application Ser. No. 08/306,055 filed 
Sep. 14, 1994 and U.S. application Ser. No. 08/317,136, filed Oct. 3, 1994 
all of which are fully incorporated herein by reference. 
In a preferred embodiment of the invention the process is a gas phase 
polymerization process operating in a condensed mode. For the purposes of 
this patent specification and appended claims the process of purposefully 
introducing a liquid and a gas phase into a reactor such that the weight 
percent of liquid based on the total weight of the recycle stream is 
greater than about 2.0 weight percent is defined to be operating a gas 
phase polymerization process in a "condensed mode". 
In one embodiment of the process of the invention the weight percent of 
liquid in the recycle stream based on the total weight of the recycle 
stream is in the range of about 2 to about 50 weight percent, preferably 
greater than 10 weight percent and more preferably greater than 15 weight 
percent and even more preferably greater than 20 weight percent and most 
preferably in the range between about 20 and about 40 percent. However, 
any level of condensed can be used depending on the desired production 
rate. 
In another embodiment of the process of the invention a surface modifier or 
antistatic agent as described in U.S. Pat. No. 5,238,278 and U.S. 
application Ser. No. 08/322,675, filed Oct. 13, 1994 can be introduced 
into the reactor together, separately or apart, from the catalyst system 
of the invention. 
A slurry polymerization process generally uses pressures in the range of 
about 1 to about 500 atmospheres or even greater and temperatures in the 
range of -60.degree. C. to about 280.degree. C. In a slurry 
polymerization, a suspension of solid, particulate polymer is formed in a 
liquid polymerization medium to which ethylene and comonomers and often 
hydrogen along with catalyst are added. The liquid employed in the 
polymerization medium can be alkane or cycloalkane, or an aromatic 
hydrocarbon such as toluene, isobutylene, ethylbenzene or xylene. The 
medium employed should be liquid under the conditions of polymerization 
and relatively inert. Preferably, hexane or isobutane is employed. 
In one embodiment of the process of the invention, the catalyst system is 
prepolymerized in the presence of monomers, ethylene and/or an 
alpha-olefin monomer having 3 to 20 carbon atoms prior to the main 
polymerization. The prepolymerization can be carried out batchwise or 
continuously in gas, solution or slurry phase including at elevated 
pressures. The prepolymerization can take place with any monomer or 
combination thereof and/or in the presence of any molecular weight 
controlling agent such as hydrogen. For details on prepolymerization see 
U.S. Pat. Nos. 4,923,833 and 4,921,825 and EP-B-0279 863, published Oct. 
14, 1992 all of which are incorporated fully herein by reference. 
In a preferred embodiment of the process of the invention the process is 
operated essentially free of a scavenger as is described in U.S. 
application Ser. No. 08/306,055, filed Sep. 14, 1994. 
For the purposes of this patent specification and appended claims a 
"scavenger" is any organometallic compound which is reactive towards 
oxygen and/or water and/or polar compounds and which does not include the 
catalyst components of the invention. Non-limiting examples of scavengers 
can be generally represented by the formula R.sub.n A, where A is a Group 
12 or 13 element, each R, which can be the same or different, is a 
substituted or unsubstituted, straight or branched alkyl radical, cyclic 
hydrocarbyl, alkyl-cyclo hydrocarbyl radicals or an alkoxide radical, 
where n is 2 or 3. Typical scavengers include trialkylaluminum compounds 
such as trimethylaluminum, triethylaluminum, triisopropyl aluminum, 
tri-sec-butyl aluminum, tri-t-butyl aluminum triisobutyl aluminum, 
trialkyl boranes and alkoxides and the like. 
In one embodiment of the process of the invention the process is 
essentially free of a scavenger. For the purposes of this patent 
specification and appended claims the term "essentially free" means that 
during the process of the invention no more than 10 ppm of a scavenger 
based on the total weight of the recycle stream is present at any given 
point in time during the process of the invention. 
In another embodiment during reactor start-up to remove impurities and 
ensure polymerization is initiated, a scavenger is present in an amount 
less than 300 ppm, preferably less than 250 ppm, more preferably less than 
200 ppm, even more preferably less than 150 ppm, still more preferably 
less than 100 ppm, and most preferably less than 50 ppm based on the total 
bed weight of a fluidized bed during the first 12 hours from the time the 
catalyst is placed into the reactor, preferably up to 6 hours, more 
preferably less than 3 hours, even more preferably less than 2 hours, and 
most preferably less than 1 hour and then the introduction of the 
scavenger is halted. 
Polymer Compositions and Applications of the Invention 
The melt index of the polymers of the invention as measured by ASTM D-1238E 
are generally in the range of about 0.1 dg/min to about 1000 dg/min, 
preferably about 0.2 dg/min to about 300 dg/min, more preferably about 0.3 
to about 200 dg/min and most preferably about 0.5 dg/min to about 100 
dg/min. 
The polymer compositions of the invention have a density in the range of 
from about 0.86 g/cm.sup.3 to about 0.97 g/cm.sup.3, preferably about 0.88 
g/cm.sup.3 to about 0.97 g/cm.sup.3, more preferably between about 0.90 
g/cm.sup.3 to about 0.97 g/cm.sup.3 and most preferably between about 0.91 
g/cm.sup.3 to about 0.97 g/cm.sup.3. 
The MWD of the polymers of the invention are in the range of greater than 
about 1.8 to about greater than 30, preferably in the range of greater 
than about 2 to about 50, more preferably in the range of greater than 
about 3 to 40 and most preferably in the range of 4 to 30. 
Another important characteristic of the polymer of the invention is its 
composition distribution (CD). A measure of composition distribution is 
the "Composition Distribution Breadth Index" ("CDBI"). CDBI is defined as 
the weight percent of the copolymer molecules having a comonomer content 
within 50% (that is, 25% on each side) of the median total molar comonomer 
content. The CDBI of a copolymer is readily determined utilizing well 
known techniques for isolating individual fractions of a sample of the 
copolymer. One such technique is Temperature Rising Elution Fraction 
(TREF), as described in Wild, et al., J. Poly. Sci., Poly. Phys. Ed., vol. 
20, p. 441 (1982) and U.S. Pat. No. 5,008,204, which are incorporated 
herein by reference. 
To determine CDBI, a solubility distribution curve is first generated for 
the copolymer. This may be accomplished using data acquired from the TREF 
technique described above. This solubility distribution curve is a plot of 
the weight fraction of the copolymer that is solubilized as a function of 
temperature. This is converted to a weight fraction versus composition 
distribution curve. For the purpose of simplifying the correlation of 
composition with elution temperature the weight fractions are assumed to 
have a Mn.gtoreq.15,000, where Mn is the number average molecular weight 
fraction. Low weight fractions generally represent a trivial portion of 
the polymer of the present invention. The remainder of this description 
and the appended claims maintain this convention of assuming all weight 
fractions have a Mn.gtoreq.15,000 in the CDBI measurement. 
From the weight fraction versus composition distribution curve the CDBI is 
determined by establishing what weight percent of the sample has a 
comonomer content within 25% each side of the median comonomer content. 
Further details of determining the CDBI of a copolymer are known to those 
skilled in the art. See, for example, PCT Patent Application WO 93/03093, 
published Feb. 18, 1993. 
The polymers of the present invention have CDBI's generally in the range of 
10 to 99%, preferably greater than 20%, most preferably greater than 30%. 
In another embodiment the polymers of the invention have a CDBI in the 
range of greater than 50% to 99%, preferably in the range of 55% to 85%, 
and more preferably 60% to 80%, even more preferably greater than 60%, 
still even more preferably greater than 65%. Obviously, higher or lower 
CDBI's may be obtained using other catalyst systems with changes in the 
operating conditions of the process employed. 
The polymers produced by the process of the invention are useful in such 
forming operations include film, sheet, and fiber extrusion and 
co-extrusion as well as blow molding, injection molding, sheet 
thermoforming and rotational molding. Films include blown or cast films in 
mono-layer or multilayer constructions formed by coextrusion or by 
lamination. Such films are useful as shrink film, cling film, stretch 
film, sealing films, oriented films, snack packaging, heavy duty bags, 
grocery sacks, baked and frozen food packaging, medical packaging, 
industrial liners, membranes, etc. in food-contact and non-food contact 
applications. Fiber forming operations include melt spinning, solution 
spinning and melt blown fiber operations. Such fibers may be used in woven 
or non-woven form to make filters, diaper fabrics, medical garments, 
geotextiles, etc. General extruded articles include medical tubing, wire 
and cable coatings, geomembranes, and pond liners. Molded articles include 
single and multi-layered constructions in the form of bottles, tanks, 
large hollow articles, rigid food containers and toys, etc. 
In some instances where it is necessary to improve processability and 
manipulate final end product characteristics the polymers produced by this 
present invention can be blended or coextruded into single or multilayer 
films or the like with various other polymers well known in the art, for 
instance, LLDPE, LDPE, HDPE, polypropylene, PB, EVA and the like and 
static controlling agents such as sorbitol.

EXAMPLES 
In order to provide a better understanding of the present invention 
including representative advantages and limitations thereof, the following 
examples are offered. 
Density is measured in accordance with ASTM-D-1238. The ratio of Mw/Mn can 
be measured directly by gel permeation chromatography techniques. For the 
purposes of this patent specification the MWD of a polymer is determined 
with a Waters Gel Permeation Chromatograph equipped with Ultrastyrogel 
columns and a refractive index detector. In this development, the 
operating temperatures of the instrument was set at 145.degree. C., the 
eluting solvent was trichlorobenzene, and the calibration standards 
included sixteen polystyrenes of precisely known molecular weight, ranging 
from a molecular weight of 500 to a molecular weight of 5.2 million, and a 
polyethylene standard, NBS 1475. 
EXAMPLE 1 
Catalyst Preparation 
Into a 1 liter flask equipped with a mechanical stirrer, 180 ml of 
trimethylaluminum (TMA) in a 15 weight percent heptane solution and 90 ml 
of hexane is introduced. The solution was cooled to a temperature of about 
50.degree. F. (10.degree. C.). 40 g of silica (available from Davison 
Chemical Company a division of W. R. Grace, Baltimore, Md.) having an 
average particle size of 100 micron, which contained 12.2 wt % of water 
(measured by LOI), was slowly added into the flask. The result of this 
first step is the supported activator of the invention. To the supported 
activator 0.9 g of (n-BuCp).sub.2 ZrCl.sub.2 (a metallocene catalyst 
component) dissolved in 10 ml of toluene was mixed with a 0.25 ml of 
TiCl.sub.4 (a non-metallocene catalyst component) in hexane solution 
(0.91M concentration of TiCl.sub.4). The mixture was then added into the 
flask. The material in the flask was allowed to react at 165.degree. F. 
(74.degree. C.) for about 1 hr. At the end of the reaction, the solid was 
dried with nitrogen purging and under pressure. A free flowing solid, the 
catalyst system of the invention was obtained at the end of the 
preparation. 
Polymerization 
Into a clean 2 liter autoclave, 800 ml of hexane followed by the 
introduction of 5 ml of hexene-1 were charged. 2.0 ml of TIBAL in heptane 
solution (1.78 mmole Al) was charged into the autoclave. Hydrogen was then 
charged into the autoclave to increase the total pressure by 2 psi (14 
kPa). The reactor was allowed to reach a temperature of 85.degree. C. 125 
mg of the catalyst prepared above was then charged into the autoclave 
through a catalyst injection tube. The catalyst entered into the autoclave 
with ethylene under pressure. The autoclave was pressurized with ethylene 
to a total pressure of 150 psig (1034 kPa). Ethylene was continuously fed 
into the autoclave by setting the ethylene feed regulator at 150 psig 
(1034 kPa). Polymerization was allowed to proceed at 85.degree. C. for 30 
minutes. After the polymerization was halted, the polymer slurry was 
transferred into a evaporation dish. The surface of autoclave wall and 
agitator were clean. The polymer product was recovered by allowing the 
solvent of the polymer slurry to evaporate. A total of 73 g of polymer 
product having a Mw/Mn equal to about 5.5 was obtained. 
EXAMPLE 2 
Example 1 was repeated except that after the TMA/wet silica reaction to 
form the supported activator, the following three components were prepared 
and were added in sequence 1, 2 and 3 to the supported activator. (1) 0.9 
g of (n-BuCp).sub.2 ZrCl.sub.2 dissolved in 10 ml of toluene, (2) 8.5 ml 
of butylethylmagnesium (BEM) (a magnesium containing compound) in heptane 
(1.31M), and (3) 12 ml of TiCl.sub.4 in hexane (0.91M). After the 
preparation, the catalyst was still in solution and was not dried. 
Polymerization was carried out as described in example 1. A total of 45 g 
polymer having a Mw/Mn equal to about 40.8 was obtained. 
EXAMPLE 3 
Example 2 was repeated except in the preparation of the catalyst 4.3 ml of 
BEM in heptane and 6 ml of TiCl.sub.4 in hexane was used. Polymerization 
was carried out as described in example 1. A total of 38 g of polymer 
having a Mw/Mn equal to about 28.3 was obtained. 
EXAMPLE 4 
Example 3 was repeated except that in the preparation of the catalyst, 2 ml 
of CHCl.sub.3 (a chlorinating agent) was added before the addition of BEM. 
Polymerization was carried out as described in example 1. A total of 127 g 
of polymer was obtained. 
EXAMPLE 5 
Example 3 was repeated except that a mixture containing 10 ml of heptane, 
4.3 ml of BEM in a heptane solution and 0.5 ml of CHCl.sub.3 was added 
before the addition of TiCl.sub.4. Polymerization was carried out as 
described in example 1. A total of 92 g of polymer was obtained. 
While the present invention has been described and illustrated by reference 
to particular embodiments, it will be appreciated by those of ordinary 
skill in the art that the invention lends itself to variations not 
necessarily illustrated herein. For example, it is within the scope of 
this invention to mix at least two of the catalysts of the invention or to 
use the catalyst of the invention with any other catalyst or catalyst 
system known in the art separately. Also the catalyst system of the 
invention can be used in a single reactor or in a series reactor or even 
in a combination of a solution, slurry, high pressure or gas phase series 
reactor process. For this reason, then, reference should be made solely to 
the appended claims for purposes of determining the true scope of the 
present invention.