Addition of aluminum alkyl for improved metallocene catalyst

This invention is for a catalyst system for polymerization of olefins using an ionic metallocene catalyst with aluminum alkyl. The metallocene catalyst is an ion pair formed from a neutral metallocene compound and an ionizing compound. The invention can be used in any method of producing ionic metallocene catalyst. Use of aluminum alkyl with an ionic metallocene catalyst eliminates the need for using methylaluminoxane (MAO). Catalysts produced by the method of this invention have high activity. The invention reduces catalyst poisons which cause low activity, no activity or uncontrolled polymerizations. Polymerizations using this catalyst system are reproducible and controllable.

FIELD OF THE INVENTION 
This invention relates, in general, to an improved catalyst system and, 
specifically, to an improved metallocene catalyst system for 
polymerization of olefins by addition of an aluminum alkyl and a process 
for using such a catalyst. 
DESCRIPTION OF PRIOR ART 
Polymerization of olefins is primarily with Zeigler-Natta catalysts. One 
family of Zeigler-Natta catalyst is Group IVB metallocene compounds with 
methylaluminoxane as a cocatalyst. It has been demonstrated that a 
Zeigler-Natta catalyst for olefin polymerization can be formed by 
combining a Group IVB metallocene with an ionic compound. 
##STR1## 
Cp*--cyclopentadienyl or substituted cyclopentadienyl M--Group IVB metal 
R--alkyl 
L--ligand 
[C]--cation 
[A]--anion 
The resulting compound is a metallocene cation which acts as catalyst. The 
cation [C] of the ionic compound reacts with the metallocene to generate 
an ion pair. The anion, [A], is not coordinated or is only loosely 
coordinated with the cationic metallocene. 
The following methods have been used to produce the above reaction: 
One-Electron Oxidation--This method is illustrated in "Ethylene 
Polymerization by a Cationic Dicyclopentadienylzirconium(IV) Alkyl 
Complex", R. F. Jordan, C. S. Bajgur, R. Willett, B. Scott, J. Am. Chem. 
Soc., p. 7410-7411, Vol. 108 (1986). These early examples used a Lewis 
base to make the metal cation less electrophilic and [BPh4]--was the anion 
where Ph is C.sub.6 H.sub.5. The reaction occurred in a solvent which was 
coordinated with the cation. These materials were usually of low activity. 
Protonation--This method is illustrated by "Synthesis and Insertion 
Reactions of Cationic Alkylbis(cyclopentadienyl)titanium Complexes", M. 
Bochmann, L. M. Wilson, J. Chem. Soc. Commun., p. 1610-1611, (1986); 
"Cationic Alkylbis(cyclopentadienyl)titanium Complexes", M. Bochmann, L. 
Wilson, Organometallics, p. 2556-2563, Vol. 6, (1987); Insertion Reactions 
of Nitriles in Cationic Alkylbis(cyclopentadienyl)titanium Complexes, M. 
Bochmann, L. Wilson, organometallics, p. 1147-1154, Vol. 7 (1987). 
European Patent Application 0-277-003 relates to work by Turner on a 
catalyst prepared by a protonation method. A bis(cyclopentadienyl) metal 
compound is combined with a compound having a cation capable of donating a 
proton and an anion having a plurality of boron atoms. For example, the 
following reaction illustrates the invention: 
bis(pentamethylcyclopentadienyl)zirconium dimethyl+7,8-dicarbaundecaborane 
--&gt;bis(pentamethylcyclopentadienyl)methyl dodecahydrido 
-7,8-dicarbaundecabornato zirconium+CH.sub.4. 
European Patent Application 0-277-004 also relates to work by Turner on a 
catalyst prepared by a protonation method. A bis(cyclopentadienyl) metal 
compound is combined with an ionic compound having a cation which will 
irreversibly react with a ligand on the metal compound and an anion having 
a plurality of lipophilic radicals around a metal or metalloid ion. For 
example, the following reaction illustrates the invention: 
tri(n-butyl)ammonium 
tetra(pentafluorophenyl)boron+bis(cyclopentadienyl)zirconium 
dimethyl--&gt;[Cp.sub.2 ZrMe][BPh*.sub.4 ]+CH.sub.4 +tri(n-butyl)N wherein 
Ph* is pentafluorophenyl. A by-product of the protonation reaction is a 
Lewis base (amine) some of which can coordinate to the cations and thus 
inhibit catalyst activity. Starting materials must be chosen carefully to 
avoid generating particular amines which are catalyst poisons. 
Carbonium Ion Chemistry--This method is illustrated by "Multiple 
Metal-Carbon Bonds", R. R. Schrock, P. R. Sharp, J. Am. Chem. Soc., 
p.2389-2399, Vol. 100, No. 8 (Apr. 2, 1978). A problem with both the 
carbonium ion chemistry method and the protonation method is that they are 
poisoned by basic impurities found in olefins and solvents, often 
resulting in runaway reactions. The high reaction temperature (over 
100.degree. C.) and the short duration of the polymerization results in 
short chain lengths and low molecular weight. 
Metallocene catalyst are sensitive to poisons in the absence of a 
scavenging agent, such as methylaluminoxane. Polymerization requires high 
concentrations of the cations and frequently end up as either runaway 
reactions or yield no polymer at all. 
SUMMARY OF THE INVENTION 
Accordingly, it is an object of this invention to provide a process for 
improving metallocene catalyst activity in polymerization of olefins. 
And, it is an object of this invention to use aluminum alkyl as a 
scavenging agent for poisons which reduce metallocene catalyst activity. 
Also, it is an object of this invention to use aluminum alkyl to improve 
metallocene catalyst activity of a catalyst made by the protonation, 
carbonium ion chemistry or one electron oxidation method. 
Further, it is an object of this invention to reduce cost of a metallocene 
catalyst system. 
Additionally, it is an object of this invention to eliminate 
methylaluminoxane (MAO) as a cocatalyst in polymerization of propylene. 
As well, it is an object of this invention to produce a metallocene 
catalyst which affects a controlled polymerization of olefins without a 
methylaluminoxane cocatalyst. 
These and other objects are accomplished by mixing an aluminum alkyl with 
an olefin, preparing an ionic metallocene catalyst, then mixing the 
catalyst with the aluminum alkyl-olefin mixture without a 
methylaluminoxane cocatalyst. The metallocene catalyst is an ion pair 
formed from a neutral metallocene compound and an ionizing compound of the 
general formulae: 
EQU [(CpR.sub.5)(CpR'.sub.5)MQ.sub.p-1 ].sup.+ [A].sup.- 
or 
EQU [R".sub.n (CpR.sub.4)(CpR'.sub.4)MQ.sub.p-1 ].sup.+ [A].sup.- 
wherein 
EQU [R".sub.n (CpR.sub.4)(CpR'.sub.4)MQ.sub.p-1 ].sup.+ 
or 
EQU [(CpR.sub.5)(CpR'.sub.5)MQ.sub.p-1 ].sup.+ [A].sup.- 
is a metallocene cation is a structural bridge between (CpR.sub.4) and 
(CpR'.sub.4) imparting stereorigidity to the metallocene, Cp is 
cyclopentadienyl R and R' are hydrogen or hydrocarbyl radicals having 1-20 
carbon atoms, (CpR.sub.4) and (CpR'.sub.4) being the same or different, M 
is a Group IVB metal, Q is a hydrocarbyl radical, each Q being the same or 
different, p is the valence of M minus 2 and [A].sup.- is an anion. Q is 
preferably a hydrocarbyl radical, such as an alkyl, an aryl, an alkenyl, 
an alkylaryl or an arylalkyl having up to 20 carbon atoms and is most 
preferably an alkyl or alkoxy of up to six carbon atoms or an aryl or up 
to 10 carbon atoms. M is preferably zirconium or hafnium. The metallocene 
cation is preferably a cation of ethylenebis (tetrahydroindenyl)zirconium 
dimethyl, ethylenebis(idenyl)zirconium dimethyl, 
ethylenebis(indenyl)hafnium dimethyl and isopropylidene 
(cyclopentadienyl-1-fluorenyl)zirconium dimethyl and is most preferably 
ethylenebis(tetrahydroindenyl)zirconium dimethyl. The anion is preferably 
tetrakis(pentafluorphenyl)borato. The aluminum alkyl is of the general 
formula AlR*.sub.3, wherein R* is a halogen, hydride, alkyl having up to 
six carbon atoms, alkoxy having up to six carbon atoms or aryl having up 
to ten carbon atoms, each R* being the same or different but at least one 
R* is an alkyl and is preferably TMA or TEA1 and is most preferably TEA1. 
DESCRIPTION OF THE INVENTION 
The invention is for a process of polymerizing olefins without use of a 
methylaluminoxane cocatalyst and for a catalyst system for use in such a 
process. An aluminum alkyl is mixed with an olefin and then introduced 
into the presence of an ionic metallocene catalyst produced by mixing a 
neutral metallocene compound with an ionic ionizing agent. 
In the synthesis procedure for an ionic metallocene catalyst, an ionic 
ionizing compound is mixed with a neutral metallocene to produce the 
following reaction: 
EQU CpR.sub.5) (CpR'.sub.5)MQ.sub.p 
+[C*][A*]=&gt;[CpR.sub.5)(CpR'.sub.5)MQ.sub.p-1 ]+[A*].sup.- +R[C*] 
or 
EQU R"(CpR.sub.4)(CpR'.sub.4)MQ.sub.p 
+[C*][A*]=&gt;[R"(CpR.sub.4)(CpR'.sub.4)MQ.sub.p-1 ]+[A*].sup.- +R[C*] 
where R" is a structural bridge between (CpR.sub.4) and (CpR'.sub.4) 
imparting stereorigidity to the metallocene, Cp is cyclopentadienyl, R and 
R' are hydrogen or hydrocarbyl radicals having 1-20 carbon atoms, M is a 
Group IVB metal, Q is a hydrocarbyl radical, p is the valence of M minus 
2, C* is a cation, A*is an anion and [C*][A*] is an ionic ionizing agent 
Each (CpR.sub.4) and (CpR'.sub.4) can be the same or different. Each R and 
R' can be the same or different. M is preferably zirconium or hafnium. Q 
is preferably an alkyl, aryl, alkenyl, alkylaryl, or arylalkyl radical of 
up to 20 carbon atoms and is most preferably methyl R".sub.n 
(CpR.sub.4)(CpR'.sub.4)MQ.sub.p is preferably ethylene 
bis(tetrahydroindenyl)zirconium dimethyl, ethylene bis(indenyl)hafnium 
dimethyl, ethylene bis(indenyl)zirconium dimethyl or 
isopropylidene(cyclopentadienyl-1-fluorenyl)zirconium dimethyl and most 
preferably ethylenebis(indenyl)zirconium dimethyl. 
In one example of the new synthesis procedure each reactant is placed in a 
solvent which is not coordinated or is only loosely coordinated with the 
metallocene cation, such as methylene chloride or toluene. The preferred 
solvent is toluene. The ionic ionizing compound is [Ph.sub.3 
C][B(Ph*).sub.3 X] where Ph.sub.3 C is triphenylcarbenium cation and 
[B(Ph*).sub.3 X] is boronato anion where B(Ph*).sub.3 is 
tris(pentafluorophenyl)boron and X is phenyl or a substituted phenyl where 
the substituents are alkyl, alkylsilyl or halogen. Examples of the ionic 
ionizing compound used in this synthesis procedure are triphenylcarbenium 
tetrakis(pentafluorophenyl) boronate, triphenylcarbenium 
tris(pentafluorophenyl)(4-trimethylsilyl-2,3,5,6-tetrafluorophenyl)boronat 
e. The ionizing compound does not have an active proton and has an anion 
which is not coordinated or is only loosely coordinated to the cation of 
the metallocene. 
The neutral metallocene compound and the ionic ionizing compound are 
dissolved separately in the same solvent and mixed together at room 
temperature. The ionizing compound ionizes the metallocene and an ion pair 
is formed in which the metallocene cation acts as a catalyst. This 
procedure is covered by European Patent Application No. 90870174.1 
(publication No. 0426637A2) which is hereby incorporated by reference into 
this application. 
In another example of a synthesis procedure for a catalyst, two components, 
the first being a neutral metallocene, such as a bis(cyclopentadienyl) 
metal compound, containing at least one substituent capable of reacting 
with a proton and the second being an ionic ionizing compound with a 
cation capable of donating a proton and an anion which is a coordination 
complex of a plurality of lipophilic radicals and a metal. The anion is 
bulky, labile and capable of stabilizing the metal cation formed as a 
result of the reaction between the two compounds. The ionic ionizing 
compound is [L'H][B Ar.sub.1 Ar.sub.2 X.sub.3 X.sub.4 ] where L' is a 
neutral Lewis base; H is a hydrogen atom; [L'-H] is a Bronsted acid; B is 
boron in a valance state of 3, Ar.sub.1 and Ar.sub.2 are the same or 
different aromatic or substituted-aromatic hydrocarbon radicals containing 
from about 6 to about 20 carbon atoms and may be linked to each other 
through a stable bridging group; and X.sub.3 and X.sub.4 are radicals 
selected independently, from the group consisting of hydride radicals, 
halide radicals, with the proviso that only X.sub.3 and X.sub.4 will be 
halide at the same time, hydrocarbyl radicals containing from 1 to about 
20 carbon atoms, substituted-hydrocarbyl radicals, wherein one or more of 
the hydrogen atoms is replaced by a halogen atom, containing from 1 to 
about 20 carbon atoms, hydrocarbyl-substituted metal (organometalloid) 
radicals wherein hydrocarbyl substitution contains from 1 to about 20 
carbon atoms and said metal is selected from Group IV-A of the Period 
Table of the Elements and the like and wherein [L'H][B Ar.sub.1 Ar.sub.2 
X.sub.3 X.sub.4 ] is a trialkyl substituted ammonium salt. Examples of 
this ionic ionizing compound used in this synthesis procedure are 
triethylammonium tetra(phenyl)boron, tripropylammonium tetra(phenyl)boron, 
tri(n-butyl)ammonium tetra(phenyl)boron, trimethylammonium 
tetra(p-tolyl)boron, trimethylammonium tetra(o-tolyl)boron, 
tributylammonium tetra(pentafluorophenyl)boron, tripropylammonium 
tetra(o,p-dimethyl-phenyl)boron, tributylammonium 
tetra(m,m-dimethylphenyl) boron, tributylammonium 
tetra(p-trifluoromethylphenyl)boron, tributylammonium 
tetra(pentafluorophenyl)boron, tri(n-butyl)ammonium tetra(o-tolyl)boron 
and the like: N,N-dialkyl anilinium salts such as N,N-dimethylanilinium 
tetra(phenyl)boron, N,N-diethylanilinium tetra(phenyl)boron, 
N,N-2,4,6-pentamethylanilinium tetra(phenyl)boron and the like: dialkyl 
ammonium salts such as di-(i-propyl)ammonium 
tetra(pentafluorophenyl)boron, dicyclohexylammonium tetra(phenyl)boron and 
the like; and triaryl phosphonium salts such as triphenylphosphonium 
tetra(phenyl)boron, tri(methylphenyl)phosphonium tetra(phenyl)boron, 
tri(dimethylphenyl) phosphonium tetra(phenyl)boron and 
N,N-dimethylanilinium tetrakis(pentafluorophenyl)boron. The ionic compound 
is preferably N,N-dimethylanilinium tetrakis (pentafluorophenyl) boronate. 
A proton provided by the cation reacts with a ligand of the metallocene. 
An active catalyst is recovered as a direct product or decomposition 
product of the reaction. This is the protonation method described above. 
The above procedure is covered by European Patent Application Publication 
No. 0-277-004 which is hereby incorporated by reference into this 
application. 
In another example of a synthesis procedure for a catalyst, a neutral 
metallocene, such as a cyclopentadienyl metal compound containing a 
halogen or alkyl coordinated in the metal is combined with a 
tetraphenylborate metal compound. The halogen or alkyl is abstracted from 
the metallocene by the metal of the tetraphenylborate metal compound, 
resulting in an ion pair with a metallocene cation and a tetraphenyl 
borate anion. 
The advantages of the invention are best realized when an aluminum alkyl of 
the general formula AlR*.sup.3 is mixed with an olefin. R* is a halogen, 
hydride, alkyl having up to six carbon atoms, alkoxy having up to six 
carbon atoms, or aryl having up to ten carbon atoms, each R* being the 
same or different but at least one R is an alkyl. Preferably, R* is an 
alkyl having up to four carbon atoms, Most preferably, R* is 
triethylaluminum (TEA1) or trimethylaluminum (TMA). The most advantageous 
aluminum alkyl with the ionic metallocene catalyst evaluated appeared to 
be TEA1. The olefin is any olefin but preferably propylene or ethylene and 
most preferably propylene. The mixture of the aluminum alkyl and olefin is 
brought in contact with an ionic metallocene catalyst, preferably one 
produced by one of the methods above. After mixing, the 
catalyst-aluminumalkyl-olefin mixture is brought to conditions to effect 
polymerization. The polyolefin is then extracted. 
The following metallocene-ionizing agent systems were evaluated with and 
without addition of an aluminum alkyl: 
1. Et(Ind).sub.2 ZrMe.sub.2 /[Ph.sub.3 C][BPh*.sub.4 ] 
2. Et(Ind).sub.2 HfMe.sub.2 /[Ph.sub.3 C][BPh*.sub.4 ] 
3. Et(Ind).sub.2 ZrMe.sub.2 /[Me.sub.2 PhNH][BPh*.sub.4 ] 
4. iPr(Cp-1-Flu)ZrMe.sub.2 /[Ph.sub.3 C][BPh*.sub.4 ] 
5. Et(H.sub.4 Ind).sub.2 ZrMe.sub.2 /[Ph.sub.3 C][BPh*.sub.4 ] 
6. Et(H.sub.4 Ind).sub.2 ZrMe.sub.2 /[Me.sub.2 PhNH][BPh*.sub.4 ] 
Et(Ind).sub.2 ZrMe.sub.2 is ethylene bis (indenyl) zirconium dimethyl, 
iPr(Cp-1-Flu)ZrMe.sub.2 is isopropylidene (cyclypentadienyl-1-fluorenyl) 
zirconium dimethyl, Et(H.sub.4 Ind).sub.2 ZrMe.sub.2 is ethylene bis 
(tetradroindenyl) zirconium dimethyl, [Ph.sub.3 C][BPh*.sub.4 ] is 
triphenylcarbenium tetrakis(pentafluorophenyl)boronate, [Me.sub.2 
PhNH][BPh*.sub.4 ] is N,N-dimethylanilinium 
tetrakis(pentafluorphenyl)boronate.

The invention having been generally described, the following examples are 
given as particular embodiments of the invention and to demonstrate the 
practice and advantages thereof. It is understood that the examples are 
given by way of illustration and are not intended to limit the 
specification or the claims to follow in any manner. 
GROUP 1 
Example I 
100 mg of [Ph.sub.3 C][BPh*.sub.4 ] was dissolved in 10 ml of toluene. 60 
mg of Et(Ind).sub.2 ZrMe.sub.2 was dissolved in 10 ml of toluene. The two 
solutions were mixed together for 5 minutes at room temperature. 
Reactor temperature was set to 50.degree. C. and one liter of propylene was 
pumped into the reactor. The catalyst mixture was added to a 40 ml 
stainless steel bomb equipped with ball valves on each end. 400 ml of 
propylene was pumped through the bomb into the reactor. The reactor 
temperature remained at 50.degree. C. and the contents of the reactor were 
agitated for sixty minutes. At the end of the polymerization, the reactor 
is cooled and the unreacted propylene was vented from the reactor. 
The reaction product was dried under vacuum at approximately 40.degree. C. 
for 12 hours. The polymer was then weighed and analyzed for melting point. 
The melting point was derived from differential scanning calorimetry 
(DSC). The results are shown in Table I. 
Example II 
The procedure of Example I was repeated with the contents of the reactor 
being agitated for 30 minutes. The results are shown in Table I. 
Example III 
The procedure of Example I was repeated with the contents of the reactor 
set point temperature being set at 70.degree. C. The results are shown in 
Table I. 
Example IV 
0.32 mmol of trimethylaluminum (TMA) was dissolved in 5 ml of toluene and 
was added to a 2 liter Zipperclave reactor under 5 psig of nitrogen. 
Reactor temperature was set to 70.degree. C. and one liter or propylene 
was pumped into the reactor. The mixture was stirred for ten minutes at 
1200 rpm. 
100 mg of [Ph.sub.3 C][BPh*.sub.4 ] was dissolved in 10 ml of toluene. to 
mg of Et(Ind).sub.2 ZrMe.sub.2 was dissolved in 10 ml of toluene. The two 
solutions were mixed together for 5 minutes at room temperature. 
The catalyst mixture was added to a 40 ml stainless steel bomb equipped 
with ball valves on each end. 400 ml of propylene was pumped through the 
bomb into the reactor. The reactor temperature remained at 70.degree. C. 
and the contents of the reactor were agitated for sixty minutes. At the 
end of the polymerization, the reactor is cooled and the unreacted 
propylene was vented from the reactor. 
The reaction product was dried under vacuum at approximately 40.degree. C. 
for 12 hours. The polymer was then weighed and analyzed for melting point. 
The melting point was derived from differential scanning calorimetry 
(DSC). The results are shown in Table I. 
Example V 
The procedure of Example II was repeated using 0.33 mmol of 
triethylaluminum (TEA1) and agitating the contents of the reactor for 10 
minutes. The results are shown in Table I. 
Example VI 
The procedure of Example II was repeated using 0.33 mmol of 
triethylaluminum (TEA1), 50 mg of [Ph.sub.3 C][BPh*.sub.4 ] and 30 mg of 
Et(Ind).sub.2 ZrMe.sub.2. The contents of the reactor were agitated for 5 
minutes. The results are shown in Table I. 
Example VII 
The procedure of Example II was repeated using 0.33 mmol of 
triethylaluminum (TEA1), 16 mg of [Ph.sub.3 C][BPh*.sub.4 ] and 10 mg of 
Et(Ind).sub.2 ZrMe.sub.2. The contents of the reactor were agitated for 
ten minutes. The results are shown in Table I. 
Example VIII 
The procedure of Example II was repeated using 0.66 mmol of 
triethylaluminum (TEA1), 8 mg of [Ph.sub.3 C][BPh*.sub.4 ] and 2.5 mg of 
Et(Ind).sub.2 ZrMe.sub.2. The contents of the reactor were agitated for 
sixty minutes. The results are shown in Table I. 
Example IX 
The procedure of Example II was repeated using 0.66 mmol of 
triethylaluminum (TEA1), 8 mg of [Ph.sub.3 C][BPh*.sub.4 ] and 1.25 mg of 
Et(Ind).sub.2 ZrMe.sub.2. The contents of the reactor were agitated for 
sixty minutes. The results are shown in Table I. 
Example X 
The procedure of Example II was repeated using 0.66 mmol of 
triethylaluminum (TEA1), 8 mg of [Ph.sub.3 C][BPh*.sub.4 ] and 2.5 mg of 
Et(Ind).sub.2 ZrMe.sub.2. The contents of the reactor were agitated for 
thirty minutes. The results are shown in Table I. 
Example XI 
The procedure of Example II was repeated using 0.66 mmol of 
triethylaluminum (TEA1), 8 mg of [Ph.sub.3 C][BPh*.sub.4 ] and 2.5 mg of 
Et(Ind).sub.2 ZrMe.sub.2. The contents of the reactor were agitated for 
forty minutes. The results are shown in Table I. 
Example XII 
The procedure of Example II was repeated using 0.33 mmol of 
triethylaluminum (TEA1), 8 mg of [Ph.sub.3 C][BPh*.sub.4 ] and 5 mg of 
Et(Ind).sub.2 ZrMe.sub.2. The contents of the reactor were agitated for 
thirty minutes. The results are shown in Table I. 
Example XIII 
The procedure of Example II was repeated with 5 mg of Et(Ind).sub.2 
ZrMe.sub.2, 8 mg of [Ph.sub.3 C][BPh*.sub.4 ], 0.66 mmol of 
triethylaluminum and a run time of 30 minutes. The results are shown in 
Table I. 
Example XIV 
The procedure of Example II was repeated with 2.5 mg of Et(Ind).sub.2 
ZrMe.sub.2, 8 mg of [Ph.sub.3 C][BPh*.sub.4 ]. 0.66 mmol of 
triethylaluminum and a run time of 60 minutes. The results are shown in 
Table I. 
Example XV 
The procedure of Example II was repeated with 2.5 mg of Et(Ind).sub.2 
ZrMe.sub.2, 4 mg of [Ph.sub.3 C][BPh*.sub.4 ], 0.66 mmol of TEA1 and a run 
time of 30 minutes. The results are shown in Table I. 
Example XVI 
The procedure of Example II was repeated with 2.5 mg of Et(Ind).sub.2 
ZrMe.sub.2, 4 mg of [Ph.sub.3 C][BPh*.sub.4 ], 0.99 mmol of TEA1 and a run 
time of 30 minutes. The results are shown in Table I. 
Example XVII 
The procedure of Example II was repeated with 2.5 mg of Et(Ind).sub.2 
ZrMe.sub.2, 24 mg of [Ph.sub.3 C][BPh*.sub.4 ], 0.66 mmol of TEA1 and a 
run time of 30 minutes. The results are shown in Table I. 
Example XVIII 
The procedure of Example II was repeated with 2.5 mg of Et(Ind).sub.2 
ZrMe.sub.2, 24 mg of [Ph.sub.3 C][BPh*.sub.4 ], 2.00 mmol of TEA1 and a 
run time of 30 minutes. The results are shown in Table I. 
GROUP 2 
Example XIX 
The procedure of Example II was repeated with 20 mg of Et(Ind).sub.2 
ZrMe.sub.2, 80 mg of [Ph.sub.3 C][BPh*.sub.4 ], 0.42 mmol of 
trimethylaluminum and a run time of 30 minutes. The results are shown in 
Table I. 
GROUP 3 
Example XX 
The procedure of Example I was repeated with 2.5 mg of Et(Ind).sub.2 
ZrMe.sub.2, 7 mg of [Me.sub.2 PhNH][BPh*.sub.4 ], and a run time of 60 
minutes. The results are shown in Table I. 
Example XXI 
The procedure of Example II was repeated with 2.5 mg of Et(Ind).sub.2 
ZrMe.sub.2, 7.0 mg of [Me.sub.2 PhNH][BPh*.sub.4 ], 0.66 mmol 
triethylaluminum and a run time of 60 minutes. The results are shown in 
Table I. 
Example XXII 
The procedure of Example II was repeated with 0.66 mmol of triethylaluminum 
(TEA1), 7.0 mg of [Me.sub.2 PhNH][BPh*.sub.4 ], and 2.5 mg of 
Et(Ind).sub.2 ZrMe.sub.2. The contents of the reactor were agitated for 25 
minutes. The results are shown in Table I. 
Example XXIII 
The procedure of Example II was repeated using 0.66 mmol of 
triethylaluminum (TEA1), 3.5 mg of [Me.sub.2 PhNH][BPh*.sub.4 ] and 1.25 
mg of Et(Ind).sub.2 ZrMe.sub.2. The contents of the reactor were agitated 
for 30 minutes. The results are shown in Table I. 
Example XXIV 
The procedure of Example II was repeated with 1.25 mg of Et(Ind).sub.2 
ZrMe.sub.2, 3.5 mg of [Me.sub.2 PhNH][BPh*.sub.4 ]2, 0.66 mmol of 
triethylaluminum and a run time of 60 minutes. The results are shown in 
Table I. 
Example XXV 
The procedure of Example II was repeated with 0.625 mg of Et(Ind).sub.2 
ZrMe.sub.2, 1.75 mg of [Me.sub.2 PhNH][BPh*.sub.4 ], 0.66 mmol of 
triethylaluminum and a run time of 60 minutes. The results are shown in 
Table I. 
GROUP 4 
Example XXVI 
The procedure of Example I was repeated with 60 mg of 
iPr(Cp-1-Flu)ZrMe.sub.2, 100 mg of [Ph.sub.3 C][BPh*.sub.4 ], and a run 
time of 60 minutes. The results are shown in Table I. 
Example XXVIII 
The procedure of Example II was repeated with 60 mg of 
iPr(Cp-1-Flu)ZrMe.sub.2, 100 mg of [Ph.sub.3 C][BPh*.sub.4 ], 0.16 mmol of 
trimethylaluminum and a run time of 60 minutes. The results are shown in 
Table I. 
Example XXIX 
The procedure of Example II was repeated using 0.48 mmol of 
trimethylaluminum (TMA), 100 mg of [Ph.sub.3 C][BPh*.sub.4 ] and 60 mg of 
iPr(Cp-1-Flu)ZrMe.sub.2, and a run time of 60 minutes. The results are 
shown in Table I. 
Example XXX 
The procedure of Example II was repeated with 20 mg of 
iPr(Cp-1-Flu)ZrMe.sub.2, 60 mg of [Ph.sub.3 C][BPh*.sub.4 ], 0.16 mmol of 
trimethylaluminum and a run time of 60 minutes. The results are shown in 
Table I. 
GROUP 5 
Example XXXI 
The procedure of Example I was repeated with 15 mg of Et(H.sub.4 Ind).sub.2 
ZrMe.sub.2, 30 mg of [Ph.sub.3 C][BPh*.sub.4 ], and a run time of 60 
minutes. The results are shown in Table I. 
Example XXXII 
The procedure of Example I was repeated with 20 mg of Et(H.sub.4 Ind).sub.2 
ZrMe.sub.2, 40 mg of [Ph.sub.3 C][BPh*.sub.4 ], and a run time of 60 
minutes. The results are shown in Table I. 
Example XXXIII 
The procedure of Example I was repeated with 20 mg of Et(H.sub.4 Ind).sub.2 
ZrMe.sub.2, 40 mg of [Ph.sub.3 C][BPh*.sub.4 ], and a run time of 5 
minutes. The results are shown in Table I. 
Example XXXIV 
The procedure of Example II was repeated with 2.5 mg of Et(H.sub.4 
Ind).sub.2 ZrMe.sub.2, 8 mg of [Ph.sub.3 C][BPh*.sub.4 ], 0.66 mmol of 
TEA1 and a run time of 60 minutes. The results are shown in Table I. 
GROUP 6 
Example XXXV 
The procedure of Example I was repeated with 50 mg of Et(H.sub.4 Ind).sub.2 
ZrMe.sub.2, 40 mg of [Me.sub.2 PhNH][BPh*.sub.4 ], and a run time of 120 
minutes. The results are shown in Table I. 
Example XXVI 
The procedure of Example II was repeated with 2.5 mg of Et(H.sub.4 
Ind).sub.2 ZrMe.sub.2, 9.2 mg of [Me.sub.2 PhNH][BPh*.sub.4 ], 0.66 mmol 
of TEA1 and a run time of 60 minutes. The results are shown in Table I. 
The following results are from the experimental runs described above using 
the method of the present invention. 
TABLE I 
__________________________________________________________________________ 
Ionizing Polymer Melting 
Metallocene 
Agent Al-alkyl Run Time 
zation 
Yield 
Temp 
Run # 
umol (mg) umol (mg) mmol Ratio min. temp (.degree.C.) 
(gms) 
(.degree.C.) 
__________________________________________________________________________ 
Et(Ind).sub.2 ZrMe.sub.2 
[Ph.sub.3 C][BPh*.sub.4 ] 
1 159(60) 109(100) 0 -- 60 50 19 137 
2 159(60) 109(100) 0 -- 30 50 11 125 
3 159(60) 109(100) 0 -- 60 70 8 126 
4 159(60) 109(100) TMA 
0.32 1.5:1:2.9 
60 70 270 124 
5 159(60) 109(100) TEA1 
0.33 1.5:1:3.0 
10 70* 340 126 
6 80(30) 54(50) 0.33 1.5:1:6.1 
5 70* 432 No Melt 
7 26.5(10) 17.3(16) 0.33 1.5:1:19.1 
10 70* 260 118 
8 6.63(2.5) 8.64(8) 0.66 0.77:1:76.4 
60 70 319 129 
9 3.36(1.25) 
8.64(8) 0.66 0.4:1:76.4 
60 70 89 132 
10 6.63(2.5) 8.64(8) 0.66 0.77:1:76.4 
30 70 117 
11 6.63(2.5) 8.64(8) 0.66 0.77:1:76.4 
40 70* 377 131 
12 13.3(5) 8.6(8) 0.33 1.5:1:38.4 
30 70 22 132 
13 13.3(5) 8.64(8) 0.66 1.5:1:76.4 
30 70 51 131 
14 6.63(2.5) 8.64(8) 0.66 0.77:1:76.4 
60 70* 357 127 
15 6.63(2.5) 4.3(4) 0.66 1.5:1:153.5 
30 70 9 132 
16 6.63(2.5) 4.3(4) 0.99 1.5:1:230.2 
30 70 11 134 
17 6.63(2.5) 26(24) 0.66 0.255:1:25.4 
30 70 149 131 
18 6.63(2.5) 26(24) 2.00 0.255:1:76.9 
30 70 62 130 
Et(Ind).sub.2 HfMe.sub.2 
[Ph.sub.3 C][BPh*.sub.4 ] 
19 53(20) 85(80) TMA 
0.42 0.62:1:4.9 
30 70 51 131 
Et(Ind).sub.2 ZrMe.sub.2 
[Me.sub.2 PhNH][BPh*.sub.4 ] 
20 6.6(2.5) 8.7(7.0) 0 -- 60 70 -- -- 
21 6.6(2.5) 8.7(7.0) TEA1 
0.66 0.76:1:75.9 
5 70* 106 125 
22 6.6(2.5) 8.7(7.0) 0.66 0.76:1:75.9 
25 70* 405 127 
23 3.3(1.25) 4.35(3.5) 0.66 0.76:1:151.7 
30 70* 434 127 
24 3.3(1.25) 4.35(3.5) 0.66 0.76:1:151.7 
60 70 385 131 
25 1.65(.0625) 
2.175(1.75) 
0.66 0.76:1:303.4 
60 70 253 131 
iPr(Cp-1-Flu)ZrMe.sub.2 
[Ph.sub.3 C][BPh*.sub.4 ] 
26 102(40) 65(60) 0 -- 60 80 2 -- 
27 154(60) 109(100) 0 -- 60 70 51 -- 
28 154(60) 109(100) TMA 
0.16 1.5:1:1.5 
60 70* 284 116 
29 154(60) 109(100) 0.48 1.5:1:4.4 
60 70* 268 117 
30 51(20) 65(60) 0.16 1.78:1:2.5 
60 70* 156 116 
Et(H.sub.4 Ind).sub.2 ZrMe.sub.2 
[Ph.sub.3 C][BPh.sub.4 ] 
31 40(15 33(30) 0 -- 60 50 2 142 
32 53(20) 44(40) 0 -- 60 50 35 138 
33 80(30) 67(60) 0 -- 5 120 70 127 
34 7(2.5) 8.8(8.0)TEA1 
0.66 0.8:1:75 
60 70 154 115 
Et(H.sub.4 Ind).sub.2 ZrMe.sub.2 
[Me.sub.2 PhNH][BPh.sub.4 ] 
35 133(50) 44(40) 0 -- 120 50 50 133 
36 7(2.5) 10(9.2) TEA1 
0.66 0.7:1:66 
60 70 116 116 
__________________________________________________________________________ 
*Exotherm; reaction temperature increased by more than 10.degree. C. 
Molar ratios for metallocene:ionizing compound:aluminum alkyl range from 
about 0.25:1:2.5 to about 1.5:1:300 and are preferably from about 
0.25:1:25 to about 1.5:1:230 and are most preferably about 0.76:1:150. 
The process described by this invention synthesizes cations which are used 
as catalysts in olefin polymerization. The process of making catalysts 
with this invention produces catalysts having high activity and reduces 
the by-products which can inhibit catalyst activity. This new synthesis 
also reduces the catalyst poisons found in the solvents which can inhibit 
catalyst activity. 
The addition of an aluminum alkyl to ionic metallocene catalyst systems was 
found to result in reproducible, controllable, high efficiency 
polymerizations. The addition of an alkyl aluminum provides a scavenging 
agent for catalyst poisons. The quantity of aluminum alkyl added is 
relatively small and aluminum alkyls are relatively inexpensive. The 
metallocene cation/aluminum alkyl combination results in a better catalyst 
system than the cations alone and give consistently high activities. 
Obviously, numerous modifications and variations of the present invention 
are possible in light of the above teachings. It is therefore to be 
understood that within the scope of the appended claims, the invention may 
be practiced otherwise than as specifically described herein.