Gas phase polymerization reactions utilizing soluble unsupported catalysts

Gas phase polymerization processes are disclosed which utilize unsupported soluble transition metal coordination catalysts. The catalysts are introduced into the reactor as a solution.

FIELD OF THE INVENTION 
This invention generally pertains to the field of gas phase polymerization 
reactions. More particularly, the present invention is directed to the 
utilization of soluble, unsupported transition metal catalysts and their 
co-catalysts in such gas phase polymerization reactions. 
BACKGROUND OF THE INVENTION 
Gas phase reactions for the production of olefin polymers are well known in 
the art. Such gas phase reactions are typically carried out by fluidized 
bed, stirred or paddle-type reaction systems, and the like, as described 
in, for example, U.S. Pat. Nos. 4,588,790, 3,256,263, 3,625,932, British 
Patent Nos. 1,248,951, 1,248,952, 1,248,953, and the like. As used herein, 
a "polyolefin" is meant to include homopolymers, copolymers, and 
terpolymers of alpha-olefins and may optionally contain dienes, aromatic 
compounds with vinyl unsaturation and/or carbon monoxide. 
Generally, the alpha-olefin monomers have from 2 to 12 carbon atoms and 
typically include, but are not limited to, ethylene, propylene, butene-1, 
pentene-1, 4-methylpentene-1, hexene-1, styrene, and the like. Preferred 
dienes which may optionally be polymerized with the alpha-olefins are 
those which are non-conjugated. These non-conjugated diene monomers may be 
straight chain, branched chain or cyclic hydrocarbon dienes having from 
about 5 to about 15 carbon atoms. Dienes which are especially preferred 
include 1,4-hexadiene, 5-ethylidene-2-norbornene. 
Preferred aromatic compounds having vinyl unsaturation which also may be 
optionally polymerized with the alpha-olefins include styrene and 
substituted styrene. 
So too, Group VIII transition metal compounds may be utilized to 
copolymerize carbon monoxide and alpha-olefins to form alternating 
co-polymer. 
A catalyst is usually required to cause polymerization of the one or more 
alpha-olefin monomers, and the optional dienes, to take place. Such 
catalysts may include, but are not limited to, coordinated anionic 
catalysts; cationic catalysts; free-radical catalysts; anionic catalysts, 
and the like. 
As more fully described in, for example, U.S. Pat. Nos. 3,779,712; 
3,876,602; and 3,023,203, such catalysts are generally introduced into the 
reaction zone as solid particulates in which the catalytically active 
material is impregnated onto an inert support typically made of alumina or 
silica, and the like, to form the useable catalyst. As used herein, the 
term "inert" modifying a particular material, be it a catalyst support or 
a solvent, etc., means that the material being referred to is 
non-deactivating in the reaction zone under the conditions of the gas 
phase polymerization reaction and is non-deactivating with the catalyst in 
or out of the reaction zone. 
Those skilled in the art have long believed that for polymerization 
reactions, particularly gas phase polymerization reactions, it is 
necessary to provide the catalyst impregnated on an inert support so as to 
facilitate control of polymer particle size and thereby control of the 
product bulk density. See, for example, U.S. Pat. No. 5,057,475. In 
particular, those skilled in the art believe that the size of the 
supported particulate catalyst is determinative of the polymer particles 
that are produced during the reaction, i.e., the polymer particles are 
about 10 to 15 times greater than the size of the supported particulate 
catalyst. Consequently, those skilled in the art would expect that the use 
of a catalyst which was unsupported would produce undesirable results. 
Indeed, in published European Patent Application No. 0 232 595 B1, in 
discussing slurry polymerization reactions utilizing a homogeneous 
catalyst system, i.e., an unsupported catalyst, it is taught that a 
disadvantage of such a catalyst system is that the polymer product 
produced manifests a small particle size and low bulk density. Moreover, 
impregnating the catalytically active material on a support is believed by 
those skilled in the art to desirably dilute the active centers of the 
catalyst. This is believed to provide greater isolation of such active 
centers and expose more of such sites to the monomer so as to facilitate 
polymerization. 
One of the disadvantages associated with supported catalysts which are 
conventionally used in gas phase polymerization reactions, however, is 
that the support material, such as the alumina, silica, and the like, 
remains behind in the polymer product as inorganic residual ash thereby 
increasing the overall impurity level of the polymer depending upon the 
amount of such impurity, some of the properties of the polymers may 
possibly be affected, such as film appearance rating, impact resistance, 
tear strength, and the like. 
So too, by being impregnated on a support, the activity of the catalyst is 
generally influenced by the available exposed catalyst surface area that 
comes into contact with the reactants. This is typically a function, among 
other things, of the porosity and volume of the support that is being 
utilized. When a support fails to provide an adequate surface area to 
volume ratio, then the catalyst will not exhibit high activity. 
SUMMARY OF THE INVENTION 
By virtue of the present invention, it has surprisingly been found that 
despite the admonitions of the prior art, unsupported, soluble olefin 
polymerization coordination catalysts are indeed useful in gas phase 
reactions and can be introduced into the reaction zone in liquid form 
without producing undesirable results. As used herein, "liquid form" 
includes solutions in which the catalyst or co-catalyst(s) are dissolved 
and, if the co-catalyst is a liquid when it is introduced into the 
reaction zone, then this neat form of the co-catalyst is also included in 
this term. 
By introducing the catalyst into the reaction zone in liquid form, a number 
of significant advantages are realized. In particular, there are no costs 
associated with: (i) providing the support material per se, (ii) providing 
the support material in a form which is compatible for its intended use, 
e.g., having the necessary ratio of surface area to volume; and (iii) 
processing the support so as to impregnate the active catalyst thereon. Of 
course, by not using a support, the problem of residual ash remaining in 
the polymer product originating from the support is entirely eliminated. 
So too, by providing the catalyst in liquid form, a very high catalyst 
surface area to volume ratio is realized. 
Moreover, the ability to add the catalyst to the reaction zone in an 
unsupported, liquid form provides an easy, convenient and efficient way of 
catalyst introduction, avoiding solid materials handling which generally 
is more costly and complicated. The catalyst is simply dissolved in a 
suitable solvent and the resulting catalyst solution (and if necessary, a 
co-catalyst in liquid form) is then sprayed or injected into the reaction 
zone. The catalyst and co-catalyst may be premixed and introduced into the 
reaction zone simultaneously or, if desired, they may be introduced 
separately. 
Surprisingly, while it might have been expected by one skilled in the 
catalyst/polymerization art that the introduction of a catalyst into the 
reaction zone in liquid form would produce poor results, or even no 
results at all, we have discovered that doing so provides very good 
results and, in some instances, provides a catalyst activity which is even 
greater than that found with the supported form of the catalyst. In 
addition to expecting small particle size and low bulk density, as 
discussed above, one skilled in the art would have expected that 
introducing the catalyst and co-catalyst in liquid form would cause 
undesirable swelling of the polymer or at the very least, cause 
aggregation and agglomeration of the polymer particles in the particle 
bed. Such agglomerated polymer particles would be expected by those 
skilled in the art to undesirably plug the gas distributor plate, plug the 
product discharge valve, coat the walls of the reactor and form sheets, 
disrupt the flow of solids and gas in the bed, and be the precursors of 
large chunks that may extend throughout the entire reactor. So too, it 
would also be expected by those skilled in the art that carryover of the 
liquid catalyst would occur thereby undesirably coating the walls of the 
heat exchanger and other downstream equipment with polymer. Moreover, one 
skilled in the art would also expect that the highly reactive combination 
of catalyst and monomer would cause polymerization right at the catalyst 
feeder orifice causing it to plug as well. Despite such expectations, we 
have now found that such problems generally do not occur and that good 
polymer product is obtained using the polymerization methods of the 
present invention. 
The advantages of introducing the catalyst into the gaseous reaction zone 
in an unsupported form are many. In addition to reducing both cost and 
avoiding residual ash which have been noted earlier, the ease with which 
such a catalyst is prepared and introduced is also very significant. This 
is particularly true when more than one catalyst is to be utilized. In 
order to control molecular weight distribution Of the polymer, for 
example, it is desirable to use a mixture of catalysts such as 
metallocenes as discussed in, for example, U.S. Pat. No. 4,530,914. The 
polymerization methods of the present invention, using solutions of such 
catalysts instead of conventional supported forms thereof, greatly 
simplifies the ease of preparing and using such a multicatalyst system. 
Accordingly, in one embodiment, the present invention is directed to a 
process for producing polymer from in a gas phase polymerization reaction 
which comprises: 
a) continuously introducing a gaseous stream comprising one or more 
monomers having from 2 to 12 carbon atoms into a reaction zone; 
b) introducing a polymerization catalyst in liquid form into said reaction 
zone; and 
c) withdrawing polymeric product from said reaction zone. 
In an alternative embodiment, the present invention is directed to a 
process for producing polymer from monomer in a gas fluidized bed reactor 
having a reaction zone containing a bed of growing polymer particles, a 
lower gas diffusion zone, an upper reduced gas velocity zone, a gas inlet 
into said gas diffusion zone, and a gas outlet above said reduced gas 
velocity zone which comprises: 
a) continuously passing a gaseous stream containing monomer through said 
gas diffusion zone and into said reaction zone with an upward velocity 
sufficient to maintain said particles in a suspended and gas fluidized 
condition; 
b) introducing a catalyst in liquid form into said reaction zone; 
c) withdrawing polymer product from said reaction zone; 
d) continuously withdrawing a stream of unreacted gases comprising monomer 
from said reaction zone, compressing and cooling said stream; and 
e) continuously introducing said stream into said gas diffusion zone. 
Generally, catalysts that are typically utilized for preparing polyolefins 
from alpha-olefin monomers are coordination catalysts which include the 
transition metal compounds selected from Groups IIIB to VIII of the 
Periodic Table of the Elements. From these, the transition metal olefin 
polymerization catalysts that are suitable for use in the present 
invention are those which are soluble in hydrocarbon, substantially 
non-coordinating solvents so that solutions of such transition metal 
compounds may be prepared. These hydrocarbon, substantially 
non-coordinating solvents are inert and do not interfere with the 
catalytic activity of the catalyst or with the polymerization reaction. 
Among the preferred transition metal compounds are those from Groups IVB, 
VB and VIB and most preferred are the metallocenes. Typically, transition 
metal olefin polymerization catalysts are utilized with a co-catalyst, 
such as one or more suitable organometallic compounds which are well known 
to those skilled in the art. 
Accordingly, in a preferred embodiment of the present invention, a process 
for producing polymer in a gas phase polymerization reaction is disclosed 
which comprises: 
a) continuously introducing a gaseous stream comprising one or more 
monomers having from 2 to 12 carbon atoms into a reaction zone; 
b) introducing a polymerization catalyst into said reaction zone comprising 
(i) a transition metal compound selected from Groups IIIB to VIII and (ii) 
an organometallic compound wherein (i) and (ii) are in liquid form; and 
c) withdrawing polymeric product from said reaction zone. 
In a more preferred embodiment, polyolefins are produced by a gas phase 
polymerization reaction in a reaction zone which comprises: 
a) continuously introducing a gaseous stream comprising one or more 
alpha-olefin monomers having from two to twelve carbon atoms into said 
reaction zone; 
b) introducing an olefin polymerization catalyst into said reaction zone 
comprising (i) at least one metallocene compound containing a transition 
metal selected from Groups IIIB to VIII and (ii) aluminoxane wherein (i) 
and (ii) are in liquid form; and 
c) withdrawing polyolefin product from said reaction zone. 
In all of the various embodiments noted above, the monomers used for 
preparing the polymers have from two to twelve carbon atoms, preferably 
two to six carbon atoms. 
Preferably, the polyolefins are produced utilizing a liquid catalytically 
active reaction product formed by reacting one or more metallocenes with 
one or more aluminoxanes. The metallocenes may be represented by the 
general formula: 
EQU (C.sub.5 R.sub.x).sub.y R'.sub.z (C.sub.5 R.sub.m)MQ.sub.n-y-1(I) 
wherein: 
M is a metal of from Groups IIIB to VIII of the Periodic Table of the 
Elements; 
(C.sub.5 R.sub.x) and (C.sub.5 R.sub.m) are the same or different 
cyclopentadienyl or substituted cyclopentadienyl groups bonded to M; 
R is the same or different and is hydrogen or a hydrocarbyl radical such as 
alkyl, alkenyl, aryl, alkylaryl, or arylalkyl radical containing from 1 to 
20 carbon atoms or two carbon atoms are joined together to form a C.sub.4 
-C.sub.6 ring; 
R' is a C.sub.1 -C.sub.4 substituted or unsubstituted alkylene radical, a 
dialkyl or diaryl germanium or silicon, or an alkyl or aryl phosphine or 
amine radical bridging two (C.sub.5 R.sub.x) and (C.sub.5 R.sub.m) rings; 
Q is a hydrocarbyl radical such as aryl, alkyl, alkenyl, alkylaryl, or aryl 
alkyl radical having from 1-20 carbon atoms, hydrocarboxy radical having 
from 1-20 carbon atoms or halogen and can be the same or different from 
each other; 
z is 0 or 1; 
y is 0, 1 or 2; 
z is 0 when y is 0; 
n is 0, 1, 2, 3, or 4 depending upon the valence state of M; 
and n-y is.gtoreq.1. 
The aluminoxane is a poly(hydrocarbylaluminum oxide) and may be formed by 
reacting water with an alkylaluminum compound. The aluminoxane contains 
repeating units represented by the general formula: 
##STR1## 
wherein generally R'' is an alkyl radical containing from 1 to about 12 
carbon atoms or an aryl radical such as a substituted or unsubstituted 
phenyl or naphthyl radical. 
In the preferred embodiment, the present invention is directed to a process 
for producing polyolefins from alpha-olefin monomer by a gas phase 
polymerization reaction in a reaction zone which comprises: 
a) continuously introducing a gaseous stream comprising one or more 
alpha-olefin monomers having from 2 to 12 carbon atoms into said reaction 
zone; 
b) introducing an olefin polymerization catalyst into said reaction zone, 
said polyolefin polymerization catalyst comprising a solution of at least 
one metallocene compound containing a transition metal selected from 
Groups IIIB to VIII and aluminoxane in liquid form; and 
c) withdrawing polyolefin product from said reaction zone.

DETAILED DESCRIPTION OF THE INVENTION 
As briefly noted above, gas phase polymerization reactions may be carried 
out in fluidized bed reactors and stirred or paddle-type reaction systems. 
While the following discussion will feature fluidized bed systems, where 
the present invention has been found to be preferred and especially 
advantageous, it is to be understood that the general concepts relating to 
the use of the transition metal olefin polymerization catalysts in liquid 
form, which are discussed relevant to the preferred fluidized bed system, 
are also applicable to the stirred or paddle-type reaction systems as 
well. The present invention is not limited to any specific type of gas 
phase reaction system. 
In very general terms, a conventional fluidized bed process for producing 
resins is conducted by passing a gaseous stream containing one or more 
monomers continuously through a fluidized bed reactor under reactive 
conditions and in the presence of catalyst at a velocity sufficient to 
maintain the bed of solid particles in a suspended condition. The gaseous 
stream containing unreacted gaseous monomer is withdrawn from the reactor 
continuously, compressed, cooled and recycled into the reactor. Product is 
withdrawn from the reactor and make-up monomer is added to the recycle 
stream. 
A basic, conventional fluidized bed system is illustrated in FIG. 1. The 
reactor 10 comprises a reaction zone 12 and a velocity reduction zone 14. 
While a reactor configuration comprising a generally cylindrical region 
encompassing the fluidized bed beneath an expanded section is shown in 
FIG. 1, alternative configurations such as a reactor configuration 
comprising an entirely or partially tapered reactor may also be utilized. 
In such configurations, the fluidized bed is located within a tapered 
reaction zone but below a region of greater cross-sectional area which 
serves as the velocity reduction zone of the more conventional reactor 
configuration shown in FIG. 1. 
In general, the height to diameter ratio of the reaction zone can vary in 
the range of about 2.7:1 to about 5:1. The range may vary to larger or 
smaller ratios and depends upon the desired production capacity. The 
cross-sectional area of the velocity reduction zone 14 is typically within 
the range of from about 2.5 to about 2.9 multiplied by the cross-sectional 
area of the reaction zone 12. 
The reaction zone 12 includes a bed of growing polymer particles, formed 
polymer particles and a minor amount of catalyst all fluidized by the 
continuous flow of polymerizable and modifying gaseous components, 
including inerts, in the form of make-up feed and recycle fluid through 
the reaction zone. To maintain a viable fluidized bed, the superficial gas 
velocity through the bed must exceed the minimum flow required for 
fluidization which is typically from about 0.2 to about 0.5 ft/sec. 
Preferably, the superficial gas velocity is at least 0.2 ft/sec above the 
minimum flow for fluidization or from about 0.4 to about 0.7 ft/sec. 
Ordinarily, the superficial gas velocity will not exceed 5.0 ft/sec and is 
usually no more than about 2.5 ft/sec. 
On start-up, the reactor is generally charged with a bed of particulate 
polymer particles before gas flow is initiated. Such particles help to 
prevent the formation of localized "hot spots" when catalyst feed is 
initiated. They may be the same as the polymer to be formed or different. 
When different, they are withdrawn with the desired newly formed polymer 
particles as the first product. Eventually, a fluidized bed consisting of 
desired polymer particles supplants the start-up bed. 
Fluidization is achieved by a high rate of fluid recycle to and through the 
bed, typically on the order of about 50 times the rate of feed or make-up 
fluid. This high rate of recycle provides the requisite superficial gas 
velocity necessary to maintain the fluidized bed. The fluidized bed has 
the general appearance of a dense mass of individually moving particles as 
created by the percolation of gas through the bed. The pressure drop 
through the bed is equal to or slightly greater than the weight of the bed 
divided by the cross-sectional area. 
Make-up fluids are fed at point 18 via recycle line 22. The composition of 
the recycle stream is typically measured by a gas analyzer 21 and the 
composition and amount of the make-up stream is then adjusted accordingly 
to maintain an essentially steady state gaseous composition within the 
reaction zone. The gas analyzer 21 can be positioned to receive gas from a 
point between the velocity reduction zone 14 and heat exchanger 24, 
preferably, between compressor 30 and heat exchanger 24. 
To ensure complete fluidization, the recycle stream and, where desired, at 
least part of the make-up stream are returned through recycle line 22 to 
the reactor at point 26 below the bed. Preferably, there is a gas 
distributor plate 28 above the point of return to aid in fluidizing the 
bed uniformly and to support the solid particles prior to start-up or when 
the system is shut down. The stream passing upwardly through and out of 
the bed removes the heat of reaction generated by the exothermic 
polymerization reaction. 
The portion of the gaseous stream flowing through the fluidized bed which 
did not react in the bed becomes the recycle stream which leaves the 
reaction zone 12 and passes into the velocity reduction zone 14 above the 
bed where a major portion of the entrained particles drop back onto the 
bed thereby reducing solid particle carryover. 
The recycle stream is then compressed in compressor 30 and passed through 
heat exchanger 24 where the heat of reaction is removed from the recycle 
stream before it is returned to the bed. The recycle stream exiting the 
heat exchange zone is then returned to the reactor at its base 26 and 
thence to the fluidized bed through gas distributor plate 28. A fluid flow 
deflector 32 is preferably installed at the inlet to the reactor to 
prevent contained polymer particles from settling out and agglomerating 
into a solid mass and to maintain entrained or to re-entrain any particles 
or liquid which may settle out or become disentrained. 
Particulate polymer product is discharged from line 44. Although not shown, 
it is desirable to separate any fluid from the product and to return the 
fluid to reactor vessel 10. 
In accordance with the present invention, the polymerization catalyst 
enters the reactor in liquid form at a point 42 through line 48. If the 
catalyst requires the use of one or more co-catalysts, as is usually the 
case, the one or more co-catalysts may be introduced separately into the 
reaction zone where they will react with the catalyst to form the 
catalytically active reaction product. It is conventional, however, to 
premix the catalyst and co-catalyst(s) prior to their introduction into 
the reaction zone. 
For example, in the catalyst system comprising metallocene as the catalyst 
and aluminoxane as the co-catalyst, it is the reaction product of the 
metallocene and the aluminoxane which forms the catalytically active 
material needed for polymerization of the olefins. The metallocene(s) and 
the aluminoxane(s) may be mixed With one another and the reacted mixture, 
which is still in liquid form, is introduced into the reaction zone. 
Alternatively, the metallocene(s) which are in liquid form and the 
aluminoxane(s) which are also in liquid form may be independently added to 
the reaction zone. It is in the reaction zone where the metallocene(s) and 
the aluminoxane(s) react to form the catalytically active material. As a 
still further embodiment, although not preferred, it is also within the 
scope of the present invention to react the catalyst with the co-catalyst, 
such as the metallocene(s) with the aluminoxane(s), and isolate a solid 
reaction product thereof. This catalytically active solid reaction product 
is then dissolved in a suitable solvent when desired and introduced into 
the reaction zone as a solution. It is to be understood that all of the 
various embodiments discussed above for introducing the polymerization 
catalyst into the reaction zone are broadly applicable to the more general 
transition metal olefin polymerization catalyst and organometallic 
co-catalyst as well. 
In the embodiment illustrated in FIG. 1, the catalyst and co-catalyst are 
mixed prior to their introduction into the reaction zone. A soluble 
transition metal catalyst from tank 50 is fed through line 45 to a mixing 
tee 62 where it is mixed with one or more co-catalysts from tank 60 which 
is fed to mixing tee 62 through line 43. The catalyst and co-catalyst(s) 
are provided in liquid form. Once the mixture is in line 46, the 
catalyst/co-catalysts mixture react with one another to form the desired 
catalytic reaction product in situ. Generally, the length of line 46 is 
such that it provides ample residence time for the catalyst/co-catalyst(s) 
to react with one another and form the desired reaction product which 
remains in solution. In this manner, once the catalyst reaches line 48 and 
enters the reactor at point 42, substantially all of the 
catalyst/co-catalyst(s) will have reacted and catalytically reactive 
reaction product, which will have formed in situ, will desirably be 
introduced into the reaction zone in liquid form. 
The solvents that are desirably utilized to form solutions of the soluble 
transition metal polymerization catalyst compounds are inert solvents, 
preferably non-functional hydrocarbon solvents and may include aliphatic 
hydrocarbons such as butane, isobutane, ethane, propane, pentane, 
isopentane, hexane, octane, decane, dodecane, hexadecane, octadecane, and 
the like; alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, 
cyclohexane, cyclooctane, norbornane, ethylcyclohexane and the like; 
aromatic hydrocarbons such as benzene, toluene, ethylbenzene, 
propylbenzene, butylbenzene, xylene, and the like; and petroleum fractions 
such as gasoline, kerosene, light oils, and the like. Likewise, 
halogenated hydrocarbons such as methylene chloride, chlorobenzene, and 
the like, may also be utilized. By "non-functional", it is meant that the 
solvents do not contain groups such as strong polar groups which can 
deactivate the active transition metal sites. 
The concentration of catalyst or co-catalyst that is provided in solution 
as it is being introduced into the reaction zone may be as high as the 
saturation point of the particular solvent being used. Preferably, the 
concentration is in the range of from about 0.01 to about 10,000 
millimoles/liter. Of course, if the co-catalyst is being used in its neat 
form, i.e., in its liquid state with no solvent, it will be comprised of 
essentially pure co-catalyst. 
It is to be understood that in the text that follows, any reference made to 
a "catalyst in liquid form" includes a catalyst and a co-catalyst in such 
liquid form and a mixture of the two. 
The size of the droplets formed when introducing the catalyst into the 
reactor is generally determined by the manner and place in which the 
catalyst is introduced. 'It is desirable to use a means of introduction 
which is able to provide liquid droplets within the reactor having an 
average diameter which is in the range of from about 5 to about 1000 
microns, preferably within the range of from about 50 to about 500 
microns, so as to desirably form polymer product having a particle size 
within the range of from about 500 to about 5,000 microns. 
The catalyst in liquid form (with or without a co-catalyst) may be 
introduced into the reaction zone by simply passing the catalyst in liquid 
form, under pressure, through a conduit extending into the reactor, which 
may be assisted by an inert gas (such as nitrogen) and/or an inert liquid 
(such as isopentane, propane, and the like) to aid in atomization so as to 
provide the desired liquid droplet size. The catalyst in liquid form may 
be introduced by conventional means such as, for example, using positive 
displacement pumps, pressurizing the holding tank with an inert gas, and 
the like. The extent of pressurization, the diameter of the conduit, the 
type and size of atomization nozzle (if one is used), the velocity with 
which the catalyst is introduced into the reactor, the superficial gas 
velocity of the fluids within the reactor, as well as the pressure within 
the reaction zone will all influence the liquid droplet size that is 
formed. It is well within the knowledge of those skilled in this art to 
vary one or more of these parameters to the extent desired while adjusting 
still others to obtain a desired droplet size within the reaction zone. 
Preferably, the catalyst in liquid form is introduced into the reactor by 
means of a conventional two fluid spray nozzle in which an inert gas is 
used to help atomize the catalyst. The use of such a spray nozzle allows 
for greater control of the liquid droplet size that is produced in the 
reaction zone by providing enhanced atomization capability. The selection 
of a particular spray nozzle/tip for use with the catalyst in liquid form 
to provide a desired average droplet size, taking into account the 
reaction conditions within the reactor as well as the flow rate of the 
catalyst, is well within the knowledge of those skilled in the art. 
Generally, the orifice diameter in the spray nozzle/tip is in the range of 
from about 0.01 to about 0.15 inch, preferably from about 0.02 to about 
0.05 inch. 
The catalyst in liquid form can be introduced intermittently or 
continuously into the reaction zone at a desired rate at point 42, which 
is above distributor plate 28. Intermittent catalyst feeding may be used 
to help keep the catalyst solution flow rate in the proper range for 
optimum nozzle performance while independently maintaining the desired 
average catalyst feed rate. It is desirable to maintain a continuous flow 
of the inert carrier through the nozzle, be it a liquid or gas, at a rate 
sufficient to prevent fouling of the injection nozzle. Conventional 
metering valves or pumps can be used to deliver a precise flow of the 
catalyst to the reaction zone. Controlled intermittent catalyst flow may 
be delivered to the reaction zone using conventional syringe or positive 
displacement pumps. 
Injection of the catalyst in liquid form into the reactor is preferably 
carried out in the upper portion of the fluidized bed to provide uniform 
distribution and to minimize catalyst carryover into the recycle line 
where polymerization may begin and plugging of the recycle line and heat 
exchanger may eventually occur. Carryover of catalyst into the recycle 
line can result in polymerization occurring outside the reactor reaction 
zone which can cause plugging of the recycle line and fouling in the heat 
exchanger. However, if desired, the catalyst in liquid form may be 
introduced into the reaction zone entirely above the fluidized bed at a 
point in the reactor which is still low enough so as to minimize any 
catalyst carryover into the recycle line taking into account the 
cross-sectional area of the reactor at the point of catalyst injection, 
the velocity of the gaseous stream passing through the fluidized bed, the 
entry point into the reactor for the catalyst and the droplet size of the 
catalyst. 
The rate of polymer production in the bed depends on the rate of catalyst 
injection, the activity of the catalyst, and the concentration of 
monomer(s) in the recycle stream at the particular reaction conditions. 
Generally, from about 100,000 to about 1,000,000 pounds of polyolefins are 
produced for every pound of transition metal contained within the catalyst 
that is introduced into the reaction zone. The production rate is 
conveniently controlled by simply adjusting the rate of catalyst 
introduction. 
Under a given set of operating conditions, the fluidized bed is maintained 
at essentially a constant height by withdrawing a portion of the bed as 
product at a rate essentially equivalent to the rate of formation of the 
particulate polymer product. 
The fluid bed reactor is operated at a temperature below the sintering 
temperature of the polymer particles to ensure that sintering will not 
occur. The sintering temperature is a function of resin density. 
Accordingly, temperatures of from about 75.degree. C. to about 95.degree. 
C. may be used to prepare ethylene copolymers having a density of from 
about 0.91 g/cm.sup.3 to about 0.95 g/cm.sup.3, while temperatures of from 
about 90.degree. C. to about 115.degree. C. may be used to prepare 
ethylene copolymers or homopolymers having a density of from about 0.95 
g/cm.sup.3 to about 0.97 g/cm.sup.3. 
The temperature of the catalyst in liquid form as it is introduced into the 
reaction zone is not critical. Typically, the temperature of the catalyst 
in liquid form may simply be at ambient temperature. 
The fluid bed reactor is typically operated at pressures of up to about 
1,000 psig. For polyolefin resin production, the reactor is preferably 
operated at a pressure of from about 250 to about 500 psig, with operation 
at the higher pressures in such ranges being favorable since higher heat 
transfer is experienced due to an increase in the unit volume heat 
capacity of the gas as the pressure is increased. 
The catalyst precursor compounds that can be used in the present invention 
include transition metal compounds from Groups IIIB-VIII of the Periodic 
Table that are soluble in hydrocarbon solvents. Among the preferred 
transition metal compounds are compounds from Groups IVB-VIB. Compounds 
based on magnesium/titanium electron-donor complexes that are useful are 
described in, for example, U.S. Pat. Nos. 4,302,565 and 4,302,566. The 
MgTiCl.sub.6 (ethyl acetate).sub.4 derivative is particularly preferred. 
British Patent Application 2,105,355 describes a range of hydrocarbon 
soluble vanadium compounds which are also suitable. 
The vanadium compounds which can be used in liquid form to practice the 
polymerization processes of the present invention are hydrocarbon-soluble 
vanadium salts. Of course, mixtures of these vanadium compounds may also 
be used. Non-limiting, illustrative examples of these compounds are as 
follows: 
A. vanadyl trihalide, alkoxy halides and alkoxides such as VOCl.sub.3, 
VOCl.sub.2 (OBu) where Bu =butyl and VO(OC.sub.2 H.sub.5).sub.3. 
B. vanadium tetrahalide and vanadium alkoxy halides such as VCl.sub.4 and 
VCl.sub.3 (OBu). 
C. vanadium and vanadyl acetyl acetonates and chloroacetyl acetonates such 
as V(AcAc).sub.3 and VOCl.sub.2 (AcAc) where (AcAc) is an acetyl 
acetonate. 
The preferred vanadium compounds are VOCl.sub.3, VCl.sub.4 and VOCl.sub.2 
-OR where R is a hydrocarbon radical, preferably a C.sub.1 to C.sub.10 
aliphatic or aromatic hydrocarbon radical such as ethyl, phenyl, 
isopropyl, butyl, propyl, n-butyl, i-butyl, t-butyl, hexyl, cyclohexyl, 
naphthyl, etc., and vanadium acetylacetonates. 
Hydrocarbon soluble chromium compounds which are suitable for use in liquid 
form in the present invention include chromyl chloride (CrO.sub.2 
Cl.sub.2), chromium 2-ethylhexanoate, chromium acetylacetonate 
(Cr(AcAc).sub.3), and the like, which are disclosed in, for example, U.S. 
Pat. Nos. 3,242,099 and 3,231,550. 
Still other transition metal polymerization catalysts which are suitable 
for use in the present invention are disclosed in U.S. Pat. Nos. 
4,124,532, 4,302,565 and 4,302,566 and published European Patent 
Application Nos. 0 416 815 A2 and 0 420 436 A1. Such additional compounds 
have the general formula: 
EQU M'.sub.t M''X.sub.2t Y.uE (III) 
where 
M'=Mg, Mn and/or Ca; 
t=a number from 0.5 to 2; 
M''=Ti, V and/or Zr; 
X=Cl, Br or I; 
Y=may be the same or different and is halogen, alone or in combination with 
oxygen, --NR.sub.2, --OR, --SR, 
##STR2## 
(in which R is a hydrocarbon radical, in particular an alkyl, aryl, 
cycloalkyl or aralkyl radical), acetylacetonate anion; acetylacetonate 
anion, being present in such an amount as to satisfy the valence of M'; 
u=a number from 0.5m to 20m; 
E=an electron-donor compound selected from the following classes of 
compounds: 
(a) esters of organic carboxylic acids; 
(b) alcohols; 
(c) ethers; 
(d) amines; 
(e) esters of carbonic acid; 
(f) nitriles; 
(g) phosphoramides, 
(h) esters of phosphoric and phosphorous acid, and 
(j) phosphorus oxychloride 
Complexes within the above general formula include: 
MgTiCl.sub.5.2CH.sub.3 COOC.sub.2 H.sub.5 
Mg.sub.3 Ti.sub.2 Cl.sub.12.7CH.sub.3 COOC.sub.2 H.sub.5 
MgTiCl.sub.5.6C.sub.2 H.sub.5 OH 
MgTiCl.sub.5.100CH.sub.3 OH 
MgTiCl.sub.5.tetrahydrofuran 
MgTi.sub.2 Cl.sub.12.7C.sub.6 H.sub.5 CN 
Mg.sub.3 Ti.sub.2 Cl.sub.12.6C.sub.6 H.sub.5 COOC.sub.2 H.sub.5 
MgTiCl.sub.6.2CH.sub.3 COOC.sub.2 H.sub.5 
##STR3## 
MgtiCl.sub.6.6C.sub.5 H.sub.5 N MgTiCl.sub.5 (OCH.sub.3).2CH.sub.3 
COOC.sub.2 H.sub.5 
MgTiCl.sub.5 N(C.sub.6 H.sub.5).sub.2.3CH.sub.3 COOC.sub.2 H.sub.5 
MgTiBr.sub.2 Cl.sub.4.2(C.sub.2 H.sub.5).sub.2 O 
MnTiCl.sub.5.4C.sub.2 H.sub.5 OH 
Mg.sub.3 V.sub.2 Cl.sub.12.7CH.sub.3 COOC.sub.2 H.sub.5 
MgZrCl.sub.6.4 tetrahydrofuran 
Another type of transition metal olefin polymerization catalyst precursors 
which in liquid form can be used in accordance with the invention are 
metal coordination complexes corresponding to the formula: 
##STR4## 
wherein: M is a metal of Group IIIB to VIII of the Periodic Table of the 
Elements: 
Cp is a cyclopentadienyl or substituted cyclopentadienyl group bound in an 
.eta..sup.5 bonded mode to M; 
Z is a moiety comprising boron, or a member of Group IVB of the Periodic 
Table of the Elements and optionally sulfur or oxygen, said moiety having 
up to 20 non-hydrogen atoms, and optionally Cp and Z together form a fused 
ring system; 
X' is an anionic ligand group or a neutral Lewis base ligand group having 
up to 30 non-hydrogen atoms; 
a is 0, 1, 2, 3 or 4 depending on the valance of M; and 
Y' is an anionic or non-anionic ligand group bonded to Z and M and is 
nitrogen, phosphorus, oxygen or sulfur having up to 20 non-hydrogen atoms, 
and optionally Y and Z together form a fused ring system. 
Such metal coordination complexes are well known to those skilled in the 
art and are disclosed in, for example, U.S. Pat. Nos. 5,026,798 and 
5,055,438 and published European Application No. 0 416 815 A2. 
Illustrative but non-limiting examples of the compounds represented by the 
above formula are: 
______________________________________ 
Z Cp Y X M 
______________________________________ 
dimethylsilyl 
cyclopenta- 
t-butylamido 
chloride 
titanium 
dienyl 
methyl- fluorenyl phenylamido 
methyl zirconi- 
phenyl- um 
silyl 
diphenylsilyl 
indenyl cyclohexyl- hafnium 
amido 
tetramethyl- oxo 
ethylene 
ethylene tetramethyl- 
cyclopenta- 
dienyl 
diphenyl- 
methylene 
______________________________________ 
Typical organometallic co-catalysts other than the aluminoxanes that are 
suitable in liquid form for the purposes of the present invention are any 
of the compounds of the general formula: 
EQU M.sup.3 M.sup.4.sub.v X.sup.2.sub.c R.sup.3.sub.b-c (V) 
herein M.sup.3 is a metal of Groups IA, IIA and IIIA of the periodic table; 
M.sup.4 is a metal of Group IA of the Periodic table; v is a number from 0 
to 1; each X.sup.2 is any halogen; c is a number from 0 to 3; each R.sup.3 
is a monovalent hydrocarbon radical or hydrogen; b is a number from 1 to 
4; and wherein b-c is at least 1. 
Compounds having only one Group IA, IIA or IIIA metal which are suitable 
for the practice of the invention include compounds having the formula: 
EQU M.sup.3 R.sup.3.sub.k (VI) 
wherein: 
M.sup.3 is a Group IA, IIA or IIIA metal, such as lithium, sodium, 
beryllium, barium, boron, aluminum, zinc, cadmium, and gallium; 
k equals 1, 2 or 3 depending upon the valency of M.sup.3 which valency in 
turn normally depends upon the particular group (i.e., IA, IIA or IIIA) to 
which M.sup.3 belongs; and 
each R.sup.3 may be any monovalent hydrocarbon radical. 
Examples of suitable R.sup.3 groups include any of the R.sup.3 groups 
aforementioned in connection with formula (V). 
Entirely suitable for the purposes of the present invention are the 
organometallic compounds of Groups IA, IIA, and IIIA, such as methyl and 
butyllithium, dihexylmercury, butylmagnesium, diethylcadmium, 
benzylpotassium, diethylzinc, tri-n-butylaluminum, diisobutyl ethylboron, 
diethylcadmium, di-n-butylzinc and tri-n-amylboron, and, in particular, 
the aluminum alkyls, such as trihexylaluminum, triethylaluminum, 
trimethylaluminum, and triisobutylaluminum. 
In addition, mono-organohalides and hydrides of Group IIA metals, and mono- 
or di-organohalides and hydrides of Group IIIA metals conforming to the 
general formula (VI) are also suitable. Specific examples of such 
compounds are diisobutylaluminum bromide, isobutylboron dichloride, methyl 
magnesium chloride, ethylberyllium chloride, ethylcalcium bromide, 
diisobutylaluminum hydride, methylcadmium hydride, diethylboron hydride, 
hexylberyllium hydride, dipropylboron hydride, octylmagnesium hydride, 
butylzinc hydride, dichloroboron hydride, dibromoaluminum hydride and 
bromocadmium hydride. Such organometallic co-catalyst compounds are well 
known to those skilled in the art and a more complete discussion of these 
compounds may be found in U.S. Pat. Nos. 3,221,002 and 5,093,415. 
In a preferred embodiment of the present invention, the polyolefins are 
produced utilizing the catalytically active reaction product of one or 
more metallocenes with aluminoxane, which is introduced into the gas phase 
fluidized bed reactor in liquid form. 
The metallocenes are organometallic compounds which are cyclopentadienyl 
derivatives of a Group IVB, VB, VIB or VIII metal of the Periodic Table 
and include mono, di and tricyclopentadienyls and their derivatives of the 
transition metals. Particularly desirable are metallocene complexes of a 
Group IVB and VB metal such as titanium, zirconium, hafnium and vanadium. 
The aluminoxanes are well known in the art and comprise oligomeric linear 
and/or cyclic alkyl aluminoxanes represented by the formula: 
##STR5## 
for oligomeric, linear aluminoxanes; and 
##STR6## 
for oligomeric, cyclic aluminoxane; wherein s is 1-40, preferably 10-20, p 
is 3-40, preferably 3-20 and R'' is a C.sub.1 -C.sub.12 alkyl group, 
preferably methyl and an aryl radical such as a substituted or 
unsubstituted phenyl or naphthyl radical. 
Generally, in the preparation of aluminoxanes from, for example, aluminum 
trimethyl and water, a mixture of linear and cyclic compounds is obtained. 
The aluminoxanes may be prepared in a variety of ways. For example, the 
aluminum alkyl may be treated with water in the form of a moist solvent. 
Alternatively, the aluminum alkyl, such as aluminum trimethyl may be 
contacted with a hydrated salt such as hydrated ferrous sulfate. This 
latter method comprises treating a dilute solution of aluminum trimethyl 
in, for example, toluene with a suspension of ferrous sulfate 
heptahydrate. It is also possible to form methylaluminoxanes by the 
reaction of a tetraalkyldialuminoxane containing C.sub.2 or higher alkyl 
groups with trimethylaluminum using an amount of trimethylaluminum which 
is less than a stoichiometric excess. The synthesis of methylaluminoxanes 
may also be achieved by the reaction of a trialkylaluminum compound or a 
tetraalkyldialuminoxane containing C.sub.2 or higher alkyl groups with 
water to form a polyalkyl aluminoxane which is then reacted with 
trimethylaluminum. Further, methylaluminoxanes, which are also known as 
modified aluminoxanes, may be synthesized by the reaction of a polyalkyl 
aluminoxane containing C.sub.2 or higher alkyl groups with 
trimethylaluminum and then with water as disclosed in, for example, U.S. 
Pat. No. 5,041,584. 
The preferred metallocenes may be represented by the general formula: 
EQU (C.sub.5 R.sub.x).sub.y R'.sub.z (C.sub.5 R.sub.m)MQ.sub.n-y-1(I) 
wherein: 
M is a metal of Groups IIIB to VIII of the Periodic Table of the Elements; 
(C.sub.5 R.sub.x) and (C.sub.5 R.sub.m) are the same or different 
cyclopentadienyl or substituted cyclopentadienyl groups bonded to M; 
R is the same or different and is hydrogen or a hydrocarbyl radical such as 
alkyl, alkenyl, aryl, alkylaryl, or arylalkyl radical containing from 1 to 
20 carbon atoms or two carbon atoms are joined together to form a C.sub.4 
-C.sub.6 ring; 
R' is a C.sub.1 -C.sub.4 substituted or unsubstituted alkylene radical, a 
dialkyl or diaryl germanium or silicon, or an alkyl or aryl phosphine or 
amine radical bridging two (C.sub.5 R.sub.x) and (C.sub.5 R.sub.m) rings; 
Q is a hydrocarbyl radical such as aryl, alkyl, alkenyl, alkylaryl, or aryl 
alkyl radical having from 1-20 carbon atoms, hydrocarboxy radical having 
from 1-20 carbon atoms or halogen and can be the same or different from 
each other; 
z is 0 or 1; 
y is 0, 1 or 2; 
z is 0 when y is 0; 
n is 0, 1, 2, 3, or 4 depending upon the valence state of M; 
and n-y is.gtoreq.1. 
Illustrative but non-limiting examples of the metallocenes represented by 
the above formula are dialkyl metallocenes such as 
bis(cyclopentadienyl)titanium dimethyl, bis(cyclopentadienyl)titanium 
diphenyl, bis(cyclopentadienyl)zirconium dimethyl, 
bis(cyclopentadienyl)zirconium diphenyl, bis(cyclopentadienyl)hafnium 
dimethyl and diphenyl, bis(cyclopentadienyl)titanium di-neopentyl, 
bis(cyclopentadienyl)zirconium di-neopentyl, bis(cyclopentadienyl)titanium 
dibenzyl, bis(cyclopentadienyl)zirconium dibenzyl, 
bis(cyclopentadienyl)vanadium dimethyl; the mono alkyl metallocenes such 
as bis(cyclopentadienyl)titanium methyl chloride, 
bis(cyclopentadienyl)titanium ethyl chloride, 
bis(cyclopentadienyl)titanium phenyl chloride, 
bis(cyclopentadienyl)zirconium methyl chloride, 
bis(cyclopentadienyl)zirconium ethyl chloride, 
bis(cyclopentadienyl)zirconium phenyl chloride, 
bis(cyclopentadienyl)titanium methyl bromide; the trialkyl metallocenes 
such as cyclopentadienyl titanium trimethyl, cyclopentadienyl zirconium 
triphenyl, and cyclopentadienyl zirconium trineopentyl, cyclopentadienyl 
zirconium trimethyl, cyclopentadienyl hafnium triphenyl, cyclopentadienyl 
hafnium trineopentyl, and cyclopentadienyl hafnium trimethyl; 
monocyclopentadienyls titanocenes such as, pentamethylcyclopentadienyl 
titanium trichloride, pentaethylcyclopentadienyl titanium trichloride; 
bis(pentamethylcyclopentadienyl) titanium diphenyl, the carbene 
represented by the formula bis(cyclopentadienyl)titanium.dbd.CH.sub.2 and 
derivatives of this reagent; substituted bis(cyclopentadienyl)titanium 
(IV) compounds such as: bis(indenyl)titanium diphenyl or dichloride, 
bis(methylcyclopentadienyl)titanium diphenyl or dihalides; dialkyl, 
trialkyl, tetra-alkyl and penta-alkyl cyclopentadienyl titanium compounds 
such as bis(1,2-dimethylcyclopentadienyl)titanium diphenyl or dichloride, 
bis(1,2-diethylcyclopentadienyl)titanium diphenyl or dichloride; silicon, 
phosphine, amine or carbon bridged cyclopentadiene complexes, such as 
dimethyl silyldicyclopentadienyl titanium diphenyl or dichloride, methyl 
phosphine dicyclopentadienyl titanium diphenyl or dichloride, 
methylenedicyclopentadienyl titanium diphenyl or dichloride and other 
dihalide complexes, and the like; as well as bridged metallocene compounds 
such as isopropyl(cyclopentadienyl)(fluorenyl)zirconium dichloride, 
isopropyl(cyclopentadienyl) (octahydrofluorenyl)zirconium dichloride 
diphenylmethylene(cyclopentadienyl)(fluorenyl) zirconium dichloride, 
diisopropylmethylene (cyclopentadienyl)(fluorenyl)zirconium dichloride, 
diisobutylmethylene(cyclopentadienyl)(fluorenyl) zirconium dichloride, 
ditertbutylmethylene (cyclopentadienyl)(fluorenyl)zirconium dichloride, 
cyclohexylidene(cyclopentadienyl)(fluorenyl) zirconium dichloride, 
diisopropylmethylene (2,5-dimethylcyclopentadienyl)(fluorenyl)zirconium 
dichloride, isopropyl(cyclopentadienyl)(fluorenyl) hafnium dichloride, 
diphenylmethylene (cyclopentadienyl) (fluorenyl)hafnium dichloride, 
diisopropylmethylene(cyclopentadienyl) (fluorenyl)hafnium dichloride, 
diisobutylmethylene(cyclopentadienyl) (fluorenyl)hafnium dichloride, 
ditertbutylmethylene(cyclopentadienyl) (fluorenyl)hafnium dichloride, 
cyclohexylidene(cyclopentadienyl)(fluorenyl)hafnium dichloride, 
diisopropylmethylene(2,5-dimethylcyclopentadienyl) (fluorenyl)hafnium 
dichloride, isopropyl(cyclopentadienyl)(fluorenyl)titanium dichloride, 
diphenylmethylene(cyclopentadienyl) (fluorenyl)titanium dichloride, 
diisopropylmethylene(cyclopentadienyl) (fluorenyl)titanium dichloride, 
diisobutylmethylene(cyclopentadienyl) (fluorenyl)titanium dichloride, 
ditertbutylmethylene(cyclopentadienyl) (fluorenyl)titanium dichloride, 
cyclohexylidene(cyclopentadienyl) (fluorenyl)titanium dichloride, 
diisopropylmethylene(2,5 dimethylcyclopentadienyl fluorenyl)titanium 
dichloride, racemic-ethylene bis (1-indenyl) zirconium (IV) dichloride, 
racemic-ethylene bis (4,5,6,7-tetrahydro-1-indenyl) zirconium (IV) 
dichloride, racemic-dimethylsilyl bis (1-indenyl) zirconium (IV) 
dichloride, racemic-dimethylsilyl bis (4,5,6,7-tetrahydro-1-indenyl) 
zirconium (IV) dichloride, racemic-1,1,2,2- tetramethylsilanylene bis 
(1-indenyl) zirconium (IV) dichloride, 
racemic-1,1,2,2-tetramethylsilanylene bis (4,5,6,7-tetrahydro-1- indenyl) 
zirconium (IV), dichloride, ethylidene (1-indenyl 
tetramethylcyclopentadienyl) zirconium (IV) dichloride, racemic- 
dimethylsilyl bis (2-methyl-4-t-butyl-1-cyclopentadienyl) zirconium (IV) 
dichloride, racemic-ethylene bis (1-indenYl) hafnium (IV) dichloride, 
racemic-ethylene bis (4,5,6,7-tetrahydro-1-indenyl) hafnium (IV) 
dichloride, racemic-dimethylsilyl bis (1-indenyl) hafnium (IV) dichloride, 
racemic-dimethylsilyl bis (4,5,6,7-tetrahydro-1- indenyl) hafnium (IV) 
dichloride, racemic-1,1,2,2- tetramethylsilanylene bis (1-indenyl) hafnium 
(IV) dichloride, racemic-1,1,2,2-tetramethylsilanylene bis 
(4,5,6,7-tetrahydro-1- indenyl) hafnium (IV), dichloride, ethylidene 
(1-indenyl-2,3,4,5-tetramethyl-1-cyclopentadienyl) hafnium (IV) 
dichloride, racemic- ethylene bis (1-indenyl) titanium (IV) dichloride, 
racemic-ethylene bis (4,5,6,7-tetrahydro-1-indenyl) titanium (IV) 
dichloride, racemic- dimethylsilyl bis (1-indenyl) titanium (IV) 
dichloride, racemic- dimethylsilyl bis (4,5,6,7-tetrahydro-1-indenyl) 
titanium (IV) dichloride, racemic-1,1,2,2-tetramethylsilanylene bis 
(1-indenyl) titanium (IV) dichloride racemic-1,1,2,2-tetramethylsilanylene 
bis (4,5,6,7-tetrahydro-1-indenyl) titanium (IV) dichloride, and 
ethylidene (1-indenyl-2,3,4,5-tetramethyl-1-cyclopentadienyl) titanium IV) 
dichloride. 
The reaction products of the metallocene and aluminoxane which are 
generally solid materials when produced in aliphatic solvents and oils 
when produced in aromatic solvents can be recovered by any well known 
technique. For example, the solid material can be recovered from the 
liquid by vacuum filtration or decantation. The oils can be recovered by 
decantation, and when dried, become glassy solids. The recovered material 
is thereafter dried under a stream of pure dry nitrogen, dried under 
vacuum, or by any other convenient manner. The recovered solid is the 
catalytically active material. 
This catalytically active material, in accordance with the present 
invention, may be dissolved in a suitable solvent so as to be provided as 
a solution to the reaction zone. Of course, as was noted above, the 
catalytically active material, which is the reaction product of the 
metallocene and the aluminoxane, is most preferably and conveniently 
formed in situ by mixing the metallocene catalyst and the aluminoxane 
co-catalyst just prior to introducing the mixture into the reactor while 
providing enough residence time for the reaction to occur so as to form 
the catalytically active material. Although this embodiment is more 
desirable than first forming and separating the solid reaction product and 
then forming a solution thereof which is introduced into the reaction 
zone, this latter embodiment is still within the scope of the present 
invention. 
The amount of aluminoxane and metallocene usefully employed in preparation 
of the catalytically active material, whether the active material is 
formed in situ as it is being introduced into the gas phase reactor or 
formed well in advance and introduced as such while in liquid form, can 
vary over a wide range. The mole ratio of aluminum atoms contained in the 
aluminoxane to metal atoms contained in the metallocene is generally in 
the range of from about 2:1 to about 100,000:1, preferably in the range of 
from about 10:1 to about 10,000:1, and more preferably in the range of 
from about 50:1 to about 2,000:1. 
A metallocene is typically converted to an active catalyst with an ionizing 
agent such as the aluminoxanes discussed above. Such an ionizing agent 
reacts with the neutral metallocene to form a cationic metallocene which 
operates as the active catalyst. The ionizing agent can be a co-catalyst 
compound such as the aluminoxane or it may be an ionizing ionic compound 
that forms an anion which is chemically unreactive with the cationic 
metallocene. The anion is not coordinated or is loosely coordinated with 
the cationic metallocene. The use of such ionizing agents containing 
unreactive anions are disclosed in, for example, European Patent 
Application Publication Nos. 0 426 637, 0 426 638, and 0 427 697. Methods 
for generating cationic metallocenes are also disclosed in the following 
publications: European Patent Application Publication Nos. 0 277 003 and 0 
277 004; "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); 
"Synthesis and Insertion Reactions of Cationic 
Alkylbis(cyclopentadienyl)titanium Complexes," M. Bochmann, L. M. Wilson, 
J. Chem. Soc. Commun., p. 1610-1611 (1986); "Insertion Reactions of 
Nitriles in Cationic Alkylbis(cyclopentadienyl)titanium Complexes, M. 
Bochmann, L. Wilson, Organometallics, p. 1147-1154, Vol 7 (1987); and 
"Multiple Metal-Carbon Bonds," R.R. Schrock, P.P. Sharp, J. Am. Chem. Soc. 
p. 2389-2399, Vol 100 (1978). 
The ionizing ionic agent is typically mixed with an equimolar quantity of 
the neutral derivative of the metallocene producing the following 
reaction: 
EQU (C.sub.5 R.sub.x).sub.y R'.sub.z (C.sub.5 R.sub.m)MR".sub.2 
+[C][A].fwdarw.[(C.sub.5 R.sub.x).sub.y R'.sub.z (C.sub.5 
R.sub.m)MR"]+[A]-+R"[C] 
wherein: 
[C] is a carbonium, oxonium, or sulfonium cation 
[A] is an anion is not coordinated or is only loosely coordinated with the 
cationic metallocene and is chemically unreactive with the cationic 
metallocene 
R and R" are the same or different and is hydrogen or a hydrocarbyl radical 
such as alkyl, alkenyl, aryl, alkylaryl, or arylalkyl radical containing 
from 1 to 20 carbon atoms or two carbon atoms joined together to form a 
C.sub.4 -C.sub.6 ring; 
M is a metal of from Groups IIIB to VIII of the Periodic Table of the 
Elements; 
(C.sub.5 R.sub.x) and (C.sub.5 R.sub.m) are the same or different 
cyclopentadienyl or substituted cyclopentadienyl groups bonded to M; 
R' is a C.sub.1 -C.sub.4 substituted or unsubstituted alkylene radical, a 
dialkyl or diaryl germanium or silicon, or an alkyl or aryl phosphine or 
amine radical bridging two (C.sub.5 R.sub.x) and (C.sub.5 R.sub.m) rings; 
z is 0 or 1; 
y is 0, 1 or 2; 
z is 0 when y is 0; 
Ionizing ionic compounds containing a carbonium, oxonium, or sulfonium 
cation are applicable. Triphenylmethyltetrakis(pentafluorophenyl) borate 
is preferred. 
A catalyst system that does not require an aluminoxane includes metallocene 
complexes with one or more dinegative ligands substituted for the 
uninegative cyclopentadienyl ligands. The use of such compounds is 
disclosed in commonly assigned U.S. patent application Ser. No. 814,809, 
filed Dec. 31, 1991 now U.S. Pat. No. 5,214,173 and U.S. patent 
application Ser. No. 814,810, filed Dec. 31, 1991 now U.S. Pat. No. 
5,162,466. Examples of such polyolefin catalysts include: 
[C.sub.5 (CH.sub.3).sub.5 ][C.sub.2 B.sub.9 H.sub.11 ]ZrCH.sub.3 and 
[[C.sub.5 (CH.sub.3).sub.5 ][C.sub.2 B.sub.9 H.sub.11 ]Zr].sub.2 
-.mu.-CH.sub.2. 
As discussed, the present invention is particularly advantageous when 
utilizing two or more metallocene compounds. U.S. Pat. No. 4,530,914 
discloses the use of mixtures of at least two different metallocene 
compounds to control the molecular weight distribution. Mono or 
biscyclopentadienyl transition metal compound catalysts being homogeneous, 
produce polyolefins with narrow molecular weight distribution and narrow 
compositional distribution. Changes in the ligand substituents or metal 
component of the mono or biscyclopentadienyl transition metal compound are 
known to affect polymerization propagation and termination rate constants 
which in turn affect molecular weight and comonomer distribution of the 
resulting polyolefin product. The proper choice of a mixture of different 
mono or biscyclopentadienyl transition metal compound permits the control 
of molecular weight distribution and compositional distribution directly 
in the polymerization process without requiring energy intensive blending 
techniques following the polymerization. 
The polyolefins formed by the methods of the present invention may 
optionally contain dienes. Examples of suitable non-conjugated dienes are 
straight chain acyclic dienes such as 1,4-hexadiene, 1,5-hexadiene, 
1,7-octadiene, 1,9-decadiene and 1,6-octadiene; branched chain acyclic 
dienes such as 5-methyl-1,4-hexadiene, 3,7-dimethyl-1,6-octadiene, 
3,7-dimethyl-1,7-octadiene and mixed isomers of dihydromyricene and 
dihydrocinene; single ring alicyclic dienes such as 1,3-cyclopentadiene, 
1,4-cyclohexadiene, 1,5- cycloctadiene and 1,5-cyclododecadiene; and 
multi-ring alicyclic fused and bridged ring dienes such as 
tetrahydroindene, methyl tetrahydroindene, dicyclopentadiene, 
bicyclo-(2,2,1)-hepta-2,5-diene, alkenyl, alkylidene, cycloalkenyl and 
cycloalkylidene norbornenes such as 5-methylene-2-norbornene, 
5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, 
5-(4-cyclopentenyl)-2-norbornene, 5-cyclohexylidene-2-norbornene, 
5-vinyl-2-norbornene and norbornadiene. 
Conventional catalyst additives may be introduced into the reaction zone as 
part of the catalyst solution provided that they do not interfere with the 
desired atomization of the catalyst solution. In order for such additives 
to be added to the reaction zone as part of the catalyst solution, they 
must be liquids or capable of being dissolved in the catalyst solution. If 
the additives are solids, they can be introduced into the reaction zone 
independently of the catalyst solution. 
Such additives may include promoters, chain transfer agents, scavenging 
agents, and the like. Typical promoters include halogenated hydrocarbons 
such as CHCl.sub.3, CFCl.sub.3, CH.sub.3 CCl.sub.3, CF.sub.2 ClCCl.sub.3, 
and ethyltrichloroacetate, Such promoters are well known to those skilled 
in the art and are disclosed in, for example, U.S. Pat. No. 4,988,783. 
Chain transfer agents may be used to control polymer molecular weight. 
Examples of these compounds are hydrogen and metal alkyls of the general 
formula 
EQU M.sup.3 R.sup.5.sub.g (IX) 
where M.sup.3 is a Groups IA, IIA, or IIIA metal, R.sup.5 is an alkyl or 
aryl, and g is 1, 2, or 3. M.sup.3 R.sup.5 is preferably a zinc alkyl and 
is most preferably diethylzinc. Other organometallic compounds such as 
scavenging agents for poisons may also be employed to increase the 
catalyst activity. Examples of these compounds are also metal alkyls 
having the same general formula (V) as noted above and preferably are an 
aluminum alkyls, most preferably triisobutyl-aluminum. The use of these 
additives and the manner of doing so is well within the skill of those 
skilled in the art. 
The polymers that are produced in accordance with the present invention 
using the catalysts in liquid form have excellent properties and are at 
least equal to, if not better, than those obtainable with conventional, 
supported catalysts. These polymers have a narrow molecular weight 
distribution as measured by gel permeation chromatography with M.sub.w 
/M.sub.n values ranging from 2 to 4 and melt flow ratios of from 20 to 40. 
The molecular weight can be varied to obtain melt indices from 
approximately 0.1 to 1000 dg/min. Polymers with densities ranging from 
0.86 to 0.97 g/ml can be prepared by varying the amount of comonomer(s) 
used in the polymerization. The n-hexane extractables values obtained for 
the catalysts of the present invention are typically lower than the values 
that would be expected for conventional supported catalysts. The film 
appearance ratings and mechanical properties of the polymers are at most 
equal to those of the conventional catalysts. The melt temperatures and 
head pressures required for processing of the polymers are also at most 
equal to the conventional supported catalysts. The stereoregularities of 
polypropylenes prepared using the catalysts in the liquid form are 
comparable to those of the supported catalysts. Syndiotacticties as 
measured by .sup.13 CNMR with greater than 0.85 rrrr pentad fractions and 
isotacticites with greater than 0.85 mmmm pentad fractions are obtained. 
Catalyst activities are also at least equal to the conventional supported 
catalysts. 
EXAMPLES 
I. NOMENCLATURE 
The following terms and chemical abbreviations are used in the examples: 
MAO--solution of methyl aluminoxane in toluene, approximately 1.8 molar in 
aluminum, obtained from Ethyl Corporation (Baton Rouge, La.) 
MMAO in isopentane--solution of modified methyl aluminoxane containing 
isobutyl groups in isopentane, approximately 2.3 molar in aluminum, 
obtained from Akzo Chemicals Inc. as "MMAO-3A" (Chicago, Ill.) 
MMAO in heptane--solution of modified methyl aluminoxane containing 
isobutyl groups in heptane, approximately 2.3 molar in aluminum, obtained 
from Akzo Chemicals Inc. as "MMAO-3A" (Chicago, Ill.) 
iPrCp(Flu)ZrCl.sub.2 --isopropyl (cyclopentadienyl-9-fluorenyl) zirconium 
dichloride Me.sub.2 C(Cp)(Flu)ZrCl.sub.2 
DPZ--diphenylmethylene(cyclopentadienyl-9-fluorenyl) zirconium dichloride 
and lithium chloride .phi..sub.2 C(Cp)(Flu)ZrCl.sub.2 /2LiCl 
Me.sub.2 Si(Ind).sub.2 ZrCl.sub.2 --dimethylsilyl(bis-indenyl) zirconium 
dichloride 
(MeCp).sub.2 ZrCl.sub.2 --1,1'-bis-methylcyclopentadienyl zirconium 
dichloride obtained from Schering Berlin Polymers Inc. (Dublin, Ohio) 
(CH.sub.3 C.sub.5 H.sub.4).sub.2 ZrCl.sub.2 
Cp--C.sub.5 H.sub.5 cyclopentadienyl ligand 
Flu--Cl.sub.3 H.sub.8 fluorenyl ligand 
Ind--C.sub.9 H.sub.7 indenyl ligand 
sPP--syndiotactic polypropylene 
LLDPE--linear low density polyethylene 
EPDM--ethylene propylene ethylidene norbornene terpolymer 
EBDM--ethylene butene ethylidene norbornene terpolymer 
THF--tetrahydrofuran 
TIBA--triisobutyl aluminum 
ENB--5-ethylidene-2-norbornene 
"Std tube" means that the mixed catalyst/cocatalyst solutions were 
introduced into the reactor with nitrogen from a 1/8" Swagelok Tee through 
a 1/8" injection tube using a conventional positive displacement pumps and 
a continuous nitrogen source. The transition metal catalyst positive 
displacement pump delivers sharp shots of 0.1 ml once every 4-12 seconds 
depending on the desired catalyst feed rate. The MMAO positive 
displacement pump delivers a half-sine pulse form of injection for a 
period of about 3 seconds/pulse. 
"Nozzle" means the use of a pneumatic nozzle with the conventional positive 
displacement pumps and continuous nitrogen source. 
"Pulse" means that in addition to the sharp pulses from the catalyst pump, 
the MMAO was pumped in sharp shots (rather than the slow half-sine flow) 
coincident with the catalyst pump shots. In addition, a burst of about 3.5 
lb/hr of nitrogen was fed into the injector coincident with the pump 
strokes. This pulse feed technique was used with both the nozzle and the 
tube injectors. 
II. TEST METHODS AND TERMS 
C.sub.3 (wt %)--propylene content determined by .sup.1 HNMR 
ENB (wt %)--5-ethylidene-2-norbornene content determined by .sup.1 HNMR 
MF--melt flow--ASTM D-1238, Condition L measured at 230.degree. C. with a 
2160 g load, reported as grams per 10 minutes 
MI--melt index--ASTM D-1238, Condition E measured at 190.degree. C., 
reported as grams per 10 minutes 
FI--flow index--ASTM D-1238, Condition F measured at 190.degree. C. with a 
21.6 kg load 
MFR--melt flow ratio--FI/MI 
ICP--inductively coupled plasma analysis of metal residue 
APS--average particle size 
Density--a plaque is made and conditioned for one hour at 100.degree. C. to 
approach equilibrium crystallinity, measurement for density is then made 
in a density gradient column 
Bulk Density--the resin is poured via 3/8" diameter funnel into a 100 ml 
graduated cylinder to 100 ml line without shaking the cylinder, and 
weighed by difference 
Molecular Weight Distribution (M.sub.w /M.sub.n)--gel permeation 
chromatography; cross-linked polystyrene column, pore size sequence: 1 
column less than 1000 .ANG., 3 columns of mixed 5.times.10.sup.7 .ANG.; 
1,2,4-trichlorobenzene solvent at 140.degree. C. with refractive index 
detection 
Film Rating--a sample of film is viewed with the naked eye to note the size 
and distribution of gels or other foreign particles in comparison to 
standard film samples; the appearance of the film as thus compared to the 
standard samples is then given a rating on a scale of -100 (very poor) to 
+100 (excellent) 
n-hexane extractables--(FDA test used for polyethylene film intended for 
food contact applications); a 200 square inch sample of 1.5 mil gauge film 
is cut into strips measuring 1".times.6" and weighted to the nearest 0.1 
mg; the strips are placed in a vessel and extracted with 300 ml of 
n-hexane at 50.degree..+-.1.degree. C. for 2 hours; the extract is then 
decanted into tared culture dishes; after drying the extract in a vacuum 
desiccator the culture dish is weighed to the nearest 0.1 mg; the 
extractables normalized with respect to the original sample weight is then 
reported as the weight fraction of n-hexane extractables 
Stereoregularity--determined by .sup.13 CNMR; calculations follow the work 
of F.A. Bovey in "Polymer Conformation and Configuration", Academic Press, 
New York, 1969 
III. SYNTHESIS 
The following sets forth the synthesis for the catalysts that were used in 
the examples: 
1. Synthesis of isopropyl(cyclopentadienyl fluorenyl)zirconium dichloride 
The isopropyl(cyclopentadienyl fluorenyl)zirconium dichloride, was prepared 
as follows. The ligand was prepared under nitrogen by dropwise addition 
over a 5 minute period of 118 ml of a hexane solution of 1.6 M butyl 
lithium to a -20.degree. C. stirring solution of 30.6 g fluorene dissolved 
in 300 ml THF and contained in a 1 liter round bottom flask equipped with 
a side arm and a dropping funnel. The dark orange solution was slowly 
warmed to ambient temperature with stirring over a two hour period and 
during that period gas evolution ceased. The solution was cooled to 
-78.degree. C. and a solution of 20.4 g 6,6-dimethylfulvene dissolved in 
200 ml THF was added dropwise over a 30 minute period. The red THF 
solution was gradually warmed to ambient temperature and stirred 
overnight. The solution was then mixed with 300 ml water and stirred for 
10 minutes. THF was removed by rotary evaporation and the slurry was 
extracted with 600 ml hexane. The organic layer was separated, dried over 
magnesium sulfate, hexane was removed via rotary evaporation, and 31 g 
(70% yield) of pale yellow needles of isopropyl(cyclopentadiene-9- 
fluorene) were obtained by recrystallization from 300 ml of absolute 
ethanol. An additional 15% yield was obtained by concentrating and cooling 
the filtrate. 
The metallocene was prepared by first generating the 
isopropyl(cyclopentadienyl-9-fluorenyl) dianion via dropwise syringe 
addition of 74 ml of a hexane solution of 1.6 M butyl lithium to a 
-30.degree. C. solution of 16.2 g of the ligand dissolved in 400 ml THF 
contained in a 500 ml round bottom flask equipped with a side arm. The 
solvents were removed under high vacuum, the solid red dilithio salt was 
cooled to -100.degree. C., and 400 ml dichloromethane was added. A slurry 
of 13.8 g ZrCl.sub.4 in 70 ml dichloromethane was rapidly cannulated into 
the stirring slurry of the dianion. The mixture was stirred for 2 hours at 
-100.degree. C., allowed to warm slowly to ambient temperature, and 
stirred overnight. White LiCl, a red solid, and a red solution were 
separated via centrifugation. 4.7 g (18% yield) iPr[CpFlu]ZrCl.sub.2 was 
obtained by concentrating the supernatant liquid. The red solid was 
extracted with dichloromethane to obtain an additional 20% yield. 
2. Synthesis of diphenylmethylene (cyclopentadienyl)(fluorenyl)zirconium 
dichloride 
A solution of n-butyllithium in hexane (75 ml, 187.5 mmol) was added 
dropwise under nitrogen to a stirred solution of 30.45 g (183 mmol) 
fluorene in 225 ml THF held at ambient temperature by immersion in a cold 
water bath. The resulting deep red mixture was stirred for 1.5 hours. 
A solution of 42.76 g (186 mmol) diphenylfulvene in 200 ml THF was added to 
this fluorenyl anion solution via an addition funnel. The mixture was 
stirred for 40 h at room temperature. 
The reaction mixture was quenched by careful addition of 300 ml saturated 
aqueous ammonium chloride. The organic fraction was collected, combined 
with ether washings of the aqueous fraction, and stripped of most of the 
solvent on a rotary evaporator, leaving an orange slurry. 250 ml diethyl 
ether were added to this slurry, the mixture was filtered, and the solid 
washed with additional ether. The solid was dried in vacuo overnight, 
yielding 31.09 g of (Cyclopentadienyl)(fluorenyl) diphenylmethane (43%). 
A solution of methyllithium in diethyl ether (115 ml, 161 mmol) was added 
dropwise to 30.98 g (78 mmol) of the (cyclopentadienyl)(fluorenyl) 
diphenylmethane slurried in 500 ml THF held at 0.degree. C. Following the 
addition, the solution was allowed to warm to ambient temperature. After 2 
hours, most of the solvents were removed from the blood-red solution in 
vacuo and 400 ml hexane were stirred with the red slurry overnight. The 
brown solid was collected on a filter and dried for 3 hours in vacuo. 
38.99 g of dilithio(cyclopentadienyl) (fluorenyl)diphenylmethane 
bis(tetrahydrofuran) were obtained, 90%. 
16.6 g (71 mmol) solid zirconium tetrachloride under argon were slowly 
added to a slurry of 38.99 g (71 mmol) of dilithio(cyclopentadienyl) 
(fluorenyl)diphenylmethane bis(tetrahydrofuran) (71 mmol) in 250 ml 
hexane. The slurry was stirred at room temperature overnight. The 
resulting slurry was centrifuged to settle the solids. The supernatant was 
removed by cannula and discarded, while the solid residues were dried in 
vacuo for 3.25 h. The result was a mixture of 
diphenylmethylene(cyclopentadienyl)(fluorenyl) zirconium dichloride and 
lithium chloride, 45.57 g (100%). 
3. Synthesis of dimethylsilylbis(indenyl) zirconium dichloride 
A solution of 51 g (440 mmol) indene in 200 ml THF under N.sub.2 was cooled 
in an ice bath. Slowly, 185 ml n- BuLi/hexanes (2.5 M) were added, turning 
the pale yellow solution red-brown. The solution was stirred for 2.5 
hours, then cooled to -78.degree. C. To this solution were added 27.1 g 
(210 mmol) dichlorodimethylsilane. The red solution was stirred for 64 
hours at ambient temperature, followed by reflux for one hour. The ligand 
solution was washed with 0.6 M aqueous NaCl solution, separated, combined 
with ether washings, dried with anhydrous MgSO.sub.4, filtered, and 
reduced in vacuo to a dark-brown oil. The oil was dissolved in 100 ml 
hexanes and run down a column of silica gel/hexanes. All yellow fractions 
were recovered and reduced to a viscous orange liquid, from which 16.5 g 
were removed and dissolved in 250 ml THF. To this solution were added 48 
ml (120 mmol) 2.5 M n-BuLi/hexanes at 0.degree. C. This solution was 
stirred at ambient temperature for 1.5 hours, turning brown-black. This 
solution was transferred to a flask containing 21.3 g (56 mmol) zirconium 
tetrachloride-THF solvate in 200 ml THF. The resulting orange-brown slurry 
was stirred overnight. The slurry was then reduced in vacuo to 250 ml, 
then combined with 700 ml dry hexanes and stirred for about 0.5 hour, 
resulting in a black tar at bottom. The supernatant was decanted and 
stripped of all solvents. The tarry orange mass was then broken up in 100 
ml hexanes and stirred overnight, followed by filtration and drying. 
Another 1.7 g metallocene were recovered by repetition of the hexane/THF 
washing step. The combined yield of crude dimethylsilylbis(indenyl) 
zirconium dichloride: 5.0 g (20%). 
EXAMPLES 1 TO 25 
In Examples 1 to 25, polypropylene, LLDPE, EPDM and EBDM were prepared in a 
horizontally mixed reactor with various metallocene catalyst solutions. 
FIG. 2 depicts the horizontally mixed reactor system. This reactor was a 
two-phase (gas/solid) stirred bed, back mixed reactor. A set of four 
"plows" 100 were mounted horizontally on a central shaft rotating at 200 
rpm to keep the particles in reactor 110 mechanically fluidized. The 
reactor cylinder swept by these plows measured 40.6 cm (16 in.) long by 
39.7 cm (15.6 in.) in diameter, resulting in a mechanically fluidizable 
volume of 46 liters (1.6 ft.sup.3). The gas volume, larger than the 
mechanically fluidizable volume due to the vertical cylindrical chamber, 
totaled 54.6 liters (1.93 ft.sup.3). A disengager vessel 120 was mounted 
atop reactor 110. This vessel had a gas volume of 68 liters (2.41 
ft.sup.3), more than doubling the gas volume of the reactor. Gas was 
continually recirculated through both the reactor and disengager via a 
blower 130, so that the gas composition was homogeneous throughout. 
The reactor pressure used was typically 300-400 psig. Monomers and hydrogen 
(for molecular weight control) were fed to the reactor continuously via 
control valves through line 140. Partial pressures of monomer ranged 
typically between 150-300 psi. Comonomer (if any) was introduced via 
control valves through line 150 and vaporizer 160 and its content in the 
polymer was controlled by adjusting feed rates to maintain a constant 
comonomer/monomer molar ratio in the gas phase. Gas composition was 
measured at 4-6 minute intervals by a gas chromatograph analyzer. 
Molecular weight of the polymer was controlled by adjusting hydrogen feed 
rate to maintain a constant mole ratio of hydrogen to monomer in the gas 
phase. Nitrogen made up the majority of the balance of the composition of 
the gas, entering with the catalyst through line 170 and leaving via a 
small vent 180 with the reactor gases including volatilized solvents. The 
vent opening was adjusted via computer to maintain constant total pressure 
in the reactor. 
The reactor was cooled by an external jacket of chilled glycol. The bed 
temperature was measured with a temperature probe in a thermowell 
protruding into the bed at a 60.degree. angle below horizontal, between 
the inner set of plows. Reactor temperature were controlled to values in 
the range of 10.degree.-110.degree. C., although 50.degree.-85.degree. C. 
were typical for LLDPE and polypropylene production. 
Solution catalyst is metered in shots via line 190 and mixed with a 
continuous stream of methylaluminoxane co-catalyst solution introduced via 
line 200. This mixture is fed through a coil 210 of 1/8" tubing where the 
components react for typically 2-10 minutes. Upon leaving this precontact 
coil, the mixed solution feed is sprayed into the reactor by a constant 
flow of nitrogen. This spray can be directed into the bed or above the 
bed, as desired. 
Typical batch yields of granular polymer in this reactor are 20-25 lbs, 
with 30-35 lbs being the upper limit. Batch runs typically last 3-6 hours. 
Alternatively, the reactor can be run in continuous mode, in which 
granular polymer is withdrawn at 220 in typically 0.4 lb portions while 
the polymerization is in progress. In the continuous mode, the product 
discharge system is enabled after the bed weight builds to typically 15-25 
lbs, and the rate of discharge is altered to maintain constant bed weight. 
A typical run commences with monomers being charged to the reactor and 
feeds adjusted until the desired gas composition is reached. An initial 
charge of cocatalyst is added prior to starting catalyst feeding in order 
to scavenge any poisons present in the reactor. After catalyst feed 
starts, monomers are added to the reactor sufficient to maintain gas 
concentrations and ratios. As the catalyst inventory builds up, polymer 
production rate increases to 5-10 lbs/hr, at which point catalyst feed is 
adjusted to maintain constant polymer production rate. Cocatalyst feed 
rate is maintained in proportion to the catalyst feed rate. If a 
long-lived catalyst such as a metallocene is used, the catalyst and 
cocatalyst feeds can be turned off well before the batch weight target is 
achieved, since sufficient activity is often retained to continue 
polymerization for many hours. After the desired batch weight is made, the 
reactor is quickly vented, and monomers are purged from the resin with 
nitrogen. The batch is then discharged through valve 220 to the open 
atmosphere. 
TABLE I 
______________________________________ 
Preparation of LLDPE with bis (MeCp).sub.2 ZrCl.sub.2 /MMAO.sup.1 : 
Ethylene-Hexene Copolymers 
Example 
1 2 
______________________________________ 
Catalyst Injection Parameters 
Catalyst Feed Rate (cc/hr) 
23.4 15.6 
Cocatalyst Feed Rate (cc/hr) 
150 100 
Nitrogen Carrier Rate (lb/hr) 
1-1.3 1-1.3 
Nitrogen Carrier Velocity (cm/sec) 
140-180 140-180 
Al/Zr (aim) 2000 2000 
Precontact Time (min) 
7 10 
Injection Configuration 
Std tube Std tube 
Polymerization Conditions 
Temperature (.degree.C.) 
50 60 
Total Pressure (psig) 
300 300 
Ethylene Partial Pressure (psi) 
140 140 
H.sub.2 /C.sub.2 (molar ratio) 
0 0 
C.sub.6 /C.sub.2 (molar ratio) 
0.022 0.022 
Polymer Measurements 
MI (dg/min) 0.30 0.16 
Density (g/cc) 0.918 0.916 
Bulk Density (lbs/ft.sup.3) 
13 14 
APS (in) -- 0.065 
Yield (lb) 10.5 11.7 
Zr Residue by ICP (ppmw) 
4.2 3.4 
______________________________________ 
.sup.1 MMAO in nheptane 
TABLE II 
__________________________________________________________________________ 
Preparation of LLDPE with DPZ/MMAO.sup.1 : Ethylene-Butene Copolymers 
Example 
3 4 5 6 7 8 
__________________________________________________________________________ 
Catalyst Injection Parameters 
Catalyst Feed Rate (cc/hr) 
45.2 31.4 31.4 45.2 90.5 24 
Cocatalyst Feed Rate (cc/hr) 
66 91 137 66 66 10.5 
Nitrogen Carrier Rate (lb/hr) 
0.5 0.5 0.5 0.5 0.5 0.5 
Nitrogen Carrier Velocity (cm/sec) 
60 60 60 60 60 60 
Al/Zr (aim) 500 1000 1500 500 250 1500 
Precontact Time (min) 
11 10 7 11 8 9 
Injection Configuration 
Std tube 
Std tube 
Std tube 
Std tube 
Std tube 
Std tube 
Polymerization Conditions 
Temperature (.degree.C.) 
70 75 75 75 75 85 
Total Pressure (psig) 
350 350 350 350 350 350 
Ethylene Partial Pressure (psi) 
240 240 240 240 240 240 
H.sub.2 /C.sub.2 (molar ratio) 
0.015 
0 0.015 
0.015 
0.015 
0.01 
C.sub.4 /C.sub.2 (molar ratio) 
0.035 
0.015 
0.02 0.024 
0.024 
0.022 
Resin Properties 
MI (dg/min) 0.44 NF 3.0 0.7 0.5 0.7 
Density (g/cc) 0.908 
0.92 0.93 0.920 
0.919 
0.919 
Bulk Density (lbs/ft.sup.3) 
20 23 27 26 20 27 
APS (in) 0.07 0.05 0.05 0.07 0.1 0.06 
Yield (lb) 29.5 -- -- 25.3 19.2 -- 
Zr Residue Predicted (ppmw) 
2.7 -- -- 3.2 4.3 -- 
__________________________________________________________________________ 
.sup.1 MMAO in isopentane 
TABLE III 
______________________________________ 
Preparation of LLDPE with DPZ/MMAO.sup.1 : 
Ethylene-Hexene Copolymers 
Example 
9 10 11 12 
______________________________________ 
Catalyst Injection 
Parameters 
Catalyst Feed Rate 
31.4 41.5 41.5 31.4 
(cc/hr) 
Cocatalyst Feed Rate 
137 185 185 137 
(cc/hr) 
Nitrogen Carrier Rate 
0.5 0.5 0.5 0.5 
(lb/hr) 
Nitrogen Carrier 
60 60 60 60 
Velocity (cm/sec) 
Al/Zr (aim) 1500 1400 1400/ 1500 
Precontact Time (min) 
7 6 6 7 
Injection Std tube Std tube Std tube 
Std tube 
Configuration 
Polymerization 
Conditions 
Temperature (.degree.C.) 
75 75 75 85 
Total Pressure (psig) 
350 350 350 350 
Ethylene Partial 
240 240 240 240 
Pressure (psi) 
H.sub.2 /C.sub.2 (molar ratio) 
0.016 0.016 0.016 0.012 
C.sub.6 /C.sub.2 (molar ratio) 
0.0053 0.003 0.003 0.0043 
Resin Properties 
MI (dg/min) 0.7 7.0 -- 0.7 
Density (g/cc) 
0.913 0.934 0.937 0.915 
Bulk Density (lbs/ft.sup.3) 
17 26 25 22 
APS (in) 0.068 0.056 0.06 0.083 
Yield (lb) 30.8 21.5 20.2 20.0 
Zr Residue by ICP 
1.5 5.1 4.9 2.2 
(ppmw) 
______________________________________ 
.sup.1 MMAO in isopentane 
TABLE IV 
______________________________________ 
Effect of Nozzle Configuration on LLDPE Production 
Using DPZ/MMAO.sup.1 : Ethylene-Hexene Copolymers 
Example 
13 14 15 
______________________________________ 
Catalyst Injection Parameters 
Catalyst Feed Rate (cc/hr) 
41.6 41.6 41.6 
Cocatalyst Feed Rate (cc/hr) 
185 185 185 
Nitrogen Carrier Rate (lb/hr) 
0.5 0.25/3.5 0.25/3.5 
Nitrogen Carrier Velocity 
-- -- 30/420 
(cm/sec) 
Al/Zr (aim) 1400 1400 1400 
Precontact Time (min) 
6 6 6 
Injection Configuration 
Nozzle Nozzle/ Tube/Pulse 
Pulse 
Polymerization Conditions 
Temperature (.degree.C.) 
75 75 75 
Total Pressure (psig) 
350 350 350 
Ethylene Partial Pressure (psi) 
240 240 240 
H.sub.2 /C.sub.2 (molar ratio) 
0.01 0.01 0.01 
C.sub.6 /C.sub.2 (molar ratio) 
0.005 0.006 0.006 
Resin Properties 
MI (dg/min) 3.5 2.8 2.0 
Density (g/cc) 0.927 0.923 0.924 
Bulk Density (lbs/ft.sup.3) 
23 20 15 
APS (in) 0.065 0.069 0.08 
Yield (lb) 23.8 23.0 23.5 
Zr Residue Predicted (ppmw) 
4.0 4.0 3.8 
______________________________________ 
.sup.1 MMAO in isopentane 
TABLE V 
__________________________________________________________________________ 
Preparation of EPDM (EBDM) with DPZ/MMAO.sup.1 
Example 
16 17 18 19 (EBDM) 
__________________________________________________________________________ 
Catalyst Injection Parameters 
Catalyst Feed Rate (cc/hr) 
60 45.2 45.2 72 
Cocatalyst Feed Rate (cc/hr) 
182 133 133 211 
Nitrogen Carrier Rate (lb/hr) 
0.5 0.5 0.5 0.5 
Nitrogen Carrier Velocity (cm/sec) 
60 60 52 52 
Al/Zr (aim) 1000 1000 1000 1000 
Precontact Time (min) 
3.3 4.3 4.3 2.7 
Injection Configuration 
Std tube 
Std tube 
Std tube 
Std tube 
Polymerization Conditions 
Temperature (.degree.C.) 
40 50 55 50 
C.sub.3 /C.sub.2 (molar ratio) 
0.08 0.079 
0.11-0.108 
0.12-0.045 C.sub.4 
ENB Fed (wt %) 3.5 3.8 6.7 3.3 
Carbon Black (wt %) 
23 25 28 15 
Polymer Measurements 
FI (dg/min) 33 36 51 7.5 
C.sub.3 (wt %) 18 15 21 19 C.sub.4 
ENB (wt %) 2.4 3.1 4.2 3.5 
Yield (lb) 17.3 16.1 14.5 19.7 
Zr Residue Predicted (ppmw) 
21 22 20 14 
__________________________________________________________________________ 
.sup.1 MMAO in isopentane 
TABLE VI 
______________________________________ 
Preparation.sup.1 of Syndiotactic Polypropylene (sPP) 
with iPrCp(Flu)ZrCl.sub.2 /MMAO.sup.2 
Example 
20 
______________________________________ 
Catalyst Injection Parameters 
Catalyst Feed Rate (cc/hr) 
31.5 
Cocatalyst Feed Rate (cc/hr) 
202 
Nitrogen Carrier Rate (lb/hr) 
0.8-1 
Nitrogen Carrier Velocity (cm/sec) 
110-140 
Al/Zr (aim) 1600/1780 
Precontact Time (min) 5 
Injection Configuration 
Std tube 
Polymerization Conditions 
Temperature (.degree.C.) 
60 
Total Pressure (psig) 300 
Propylene Partial Pressure (psi) 
225 
H.sub.2 /C.sub.3 (molar ratio) 
0 
Polymer Measurements 
MF (dg/min) 132 
Bulk Density (lbs/ft.sup.3) 
25 
APS (in) 0.09 
Yield (lb) 26 
Zr Residue by ICP (ppmw) 
2.3 
______________________________________ 
.sup.1 Initial Polymer Bed of sPP 
.sup.2 MMAO in heptane 
TABLE VII 
______________________________________ 
Preparation (No Pre-Bed) of Syndiotactic Polypropylene (sPP) 
with iPrCp(Flu)ZrCl.sub.2 /MMAO.sup.1 
Example 
21 22 23 24 
______________________________________ 
Catalyst Injection 
Parameters 
Catalyst Feed Rate 
31.5 31.5 31.5 15.6-22 
(cc/hr) 
Cocatalyst Feed Rate 
253 202 202 141-202 
(cc/hr) 
Nitrogen Carrier Rate 
0.8-1 0.8-1 0.8-1 1.3 
(lb/hr) 
Nitrogen Carrier 
110-140 110-140 110-140 
180 
Velocity (cm/sec) 
Al/Zr (aim) 2000/1625 
1600/1450 
1600/1460 
1600/-- 
Precontact Time (min) 
4 5 5 5-7 
Injection Configuration 
Std tube Std tube Std tube 
Std tube 
Polymerization 
Conditions 
Temperature (.degree.C.) 
25 50 60 70 
Total Pressure (psig) 
300 300 300 300 
Propylene Partial 
120 210 225 225 
Pressure (psi) 
H.sub.2 /C.sub.3 (molar ratio) 
0 0 0 0 
Polymer 
Measurements 
MF (dg/min) 35 82 60 351 
Bulk Density (lbs/ft.sup.3) 
14 25 2631 
APS (in) 0.06 0.10 0.07 0.07 
Yield (lb) 18 25 25 23 
Zr Residue by ICP 
6.6 2.5 2.1 3.2 
(ppmw) 
______________________________________ 
.sup.1 MMAO in heptane 
TABLE VIII 
______________________________________ 
Preparation (No Pre-Bed) of Isotactic Polypropylene (iPP) 
with Me.sub.2 Si(Ind).sub.2 ZrCl.sub.2 /MMAO.sup.1 
Example 
25 
______________________________________ 
Catalyst Injection Parameters 
Catalyst Feed Rate (cc/hr) 
8.4-10.8 
Cocatalyst Feed Rate (cc/hr) 
250 
Nitrogen Carrier Rate (lb/hr) 
1-1.3 
Nitrogen Carrier Velocity (cm/sec) 
140-180 
Al/Zr (aim/ICP) 1500/2000 
Precontact Time (min) 4.5 
Injection Configuration 
Std tube 
Polymerization Conditions 
Temperature (.degree.C.) 
50 
Total Pressure (psig) 300 
Propylene Partial Pressure (psi) 
210 
H.sub.2 /C.sub.3 (molar ratio) 
0 
Polymer Measurements 
MF (dg/min) &gt;1000 
Bulk Density (lbs/ft.sup.3) 
23 
APS (in) 0.04 
Yield (lb) 6.7 
Zr Residue Predicted (ppmw) 
12 
______________________________________ 
.sup.1 MMAO in nheptane 
EXAMPLES 26 TO 28 
In Examples 26 through 28, LLDPE was prepared in a fluid bed reactor with 
DPZ solutions. FIG. 1 depicts the reaction system employed for these 
examples. The reactor had a lower section 10 feet high and 13.5 inches in 
inner diameter and an upper section which was 16 feet high and 23.5 inches 
in inner diameter. The orange 7 millimolar solution of DPZ catalyst in 
methylene chloride and the colorless 2 molar cocatalyst solution of Akzo 
MMAO Type 3A in isopentane were fed with a syringe pumps through a coil of 
1/8" tubing. The components typically reacted for two minutes in this 
precontact coil. Upon leaving this coil, the purple mixed solution feed 
was sprayed into the reactor by a constant flow of nitrogen and 
isopentane. This spray was directed into different places in the bed or 
above the bed, as desired. A 5% solution of TIBA was fed separately into 
the bed at a level of four feet above the gas distributor plate. 
TABLE IX 
__________________________________________________________________________ 
LLDPE Preparation in a Fluid Bed Reactor with DPZ Solutions 
Example 
26 27 28 
__________________________________________________________________________ 
Catalyst Injection Parameters 
DPZ Feed (cc/hr) 
50 50 100 
MMAO Feed (cc/hr) 
150 150 200 
TIBA Feed (cc/hr) 
244 284 623 
MMAO Al/Zr 1095 1095 727 
TIBA Al/Zr 246 287 367 
N2 Carrier Feed Rate (lb/hr) 
1 2.5 2 
N2 Carrier Velocity (cm/sec) 
185 462 370 
iC5 Carrier Feed Rate (lb/hr) 
2 3.5 3 
Liquid Velocity (cm/sec) 
19 32 29 
Configuration straight tube 
Tube with angled 
straight tube 
into bed 
orifice shot into 
into bed 
1 ft level) 
top of bed 
(1 ft level) 
(8 ft level).sup.1 
Polymerization Conditions 
Temperature (/C.) 
80 80 65 
Pressure (psig) 
350 350 370 
C2 Part. Pres. (psia) 
250 250 250 
C6/C2 0.0035 0.0035 0 
H2/C2 0.015 0.015 .010-.015 
Bed Weight (lbs.) 
98 117 113 
Fluidized Bulk Density (lb/ft3) 
10 to 12 
12 12 to 16 
Production rate (lb/hr) 
23 25 12 
Catalyst Residence Time (hr) 
4.4 4.7 9.4 
Superficial Vel. (ft/sec) 
.about. 1.7 
.about.1.7 
.about.1.7 
Polymer Measurements 
MI (dg/min) 0.57 1.78 3.45 
Density (g/cc) 0.92 0.923 0.954 
Bulk Density (lb/ft3) 
19.6 20.7 33 
APS (inches) 0.09 0.06 0.03 
Zr Residue Predicted (ppm) 
3.1 2.8 12 
__________________________________________________________________________ 
.sup.1 Straight tube having a plugged end and a 45.degree. angled side 
opening. 
EXAMPLES 29 AND 30 
Examples 29 and 30 set forth a comparison of preparing polyolefin resin 
using the reaction product of iPrCp(Flu)ZrCl.sub.2 and MAO when on a 
silica support and in an unsupported liquid form to demonstrate that the 
activity of the catalytically active reaction product is greater when 
utilized in the unsupported liquid form, in accordance with the present 
invention. 
EXAMPLE 29--COMATIVE EXAMPLE 
Preparation of Supported iPrCp(Flu)ZrCl.sub.2 and MAO on Silica 
In a Vacuum Atmospheres dry box, 0.0171 g iPrCp(Flu)ZrCl.sub.2 was 
dissolved in 14.5 g distilled toluene. 11.3 g of the orange solution 
(0.0308 mmol Zr) was added to 17 ml of a colorless toluene solution of 
methyl aluminoxane (30.6 mmol Al) obtained from Ethyl Corporation. The 
resulting purple solution was stirred for 5 min, then added to 20.04 g 
Davison 955 silica which had been dehydrated at 600.degree. C. The mixture 
was stirred to yield a free-flowing material, then evacuated at 0.3 mm Hg 
for 2.5 hours. A pink solid weighing 21.2 g was recovered (0.00145 mmol 
Zr/g and 1.4 mmol Al/g). 
Liquid Propylene Polymerization of Supported iPrCp(Flu)ZrCl.sub.2 and MAO 
on Silica 
In a Vacuum Atmospheres dry box, 2.06 g (0.00299 mmol Zr) of the supported 
iPrCp(Flu)ZrCl.sub.2 and MAO on silica was added to a stirring solution 
consisting of 20 ml distilled toluene and 0.5 ml of a toluene solution of 
MAO (1.8 M in Al). 
A one-liter stirred autoclave reactor was dried by heating at a temperature 
of greater than 96.degree. C. under a stream of nitrogen for 20 min. After 
cooling the reactor to 21.degree. C., the slurry containing the supported 
catalyst was transferred to the reactor via cannula followed by 800 ml of 
liquid propylene. The reactor was sealed, stirred at 22.degree. C. for 
five min, then heated to 83.degree. C. for an instant, followed by a 30 
minute polymerization at 40.degree. C. 6.63 g of product was obtained 
which corresponds to 31% silica and an activity of 1530 g sPP/mmol Zr. 
EXAMPLE 30 
Liquid Propylene Polymerization of iPrCp(Flu)ZrCl.sub.2 
In a Vacuum Atmospheres dry box, 0.0143 g (0.0331 mmol Zr) 
iPrCp(Flu)ZrCl.sub.2 was dissolved in 12.39 g distilled toluene. 0.9714 g 
of this solution (0.00259 mmol Zr) and 1.5 MAO (2.70 mmol) were stirred 
for 5 min. 
A one-liter stirred autoclave reactor was dried by heating at a temperature 
of greater than 96.degree. C. under a stream of nitrogen for 20 min. After 
cooling the reactor to 21.degree. C., the slurry containing the catalyst 
in liquid form was transferred to the reactor via syringe followed by 800 
ml of liquid propylene. The reactor was sealed, stirred at 22.degree. C. 
for 5 min, then heated to 66.degree. C. for an instant, followed by a 30 
minute polymerization at 40.degree. C. 34.83 g of product was obtained, 
corresponding to an activity of 13,400 g sPP/mmol Zr, an activity value 
which is about 9 times greater than that obtained in Comparative Example 
29 where the same catalyst was used on a support.