CA2026338A1

CA2026338A1 - Process for producing sticky polymers

Info

Publication number: CA2026338A1
Application number: CA002026338A
Authority: CA
Inventors: Seung J. Rhee; Edgar C. Baker; David N. Edwards; Kiu H. Lee; John H. Moorhouse; Leonard S. Scarola; Frederick J. Karol
Original assignee: Seung J. Rhee; Edgar C. Baker; David N. Edwards; Kiu H. Lee; John H. Moorhouse; Leonard S. Scarola; Frederick J. Karol; Union Carbide Chemicals And Plastics Company Inc.; Union Carbide Chemicals And Plastics Company
Current assignee: Union Carbide Chemicals and Plastics Technology LLC
Priority date: 1989-09-28
Filing date: 1990-09-27
Publication date: 1991-03-29
Also published as: ATE190069T1; FI904765A0; MX167157B; AR244251A1; AU6316190A; KR910006331A; CN1051737A; DE69033470D1; EP0422452A2; EP0422452B1; NO904203D0; JPH03217402A; AU620736B2; DE69033470T2; NO904203L; JPH0647606B2; US4994534A; HU906245D0; ES2142788T3; EP0422452A3

Abstract

PROCESS FOR PRODUCING STICKY POLYMERS
ABSTRACT
A process for producing sticky polymers at polymerization reaction temperatures in excess of the softening temperature of the sticky polymers in a fluidized bed reactor catalyzed by a transition metal catalyst, which comprises conducting the polymerization reaction above the softening temperatures of the sticky polymers in the presence of about 0.3 to about 60 weight percent, based on the weight of the final product of an inert particulate material having a mean particle size of from about 0.01 to about 10 micron meters whereby polymer agglomeration of the sticky polymers is maintained at a size suitable for continuously producing the sticky polymers.

Description

2 ~ 3 ~ ~3 ROCESS FOR PRODUCING STICKY POLYMERS
BACKGROUND OF THE INVENTION

Field of the Invention The present invention relates to a process for producing sticky polymers and more particularly to a process for producing sticky polymers in gas phase reactors at reaction temperatures in excess of the softening temperature of said sticky polymers.
Description of the Prior Art The introduction of high activity Ziegler-Natta catalyst systems has lead to the development of new polymerization processes based on gas phase reactors such as disclosed in U.S. Patent 4,482,687 issued November 13, 1984. These processes offer many advantages over bulk monomer slurry processes or solvent processes. They are more economical and inherently safer in that they eliminate the need to handle and recover large quantities of solvent while advantageously providing low pressure process operation.
The versatility of the gas phase fluid bed reactor has contributed to its rapid acceptance.
Alpha-olefins polymers produced in this type ~f reactor cover a wide range of density, molecular weight distribution and melt indexes. In fact new and better products have been synthesized in gas phase reactors because of the flexibility and adaptability of the gas phase reactor to a large s~ectrum of operating conditions.
The term "sticky polymer" is defined as a 2~2~33~, polymer, which, although particulate at temperatures below the sticking or softening temperature, agglomerates at temperatures above the sticking or softening temperature. The term "sticking temperature", which, in the context of this specification, concerns the sticking temperature of particles of polymer in a fluidized bed, is defined as the tempera~ure at which fluidization ceases due to excessive agglomeration of particles in the bed.
The agglomeration may be spontaneous or occur on short periods of settling.
A polymer may be inherently sticky due to its chemical or mechanical properties or pass through a sticky phase during the production cycle.
Sticky polymers are also referred to as non-free flowing polymers because of their tendency to compact into agglomerates of much larger size than the original particles. Polymers of this type show acceptable fluidity in a gas phase fluidized bed reactor; however, once motion ceases, the additional mechanical force provided by the fluidizing gas passing through the distributor plate is insufficient to break up the agglomerates which form and the bed will not refluidize. These polymers are classified as those, which have a minimum bin opening for free flow at zero storage time of two feet and a minimum bin opening for free flow at storage times of greater than five minutes of 4 to 8 feet or more.
Sticky polymers can also be defined by their bulk flow properties. This is called the Flow Function. On a scale of zero to infinity, the Flow , 3 Function of free flowing materials such as dry sand is infinite. The Flow Function of free flowing polymers is about 4 to 10, while the Flow Function of non-free flowing or sticky polymers is about 1 to 3.
Although many variables influenc~ the degree of stickiness of the resin, it is predominantly governed by the temperature and the crystallinity of the resin. Higher temperatures of the resin increase its stickiness while less crystalline products such as very low density polyethylene (VLDPE), ethylene/propylene monomer (EPM), ethylene/propylene diene monomer (EPDM) and polypropylene (PP) copolymers usually display a larger tendency to agglomerate to form larger particles.
Thus the prior art has heretoore attempted to produce polymers at temperatures below the softening temperature of the polymers. This is based primarily on the fact that operating at or above the softening temperature would cause serious agglomeration problems. Indeed BP Chemicals Limited, PCT International Publication Number WO
88/0237g, published April, 1988 which discloses use of 0.005% to less than 0.2% of a pulverulent inorganic substance during the reaction, nevertheless cautions against the use of temperatures in excess of the softening temperatures of the produced polyolefin. Moreover, this reference specifically discourages use of quantities of pulverulent inorganic substances in the reactor in excess of 0.2% by weight since as stated therein - 4 - 2~P3 there is no further improvement in the polymeriz-ation or copolymerization process in the gaseous phase and use of amounts in excess of 0.2%
deleteriously affect the quality of the polymer or copolymer produced.
It would be extremely beneficial to conduct these type polymerizations at temperatures at or above the softening point of the sticky polymers since it is well known that increases in polymerization temperatures generally enhance the yield of product in relation to the catalyst. In addition, purging of the polymer product becomes more efficient.
SUMMARY OF THE INVENTION
Broadly contemplated, the present invention provides a process for producing sticky polymers at polymerization reaction temperatures in excess of the softening temperature of said sticky polymers in a fluidized bed reactor in the presence of a catalyst, which comprises conducting said polymerization reaction above the softening temperatures of said sticky polymers in the presence of about 0.3 to about 80 weight percent, preferably about 5~ to about 75% based on the weight of the final product of arl inert particulate material having a mean particle size of from about 0.01 to about 10 micrometers or microns whereby polymer agglomeration of said sticky polymers is maintained at a size suitable for continuously p~oducing said sticky polymers.
In the case when the inert particulate material is a carbon black or silica, the mean particle size is the average size of aggregate.

- 5 ~ ciù

BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 illustrates a typical gas fluidized bed reaction scheme for producing sticky polymers.
~ igure 2 is a graph which correlates the softening point of polymers having different densities.
Figure 3 is a graph which correlates the density of polymer versus propylene content.
DETAILED DESCRIPTION OF THE INVENTION
The fluidized bed reac~or can be the one described in U.S. Patent No. 4,558,790 except that the heat exchanger is preferably located prior to the compressor and the introduction of the inert particulate material is at the bottom of the reactor or to the recycle line directed to the bottom of the reactor. Other ~ypes of conventional reactors for the gas phase production of, for example, polyethylene or ethylene copolymers and terpolymers can also be employed. At the start up the bed is usually made up of polyethylene granular resin.
During the course of the polymerization, the bed comprises formed polymer particles, growing polymer particles, and catalyst particles fluidized by polymerizable and modifying gaseous components introduced at a flow rate or veloci1:y sufficient to cause the particles to separate and act as a fluid.
The fluidizing gas is made up of the initial feed, make-up feed, and cycle (recycle) gas, i.e., monomer and, if desired, modifiers and/or an inert carrier gas. The fluidizing gas can also be a halogen or other gas. A typical cycle gas is comprised of ~-15675 - 6 - ~J ~J ~ 3 ~ ~

ethylene, nitrogen, hydrogen, propylene, butene, or hexene monomers, diene monomers, either alone or in combination.
Examples of sticky polymers, which can be produced by subject process include ethylene/
propylene rubbers and ethylene/propylene/diene termonomer rubbers, polybutadiene rubbers, high ethylene content propylene/ethylene block copolymers, poly (l-butene) (when produced under certain reaction conditions), ver~ low density (low modulus) polyethylenes i.e., ethylene butene rubbers or hexene containing terpolymers, ethylene/propylene/
ethylidenenorbornene and ethylene/propylene hexadiene terpolymers of low density.
Subject process can be carried out in a batch or continuous mode, the latter being preferred.
Characteristic of two types of resins which can be produced in subject process are as follows:
~ ne type of resin is an ethylene/propylene rubber containing 25 to 65 percent, by weight, propylene. This material is sticky to the touch at reactor temperatures of 20C to 40C and has a severe tendency to agglomerate when allowed to settle for periods of more than two to five minutes. Another sticky resin is an ethylene/butene copolymer produced at reactor temperatures of 50C
-to 80C at density levels of 880 to 905 kilograms per cubic meter and melt index levels of 1 to 20 and chlorinated or chlorosulfonated after being produced in the fluidized bed reactor.
The inert particulate material employed according to the present invention are materials _ 7 - ~J~

which are chemically inert to the reaction.
Examples of inert particulate materials include carbon black, silica, clays and other like materials. Carbon blacks are the preferred materials. The carbon black materials employed have a primary particle size of about 10 to 100 nano meters and an average size of aggregate (primary structure) of about 0.1 to about 10 microns. The specific surface area of the carbon black is about 30 to 1,500 m2/gm and display a dibutylphthalate (DBP) absorption of about 80 to about 350 cc/100 grams.
The silica's which can be employed are amorphous silicas having a primary particle size of about 5 to 50 nanometers and an average size of aggregate of about 0.1 to about 10 microns. The average size of agglomerates of silica is about 2 to about 120 microns. The silicas employed have a specific surface area of about 50 to 500 m2/gm and a dibutylphthalate (DBP) absorption of about 100 to 400 cc/100 grams.
The clays which can be employed according to the present invention have an average particle size of about 0.01 to about 10 microns and a specific surface area of about 3 to 30 m2/gm.
They exhibit oil absorption of about 20 to about 100 gms per 100 gms.
The amount of inert particulate material utilized generally depends on the type of material utilized and the type of polymer produced. When utilizing carbon black or silica as the inert material, they can be employed in amounts of about - 8 - ~'6~

0.3 to about 50% by weight preferably about 5~ to about 30% based on the weight of the final product produced. When clays are employed as the inert particulate material, the amount can range from about 0.3 to about 80% based on the weight of the final product preferably about 12% to 75% by weight.
The inert particulate materials can be introduced into the reactor either at the bottom of the reactor or to the recycle line directed into the bottom of the reactor. It is preferred to treat the inert particulate material prior to entry into the reactor to remove traces of moisture and oxygen.
This can be accomplished by purging the material with nitrogen gas, and heating by conventional procedures.
A fluidized bed reaction system which is particularly suited to production of polyolefin resin by the practice of the process of the present invention is illustrated in the drawing. With reference thereto and particularly to Fig. 1, the reactor 10 comprises a reaction zone 12 and a velocity reduction zone 14.
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, of course, can 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 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 _ 9 _ ~J '~J ~ l3~ 3 growing polymer particles, formed polymer particles and a minor amount of catalyst all fluidized by the continuous flow of polymerizable and modifying gaseous components in the form of make-up feed and recycle fluid through the reaction zone. To maintain a viable fluidized bed, the superficial gas velocity (SGV) through the bed must exceed the minimum flow required for fluidization which is typically from about 0.2 to about 0.8 ft/sec.
depending on the average particle size of the product. Preferably the SGV is at least 1.0 ft/sec.
above the minimum flow for fluidization of from about 1.2 to about 6.0 ft/sec. Ordinarily, the SGV
will not exceed 6.0 ft/sec. and it is usually no more than 5.5 ft~sec.
Particles in the bed help to prevent the forrnation of localized "hot spots" and to entrap and distribute the particulate catalyst through the reaction zone. Accordingly, on start up, the reactor is charged with a base of particulate polymer particles before gas flow is initiated.
Such particles may be the same as the polyme~ to be formed or different. When different, they are withdrawn with the desired newly formed polymer par~icles as the first product. Eventually, a fluidized bed consisting of desired polymer particles supplants the start-up bed.
The catalysts used are often sensitive to oxygen, thus the catalyst used to produce polymer in the fluidized bed is preferably stored in a reservoir 16 under a blanket of a gas which is inert to the stored material, such as nitrogen or argon.

- 1 o ~ 3 ~

Fluidization is achieved by a high rate of fluid recycle to and through the bed, typically on the order of about 50 to about 150 times the rate of feed of make-up fluid. This high rate of recycle provides the requisite superficial gas velocity necessary to maintain the fluidi7ed 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~ It is thus dependent on the geometry of the reactor.
Make-up fluid can be fed at point 18 via recycle line 22 although it is also possible to introduct make up fluid between heat exchanger 24 and velocity reduction zone 14 in recycle line 22~
The composition of the recycle stream is 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 is a conventional gas analyzer which operates in conventional manner to indicate recycle stream composition and which is adapted to regulate the feed and is commercially available from a wide variety of sources. The gas analyzer 21 can be positioned to receive gas from a point between the velocity reduction zon~ 14 and the dispenser 38, preferably after th~ compressor 30.
To ensure complete fluidization, the recycle stream and, where desired, part of the 3 2 ~

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 the bed absorbs the heat of reaction generated by the 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 a velocity reduction zone 14 above the bed where a major portion of the entrained particles drop back into the bed thereby reducing solid particle carryover.
The recycle stream exiting the compressor is then returned to the reactor at its base 26 and thence to the fluidized bed through a 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 liquid or solid particles which may settle out or become disentrained.
The fluid flow deflector, comprises an annular disc supported at a stand off distance above the reactor inlet 26 by the spacers 32a and divides the entering recycle stream into a central upward flow stream and an upward peripheral annular flow stream along the lower side walls of the reactor.
The flow streams mix and then pass through ~ 12 - 2r`~ 3r`3 protective screen 27, the holes or ports 29 of the distributor plate 28 and the angle caps 36a and 36b, secured to the upper surface of the distributor plate, and eventually into the fluidized bed.
The central upward flow stream in the mixing chamber 26a assists in the entrainment of liquid droplets in the bottom head or mixing chamber and in carrying the entrained liquid to the fluidized bed section during a condensing mode of reactor operation. The peripheral flow assists in minimizing build-up of solid particles in the bottom head because it sweeps the inner surfaces of the reactor walls. The peripheral flow also contributes to the re-a~omization and re-entrainment of any liquid which may be disentrained at the walls or accumulate at the bottom of the diffuser mixing chamber, particularly with a high level of liquid in the recycle stream. The annular deflector means 32, which provides both central upward and outer peripheral flow in the mixing chamber, permits a reactor to be operated without the problems of liquid flooding or excessive build up of solids at the bottom of the reactor.
The temperature of the bed is basically dependent on three factors: (1) the rate of catalyst injection which controls the rate of polymerization -and the att'endant rate of heat generation; (2) the temperature of the gas recycle stream and (3) the volume of the recycle stream passing through the fluidized bed. Of course, the amount of liquid introduced into the bed either with the recycle stream and/or by separate introduction also affects - 13 - 2 ~ 3 ~ ~, the temperature since this liquid vaporizes in the bed and serves to reduce the temperature. Normally the rate of catalyst injection is used to control the rate of polymer production. The temperature of the bed is controlled at an essentially constant temperature under steady state conditions by constantly removing the heat of reaction. By "steady state" is meant a state of operation where there is no change în the system with time. Thus, the amount of heat generated in the process is balanced by the amount of heat being removed and the total quantity of material ~ntering the system is balanced by the amount of material being removed.
As a result, the temperature, pressure, and composition at any given point in the system is not changing with time. No noticeable temperature gradient appears to exist within the upper portion of the bed. A temperature gradient will exist in the bottom of the bed in a layer or region extending above the distributor plate, e.g., for about 6 to about 12 inches, as a result of the difference between the temperature of the inlet fluid and temperature of the remainder of the bed. However, in the upper portion or region above this bottom layer, the temperature of the bed is essentially constant at the maximum desired temperature.
Good gas distribution plays an important role in the efficient operation of the reactor. The fluidized bed contains growing and formed particulate polymer particles, as well as catalyst particles. As the polymer particles are hot and possible active, they must be prevented from - 14 - 2 ~

settling, for if a quiescent mass is allowed to exist, any active catalyst present will continue to react and can cause fusion of the polymer particles resulting, in an extreme case, in the formation of a solid mass in the reactor which can only be removed with a great difficulty and at the expense of an extended downtime. Since the fluidized bed in a typical commercial size reactor may contain many thousand pounds of solids at any given time, the removal of a solid mass of this size would require a substantial effort. Diffusing recycle fluid through the bed at a rate sufficient to maintain fluidization throughout the bed is, therefore, essential.
Any fluid inert to the catalyst and reactants and which, if a liquid, will volatilize under the conditions present in the fluidized b~d, can also be present in the recycle stream. Other materials, such as catalyst activator compounds, if utilized are preferably added to the reaction system downstream from compressor 30. Thus the materials may be fed into the recycle system from dispenser 38 through line 40 as shown in Fig. 1.
According to the present invention, the fluid-bed reactor is operated above tne softening temperature of the polymer particles. The softening temperature is a function of resin density as shown in Fig. 2. Por example, EPR rubbers of density O.860 gm/cm has a softening point of about 30C
whereas at a density of abou~ 0.90, the softening point is about 67C.
The fluid bed reactor may be operated at - 15 - ~ ~,3 pressures of up to about 1000 psig. 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 favoring heat transfer since an increase in pressure increases the unit volume heat capacity of the gas.
The catalyst which is preferably a transition metal catalyst is injected intermittently or continuously into the bed at a desired rate at a point 42 which is above the distributor plate 28.
Preferably, the catalyst is injected at a point in the bed where good mixing with polymer particlQs occurs. Injecting the catalyst at a point above the distributor plate is an important feature for satisfactory operation of a fluidized bed polymerization reactor. Since catalysts are highly active, injection of the catalyst into the area below the distributor plate may cause polymerization to begin there and eventually cause plugging of the distributor plate. Injection into the fluidized bed aids in distributing the catalyst throughout the bed and tends to preclude the formation of localized spots of high catalyst concentration which may result in the formation of "hot spots". Injection of the catalyst into the reactor is preferably carried out in the lower 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.
The inert particulate materials are introduced into the reactor from Vessel 31 through line 31a together with inert gas or alternatively through 31b where it is joined with recycle line 22.
A gas which is inert to the catalyst, such as nitrogen or argon, is preferably used to carry the catalyst into the bed.
The rate of polymer production in the bed depends on the rate of catalyst injection and the concentration of monomer(s) in the recycle stream.
The production rate is conveniently controlled by simply adjus~ing the rate of catalyst injection.
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 the rate of formation of the particular polymer product. Complete instrumentation of both the fluidized bed and the recycle stream cooling system is, of course, useful to detect any temperature change in the bed so as to enable either the operator or a conventional automatic control system to make a suitable adjustment in the temperature of the recycle stream or adjust the rate of catalyst injection.
On discharge of particulate polymer product from the reactor 10, it is desirable, and preferable, to separate fluid from the product and to return the fluid to the recycle line 22. There are numerous ways known to the art to accomplish this. One system is shown in the drawings. Thus, fluid and product leave the reactor 10 at point 44 and enter the product discharge tank 46 through a valve 48 which is designed to have minimum restriction to flow when opened, e.g., a ball - 17 - ~ S~J ~J 3 ~ ~

valve. Positioned above and below product discharge tank 46 are conventional valves 50, 52 with the latter being adapted to provide passage of product into the product surge tank 54. The product surge tank 54 has venting means illustrated by line 56 and gas entry means illustrated by line 58. Also positioned at the base of product surge tank 54 is a discharge valve 60 which, when in the open position, discharges product for conveying to storage. Valve 50, when in the open position, releases fluid to surge tank 62. Fluid from product discharge tank 46 is directed through a ~ilter 64 and thence through surge tank 62, a compressor 66 and into recycle line 22 through line 68.
In a typical mode of operation, valve 48 is open and valves 50, 52 are in a closed position.
Product and fluid enter product discharge tank 46.
Valve 48 closes and the product is allowed to settle in product discharge tank 46. Valve 50 is then opened permitting fluid to flow from product discharge tank 46 to surge tank 62 from which it is continually compressed back into recycle line 22.
Valve 50 is then closed and valve 52 is opened and product in the product discharge tank 46 flows into the product surge tank 54. Valve 52 is then closed. The product is purged with inert gas preferably nitrogen, which enters the product surge tank 54 through line 58 and is vented through line 56. Product is then discharged from product surge tank 54 through valve 60 and conveyed through line 20 to storage.
The particular timing sequence of the - 18 - ~f~J; ~,li ~ Jf,~ iJ
valves is accomplished by the use of conventional programmable controllers which are well known in the art. The valves can be kept substantially free of agglomerated particles by installation of means for directing a stream of gas periodically through the valves and back to the reactor.
The following Examples will illustrate the present invention.
In the Examples, the softening point of an ethylene-propylene rubber (EPR) was determined by its density as shown in Fig. 2. The softening point of the pol~mer decreases with a de~rease of its density. The melt index of the polymer and the existence of particulate material on the surface of the granular polymer resin may affect its softening point. The softening points of EPR of various densities were measured by using a Dilatometer and the results are plotted in Fig. 2. On the other hand, the densities of ethylene-propylene copolymers (EPM) as well as ethylene-propylene-diene terpolymers (EPDM) decrease with an increase of the amount of propylene incorporated in the polymer as shown in Fig. 3. Therefore, once the propylene content in an EPR is measured, the softening point of the polymer can be determined by using these two figures.
- Fdr all the Examples shown below for EPM
and EPDM polymerizations, a Ziegler-Natta catalyst system was used, one such catalyst being a titanium based catalyst and the other being a vanadium based catalyst which also included a cocatalyst and a promoter. Triisobutylaluminum (TIBA~ or - 19 ~ J~ ?~

triethylaluminum (TEAL) was used as the cocatalyst.
Freon or chloroform was used as the promoter. Only the vanadium based catalyst needs such a promoter.
Since only a small amount of such cocatalyst and promoter is needed for the polymerization reaction, typically, a S or 10 weight % solution with isopentane is made and fed into the reactor to facilitate the control of the feed rate. The reactor total pressure was typically maintained at about 300 psi. The partial pressure of ethylene was typically 120 psi for the vanadium based catalyst and 50 psi for the titanium based catalyst, unless specified differently in the Examples, The superficial gas velocity in the fluidized bed reactor was in ~he range of 1.6 to 2,7 ft/s. The major operating variables were the reactor temperature and partial pressure of propylene.
The density of or propylene content in such polymers was controlled by controlling the partial pressure of propylene (comonomer), more specifically the molar ratio of propylene to ethylene (C3~C2).
The higher the ratio in the reactor, the lower the density of the polymer or the higher the propylene content in the polymer to be produced. At the beginning of each run, therefore, the value of C3/
C2 ratio was maintained low until enough bed turn-overs were attained with good polymerization reaction, more specifically three bed turn-overs.
To lower the polymer density, the ratio was then slowly in~reased to the next higher level by gradually increasing the partial pressure of propylene. Three bed turn-overs were attained again -- 20 -- ~ j 3 ~

at the desired ratio before the partial pressure of propylene was raised further. As the partial pressure of propylene was increased, the density of the polymer dropped down, so did the softening point of the polymer. When the softening point of ~he polymer produced became close to or greater than the reactor temperature, fluidization of polymer resin ceased all at once due to resin agglomeration resulting in a very undesirable channelling flow.
At a given molar ratio of propylene to ethylene ratio, propylene incorporation in EPR is reduced when the reactor temperature is raised.
This is observed with both vanadium and titanium based catalyst systems. To produce EPR of given density and propylene content at a higher reactor temperature, the molar ratio of propylene to ethylene ratio had to be maintained higher than low temperature operation cases.
The melt index (or flow index) was controlled by controlling the molar ratio of hydrogen to ethylene (H2/C2). The higher the molar ratio in the reactor, the higher the melt index of the EPR to be produced. Normally, high melt index EPR granular resin is more difficult to produce than low melt index one in a fluidized bed reactor. The diene used for the production of EPDM
was 5-ethylidene-2-norbornene (ENB). The rest of the gas composition was nitrogen. The amounts of propylene and ENB incorporated in EPR were measured by Infrared Spectroscopy. Also, the amount of particulate material in EPR was determined by Thermogravimetric Analysis.

Example 1 Production of EPM without added inert particulate materials at a reactor temperature below the softening point.
An attempt was made to produce EPM granular resin in a pilot fluidized bed reactor (inner diameter of about 14 inches) with a vanadium catalyst at a reactor temperature of 20C. As shown in Fig. 2, this reactor temperature is about 10C
below the softening points of all the EPR resins of interest. TIBA and chloroform were used as the cocatalyst and promoter, respectively. The typical value of the H2/C2 ratio was about 0.003. The superficial gas velocity was typically about 1.8 ft/s. Without having any agglomerations of resin in the reactor, it was possible to produce EPM granular resin which has a density of 0.864 g/cc and the melt index of 0.77 dg/10 min. The propylene content incorporated in the product was about 35% by weight.
The following Example 2 demonstrates the conventional problems when operating close to the softening point without the addition of the inert particulate material of the instant invention.

Exam~le 2 Utilizing the same reactor and with the same catalyst, cocatalyst, promoter, hydrogen to ethylene ratio, and superficial gas velocity described in Example 1, attempts were made to produce EPM granular resins at a reactor temperature of 30C. As shown in Fig. 2, this temperature is close to the softening point of the EPM resin which - 22 - ,~ 3 ~ ~

has a density range of about 0.860 to 0.865 g/cc.
The reactor was running well while the density was decreased from 0.870 to 0.868 g/cc by increasing the C3/C2 ratio from 0.325 to 0.376. The incorporated propylene contents were 31.7% and 34.1%
by weight for C3/C2 ratios of 0.325 and 0.376, respectively.
When the C3/C2 ratio was raised from 0.376 to 0.403 to fur~her decrease the density below 0.868 g/cc, the fluidization ceased suddenly resulting in the formation of a channelling flow evldenced by a sharp decrease of pressure drop across the bed. The reactor was shut-down, and big agglomerates and chunks were taken out from the reactor. An analysis of the agglomerates showed that the density and melt index of ~he polymer were D.867 g/cc and 0.97 dg/10 min, respectively. The incorporated propylene content was about 35% by weight.
The following Example 3 demonstrates reactor temperature operation above the softening point of the resin.
Example 3 Utilizing the same reactor and with the same catalyst, cocatalyst, and the hydrogen to ethylene ratio described in Example 1, attempts were made to produce EPM granular resin at a reactor temperature of 40C. As shown in Fig. 2, this temperature is higher than the softening point of EPM having a density less than 0.873 g/cc. When the molar ratio of propylene to ethylene was raised to 0.374, a defluidization of the bed, or the formation 2 ~ 2 ~d 3 ~ $
of the channelling flow evidenced by the same phenomena described in Example 2, called for a reactor shut-down. Many agglomerates and chunks were taken out of the reactor. They were analyzed and the density and melt index of the polymer were 0.866 g/cc and 0.31 dg/10 min., respectively. The content of propylene incorporated in the polymer was 34% by weight.
The following Example 4 demonstrates that a reactor cannot be operated at or close to the softening temperature of the polymer regardless of the catalyst sys~em used.

ExamPle 4 Reactor temperatures below and close to softening point with a titanium catalyst.
Since all the attempts at producing vanadium catalyzed EPM at reactor temperatures above its softening point failed due to the formation of agglomerates and chunks in the reactor, titanium catalysts were utilized at the reactor temperatures below and near the softening point, i.e., 20C and 30OC. The examples were conducted in the same reactor described in Example 1. The superficial gas velocity was about 1.8 ft/s for the runs. TIBA was used as a cocatalyst. The titanium catalyst system does not require a promoter. However, it requires substantially higher C3/C2 and H2/C2 ratios in the reactor than the vanadium ca~alyst system to produce EPM of the same density (or propylene incorporation) and melt index. While maintaining the H2/C2 ratio at 0.050 and the ethylene - 24 ~J~ 3 partial pressure at about 54 psi, two runs were made: one at 20C and the other at 30C. During both runs, the C3/C2 ratio was graaually increased from 1.6 to the aimed value of 2.2 in order to lower the density of EPM from 0.875 to the aimed value of 0.865. However, fluidization ceased whenever an attempt was made to lower the density below 0.870 g/cc at both reactor temperatures.
Example 5 Production of ethylene propylene diene terpolymers (EPDM) without particulate ma~erials at a reactor temperature below the softening point.
Attempts were made to produce EPDM granular resin in a fluidized bed pilot plant reactor (inner diameter of about 14 inches) with a vanadium catalyst at a reactor temperature of 30C. The partial pressure of ethylene was about 130 psi.
TIBA and chloroform were used as the cocatalyst and promoter, respectively. The typical value of H2/C2 was 0.002. The ENB concentration in the fluidized bed was about 4.5% by weight. The superficial gas velocity was about 1.8 ft/s.
Without having any reactor operability problems, it was possible to produce EPDM granular resins which had a density higher than 0.882 g/cc. The propyl~ne and ENB contents incorporated in the polymer were about 21%.and 1.5% by weight, respectively.
However, an attempt to lower the polymer density below 0.880 g/cc by increasing the C3~C2 ratio resulted in a reactor shut-down because fluidization ceased. The reactor was opened to remove the chunks and agglomerates. An analysis of the chunks showed - 25 - 2 ~Y~ ~$

that the density of, propylene content in, and ENB
content in the polymer were respectively 0.8775 g/cc, 28.0% by weight, and 2.1% by weight.
The following Example 6 demonstrates the results obtained when the reactor temperature is close to the softening point of EPDM resin.
Example 6 Utilizing the same reactor and with the same catalyst, cocatalyst, and prGmOter described in Example 5, an attempt was made to produce EPDM at a reactor temperature of 40C. The reactor conditions were the same as those in Example 5 except for the ENB concentration in the fluidized bed and the H2~
C2 ratio, both of which were higher 5.5% by weight and 0.003 respectively than those in Example 5.
When the C3/C2 ratio was raised to 0.34 in an effort to lower the polymer density below 0.885 g/cc, fluidization ceased due to the formation of a channeling flow. The reactor was shut-down and the samples of the chunks and agglomerates were analyzed. The density and melt index of the polymer were 0.883 g/cc and 0.15 dg/10 min., respectively.
The amounts of propylene and ENB incorporated in the polymer were 22.9% and 2.6% by weight, respectively.
The following examples 7-13 demonstrate ~he benefits of the invention wherein an inert particulate material is utilized.
However, when a particulate material is introduced into the reactor producing EPR granular resin, the product becomes a mixture of EPR and the particulate material. Normally, the density of the particulate material is different from the density - 26 - 2~2~,3~'~

of EPR itself. Therefore, the density of the mixture would be different from the true density of the polymer itself. The true density of the polymer, however, can be calculated by using the following correlation:
Dt = (l-x) Dm/{l - (x Dm / Dp )}
where Dt is the ~rue density of the polymer, x is the weight fraction of the particulate material, Dm is the density of the mixture, and Dp is the density of the particulate material.
Using a Dilatometer, the effect of various inert particulate materials on EPR softening point was determined to be negligible. As mentioned earlier, the mPasurement of propylene content in EPR
is an indirect measurement of its true density.
Therefore, the propylene content in and the mixture density of EPR as produced from the reactor were measured and are given in the following examples.
Also, the true density of each EPR, calculated with Equation 1, is listed in each example. It should be noted in the previous examples that no EPR, which has propylene content higher than 35% by weight, could be produced without the inert particulate material.
The following Example 7 demonstrates the production of EPM with carbon black as the inert particulate material.
ExamPle 7 Using a carbon black of primary particle size of 55 nm, an average size of aggregate of 2 D-lS675 micron~ (RAVEN-~30 a regi~tered trademark available f~om ~olumbian Chemical Co. Inc.), a ~peci~ic ~ur~ace area o~ ~4m2/gm and a DBP.of 220 ~c~100 gm. a~ the particulate ma~e~ial, the same reactor described in Example 1 wa~ u~ilized to produce EP~ granular rs~in wi~h titan~um ca~alyst ~t a rea~tor temperature of 30C. The ~ensity o~ the carbon black wa~ 1.8 ~/c~.
Before ~he carbon ~lack wa~ introduced into the r~actor throu~h the bo~tom mixin$ chamber below the dis~ribu~or plate, it was hea~e~ and purged ~imultaneou31y ~o remove absorbed water and oxygen which are ~oi~on for the reac~ion. Purging wa~ done with nitrog~n. TIBA
was u~ed a~ the cocatal~ The partial pre~sure o~
ethylene was abou~ 20 pBi. The H2~C2 ratio wa~ in the ranse of 0.03 to 0.04. The ~3/C~ ra~io was maintained in the range of 2.30 to 2.50 to produce amor~hou~ ~PM.
The conCentra~ion of the carbon bl~ck in ~he reactor wa~ ke~t a~ about 0.5 to 1.2~ by weight ~hroughou~ the ru~. An EPM polymer wa~ p~oduced close to or above the ~o~tening ~o~nS of the pol~er. An analy~is of the EPM
~mple~ ~howed that the polymers were e~entially amorphous. The density of the product W~6 in the range o~ 0.85~ to 0.865 g/cc, and the propylene co~tent wa~
from 47~ to 53~ by weight. The calculated true density o~ the EPM wa~ in the range o~ 0.854 to 0.863 g/cc.
~ ' .
U~ing a hydrophobic fumed sllica (Cab-O-Sil TS-720 a re~i~ter~d trademark a~aila~le from Cabot Cor-~oration) ha~ins a primary particle siæe o~ 14 nanometers ~ ~pecl~ic surface area o~ lOOm2/gm an~ a den~ity of A

- 28 - 2~2~

2.2g/cc as the inert particulate material, the same reactor, described in Example 1, was utilized at a reaction temperature of 30C to produce amorphous EPM. The catalyst employed was a titanium based catalyst as in E~ample 7. To remove poison from the silica, it was treated exactly the same way as the carbon black was treated. The partial pressure of ethylene was about 30 psi and the H2/C2 ratio was about 0.02. The C3/C2 ratio was kept in the range of 2.30 to 3.30 to produce amorphous EPM. The concentration of the silica in the reactor was maintained high (0.6 to 1.3% by weight) to ensure the production of large quantity of sample. The critical concentration of the silica below which fluidization ceases was not determined. An analysis of the samples produced showed that the polymers were amorphous with mixture density of 0.862 to 0.867 g/cc and propylene content of 47% to 52% by weight. Ash analysis of the samples indicated that the amount of the silica in the samples varied from 0.3 to 1.0% by weight. The calculated true density of the EPM is in the range of 0.857 to 0.~65 g/cc.
Exampl~ 9 Production of EPM with a carbon black as the inert particulate material at a reactor temperature of 50C which is above the softening point.
The same reactor as in Example 1 was utilized and was operated at 50C. The vanadium catalyst of E~ample 1 was also utilized. The carbon black was Raven T-230 carbon black. TIBA and chloroform were used as the cocatalyst and - 29 _ 2~2~

promoter. The partial pressure of ethylene was 85 psi. The C3/C2 and H2/C2 ratios were 0.46 and 0.0045, respectively. When the concentration of the carbon black in the reactor was maintained at around 1.5% to 1.8% by weight, the reactor produced carbon black incorporated EPM
granular resin without any problems. The density of the carbon black incorporated EPM was 0.870 g/cc.
The true density of the EPM, calculated with Equation 1, is about 0.863 g~cc. From Fig. 2, it is seen that the softening point of the EPM is 34C and therefore, the reactor temperature was about 16C
higher than the softening point of the polymer. At the end of the run, however, the carbon black feed did not function properly resulting in gradual decrease of the carbon concentration in the reactor. Consequently, the reactor was shut-down due to defluidization and the chunks were removed from the reactor. The amount of the carbon black in the chunks was determined to be about 0.6~ by weight. The density of and propylene content in the chunks were about 0.870 g/cc and 36% by weight, respectively. The true density of the polymer, calculated with Equation 1, is about 0.867 g~cc.
Example 10 Production of EPM with a carbon black at a reactor temperature of 66C.
The same reactor as in Example 9 was initially started up at a reactor temperature of 60C with the same vanadium catalyst, TIBA, chloroform and Raven T-230 carbon black as in Example 9. Later the reactor temperature was - 30 - ~ 3 e) ~

raised to 66C. The partial pressure of ethylene was about 89psi. The C3/C2 ratio was typically from 0.45 to 0.50. The H2/C2 ratio was 0.005.
By maintaining the concentration of the Raven T-230 carbon black in the reactor at about 5.0% by weight, granular EPM resin was produced without having any reactor operational difficulties. The average particle size of the resin was about 0.081 inches.
An analysis of the samples showed that the propylene content was in the range of 30 to 34% by weight; the melt index from 0.50 to 0.63 dg/lOmin; and the density from 0.893 to 0.895 g/cc. A
thermogravimetric analysis of the samples showed that the concentration of the carbon black in the polymer was about 4.5~- by weight. The true density of the samples, calculated with Equation 1, is about 0.873 g~cc. From Fig. 2, it is seen that the softening point of the EPM is 38C and therefore, the reactor temperature was about 28C higher than the softening point of the EPM.
For Examples 11-13 the same vanadium catalyst and reactor was employed as in Example 1.
TIBA and chloroform were used as the cocatalyst and promoter. For both TIBA and chloroform, 10%
solution (by weight) in isopentane was made and fed into the reactor at a typical rate of 100 to lSO
cc/hr. The total pressure of the reactor was 300 psi. The.partial pressure of ethylene was about 60 psi. The molar ratio of hydrogen to ethylene was in the range of 0.002 to 0.004. The partial pressure of propylene in the reactor and the ENB feed rate into the reactor were the two major variables --31-- r.J i) ~ C~

controlled. Raven T-230 carbon black was the particulate material employed to facilitate the reactor operation. The concentration of the carbo~
black in the reactor and EPDM granular resin was controlled by either controlling the production rate of polymer or the feed rate of the carbon black, or both. To enhance the fluidization and mixing of EPDM granular resin, the reactor was operated at a higher superficial gas velocity; typically, about 2.2 to 2.7 ft/s. Most of the time, the feed rate of the carbon black was maintained high to ensure proper fluidization and to reduce the average particle size of the resin by eliminating the formation of small agglomerates. Typically, the weight fraction of the carbon black in the product was higher than 5%, more specifically, higher than 10%. Due to the large amount of the carbon black in the EPDM, measurement of product density became less meaningful. The true density of each sample was determined b~ using the measured propylene content and Fig. 3, instead of measuring the mixture density and using Equation 1. Nevertheless, the carbon black in each sample was measured. Crystallinity of each sample was also measured.
E~ample 11 The reactor was operated to produce EPDM
granular resin at the following conditions:
Reactor temperature ~ 60C
Superficial gas velocity , 2.5 to 2.77 ft/s C3/C2 molar ratis . 1.1 to 1.3 H2/C2 molar ratio , 0.001 to 0.0025 ENB feed rate ~ 210 cc/hr - 32 - 2~3~

Carbon black feed rate ~ 700 to 850 g/hr.
Carbon black incorporated EPDM granular resin was produced at the rate of 5 to 8 lb/hr without encountering any serious reactor operational problems. Typical samples have the following properties:
Propylene content , ~1.2% by weight ENB incorporation , 5.1% by weight Carbon black content - 22.3% by weight Flow inde~ _ 11.5 Average particle size of resin . 0.053 inches The true density of the EPDM, from Fig. 3 with a propylene content o~ 41.2%, is about 0.86 g/cc. From Fig. 2, it is seen that the softening point of the polymer is 40C and therefore the reactor was operated at about 30C above the softening point of the polymer without having defluidization when such amount of the carbon black was used.
When the feed rate of the carbon black was reduced to about 300 to ~00 g/hr at the same production rate of EPDM, small agglomerates started to form in the reactor and came out with granular resin through the product discharge valve and product discharge tank. A typical sample was analyzed and revealed the following properties:
Propylene content , 49.1~ by weight ENB incorporation - 6.1% by weight Carbon black content - 12.6% by weight Flow inde~ . 5.2 Immediately after the small agglomerates were observed, the production rate was reduced to c, increase the carbon black concentration in the reactor. Granular EPDM resin was produced again.
The carbon black content in the resin was higher than 20% by weight, and the average particle size of the resin was typically in the range of 0.061 to 0.084 inches. Other properties of the EPDM were:
Propylene content . 45.B~ to 52.3~ by weight ENB incorporation - 3.6% to 7.5% by weight Flow inde~ . 0.6 to 1.0 When the concentration of the carbon black in the reactor became low again, fluidization ceased due to the formation of channeling flow and the reactor was shut-down. Agglomerates were removed from the reactor and analyzed to reveal the following properties:
Propylene content - 40.8% by weight ENB incorporation , 4.3% by weight Carbon black content , 12.5% by weight Example 12 Production of EPDM at 70C. The reactor was oper~ted to produce EPDM granular resin at the following conditions:
Reactor temperature - 70C
Superficial gas velocity . 2.5ft/s C3/C2 molar ratio - 1.3 H2/C2 molar ratio , 0.003 ENB feed rate , 210 cc/hr When the concentration of the carbon black in the reactor was maintained high enough, granular EPDM resin was produced. The properties of a typical sample are-Propylene content . 38.1% by weight 2~ c3 ENB incorporation _ 3.1% by weight Carbon black content - 22.5% by weight Average particle size of resin - 0.076 inches From Fig. 3, the true density of this EPDM
sample is about 0.86 g/cc. It is seen from Fig. 2 that the softening of the polymer is 30C and therefore the reactor was operated at about 40C
above the softening point of the material without having defluidization when such amount of the carbon black was used.
To determine the critical carbon black content in the product, the carbon black concentration in the reactor was gradually lowered until the fluidization ceased calling for a reactor shut-down. The chunks were removed from the reactor and analyzed to reveal the following properties:
Propylene content ~ 47.4% by weight ENB incorporation , 4.6% by weight Carbon black content , lD.9% by weight Example 13 Production of EPDM at 80C. The reactor was operated to produce EPDM granular resin at the following conditions:
Reactor temperature - 80C
Superficial gas velocity .. 2.2ft/s C3/C2 molar ratio - 1.8 H2/C2 molar ratio ~ 0.003 ENB feed rate ~ 150 to 210 cc/hr but typically 210 cc/hr.
Carbon black incorporated EPDM resin was produced at a rate of 4 to 6 lb/hr without having any reactor operational problems. Typical samples, ~ '; !, $,~ ~j ci which were produced at a C3/C2 ratio of 1.~, had the following properties:
Propylene content . 46.3~ by weight ENB incorporation ~ 2.2% by weight Carbon black content - 25.1% by weight Flow index - 5.9 Averaqe particle size of resin - 0.069 inches Small amount of resin agglomerates were observed in the product. This run was prematurely terminated due to some mechanical problems associated with the reactor system. From Fig. 3, the true density of this EPDM sample is below 0.86 g/cc, when the curve is extrapolated. From Fig. 2, the softening point of this polymer is 30C. This means that the reactor was operated at about 50C
above the softening point of the material with the amount of the carbon black indicated.

Claims

1. A process for producing sticky polymers at polymerization reaction temperatures in excess of the softening temperature of said sticky polymers in a fluidized bed reactor in the presence of a catalyst, which comprises conducting said polymerization reaction above the softening temperatures of said sticky polymers in the presence of about 0.3 to about 80 weight percent, based on the weight of the final product of an inert particulate material having a mean particle size of from about 0.01 to about 10 microns whereby polymer agglomeration of said sticky polymers is maintained at a size suitable for continuously producing said sticky polymers.

2. A process according to claim 1 wherein said inert particulate material is selected from the group consisting of carbon black, silica and clay.

3. A process according to claim 1 wherein said inert particulate material is carbon black having a primary particle size of about 10 to about 100 nanometers, an average size of aggregate of about 0.1 to about 10 microns, a specific surface area of about 30 to about 1,500 m2/gm and a dibutylphthalate absorption of about 80 to about 350 cc/100 grams.

4. A process according to claim 1 wherein said inert particulate material is silica having a primary particle size of about 5 to 50 nanometers, an average size of aggregate of about 0.1 to about 10 microns, a specific surface area of about 50 to 500 m2/gm and a dibutylphthalate absorption of about 100 to 400 cc/100 grams.

5. A process according to claim 1 wherein said inert particulate material is clay having an average particle size of about 0.01 to about 10 microns, a specific surface area of about 3 to 30 m2/gm and an oil absorption of about 20 to about 110 gm per 100/gm.

6. A process according to claim 1 wherein said sticky polymers are:
a. ethylene propylene rubbers;
b. ethylene propylene diene termonomer rubbers;
c. polybutadiene rubbers; and d. high ethylene content propylene ethylene block copolymers.

7. A process according to claim 6 wherein said ethylene propylene diene termonomers are ethylene/propylene/ethylidenenorbornene termonomers.

8. A process according to claim 6 wherein said ethylene propylene diene termonomers are ethylene/propylene/hexadiene termonomers.

9. A process according to claim 1 wherein said inert particulate material is employed in an amount of about 5% to about 75% based on the weight of the final polymer product.

10. A process according to claim 1 wherein said inert particulate material is heated and purged with nitrogen prior to entry into said reactor.

11. A process according to claim 3 wherein said carbon black is employed in an amount of about 0.3% to about 50% based on the weight of the final polymer product.

12. A process according to claim 3 wherein said carbon black is employed in an amount of about 5% to 30% based on the weight of the final product.

13. A process according to claim 4 wherein said silica is employed in an amount of about 0.3%
to about 50% based on the weight of the final product.

14. A process according to claim 4 wherein said silica is employed in an amount of about 5% to about 30% based on the weight of the final product.

15. A process according to claim 5 wherein said clay is employed in an amount of about 12% to about 75% based on the weight of the final polymer product.

16. A process for producing ethylene propylene ethylidenenorbornene terpolymers at polymerization reaction temperatures in excess of the softening temperature of said ethylene propylene ethylidenenorbornene terpolymers in a fluidized bed reactor catalyzed by a transition metal catalyst, which comprises conducting said polymerization reaction above the softening temperature of said ethylene/propylene/ethylidenenorbornene terpolymers in the presence of about 0.3 to about 50 weight percent, based on the weight of the final product of carbon black having a primary particle size of about 10 to about 100 nanometers, an average size of aggregate of about 0.1 to about 10 microns, a specific surface area of about 30 to about 1,500 m2/gm, and a dibutylphthalate absorption of about 10 to about 350 cc/100 grams, whereby polymer agglomeration of said ethylene/propylene/
ethylidenenorbornene terpolymers is maintained at a size suitable for continuously producing said ethylene/propylene/ethylidenenorbornene terpolymers.

17. A process according to claim 16 wherein said carbon black is employed in an amount of about 5% to about 30% based on the weight of the final product.

18. A process according to claim 16 wherein said carbon black is heated and purged with nitrogen prior to entry in said reactor.

19. A process for producing ethylene propylene rubbers at polymerization reaction temperatures in excess of the softening temperature of said ethylene propylene rubbers in a fluidized bed reactor catalyzed by a transition metal catalyst, which comprises conducting said polymerization reaction above the softening temperature of said copolymer in the presence of about 0.3 to about 50 weight percent, based on the weight of the final product of carbon black having a primary particle size of about 10 to about 100 nanometers, an average size of aggregate of about 0.1 to about 10 microns, a specific surface area of about 30 to about 1,500 m2/gm, and a dibutylphthalate absorption of about 10 to about 350 cc/100 grams, whereby polymer agglomeration of said ethylene propylene rubbers is maintained at a size suitable for continuously producing said ethylene propylene rubbers.

20. A process according to claim 19 wherein said carbon black is employed in an amount of about 5% to about 30% based on the weight of the final product.

21. A process according to claim 19 wherein said carbon black is heated and purged with nitrogen prior to entry in said reactor.

22. A process for producing ethylene propylene ethylidenenorbornene terpolymers at polymerization reaction temperatures in excess of the softening temperature of said ethylene propylene ethylidenenorbornene terpolymers in a fluidized bed reactor catalyzed by a transition metal catalyst, which comprises conducting said polymerization reaction above the softening temperature of said ethylene/propylene/ethylidenenorbornene terpolymers is the presence of about 0.3 to about 50 weight percent, based on the weight of the final product of silica having a primary particle size of about 5 to about 50 nanometers, an average size of aggregate of about 0.1 to about 10 microns, a specific surface area of about 50 to about 500 m2/gm, and a dibutylphthalate absorption of about 100 to about 400 cc/100 grams, whereby polymer agglomeration of said ethylene/propylene/ethylidenenorbornene terpolymers is maintained at a size suitable for continuously producing said ethylene/propylene/
ethylidenenorbornene terpolymers.

23. A process according to claim 22 wherein said silica is employed in an amount of about 5% to about 30% based on the weight of the final product.

24. A process according to claim 22 wherein said silica is heated and purged with nitrogen prior to entry in said reactor.

25. A process for producing ethylene propylene rubbers at polymerization reaction temperatures in excess of the softening temperature of said ethylene propylene rubbers in a fluidized bed reactor catalyzed by a transition metal catalyst, which comprises conducting said polymerization reaction above the softening temperature of said ethylene propylene rubbers in the presence of about 0.3 to about 50 weight percent, based on the weight of the final product of silica having a primary particle size of about 5 to about 50 nanometers, an average size of aggregate of about 0.1 to about 10 microns, a specific surface area of about 50 to about 500 m2/gm, and a dibutylphthalate absorption of about 100 to about 400 cc/100 grams, whereby polymer agglomeration of said ethylene propylene rubbers is maintained at a size suitable for continuously producing said ethylene propylene rubbers.

26. A process according to claim 25 wherein said silica is employed in an amount of about 5% to about 30% based on the weight of the final product.

27. A process according to claim 25 wherein said silica is heated and purged with nitrogen prior to entry in said reactor.