A PROCESS FOR POLYMERIZING A MONOMER CHARGE

Abstract: Process of polymerizing a monomer charge including ethylene by (1) drying an inorganic oxide having surface hydroxyl groups to form a support that is substantially free of adsorbed water, (2) reacting the surface hydroxyl groups of the support with at least a substantially stoichiometric amount of at least one organometallic compound corre­ sponding to the formula R x MR′ y R″ z , wherein M is a metal of Group III of the periodic table, R is an alkyl group containing 1 to 12 carbon atoms, R′ and R″ are independently selected from the group consisting of H, Cl, and alkyl and alkoxy groups containing 1 to 12 carbon atoms, x has a value of 1 to 3, and y and z both represent values of 0 to 2, the sum of which is not greater than 3-x, (3) reacting the thus-treated support with at least about 0.001 mol, per mol of organome­ tallic compound, of at least one vanadium compound prepared by reacting one molar proportion of VOCl₃ and/or VOBr₃ with about 0.5 to 1 molar proportion of a diol corresponding to the formula HO-R-OH, wherein R is a divalent hydrocarbon radical having a chain length of 2 to 16 carbon atoms, (4) feeding the product into a gas-phase reaction zone, (5) feeding a trialkylaluminum into the gas-­ phase reaction zone in order to form a bed comprising the product and the trialkylaluminum, (6) fluidizing the bed with a gas mixture of ethylene, hydrogen and chloroform, (7) removing polymerized ethylene particles from the reaction zone, and (8) recycling unreacted gas mixture from the top of the reaction zone to the bottom of the reaction zone.

Description: This invention relates to the polymerization of olefins. More particularly, this invention relates to a process having catalyst compositions which are useful for polymerizing one or more monomers comprising ethylene to polymers having an intermediate molecular weight distribution and a good balance of physical properties. It is known that catalysts of the type variously described as coordination, Ziegler, Ziegler-type, or Ziegler-Natta catalysts are useful for the polymerization of olefins under moderate conditions of temperature and pressure. It is also known that the properties of the polymers obtainable by the use of such catalysts, as well as the relative economies of the processes used to prepare the polymers, vary with several factors, including the choice of the particular monomers, catalyst components, polymerization adjuvants, and other polymerization conditions employed. During the years since Ziegler catalysts were first publicly disclosed, there has been a considerable amount of research conducted on the use of such catalysts; and numerous publications have resulted from that research. These publications have added much to the knowledge of how to make various types of olefin polymers by various types of processes. However, as is apparent from the amount of research on Ziegler catalysis that is still being conducted throughout the world, as well as the number of patents that are still being issued to inventors working in the field of Ziegler catalysis, the means of attaining certain results when polymerizing olefins with Ziegler catalysts are still frequently unpredictable. The fact that this situation exists is sometimes due to the need to obtain a previously-unattainable combination of results; occasionally due to difficulties in obtaining the same results in a commercial-scale apparatus as in a laboratory-scale reactor; and often due to a polymerization parameter's having an effect, or side-effect, in a given type of polymerization process that is different from effects achieved by its use in prior art processes of a different type. One aspect of Ziegler catalysis in which the need for further research has been found to exist has been in the provision of catalyst compositions suitable for use in a commerically-feasible process for preparing ethylene polymers having a good balance of physical properties and a molecular weight distribution that can be controlled so as to make the polymers formable by whichever forming technique is intended to be employed for producing articles from the polymers, e.g., injection folding or blow molding. There are, of course, known processes for preparing injection molding resins, as well as known processes for preparing blow molding resins, by polymerizing ethylene with the aid of Ziegler catalysts. However, the known processes typically suffer one or more of the disadvantages of lack of economy, inability to produce polymers having a suitable balance of properties, and/or unreliability in producing such polymers-particularly in commercial-scale operations. Moreover, the different molecular weight distribution requirements of polymers to be formed by different techniques have compounded the problem of finding a family of catalyst compositions suitable for use in a commercially-feasible process wherein the molecular weight distribution can be controlled so as to produce the desired polymers. US-A-4,003,712 (Miller) teaches a gas-phase fluidized bed system and process which are capable of being scaled up to commercial size and, being solvent-free, would be less expensive than processes which use solvents or liquid diluents. However, Miller's silyl chromate catalyst does not give polymers of the desired molecular weight distribution and good balance of physical properties. His system contains some features which tend to shorten commercial "on-stream" time. He does not teach how to avoid polymer buildup on reactor surfaces, a phenomenon variously referred to as "coating", "fouling", or "sheeting". What is still needed is a process employing a catalyst which (a) is suitable for use in a gas-phase polymerization process, (b) has sufficient activity to be economically attractive, (c) is capable of yielding polymers having a controlled molecular weight distribution and a good balance of physical properties, (d) does not cause reactor wall fouling, and (e) a gas-phase fluidized bed process which allows the catalyst to perform at its full potential at commercial scale. GB-A-1,489,410 (Monsanto) teaches gas-phase polymerization processes which, because of their use of supported Ziegler catalysts having a vanadium component and other factors, are commercially attractive processes. However, as taught in the patent, the processes are designed to result in the formation of polymers having the broad molecular weight distributions suitable for blow molding resins, i.e. molecular weight distributions such that their normalized V₃₀/V₃₀₀ melt viscosity ratios are above 2.3. Moreover, it has been found that these processes, although useful for preparing blow-molding resins of the type employed for househould chemical containers, do not appear to be adaptable to the preparation of blow-molding resins requiring somewhat narrower molecular weight distributions, e.g., liquid food containers, or to the preparation of injection-molding resins requiring still narrower molecular weight distributions. Attempts to make the processes of the Monsanto patent suitable for the preparation of injection molding resins, as well as more reliable in the preparation of desirable blow molding resins, by combining the teachings of the patents with the teachings of publications that discuss means of narrowing molecular weight distribution have not been successful. For example, polymers having a sufficiently narrow molecular weight distribution have not been obtained when Monsanto's preferred vanadium halides have been replaced with the alkoxy group-containing vanadium compounds which are within the scope of their patent and which U.S. Patent Nos. 3,457,244 (Fukuda et al.) and 3,655,583 (Yamamoto et al.) teach to result in the production of polymers having narrower molecular weight distributions when unsupported catalyst systems are employed. GB-A-1,175,593 (Stamicarbon) teaches a process for preparing ethylene/higher alkene/polyunsaturated compound terpolymers by the use of an unsupported vanadium chloride/alkylaluminum halide catalyst system, the activity of which is increased by adding an alcohol or phenol to the vanadium compound and/or the aluminum compound. According to the speculative teachings of the patent, the alcohol may be a polyhydric alcohol in which the -OH Groups are not attached to adjacent carbon atoms, but the patent does not mention any particular polyhydric alcohol that might be used or suggest the effect that the inclusion of a polyhydric alcohol might have on molecular weight distribution if the catalyst composition were being used for the preparation of crystallizable ethylene polymers, such as injection molding or blow molding resins, rather than the rubbers of the patent. US-A-3,202,645 (Yancey) presents a process for polymerizing and copolymerizing alpha mono and di-olefins by catalysts comprising (a) the product of the reaction between a compound of a metal chosen from the group consisting of the metals of Group IIb and IIIb (where the group numbers correspond to the Mendeleev Periodic Table) and hydroxyl groups on the surface of a finely-divided particulate inorganic solid, preferably finely-divided silica or alumina, and (b) a halide-type compound of a Group IVa, V, VIa, VIIa, or period 4 of Group VIII metal. The polymerization or copolymerization reaction can be effected at suitable temperatures within the range of from about -25 o C. to about+250 o C., and pressures ranging from below atmospheric upwardly to any desired maximum pressure, for example, 30,000 p.s.i.g. or even higher pressures. US-A-3,718,636 (Stevens et al) teaches obtaining polyolefins having a wide distribution of molecular weights through the use of a catalyst comprising an organometallic compound, and a solid complex component obtained by reacting a solid bivalent metal compound with an impregnation agent which consists of an orgamometallic compound, separating the solid reaction product, and reacting the solid reaction product with a halogenated derivative of a transition metal. Stevens et al teach in US-A-3,787,384 another catalyst suitable for use in olefin polymerization and olefin copolymerization which comprises (a) at least one organometallic compound, and (b) a solid catalytic component obtained by reacting a support composed of silica, alumina or both silica and alumina with a compound of the formula MR n X m-n in which M is aluminum or magnesium, R is a hydrocarbon radical containing 1 to 20 carbon atoms, X is hydrogen or a halogen, m is the valence of M, and n is a whole number not less than 1 nor greater than m, separating the solid product of the reaction, reacting said product with an excess of a halogen-containing transition metal compound, and separating the solid reaction product. US-A-3,925,338 (Ort) teaches that control of particle size of olefin polymers produced by gas-phase polymerization of at least one olefin using Ziegler-type catalysts deposited on solid supports in a fluidized-solids operation is effected by controlling the particle size of the catalyst support. U.S. Patent No. 4,232,140 also to Ort discloses the use of trichlorofluoromethane as a promoter in the polymerization and copolymerization of ethylene with supported Ziegler-type vanadium cmpound/alkylaluminum compound catalysts in the presence of hydrogen. Ort finds that polymer yields with his supported vanadium-based catalysts are too low for commercial viability unless the catalyst is promoted to high yield with the trichlorofluoromethane promoter. The viscosity ratio data in Ort's examples, which may be related to molecular weight distribution, indicate that none of the polymers have narrow molecular weight distribution. Ort does nor teach or suggest how to avoid reactor fouling. US-A-3,455,974 (Su) teaches an organo-soluble fluorine-containing vanadium compound having the formula: wherein R₁ and R₂ are alkoxy groups, wherein R₇ and R₈ are lower alkyl, lower aryl or taken together, lower alkylene groups or R₁ and R₂ are collectively an α,ω-alkylene dioxy group, said compound having from 2 to 40 carbon atoms. Su also teaches a method of making an organo-soluble fluorine containing vanadium compound which comprises contacting and reacting one molar proportion of vanadyl trifluoride with two molar proportions of a compound having the formula: R₄R₅R₆VO in the presence of an inert aprotic solvent at about ambient temperature wherein R₄, R₅, and R₆ are alkoxy groups or where R₄ and R₅ collectively are an α,ω-alkylene dioxy group. Although some of the foregoing patents are concerned with the production of polymers having narrow molecular weight distributions, none teaches or suggests an economical, gas-phase, fluidized bed process and catalyst for commercially producing ethylene polymers of controlled molecular weight distribution in combination with a good balance of physical properties. US-A-4435519 is concerned with that problem, and discloses the making of a catalyst as used in steps a-c of the present claims, also some of the matter contained in other steps of the present claims; but does not provide the combination of process conditions which according to the present invention lead to particularly advantageous results. An object of the invention is to provide an economical commercial polymerization process for preparing ethylene polymers having a controlled molecular weight distribution and a good balance of physical properties, using non-fouling catalyst compositions. The foregoing objects of this invention are broadly accomplished by providing a process of polymerizing a monomer charge including ethylene comprising the steps of: (a) drying an inorganic oxide having surface hydroxyl groups to form a support that is substantially free of adsorbed water; (b) reacting the surface hydroxyl groups of the support with at least a substantially stoichiometric amount of at least one organometallic compound corresponding to the formula R X MR' Y R'' Z , wherein M is a metal of Group III of the periodic table, R is an alkyl group containing 1 to 12 carbon atoms, R' and R'' are independently selected from the group consisting of H, Cl, and alkyl and alkoxy groups containing 1 to 12 carbon atoms, x has a value of 1 to 3, and y and z both represent values of 0 to 2, the sum of which is not greater than 3-x; (c) reacting the thus-treated support with at least about 0.001 mol, per mol of organometallic compound, of at least one vanadium compound prepared by reacting one molar proportion of VOCl₃ and/or VOBr₃ with about 0.5 to 1 molar proportion of a diol corresponding to the formula HO-R-OH, wherein R is a divalent hydrocarbon radical having a chain length of 2 to 16 carbon atoms; (d) feeding the product of step (c) into a gas-phase reaction zone; (e) feeding, separately and independently of the feeding step (d) and at a different location, a trialkylaluminum into the gas-phase reaction zone in order to form a bed in the gas-phase reaction zone which comprises the product of step (c) and the trialkylaluminum; (f) fluidizing the bed of step (e) at a pressure of between about 0.7 and 4.2 MPa and a temperature of between about 50 o to 120 o C. by diffusing underneath the bed of step (e) a gas mixture comprising ethylene, hydrogen, and chloroform at a rate sufficient enough to give a linear gas velocity in the bed of step (e) of between about 15 to 60 cm/sec; (g) removing particulate polymerized substantially ethylene particles from the reaction zone; and (h) recycling unreacted gas mixture of step (f) from the top of the reaction zone to the bottom of the reaction zone, below the distribution plate means. Further details concerning the preparation of the catalysts used may be obtained from US-A-4,435,519, as well as a discussion of criteria concerning their characteristics. The reaction of the vanadium compound with the treated support may also be accomplished by conventional means, such as any of the techniques described in GB-A-1,489,410. However, it is most desirably accomplished simply by adding the vanadium compound in neat or solution form to the slurry of treated support and maintaining it in intimate contact with the treated support for a time sufficient to provide for substantially complete reaction, usually at least about 5 minutes and preferably about 10-60 minutes, although, actually, the reaction is virtually instantaneous. Commercial preparation of the catalyst is preferably carried out as taught by Rogers in U.S. Patent No. 4,426,317. After the catalyst composition is prepared, it is subsequently introduced into a gas-phase fluidized reactor in a manner similar to that taught, for a different catalyst, by Miller in US-A-4,003,712. In a preferred embodiment of the invention, the diameter of the velocity reduction or disengaging zone at the top of Miller's reactor is enlarged and the cyclone and filter in the gas recycle system arc eliminated for stable, long-term commercial operation. It should be understood that polymerization with the catalyst compositions of this invention may be conducted in any fluidized system which has a distribution plate means and allows a monomer gas to fluidize a bed including the catalyst compositions; allows unreacted monomer gas to be recycled from the top of the fluidized system back to the bottom of the fluidized system or for admixing with the monomer gas prior to its diffusing or passing through the fluidized bed; allows a polymer product to be withdrawn from the fluidized bed; allows catalyst and a trialkylaluminum to be added to the fluidized bed at different locations; and prides for the removal of the heat of polymerization. Size, shape, pressure rating, heat removal capability, and other factors can limit the polymer production capacity of the gas-phase fluidized-bed reaction systems of this invention. The process of this invention may be practiced in commercial facilities having production capacities of 50,000 to 250,000 metric tons per year or more. The process of this invention may also be practiced in laboratory scale reactors having a production capacity of from about 0.1 to 1.0 kg/hr or in pilot plant reactors having production capacities of from 5 to 500 kg/hr. The catalyst composition is fed into the fluidized bed system at a point of between about 1/8 to about 1/2 of the height of the fluidized bed. Injection of the catalyst composition above about 1/8 of the height of the bed (as opposed to below 1/8 of the height) offers distribution of the catalyst composition throughout the entire ongoing fluidized bed to retard and/or preclude the formation of localized spots of high catalyst composition concentration which would result in the formation of "hot spots" at or near the distribution plate. A "hot spot" is a localized region in which the exothermic heat of polymerization is not dissipated before some polymer heats to the softening point of the polymer. We have found that the rate of injection of the catalyst for our polymerization process is generally preferably at a rate that maintains the concentration of the vanadium in the fluidized bed between about 0.1 ppm to about 50 ppm based on weight of vanadium metal divided by total solids in the bed. More preferably, the rate of injection of the catalyst compositions is that which would maintain the concentration of vanadium in the fluidized bed between about 0.50 ppm to about 10 ppm: most preferably, between about 1 ppm to about 4 ppm. The fluidized bed is substantially particulate polymerized ethylene polymer particles formed by polymerization of the monomer(s) on the catalyst compositions. In order for the catalyst composition to give high yield of polymer product per unit of vanadium component, we have discovered that it is necessary to add or inject at least one triakylaluminum compound into the fluidized bed system as a co-catalyst. For a variety of reasons, it is preferred to add the trialkylaluminum compound, or the mixture of trialkylaluminum compounds, that is being used as co-catalyst directly to the fluidized bed separately and independently of the catalyst and at an injection point removed from the catalyst injection point. The trialkylaluminum compounds may be fed to the fluidized bed as pure compounds, or in solution in a liquid hydrocarbon which will vaporize in the fluidized bed. Suitable hydrocarbon solvents include, but are not limited to, isobutane, isopentane, hexane,heptane, and mixtures thereof. The trialkylaluminum may be any trialkylaluminum wherein the alkyl or combination of alkyl groups contain between 1 and 36 carbon atoms. In a preferred embodiment of the invention, the alkyl group or combination of alkyl groups contain between 1 and 12 carbon atoms. Suitable trialkylaluminum compounds have been found to include trimethyl-, triethyl-, tri-i-butyl, tri-n-hexyl-, tri-n-octyl- and ethyl-di-i-butylaluminum. It should be understood that trialkylaluminum compounds add ethylene, and alpha olefins to some extent, under the operating temperatures and pressures of the polymerization process of the invention. Thus, an ethyl group on aluminum may be inserted by ethylene to become a butyl group, etc. Therefore, there is no reason to believe or require that all alkyl groups on the aluminum be the same. There is every reason to believe that mixtures of trialkylaluminum compounds are generated during polymerization and are as effective as pure compounds. Since the exact composition of the alkyl groups on aluminum during the polymerization process of this invention is not known because of the ethylene insertion reaction, all of the trialkylaluminum species in the fluidized bed are referred to collectively for the purposes herein as "trialkylaluminum". Polymer productivity from the polymerization process is not only determined by the rate of catalyst injection, but also from the rate of trialkylaluminum injection. Assuming that the trialkylaluminum compounds of this invention remain in the fluidized bed and assuming uniform distribution of trialkylaluminum throughout the fluidized bed, the molar concentration of trialxylaluminum may be calculated from the molar feed rate of the trialkylaluminum being fed into the fluidized bed reaction system and the withdrawal rate of the polymer product particles. Likewise, assuming uniform distribution of the catalyst composition throughout the fluidized bed, the molar concentration of the vanadium component of the catalyst composition may be calculated from the molar feed rate of the vanadium component of the catalyst composition being fed into the fluidized bed reaction system and the withdrawal rate of the polymer product particles. At stable, lined-out operating conditions, the ratio of the molar concentration of the trialkylaluminum to the molar concentration of the vanadium component in the bed of catalyst composition will asymptote to the ratio of the molar feed rate of the trialkylaluminum to the molar feed rate of the vanadium components of the catalyst compositions of this invention. The injection rate of the trialkylaluminum us such that the ratio in the fluidized bed of the molar concentration of the trialkylaluminum to the molar concentration of the vanadium component is between about 1 to about 5,000. We have found that the activity of the catalyst composition of the invention is maximized in a certain range of trialkylaluminum to vanadium molar ratio. Too little or too much trialkylaluminum suppresses the activity of the catalyst composition and the polymer production. It has been determined that a plot of the trialkylaluminum to vanadium molar ratio versus the catalyst activity possesses a generally flat peak and the optimum trialkylaluminum to vanadium molar ratio lies in the range of from about 2 to about 500, with from about 2 to 60 being the most preferred from the standpoint of minimizing catalyst residue levels in the polymer and trialkylaluminum cost. Therefore, the preferred injection rate of the trialkylaluminum into the fluidized bed system of this invention is that injection rate wherein the molar ratio in the fluidized bed of the molar concentration of the trialkylaluminum to the molar concentration of the vanadium composition is between about 2 to 500, and most preferably from about 2 to about 60. Although the catalyst compositions and the trialkylaluminum of this invention polymerize ethylene and other olefins over a wide range of temperatures, there is a practical limitation to the temperatures at which the gas-phase fluidized-bed process of this invention is commercially viable. For example, above about 120 o C, ethylene polymers soften and tend to agglomerate in a fluidized bed, leading to formation of lumps, loss of fluidization, and onset of an inoperable condition. Below about 50 o C, the production rate of commercial reactors becomes so low that the process is no longer profitable. It is generally desirable to operate near the highest temperature at which the polymer will not agglomerate in the bed with a temperature safety factor for small temperature upsets so that inoperable conditions are not encountered even briefly. Therefore, the preferred temperature range is from about 65-115 degrees C, with the range from about 75-110 degrees C being most preferred. The pressure at which the polymerization process of this invention is conducted is in a commercial operating range of 0.7 - 4.2 MPa. At the lower pressures, however, higher dwell or residence times in the reactor are required to reach high yields of polymer per unit of catalyst. At the higher pressures, there is little room to safely accommodate pressure upsets. These constraints lead to a preferred pressure range of 1.6 - 3.9 MPa. In order to provide sufficient mixing and agitation in the bed of polyethylene particles, trialkylaluminum and catalyst such that "hot spots" will not develop, it is necessary that the flow rate of the gas mixture through the bed of polymer particles containing traces of the catalyst and the trialkylaluminum be sufficient to fluidize the particles. For the powdered polymer particles produced by the catalyst compositions of this invention, the minimum fluidization velocity, G mf , has been determined to be about 15 cm/sec. As gas velocity increases, a point is reached at which the particles are largely swept out of the bed by the force of the rising gas (the transport velocity), which, for the particles of the present invention is about 4 G mf , or 60 cm/sec. To provide some margin for operating error, the preferred velocity range is about 1.5 - 3.0 G mf , or about 23 - 45 cm/sec, in contrast to the 3 - 5 G mf range preferred by Miller in US-A-4,003,712 for his catalysts. The catalysts would, under the commercial conditions described above, in the absence of a chain transfer agent, produce polymer of a molecular weight too high for conventional melt processing. Therefore, in the commercial practice of this invention the fluidizing gas mixture must contain hydrogen during polymerization to adjust the molecular weight (as determined by melt index) to the desired range for the product being produced. This is done by increasing the hydrogen/ethylene ratio to raise melt index (lower molecular weight), or reducing the ratio to produce the opposite effect. The catalyst compositions of this invention are sensitive to hydrogen, so it is generally not necessary to use more than 10% by vol. of hydrogen even to produce the highest melt index polymer. Furthermore, when used as described herein, altering the hydrogen/ethylene ratio to increase melt index does not cause a loss of production rate in a commercial plant within the range of melt indexes used for commercial polymers at this time. Preferably, the amount of hydrogen utilized in a preferred embodiment of the invention in order to control the molecular weight of the produced polymer is between about 0.10% to about 10.0% by volume of the total gas mixture volume. The gas mixture has to have chloroform in order that the catalyst compositions can have their activity promoted. While other halogenated carbon compounds such as methylene chloride and fluorotrichloromethane may work as promoters, from the standpoints of promotion of catalyst activity, cost, availability, ease of handling, and catalyst promotion without causing reactor fouling, chloroform is clearly the compound of choice. Only small amounts are needed because of its effectiveness. Under the conditions of polymerization, it is a gas, and generally will be present in the recycle gas at concentrations between about 0.0001 to about 1.000% by vol. of the gas mixture. Since the preferred vol% ranges for hydrogen and chloroform are respectively between about 0.10 and about 10.0 and between about 0.0001 and about 1.000, the remaining vol% for any given volume of the gas mixture would include ethylene and any of the inert gas which is used to feed the catalyst compositions to the fluidized bed in the reaction zone. In a preferred embodiment of the invention, ethylene preferably comprises between about 50.0 vol% and about 99.9 vol% of the gas mixture. It appears that the molar ratio CHCl₃/V is more useful in predicting and understanding its effect than the overall concentration in the gas, since it affects the catalyst's performance. The CHCl₃/V ratio may vary from about 2 to about 5000. Because chloroform is relatively inexpensive and used in small amounts, there is no real economic incentive to minimize its use. However, there appears to be a maximum in the curve of catalyst activity vs. CHCl₃/V ratio, with a broad optimum in the range of about 10 - 500. There also appears to be an interaction between the optima for CHCl₃/V ratio and Al/V ratio such that lower CHCl₃/V ratios are generally preferred when the Al/V ratio is low, and higher CHCl₃/V ratios are generally preferred when the Al/V is high. Other factors, such as impurity levels, may also cause a shift in the optimum CHCl₃/V ratio or Al/V ratio, but generally such factors will not shift the optima outside the preferred ranges. We have found that, in order to control the density of the produced ethylene polymer, the gas mixture of ethylene, hydrogen and chloroform may include alpha olefins which will be copolymerized with the ethylene of the gas mixture. Although the catalyst compositions will copolymerize essentially any alpha olefin with ethylene, there is a practical limit to what can he effectively done in a gas-phase reaction. Generally, olefins having more than 8 carbon atoms have too low a vapor pressure to be used in high enough concentration to have much effect on density. Propylene, butene-1, hexene-1, 4-methylpentene-1, and octene-1 are among the alpha olefins useful in copolymerization with ethylene in this invention. Preferably, mixtures of alpha olefins having 3 to 8 carbon atoms are used in a preferred embodiment of this invention. By this process, polymers generally considered to be HDPE (densities of 0.940 or greater) and LLDPE (densities below 0.940) may be made equally well by adjusting comonomer concentration in the feed or other factors. The amount of comonomer needed is determined by the density of the polymer product being made. Generally, not less than 0.5 vol% of alpha olefin will be used and not more than 30 vol% of the alpha olefin will be utilized for any given volume of the gas mixture along with any of the inert gas and between about 0.10 vol% and about 10.0 vol% of hydrogen, between about 0.0001 vol% and about 1.000 vol% chloroform, and between about 50.0 vol% and about 99.4 vol% ethylene. The catalyst compositions are preferably fed to the gas-phase fluidized-bed reactor as a dry particulate matter, such ash dry powder under the inert gas. Any gas that does not react with the catalyst is considered inert. Suitable inert gases include nitrogen, argon, and methane. Any device which can measure and convey a free flowing powder is suitable for feeding the catalyst, although the device must not allow monomer to enter the catalyst storage area of the feed device. Once the catalyst has been measured and delivered to the catalyst feed line, any good method of conveying it to the fluidized bed may be used. These include mechanical means such as screw conveyers, or gas conveying with inert gas or, as Miller teaches, with recycle gas from the reactor. Catalyst may be added continuously, semi-continuously, or discontinuously to the reactor. Continuous addition is preferred, but is virtually impossible at laboratory scale. Catalyst may be fed pure or may be diluted with any free-flowing particulate material such as pure, dry support or polymer powder from the reactor. In catalyst feeding, all that is really critical is that the catalyst be fed at a controlled rate and be dispersed in the bed before a "hot spot" develops. The produced particulate polymerized substantially ethylene particles may be removed from the gas-phase reaction zone by any suitable means and at any suitable location. Preferably, the produced ethylene polymer particles are removed in accordance with the procedure described by Miller in US-A- 4,003,712. In a preferred embodiment of the invention, the produced ethylene polymer particles are removed from the gas-phase reaction zone above and in proximity to the distribution plate. As has been mentioned, it is necessary to have good fluidization, good catalyst mixing, and good distribution of gas in the bed in order to avoid "hot-spots" which cause lumps to form in the bed. These lumps themselves disturb fluidization so, once a lump forms, the tendancy for other lumps to form is enhanced. Eventually a reactor shut down is necessary because the process becomes inoperable. Similarly, it is necessary for long-term, stable operation of commercial reactors that the surfaces of the reactor and distribution plate remain clean. If a polymer coating (fouling) builds up on a reactor surface, several undesirable things may happen. First, fouling on the distribution plate tends to perturb the desired gas distribution and restrict the ability to the polymer particles at the plate to move laterally. Both effects tend to produce "hot spots" at or near the distribution plate. Second, fouling on the reactor wall inhibits the normal downward motion of fluidized particles at the wall surface. Particles which "hang up" at a wall surface can generate "hot spots". Third, the wall coating may come loose in places, fall into the bed, and disrupt fluidization as any lump would do. Even worse, wall fouling usually is in the form of a "sheet" rather than a lump, and produces severe gas channelling in the bed if it falls off. Although poor selection of operating conditions or poor operating techniques may lead to lump formation, it appears that fouling of reactor surfaces depends primarily on the catalyst used. Some catalysts tend to produce fouling,and some do not. At this time, insufficient experience has been gained to be able to predict with accuracy which catalyst compositions will foul and which will give stable operation for months without fouling reactor surfaces. Obviously, for economical commercial operation, the catalyst must not foul reactor surfaces. Fouling in a commercial reactor leads to "down time" with consequent loss of production and extra maintenance cost for cleaning. Thus, fouling will cause a gas-phase fluidized-bed process to lose its economic advantage over slurry processes. The following examples are given to illustrate the invention and are not intended as a limitation thereof. In these examples, compositions and processes that are illustrative of the invention are distinguished from those that are outside the scope of the invention and are included only for comparative purposes by using an alphabetic designation for any example or run that is a comparative example and a numeric designation for the examples and runs that are illustrative of the invention. Yields given in the examples are measures of productivity in terms of the number of grams of polymer produced per gram of catalyst per hour, melt indices (MI₂) are those determined by ASTM test D-1238-65T using a 2160-gram weight, while the NVR values are "normalized" melt viscosity ratios determined by measuring the apparent viscosities of the polymers at 30 sec⁻¹ and 300 sec.⁻¹, respectively, at 200 o C. in an Instron capillary rheometer and (2) normalizing them to V₃₀=5 by the equation. NVR=antilog (0.14699+0.7897 log v₃₀ - log V₃₀₀) where V₃₀ and V₃₀₀ are the measured apparent viscosities. This normalization permits comparison of the viscosity ratios of polymers having different V₃₀ values, since the unnormalized V₃₀/V₃₀₀ ratio is a function of V₃₀. The NVR is constant for any given catalyst over an MI₂ range of about 1-30, and only slight deviations occur outside of that range. In the examples, the following procedures are used to prepare the catalyst compositions and polymers. PREPARATION OF CATALYSTS In the preparation of each of the catalysts, dry Davison 952 silica gel (a commercial inorganic oxide having a surface area of about 250-350 square meters per gram, a pore volume of about 1.5-1.7 cm³ per gram, and an average particle size of about 65-75 µm by heating it under dry, deoxygenated nitrogen for about 16 hours at a temperature of about 225 o -275 o C. to provide an activated oxide containing about 1.4 mmols of available hydroxyl groups per gram. Cool the activated oxide to ambient temperature under a purified nitrogen blanket, suspend it in commercial hexane, add neat trialkylaluminum, and stir the resultant slurry for about 30 minutes. Then add a vanadium compound in neat or solution form,in the cases of the catalyst compositions of the invention, using a solution that has been obtained by reacting a diol with VOCl₃ in hexane. Stir the resultant slurry for an additional 30 minutes, allow the hexane and catalyst layers to separate, decant the clear hexane layer, and remove the remaining hexane under a nitrogen purge to produce a powdered solid catalyst. The particular ingredients used to prepare the catalysts and the amounts of trialkylaluminum and vanadium compounds added per gram of inorganic oxide are shown in the examples and/or tables. LABORATORY GAS-PHASE POLYMERIZATION The laboratory apparatus consisted of a continuous polymerization reaction system essentially as depicted by Miller in the drawing of U.S. Patent No. 4,003,712, with two exceptions: there was no filter in the gas recycle line, and the catalyst was fed to the reactor with nitrogen only. The reaction zone was 10 cm in diameter, 120 cm tall. Recycle gas passed through a velocity reduction or disengaging zone atop the reactor, through a cyclone separator, through a centrifugal compressor, and into the bottom of the reactor where the gas was distributed into the fluidized bed by a dispersion or distribution plate. Heat exchange was effected by circulating pressurized, tempered water through jacketing on the recycle gas piping. This system had a rated capacity of 450 g of polymer per hour. Generally, for catalyst screening studies, the system was operated as follows: Introduce a stream or streams of ethylene,any comonomer(s), chloroform, and hydrogen to the reactor. Continuously withdraw unreacted or recycle gas from the top of the disengaging zone, pass it through a heat exchanger to maintain a bed temperature of about 95 o -100 o C., and introduce it at the bottom of the reactor at a rate sufficient to give a superficial velocity of about 25 cm/sec in the bed. Introduce make-up monomer, chloroform, and hydrogen into the recycle gas line so as to maintain constant gas composition as detected by on-line analyzers and so as to maintain the reactor pressure at about 3.5 MPa and to provide about 40 mmols of chloroform per mmol of vanadium per hour, and feed fresh catalyst particles into the reactor below the top of the bed so as to provide a vanadium feed rate of one mmol per hour. Add triethylaluminum as a scavenger and cocatalyst during the polymerization so as to provide a triethylaluminum feed rate of 20 mmol per hour. Withdraw polymer product semi-continuously from the bottom of the bed at a rate such am to maintain a constant bed level. Take aliquots of withdrawn polymer for testing. EXAMPLE A (comparative) An attempt was made to essentially repeat Example III of U.S. Pat. No. 4,232,140 using the laboratory gas-phase polymerization method described above with Ort's catalyst and CFCl₃ promoter, operating the equipment continuously 24 hours a day. After two days, and before the reaction had lined out sufficiently to get a good sample of the desired product for comparison with the products made by the catalysts of this invention, the reactor became inoperable. After the reaction system had been shut down, the reactor was opened. The reactor walls and distribution plate were found to be fouled (coated with polymer) to the extent that normal fluidization could not be maintained. The reactor was thoroughly cleaned, and the attempt repeated. This time, the reactor "fouled out" in about one day. A third attempt to run this catalyst and CFCl₃ promoter on a continuous basis was similarly unsuccessful. EXAMPLE B (comparative) A batch of catalyst having the composition of the catalyst [HO(CH₂)₃OH + VO Cl₃]/Al(C₂H₅)₃/SiO₂(0.05 mmol + 0.1 mmol/1.5 mmol/lg) is prepared as a dry powder according to Rogers, U.S. 4,426,317, and used in the laboratory gas phase polymerization procedure described above, using ethylene as the only monomer. By adjusting concentrations of hydrogen and chloroform, and feed rates of catalyst and a 3% solution of triethylaluminium co-catalyst in hexane, the reaction and polymer properties stabilize after 36 hours of continuous operation to give 400 g/hr of polyethylene product of 1.0 melt index and an NVR of 2.3. After stability ham been reached, the hydrogen feed is discontinued. Gradually, the hydrogen/ethylene ratio drops, as determined by an on-line gas analyzer, am recycle games are lost from the reaction zone through purge to the instruments and by being removed with the polyethylene product and no fresh hydrogen is added to the make-up gases. As the hydrogen level in the recycle gas decreases, the polymer melt index drops until it is unmeasurably low. The polymerization rate, am determined by ethylene uptake and by product removal from the reaction zone is unchanged, within experimental error. There is no external evidence of fouling. Hydrogen flow is them restarted, and the original hydrogen/ethylene ratio re-established as quickly as possible. Within 12 hours, the melt index is again 1.0. With the reactor restabilized, the chloroform feed is discontinued. Gradually, the CHCl₃/V ratio decreases as the CHCl₃ (promoter)concentration in the recycle gas becomes lower due to loss of recycle gas from the system and the make-up gas being promoter-free. There is no change in the melt index of-the polymer, but the polymerization rate drops to less than 40 g/hr. At this point, the catalyst and triethylaluminum feeds are discontinued to avoid having too much catalyst and co-catalyst in the reactor. Then, chloroform feed is cautiously restarted. Polymerization rate picks up immediately, as judged from an increase in both bed temperature and polymer powder production. Only after the chloroform reaches its original level in the recycle gas are the catalyst and triethylaluminum feeds restarted. About 36 hours after chloroform is re-admitted to the reaction, the reactor and polymer are restabilized to the original conditions of 400 g/hr rate and 1.0 melt index. Then the triethylaluminum feed is stopped. For about 2 hours, no change in seen, but then the polymerization rate begins to decrease dramatically. When the polymerization rate reaches about 100 g/hr, the triethylaluminum feed is restarted at the original rate. Within an hour, an increase in polymer production can be noted, and within about 24 hours the reaction is restabilized at the original condition. The reaction is then terminated intentionally, and the reactor opened for inspection. There in no visible coating or fouling on the distribution plate or reactor walls. EXAMPLE I A commercials gas-phase fluidized-bed polymerization is carried out in a polymerization system in which the reaction zone is 3.6 m in diameter and about 15 m tall. Recycle gas rate is sufficient to give a gas velocity in the bed of about 30 cm/sec. The polymerization is conducted at 3.5 MPa Pressure and 93 degrees C average bed temperature. The catalyst has the same formulation as in Example I run 5 of US-A-4,435,519 but is made in commercial batches of 450 kg each. The polymer, produced from a recycle gas consisting essentially of ethylene, hydrogen, nitrogen, and chloroform at a rate of about 8.5 metric tons per hour, is a sheet grade, has an average melt index of 0.7, an average density of 0.964, and an NVR of 2.3 plus or minus 0.1. Similar results in the narrowing of the molecular weight distribution of ethylene polymers are obtained when the examples are repeated except that the catalyst components, component proportions, comonomers, comonomer proportions, and/or polymerization conditions specified are replaced with other catalyst components, component proportions, comonomers, comomoner proportions, and/or polymerization conditions taught to be their equivalent in the specification.

Claims: A process of polymerizing a monomer charge including ethylene, chloroform and hydrogen in a gas-phase, fluidized bed, reaction zone which has distribution plate means, which comprises a bed of particulate substantially polymerized ethylene particles and is under operating conditions for polymerizing ethylene using the monomer charge, the process comprising the steps of: a) drying an inorganic oxide having surface hydroxyl groups to form a support that is substantially free of adsorbed water; b) reacting the surface hydroxyl groups of the support with at least a substantially stoichiometric amount of at least one organometallic compound corresponding to the formula R x MR' y R'' z , wherein M is a metal of Group III of the periodic table, R is an alkyl group containing 1 to 12 carbon atoms, R' and R'' are independently selected from the group consisting of H, Cl, and alkyl and alkoxy groups containing 1 to 12 carbon atoms, x has a value of 1 to 3, and y and z each can have a value of 0 to 2 and the sum of y and z is not greater than 3-x, to provide a treated support; c) reacting the thus-treated support with at least about 0.001 mol, per mol of organometallic compound, of at least one vanadium compound prepared by reacting one molar proportion of VOCl₃ and/or VOBr₃ with about 0.5 to 1 molar proportion of a diol corresponding to the formula HO-R-OH, wherein R is a divalent hydrocarbon radical having a chain length of 2 to 16 carbon atoms; d) feeding the product of step (c) into a gas-phase reaction zone in order to form part of the bed in the fluidized-bed reaction zone; e) feeding, separately and independently of said feeding step (d) and at a different location, a trialkylaluminum into the gas-phase reaction zone such that said bed in the gas-phase reaction zone comprises the product of step (c), the trialkylaluminum, and particulate substantially polymerized ethylene particles, this feeding being at a rate such as to maintain in the fluidized bed of step (f) a ratio of the molar concentration of trialkylaluminum to the molar concentration of the vanadium in the VOCl₃ and/or VOBr₃ from 1 to about 5000; f) fluidizing the bed of step (e) at a pressure of from about 0.7 to about 4.2 MPa and a temperature of from about 50 to about 120 degrees C. by diffusing underneath the bed of step (e) through the distribution plate means a gas mixture comprising ethylene, hydrogen, and chloroform at a rate sufficient to give a linear gas velocity in the bed of step (e) of from about 15 to about 60 cm/sec. and to give a molar ratio of chloroform to the vanadium in the VOCl₃ and/or VOBr₃ of from about 2 to about 5000, and the feeding of step (d) taking place at a position from about 1/8 to 1/2 of the height of the fluidized bed above the distribution plate means; g) removing particulate substantially polymerized ethylene particles from the reaction zone above and near to the distribution plate means, the particles having a controlled molecular weight distribution and, h) recycling unreacted gas mixture from steps (f) from the top of the reaction zone to the bottom of the reaction zone, below the distribution plate means. A process according to any one of the preceding claims, wherein the gas mixture comprises from about 50 to about 99.9% by volume of ethylene, from about 0.10 to about 10.0% by volume of hydrogen, and from about 0.0001 to about 1.000% by volume chloroform. A process according to any one of the preceding claims, wherein the gas mixture fed in step (f) additionally comprises an alpha-olefin. A process according to claim 3, wherein said gas mixture comprises from about 0.5 to about 30.0 vol % alpha olefin, from about 50.0 to about 99.4 vol % ethylene, from about 0.1 to about 10.0 vol % hydrogen, and from about 0.0001 to about 1.0 vol % chloroform. A process according to claim 3 or claim 4, wherein said alpha olefin is propylene, butene-1, hexene-1, 4-methyl-pentene-1, or octene-1. A process according to any one of the preceding claims, wherein: the drying in step (a) is at a temperature of from 100° to about 1000°C, the dried inorganic oxide being then cooled to ambient temperature; the or one of the organometallic compound(s) of step (b) is a compound of the formula RA1R'R''; the trialkylaluminum of step (e) is triethylaluminum or tri-n-hexylaluminum and is fed in a liquid hydrocarbon which is isobutane, iso-pentane, hexane or heptane; and the said recycling of step (h) is through a heat exchanger means. A process according to any one of the preceding claims, wherein the molar ratio of chloroform to the vanadium component is from about 10 to about 500. A process according to any one of the preceding claims, wherein the feeding step (d) includes feeding the product of step (c) as a dry powder under an inert gas.

Inventors: PENNINGTON, B. TIMOTHY, VEAZEY, RICHARD L.
Applicants: CITIES SERVICE OIL & GAS CORPORATION
Application year: 1986
Main classification: C08F10
IPC codes: C08F4, C08F2, C08F10