POLYMERIZATION OF OLEFINS WITH BLENDS OF INDEPENDENTLY SUPPORTED CATALYSTS

Abstract: Alpha-olefins are polymerized in the presence of at least two independently supported catalysts, one an inorganic halide supported titanium and/or vanadium Ziegler type catalyst and another an inorganic oxide supported, chro­ mium catalyst. This dual catalyst blend increases catalyst efficiency and/or provides more flexible control of the properties of the resulting polymers.

Description: POLYMERIZATION OF OLEFINES WITH BLENDS OF INDEPENDENTLY SUPPORTED CATALYSTS Transition metal catalysts are widely employed to prepare polymers and copolymers of a-olefins. For the most part, the polymer properties have been controlled or varied by changes in the process conditions as disclosed, for example, by Hogan et al U.S.Patent 2,825,721 or by Walker et al U.S.Patent 3,351,623. It has now been discovered that the polymer properties can be varied by employing a blend of two different catalysts during polymerization of the a-olefin. Such polymerization process provides: (1) alteration of the physical properties of the polymer without changing process conditions; (2) change in physical properties of the polymer without the use of hydrogen, (3) change in polymer composition of copolymers by changing catalyst ratios rather than comonomer ratios and/or (4) increased catalyst effIcIency. More specifically, the invention concerns a process for polymerizing one or more a-olefins in the presence of catalytic quantities of a supported transition metal catalyst characterized in that the polymerization is conducted in the-presence of a blend of catalytic quantities of at least two independently supported transition metal catalysts comprising (1) at least one inorganic halide supported Ziegler catalystcontaining titanium, vanadium or mixture there -of and (2) at least one inorganic oxide supported chromium- -containing catalyst. A. Ziegler Catalyst Any inorganic halide supported Ziegler catalyst containing titanium and/or vanadium can be employed as one of the Independently supported catalysts so log as it is catalytically active in polymerising a-olesins. Typical supported titanium and/or vanadium containing catalysts are described in U.S. Patents 4,067,822; ,091,082; 4,097,659; 4,104,198 and 4,120,820 and British Patent 1,500,873. Suitable supports for the Ziegler catalysts include the inorganic halides such as TiCl3, NgCl2, AlCl3 and mixtures thereof. Particularly suitable are magnesium dihalide supported titanium catalysts prepared from an organomagnesium compound, a halide source, a titanium tetraalkoxide and a reducing agent, preferably a reducing agent which contains aluminum and the following atomic ratios of the elements: Mg:Ti is from 0.1:1 to 200:1 preferably from 1:1 to 100:1, and most preferably from 10:1 to 50:1; Al:Ti is from 0.5:1 to 200:1 preferably from 1:1 to 100:1, and most preferably from 5:1 to 50:1; and xsX:Al is from 0:1 to 10:1 preferably from 0.01:1 to 1:1, and most preferably from 0.1:1 to 0.4:1. The "xsx" is that quantity of halide in excess of that theoretically required to convert all of the organomagnesium compound to magnesium dihalide. B. Chromium Catalyst Any supported chromium-containing catalyst sufficiently active to polymerize an a-olefin can be employed in the present invention. Suitable supported chromium catalysts include those disclosed in U.S. Patents 4,150,208 and 2,846,425 and British Patent 790,196. Suitable supports for the chromium catalysts include the inorganic oxides such as silica, alumina, silica-alumina, thoria, and zirconia. The chromium catalyst and support are employed in an atomic ratio of Ms:Cr, where Ms is the metallic element in the support as follows: Ms:Cr is from 10:1 to 1000:1, preferably from 20:1 to 500:1 and most preferably from 50:1 to 200:1. Also suitable are catalysts which contain chromium and one or more transition metals from Groups IB and/or VB of the Periodic Table. Those catalysts which employ inorganic oxide supports are suitable for use as modified chromium catalysts whereas those which employ halide type supports are suitable for use as modified Ziegler catalysts. Examples of the former are disclosed in U.S. Patents 4,041,224; 3,622,521; and 3,798,202. Examples of the latter are disclosed in U.S. Patents 3,847,957; 3,752,795; and 4,204,050. The range of catalyst ratios employed is limited only by the ability of one catalyst to produce a significant change in the properties of the polymer that would be produced by the second catalyst. Because types of catalysts vary in productivity at any given set of process conditions, the effect of one catalyst on The product resulting from the use of two catalysts is best described in terms of the fractional percent yield defined as follows for catalysts arbitrarily - designated as type n and type m: catalyst n productivity: gms. polymer produced by catalyst n Pn = gms. catalyst n x unit time catalyst n yield: Yn = gms. catalyst n x unit time x Pn total yield: T = Yn + Ym catalyst n fractional % yield: Xn = Yn/T catalyst m fractional % yield: Xm = 1 - Xn Throughout this specification, unless notedotherwise, the subdesignation 'n' pertains to the inorganic halide supported-catalyst and the subdesignation 'm' pertains to the inorganic oxide supported catalyst. Also this treatment assumes that direct linear combinations of catalysts will give results that are direct linear combinations of the results expected from each catalyst independently. This may not be entirely accurate due to catalyst synergestic interactions or concentration effects, but it serves the purpose of defining the limits of useful catalyst ratios. The fractional percent yields, Xn and Xm, should be between 0.001 and 0.999, preferably between 0.01 and 0.99 and most preferably 0.1 and 0.9. Any value less than 0.001 or higher than 0.999 will tend to give results that cannot be distinguised from those of single catalyst system. Within the range given, the value of Xn or Xm will be determined by the polymer physical properties desired. In a catalyst system using two specific catalysts, it may be desirable to empirically relate physical properties to a ratio of catalyst components (e.g. Cr/Ti). Such a relationship is valid only if the individual catalyst compositions and process conditions are held invariant. C. Monomers Olefins useful in the practice of this invention are generally aliphatic a-moloolefins and a-diolefins having from 2 to 18 carbon atoms. Illustratively, such a-olefins can include ethylene, pro pylene, butene-l, butadiene, pentene-l, 3-methylbutene-1, 4-methylpentene-l, hexene-l, octene-l, dodecene-l, octadecene-l, 1,7-octadiene, and mixtures thereof. It is understood that a-olefins may be copolymerized with other a-olefins and/or with minor amounts, i..e. up to about 25 weight percent based on the polymer, of other polymerizable ethylenically unsaturated monomers such as styrene, a-methylstyrene and similar ethylenically unsaturated monomers which do not destroy conventional Ziegler catalysts. Most benefits are realized in the polymerization of aliphatic l-monoolefins, particularly ethylene and mixtures of ethylene with up to about 50, especially from 0.1 to about 40 percent by weight, based on total monomer, of propylene, butene-l, hexene-l, octene-1, 4-methylpentene-1, 1,7-octadiene, butadiene or similar a-olefins or diolefins. D. Polymerization Conditions In practice, the independently supported catalysts are blended and mixed together just prior to entry into the reaction zone or vessel. Preferably they are fed or added separately from the a-olefin monomer. The polymerization zone is maintained at temperatures in the range from about 0 to 3000C, pre fe;-t=ly at solution polymet ation temperatures, from about 1200 to 2700C, for a residence time of a few seconds to 72 hours, preferably 15 seconds to 2 hours. It is generally desirable to carry out the polymerization in the absence of moisture and oxygen with and a catalyst blend containing about 0.0001 to 0.1 millimoles titanium per liter of diluent. However, the most advantageous catalyst concentration will depend upon polymerization conditions such as. tempera- - ture, pressure, solvent and presence of catalyst poisons. The foregoing range is given to obtain maximum catalyst yields in weight of polymer per unit weight of titanium. Generally, an inert organic diluent, solvent or excess monomer is employed in the process as a diluent and carrier. Suitable inert diluents include, liquified ethane, propane, isobutane, n-butane, n-hexane, the various isomeric hexanes, isooctane, paraffinic mixtures of alkanes having from 8 two 12 carbon atoms, cyclohexane, methylcyclopentane, dimethylcyclohexane, dodecane, and industrial solvents composed of saturated or aromatic hydrocarbons such as kerosene, naphthas, etc., especially when freed of any olefin compounds and other Impurities. Especially suitable are diluents having boiling points in the range from about -50 to 2000C. The polymerization pressures preferably employed are relatively low, e.g., from about 50 to 30,000 psig (4.4-2040 atm), especially from 100 to 700 psig t7.8-48.6 atm). However, polymerization within the scope of the present invention can occur at pressures from atmospheric up to pressures determined by the capabilities cf The polymerization cqulpment. During polymerization it is desirable td stir the polymerization recipe to obtain better temperature control and to maintain uniform polymerization mixtures throughout the polymerization zone. To optimize catalyst yields in the polymerization of ethylene, it is preferable to maintain an ethylene concentration in the solvent in the range of from about 1 to 99 weight percent, most advantageously from about 10 to 20 weight percent. Although iu the present invention it is not necessary to employ hydrogen in order to control the molecular weight of the polymer, the polymerization nevertheless can be employed in the presence of hydrogen as an additional control if so desired. To realize the full benefit of the high efficiency dual catalyst of the present invention, care must be taken to avoid oversaturation of the solvent with polymer. If such saturation occurs before the catalyst becomes depleted, the full efficiency of the catalyst is not realized. For best results, it is preferred that the amount of polymer in the carrier not exceed about 50 weight percent based on the total weight of the reaction mixture. The monomer or mixture of monomers is contacted with the catalytic reaction product in any conventional manner, preferably by bringing the catalytic reaction product and monomer together with intimate agitation provided by suitable stirring or other means. Agitation can be continued during polymerization, or in some instances, the polymerization can be allowed-to remain unstirred while the polymerization takes place. In the case of more rapid reactions with more active catalysts, means can be provided for refluxing monomer and solvent, if any of the latter is present, in order te remove the heat of reaction. In any event, adequate means should be provided for dissipating The exothermic heat of polymerization. If desired1 the monomer can be brought in the vapor phase into contact with the catalytic reaction product, In the presence or absence of liquid material. Polymerization can be effected in the batch manner, or in a continuous manner, such as, by passing the reaction mixture through an elongated reaction tube which is contacted externally with suitable cooling media to maintain the desired reaction temperature, or by passing the reaction mixture through an equilibrium overflow reactor or series. The polymer is readily recovered from the polymerization mixture by driving off any unreacted monomer and solvent. No further removal of impurIties is required. Thus, a significant advantage of the present invention is the elimination of the catalyst residue removal steps. In some instances, however, it may be desirable to add a small amount of a catalyst deactivating reagent of the types conventionally employed for deactivating Ziegler catalysts. The resultant polymer is found to contain insignIficant amounts of catalyst residue. The following examples illustrate the invention. All percentates are by weight and all parts are by molar or atomic ratio unless otherwise indicated. The melt index values I2 and I1o were determined by ASTM D 1238-70 and the density values were determined by ASTM D 1243-74. EXAMPLE 1 Preparation of an Inorganic Oxide Supported Chromium Catalyst A solution of 0.41 g of Cr VI oxide in 22 g of deionized water was mixed thoroughly with 20 g of Davidson 952 silica. The mixture was placed in a Vicor quartz tube and heated to 2000C for 2-1/2 hours fluidized by air dried by passing through a column of molecular sieves. After drying, the temperature was raised to 7500C for 21-1/2 hours. The activated catalyst was stored in a nitrogen filled dry box. The atomic ratio of Si:Cr was 81.2:1. Example 2 Preparation of an Inorganic Oxide Supported Chromium Catalyst A 0.2 g quantity of SrCO3 was added to 15 ml of deionized water and dissolved by adding 10 drops of concentrated nitric acid. To this solution was added 0.3 g of Cr VI oxide. The solution was then mixed-with 15 g of Davidson 952 silica. The mixture was then dried at 1000C for 5 hours, giving a constant weight of about 15 g. The dried catalyst was heat activated in a VICOR tube at 5350C for 10 hours while fluidizing with air dried in a molecular sieve bed. The catalyst was subsequently cooled and stored under nitrogen. The atomic ratio of Si:Cr was 83:1. EXAMPLE 3 Preparation of An Inorganic Halide Supported Titanium Catalyst In a nitrogen filled dry box, a 1.5 ml volume of 0.5 M solution of ethylaluminum dichloride in Isopar# E (an isoparaffinic hydrocarbon having a boiling range of 1160C to 1340C commercially available from the Exxon Corp.) was added to a 4 oz. catalyst bottle containing 96 ml of Isopare E. A i.5 ml volume of a 0.01 M solution of tetraisopropyl titanate in Isopar# E was added to a catalyst bottle followed by the addition of 1.5 ml of 0.4 M solution of di-n-hexyl magnesium in Isopar E with stirring. The catalyst bottle was then sealed with a rubber septum and removed from the dry box. The atomic ratio of Mg:Ti was 40:1, Al:Ti was 50:1 and xsC1:Al was 0.2:1. EXAMPLE 4 A. Present Invention To a stirred 5-liter batch reactor at 1500C containing 2 liters (25 psig, 1.76 kg/cm2, solvent vapor pressure) of Isopare E purified by passing through molecular sieves, was added 10 psig (0.70 kg/cm2) chromatographic grade hydrogen and 340 psig (23.9 kg/cm2) of ethylene which was purified by passing through molecular sieves. An Isopar E slurry containing O.i g of the catalyst prepared in Example 1 above was syringed into a 75 ml pressure bomb under a nitrogen purge. The bomb was then pressured to 450 psig (31.6 kg/cm2)-with nitrogen and the catalyst was vented into the reactor. A 1 ml volume of 15% aluminum triethyl was vented into the reactor in the same manner followed by the Injection of 15 ml of the catalyst slurry prepared in example 3 containing approximately 9 mg of catalyst. Ethylene was polymerized for 1 hour. The polymer was removed from the reactor and dried in a vacuum oen at 800C. The 220 g of recovered polymer had a melt index (12) of 16.82, a melt index (I10) of 143.5, an I10/I2 of 8.53, a density of 0.9617, and a catalyst efficiency of 220 x 103 g polymer/g Cr, or 2.0 x 106 g polymer/g Ti or 2 x 103 g polymer/g catalyst. The fractional percent yield of the inorganic halide supported catalyst, 1, was O.73 and the fractIonal percent yield of the inorganic oxide supported catalyst, Xm, was 0.27 calculated as follows: Pn = 70 g/6 mg x 30 minutes = 389 Pm = 155 g/0.2 g x 60 minutes = 13 Yn = 9 mg x 60 minutes x 389 = 210 Ym = 0.1 g x 60 minutes x 13 = 78 T = Yn + Ym = 288 Xn = Yn/T = 210/288 = 0.73 Xm = 1 - Xn = 0.27 B. Comparative Experiment Polymerization with an Inorganic Halide Supported Titanium Catalyst only In a polymerization similar to example 4A, 10 psig (0.70 kg/cm2) hydrogen and 340 psig (2.9 kg/cm2) ethylene was added to the reactor at a temperature of 1500C (25 psig, 1.76 kg/cm2, solvent vapor). A 10 ml volume of the catalyst slurry of example 3, containing approximately 6 mg of catalyst was injected into the reactor and allowed to polymerize ethylene for 30 minutes. The 70 g of polymer recovered had a melt index (12) of 5.74, a melt index (Ilo) of 46.8, an 110/12 of 8.15, and a density of 0.9633. The efficiency was 1.0 x 106 g polymer/g Ti or 11.7 x 103 g polymer/g catalyst. C. Comparative Experiment Polymerization with an Inorganic Oxide Supported Chromium Catalyst only In a polymerization similar to example 4A, 10 psig (0.70 kg/cm2) hydrogen and 340 psig (23.9 kg/cm2) ethylene were added to the reactor at a temperature of 1500C (25 psig, 1.76 kg/cm2,-solvent vapor). An Isopar E slurry containing 0.2 g of catalyst prepared in example 1 was injected into the reactor and allowed to polymerize ethylene for 1 hour. The 156 g of polymer produced had a melt index (I2) of 54.36, a melt index (iso) of 407.2, an 110/12 of 7.49, and a density of 0.9706.. The efficiency was 78 x 103 g polymer/g Cr or 0.78 x 103 g polymer/g catalyst. EXAMPLE 5 A. Present Invention In a polymerization similar to example 4A, 345 psig (24.3 kg/cm2) ethylene was added to the reactor at a temperature of 1600C (30 psig, 2.11 kg/cm2, solvent vapor). An Isopar E slurry containing 0.05 g of catalyst prepared in example 1 was injected into the reactor followed by the injection of 10 ml of a catalyst slurry as prepared in example 3, containing about 6 mg of catalyst. Ethylene was polymerized for 31 minutes. The 97 g of polymer produced had a melt index (I2) of 0.95, a melt index (Ilo) of 13.5, an I10/I2 of 14.22, and a density of 0.9642. The efficiency was-190 x 103 6 g polymer/g Cr or 1.35 x 10 g polymer/g Ti or 1.7 x 103 g polymer/g catalyst. The fractional percent yield of the inorganic halide supported catalyst, Xn, was 0.75 and the fractional percent yield of the inorganic oxide supported catalyst, Xm, was 0.25 calculated as follows: Pn = 61 g/6 mg x 30 minutes = 339 Pm = 121 g/0.2 g x 45 minutes = 13.4 Yn = 6 mg x 31 minutes x 339 = 63 Ym = 0.05 g x 31 min x 13.4 = 20.8 T = Yn + Ym = 83.8 Xn = Yn/T = 63/83.8 = 0.75 Xm = 1 - Xn = 1 - .75 = 0.25 B. ComDarative Experiment Polymerization with Inorganic Oxide Supported Chromium Catalyst only In a-polymerization similar to example 5A, usingXonly a slurry containing 0.2 g of catalyst from example 1, ethylene was polymerized for 45 minutes. The 121 g of polymer produced had a melt index (I2) of 99.95, a melt index (iso) of 809.6, an I10/I2 of 8.1, and a density of 0.9717. The efficiency was 81 x 103 g polymer/g Cr or 0.6 x 103 g polymer/g catalyst. C. Comparative Experiment Polymerization with Inorganic halide Supported Titanium Catalyst only In a polymerization similar to example 5A, using only 10 ml of the catalyst slurry as prepared in example 3, (containing about 6 mg of catalyst) ethylene - was polymerized for 30 minutes. The 61 g of polymer produced had a melt index (I2) of 0.49, a melt index (iso) of 3.66, an I10/I2 of 7.47, and a density of 0.9634. The efficiency was 0.85 x 106 g polymer/g Ti or 10 x 103 g polymer/g catalyst. EXAMPLE 6 A. Present Invention In a polymerization similar to example 4A, 357 psig (25.1 kg'cm2) ethylene was added to the reactor at a temperature of 1450C (18 psig, 0.91 kg/cm2, solvent vapor). A 100 ml volume of l-octene purged with nitrogen and stored over molecular sieves was injected into the reactor. A 10 ml of catalyst slurry as prepared in example 3, containing about 6 mg of catalyst was injected into the reactor followed by an Isopare E slurry of 0.4 g of catalyst prepared in example 2. Ethylene and 1-octene were copolymerized for 28 minutes. Tile 131 g of copolymer produced had a melt index (I2) of 4.13, a melt index (Ilo) of 47.2, an I10/I2 of 11.44, and a density of 0.9324. The efficiency was 32.8 x 103 g copolymer/g Cr or 1.8 x 106 g copolymer/g Ti or 0.32 x 103 g copolymer/g catalyst. The fractional percent yield of the inorganic halide supported catalyst, Xn, was 0.62 and the fractional percent yield of the-inorganic oxide supported catalyst, Xm, was 0-38 calculated as follows: Pn= = 72 g/6 mg x 30 minutes = 400 Pm = 88 g/0.4 g x 60 minutes = 3.67 Yn = 6 mg x 28 minutes x 400 = 67.2 Ym = 0.4 g x 28 min x 3.67 = 41.1 Xn = Yn/Yn + Ym = 67.2/108.3 = 0.62 Xm = 1 - Xn = 1 - 0.62 = 0.38 B. Comparative Experiment Polymerization with Inorganic Oxide Supported Chromium Catalyst only -In a polymerization similar to example 6A, using 200 ml of l-octene and using only 0.4 g of catalyst prepared in example 2, ethylene was copolymerized with 1-octene for 1 hour. The 88 g of copolymer produced had a melt index (I2) of 0.21, a melt index (iso) of 4.69, an I10/I2 of 22.33, and a density of 0.9500. The efficiency was 22 x 103 g copolymer/g Cr or 0.22 x 103 g copolymer/g catalyst. C. Comparative Experiment Polymerization with Inorganic Halide Supported Titanium Catalyst only In a polymerization similar to example 6A, using only 10 ml of the catalyst slurry as prepared in example 3 (containing 6 mg of catalyst), l-octene was copolymerized for 36 minutes. The 72 g of copolymer produced gave an efficiency of 1 x 106 g copolymer/g Ti or 12.6 x 103 g copolymer/g catalyst. The copolymer had a melt index (I2) of 0.249, a melt index (iso) of 3.35, an I10/I2 of 13.4S, and a density of 0.9386. EXAMPLE 7 A. Seven supported catalyst blends were prepared and twenty-two polymerizations were conducted using these catalysts separately and in combinations under the same process conditions. Where possible, the total transition metal content of the catalyst or catalysts was held constant. The resulting data summarized in the following Table demonstrate: 1. the invention compared with single catalyst systems, 2. the effect of Cr/Ti ratios, 3. the effect of catalyst fractional percent yield, and 4. the invention compared with multiple transi tion metal catalysts. B. The catalysts used were prepared as follows: Catalyst I: 1% Cr Catalyst Supported on an Inorganic Oxide A solution of 0.15 gms of CrO3 in 10 gms of water was thoroughly mixed with 8 gms of Davidson grade 952 silica. The mixture was heated for one hour at 1700C in a VICOR tube while being fluidized with nitrogen. The temperature was then increased to 7000C and the catalyst was fluidized for 5 hours with dry air. The catalyst was cooled under nitrogen purge and stored under nitrogen. This catalyst contained 88.8 Si/Cr. Catalyst II: 3% Cr Catalyst Supported on an Inorganic Oxide A catalyst was prepared as for catalyst I except that 0.45 gms of CrO3 was used to give 29.6 Si/Cr. Catalyst Ill: Ziegler Catalyst Supported on an Inorganic, Halide In a nitrogen filled dry box, 0.6 ml of 0.5 M ethyl aluminum chloride was added to 87.4 ml of Isopar E in a 4 oz catalyst bottle. A 1.5 ml volume of 0.4 M di-n-hexyl magnesium, 6.0 ml of 0.1 M titanium tetrachloride, and 4.5 ml of 0.1 M triethyl aluminum were also added to the solution in that order to form the active catalyst. The catalyst was then sealed with - a rubber septum and removed from the dry box. The atomic ratio of Mg:Ti was 1:1, Al:Ti was 1.25:1, and xsCl:Al was 2.4:1. Catalyst IV: Titanium Modified Cr Catalyst Supported on an Inorganic Oxide A catalyst was prepared as for catalyst II except that 2.1 ml of tetraisopropyl titanate was added to the N2 fluidized catalyst by syringe prior to heating with dry air at 7000C for 5 hours. Catalyst V: Titanium Modified Cr Catalyst Supported on an Inorganic Oxide A catalyst was prepared as for catalyst IV except that after addition of the titanate, the catalyst was treated 4.75 hours at 7000C while being fluidized by a 93% N2=72 CO (by volume) mixture. The catalyst was cooled to 5000C and purged with N2 for 30 minutes and then fluidized with dry air art 500 C for 15 minutes. Finally the catalyst was cooled while purging with N2 and stored in a N2 filled dry box. Catalyst VI: Chromium Modified-Ti Catalyst Supported on an Inorganic Halide In a nitrogen filled dry box, 1.5 ml of 0.5 M ethyl aluminum dichloride was added to 96 ml of Isopare E in a 4 oz. catalyst bottle. Te this solution was added 1.5 ml of 0.4 M di-n-hexyl magnesium and 1.15 ml of an Isopar E solution of the reaction product of dichloro diisopropyl titanate and CrO3 (0.013 M Ti). The catalyst was then sealed with a rubber septum and removed from the dry box. The atomic ratio of Mg:Ti was 40:1, Al:Ti was 50:1, xsCl:Al was 0.2:1, and Cr/Ti was 0.41. Catalyst VII: Chromium Modified Ti Catalyst Supported on an Inorganic Halide A catalyst was prepared as for catalyst VI except that 1.88 ml of an Isopar E solution of the reaction product of tetraisoprcpyl titanate and Cr03 (0.0081 M Ti) was used as the titanium source. The atomic ratio for Mg:Ti was 40:1, Al:Ti was 50:1, xsCl:Al was 0.2:1 and Cr/Ti was 0.16. Polymerizations Polymerizations for the catalyst comparisons were made in a 5 liter stirred batch reactor containing 2 liters of Isopar E purified by passing through molecular sieves. Each polymerization was run under the same process conditions, the only variables being the amounts and types of catalysts. The temperature was 1600C (15 psig, 105 kg/cm2, vapor pressure) and the ethylene pressure was 325 psig (22.8 kg/cm2). No hydrogen was used. The catalysts were weighed out in a nitrogen filled dry box and slurried in 50 ml. of Isopar E except for catalysts III, VI, and VII which were already slurries. In each polymerization, 5 ml of 0.1 M triethyl aluminum was injected into the reactor prior to adding the catalysts to react with any impurities that might have been present. Results of the polymerizations are listed in the following Table. TABLE IA DUAL CATALYSTS Total Transition Cr Ti Cr/Ti Metals Run mg/type (mg) (mg) (mg) 1* 360/I12 3.6 - - - - 3.6 2* 240/II13 7.2 - - - - 7.2 3* 21/III14 - - 3.6 - - 3.6 4* 200/IV15 6 8.4 0.71 14.4 5* 200/V16 6 8.4 0.71 14.4 6* 12/VI17 0.058 .14 0.41 0.2 7* 12/VII18 0.023 .14 0.16 0.16 TABLE AI (con'd) PRODUCTIVITY, YIELDS AND EFFICIENCIES PnÚ Pmê Xn Yn4 Ym5 T6 T/Cr7 T/Ti8 T/catalyst9 Run (x10-3)11 (x10-3) (g) (g) (g) (x10-3) (x10-3) (x10-3) 1* 0.519 187 51.9 - - 0.519 2* 0.542 130 18.1 - - 0.542 3* 5.76 121 - - 33.6 5.76 4* 0.20 40 6.67 4.76 0.20 5* 0.19 38 6.33 4.52 0.19 6* 12.7 152 2620. 1085. 12.7 7* 9.17 110 4782. 785. 9.17 TABLE IA (con'd) POLYMER PHYSICAL PROPERTIES Melt Index Run (I2) (I10) I10/I2 Density 1* 45.24 550.2 12.2 .9517 2* 3.32 86.12 25.9 .9491 3* .03 0.57 19.0 .9553 4* .08 3.11 38.9 .9571 5* .02 0.94 47.0 .9600 6* .34 5.50 16.2 .9598 7* .64 8.19 12.8 .9602 TABLE IB DUAL CATALYSTS Total Transition Cr Ti Cr/Ti Metals Run mg/type (mg) (mg) (mg) 8 300/I+24.5/III 12 3.6 - - - 9 420/I+17.2/III 7.2 - - - - 7.2 10 100/I+36.4/III - - 3.6 - - 3.6 11 210/I+30/III 6 8.4 0.71 14.4 12 600/I+49/III 6 8.4 0.71 14.4 13 320/II+27.4/III 0.058 .14 0.41 0.2 14 160/II+14/III 0.023 .14 0.16 0.16 15 80/II+28/III 2.4 4.8 0.54 7.2 16 300/II+24.5/III 9 4.2 2.14 13.2 17 160/II+56/III 4.8 5.6 0.54 14.4 18 70/II+70/IV19 4.2 2.9 1.44 7.1 19 240/II+6/VI 7.2 .072 100. 7.2 20 240/II+6/VII 7.2 .072 100. 7.2 21 170/III+13.7/IV 5.1 9.4 0.54 14.5 22 170/III+13.7/V 5.1 9.4 0.54 14.5 TABLE AI (con'd) PRODUCTIVITY, YIELDS AND EFFICIENCIES PnÚ Pmê Xn Yn4 Ym5 T6 T/Cr7 T/Ti8 T/catalyst9 Run (x10-3)11 (x10-3) (g) (g) (g) (x10-3) (x10-3) (x10-3) 8 0.48 269 89.7 64.0 0.83 9 0.31 232 52.2 78.6 0.53 10 0.80 142 142. 22.7 1.04 11 0.61 179 85.2 35.1 0.75 12 0.48 302 50.3 36.0 0.46 13 0.48 231 24.1 8.43 0.67 14 0.48 137 28.5 57.1 0.79 15 0.79 140 58.3 29.2 1.30 16 0.46 175 19.4 41.7 0.54 17 0.79 230 47.9 41.1 1.06 18 N.A.10 44 10.5 15.2 0.31 19 0.37 63 8.75 875. 0.26 20 0.30 76 10.5 1056. 0.31 21 0.997 125 24.5 13.3 0.68 22 0.997 102 20.0 10.9 0.56 TABLE IA (con'd) POLYMER PHYSICAL PROPERTIES Melt Index Run (I2) (I10) I10/I2 Density 8 .19 3.70 19.5 .9359 9 .23 5.17 22.5 .9465 10 .07 0.57 16.7 .9511 11 .12 3.11 15.8 .9477 12 .56 0.94 15.0 .9390 13 .23 5.50 15.1 .9470 14 .07 8.19 15.9 .9498 15 .07 0.97 13.9 .9504 16 .10 1.89 18.9 .9523 17 .13 2.06 15.8 .9499 18 .42 7.62 18.1 .9527 19 3.27 70.66 17.8 .9526 20 3.00 48.46 16.1 .9532 21 .02 0.47 23.5 .9525 22 .02 0.26 13.0 .9526 TABLE FOOTNOTES 1 Pn is gms polymer produced by catalyst 'n'/gms catalyst 'n' - unit time 2 Pm is gms polymer produced by catalyst 'm'/gms catalyst 'm' - unit time 3 Xn is Yn/Yn + Ym 4 Yn is gms catalyst 'n' x unit time x Pn 5 <RTI ID=25.5> Ym is gins catalyst 'm' x unit time x Pm 6 T is Yn + Ym 7 T/Cr is gms polymer/gms Cr = efficiency based on Cr 8 T/Ti is gms polymer/gms TI = efficiency based on Ti 9 T/catalyst is gms polymer/gms catalyst = efficiency based on catalyst 10 N.A. = non applicable 11 (x10 3) = value indicated has been multiplied by 10 3. Actual value for polymerization No. 1, Pn is 519. 12 Phillips B.P. 790,196; U.S. 3,622,521 13 Phillips B.P. 790,196; U.S. 3,622,521 14 Stamicarbon U.S 4,097,659 15 Phillips U.S. 3,622,521 16 Chemplex U.S. 4,041,224 17 Standard Oil U.S. 3,752,795 18 Bressler, et al, U.S. 4,104,050 19 Comparative Run Phillips U.S. 3,798,202 20 The productivity and yield parameters Pn, Pm, Yn and Yin are given for the single component catalysts in Table IA. C. The following comparisons can be made data given in the Table: 1. A comparison of polymerizations 1, 2 and 3 with 8-17 demonstrates the difference between single catalysts and the dual catalyst system. Each of these polymerizations has different productivities, yields, efficiencies and polymer properties even though they were run at the same process conditions and even though many were run at the same levels of transition metals. (The large difference in productivities of the seven single catalysts made it impossible to use the same T.M. level on each polymerization). 2. A comparison of polymerizations 8-11 indicate the control over physical properties that is available with the dual catalyst system of the present invention. POLYMERIZATION NO . Cr/Ti M. I . ( I ) 9 1.4 0.23 8 0.71 0.19 11 0.41 0.12 10 0.16 0.07 As can be seen, the Cr/Ti ratio is a good indication of the effect of the dual catalyst system of the present invention when changes in the Cr/Ti are dupe to changes in catalyst ratios. This effect is dependent on the process conditions only in limiting the range of physical properties possible as defined by the difference in properties of the two independent catalysts. 3. A comparison of polymerizations 8-11 with polymerizations 1 and 3 demonstrates the use of catalyst fractional percent yield. POLYMERIZATION NO. Xn MIZEN I10/I2 CATALYST 1 0.0 45.24 12.0 I(=m) 9 0.31 0.23 22.5 I + III 8 0.48 0.19 19.5 I + III 11 0.61 0.12 15.8 1 + III 10 0.80 0.07 16.7 I + III 3 1.0 0.03 19.0 III(=n) As can be seen, when the Xn approaches unity, the melt index for the dual catalyst system approaches that of catalyst 'n' alone. As Xn approaches zero, the dual catalyst system melt index approaches that for catalyst 'm'. The molecular weight distribution as represented by the I1o/I2 value is a more complex, less linear function than melt index. Broader or more narrdw molecular weight distribution can be obtained in the dual catalyst system than can be obtained with either--of the two catalysts alone. 4. A comparison of polymerizations 4 and 12 reflects the difference between the Phillips' titanium modified chromium catalyst (U.S. 3,622,521) and the -- dual catalyst system at the same Cr/Ti ratio and total transition metal content. All of the physical properties differ and the dual catalyst system of the present invention offers better efficiencies. The difference between the dual catalyst system and the Chemplex (U.S. 4,041,224) titanium modified chromium catalyst and the present invention is demonstrated by polymerizations 5 and 12. All physical properties are different and efficiencies are greater for the dual catalyst system of the present invention (12). Because of differences in productivity, it was not possible to have equal transition metal contents when comparing the dual catalyst system (11) and the Standard Oil (U.S. 3,752,795) chromium modified titanium catalyst (6). At the same Cr/Ti ratio however, it is clear that the dual catalyst system of the present invention and the Standard Oil catalysts do not get similar physical polymer properties. Although the transition metal contents in polymerizations 7 and 10 are not the same, it is obvious that the single magnesium-chloride supported chromium modified titanium catalyst (7) and the dual catalyst system of the present invention (10) give different physical polymer properties for the same Cr/Ti ratio. A comparison of polymerizations 9 and 18 indicate differences in physical properties and improved efficiencies for the dual catalyst system of The present invention (9) compared to the Phillips' (U.S 3,798,202) dual catalyst system (18). The Standard Oil chromium modified titanium catalyst (6) can be used in the dual catalyst system (19) to obtain different polymer physical properties. Likewise, the Dow chromium modified titanium catalyst can also be used in the dual catalyst system of the present invention (see polymerizations 7 and 20), and similarily the Phillips' (U.S. 3,622,521) titanium modified chromium catalyst (see polymerizations 4 and 21), and the Chemplex (U.S 4,041,224) titanium modified chromium catalyst (see polymerizations 5 and 22).

Claims: 1. A process for polymerizing one or more a-olefins in the presence of catalytic quantities of a supported transition metal catalyst characterIzed in that the polymerization is conducted in the presence of a blend of catalytic quantities of at least two independently supported transition metal -catalysts comprising (1) at least one inorganic halide supported Ziegler catalyst containing titanium, vanadium or mixture thereof and (2) at least one inorganic oxide supported chromium-containing catalyst. 2. The process of Claim 1 wherein the supported catalysts are employed in quantities so that the catalyst fractional yield from the inorganic halide supported catalyst (Xn) is 0.01 to 0.99. 3. The process of Claim 1 or 2 wherein the Ziegler catalyst is supported on a magnesium halide and the value for Xn is 0.1 to 0.9. 4. The process of Claim 1, 2 or 3 wherein polymerization is conducted under solution polymerization conditions. 5. The process of Claims 1, 1, 3 or 4, wherein the inorganic halide supported liegler catalyst (1) is a magnesium chloride supported titanium tetraalkoxide catalyst reduced with an aluminum-containing compound wherein the atomic ratios of Mg:Ti is from 0.1:1 to 200:1; Al:Ti is from 0.5:1 to 200:1 and xsCl:Al is from 0:1 to 10:1 and the inorganic oxide supported catalyst (2) is supported on silica and contains chromium oxide in an atomic ratio of Si:Cr of 10:1 to 1000:1. 6. The process of Claims 1, 2, 3, 4, or 5 wherein ethylene is polymerized under solution polymer ration conditions. 7. The process of Claim 6 wherein ethylene is copolymerized with at least one other a-olefin having from 3 to about 10 carbon atoms. 8. The process of Claim 7 wherein said other a-olefin is octene-l, hexene-i, butene-l or mixture thereof. 9. The process of Claim 8 wherein the other a-olefin is octene-l. 10. A catalyst blend of at least two independently supported transition metal catalysts comprising (1) at least one inorganic halide supported Ziegler type catalyst containing titanium, vanadium or mixture thereof and (2) at least one inorganic oxide supported chromium-containing catalyst. 11. The catalyst blend of Claim 10 wherein the inorganic halide supported catalyst and the inorganic oxide supported catalyst are present in quantities so that the catalyst fractional yield from the inorganic halide supported catalyst (Xn)-is 0.01 to 0.99. 12. The catalyst blend of Claim 10 or 11 wherein the Ziegler catalyst is supported on a magnesium dihalide and The value for Xn is 0.1 to 0.9. 13. The catalyst mixture of Claims 10-12 wherein the inorganic halide supported Ziegler type catalyst (1) is a magnesium chloride supported titanium tetraalkoxide catalyst reduced with an aluminum-containing compound wherein the atomic ratios of Mg:Ti is 0.1:1 to 200:1; Al:TI is 0.5:1 to 200:1 and xsCl:Al is 0:1 to 10:1 and the inorganic oxide supported catalyst (2) is supported on silica and contains chromium oxide in an atomic ratio of Si:Cr of 10:1 to 1000:1. 14. The catalyst mixture of Claim 13 wherein the atomic ratio of Mg:Ti is 10:1 to 50:1; the atomic ratio Al:Tl is 5:1 to 50:1; the atomic ratio of xsCl:Al is 0.1:1 to 0.4:1; and, the atomic ratio of SI:Cr is 50:1 to 200:1.

Inventors: LOWERY, KIRB, JR., VANCE, FRED LEE, JR.
Applicants: THE DOW CHEMICAL COMPANY
Application year: 1981
Main classification: C08F10
IPC codes: C08F10, C08F4