HIGH PRESSURE, HIGH TEMPERATURE POLYMERIZATION OF ETHYLENE

Abstract: A process for polymerizing or copolymerizing ethylene, either alone or in combination with other olefins, comprising contacting said ethylene or alpha-olefin, either alone or in combination with other olefins, with a catalyst comprising a cyclopentadienyl-transition metal compound and an alumoxane compound at an elevated temperature and pressure and wherein the ratio of aluminum in the alumoxane to the total metal in the metallocene is in the range of 1000:1 to 0.5:1.

Description: HIGH PRESSURE, HIGH TEMPERATURE POLYMERIZATION OF -_THYLΞ E This invention is a Continuation-In-Part of application 909,752 filed September 19, 1986. This invention relates to an improved process for polymerizing olefins. More particularly, this invention relates to a process for polymerizing ethylene, either alone or in combination with other monomers such as alpha-olefins and di-olefins at an elevated temperature and pressure. DESCRIPTION OF THE PRIOR ART Heretofore it has been proposed to use certain metallocenes such as bis(cyclopentadienyl) titanium or zirconium dialk ls in combination with aluminum alkyl/water cocatalyst as a homogeneous catalyst system for the polymerization of olefins. For example: German Patent Application 2,608,863 teaches the use of a catalyst system for the polymerization of ethylene consisting of bis(cyclopentadienyl) titanium dialkyl, aluminum trialkyl and water; German Patent Application 2,608,933 teaches an ethylene polymerization catalyst system consisting of zirconium metallocenes of the general formula (cyclopentadienyl) ZrY. , wherein n stands for a integer in the range of 1 to 4, Y for R, O- AlR p , CH 2 CH 2 A1R 2 and CH 2 CH(A1R 2 ) 2 , wherein R stands for alkyl or metal lo alkyl, an aluminum trialkyl cocatalyst and water; European Patent Application No. 0035242 teaches a process for preparing ethylene and atactic propylene polymers in. the presence of a halogen-free Ziegler catalyst system of (1) cyclopentadienyl compound of the formula (cyclopentadienyl) MeY, in which n is an integer from 1 to 4, Me 1s a transition metal, especially zirconium, and Y is either hydrogen, a C,-C 5 alkyl or metallo alkyl group or a radical having the following general formula CH 2 A1R 2 , CH 2 CH 2 A1R 2 , and CH 2 CH(A1R 2 ) 2 in which R represents a C.- alkyl or metallo alkyl group, and (2) an alumoxane; and U.S. Patent 4,564,647 teaches a low pressure process for polymerizing ethylene, either alone or 1n combination with small amounts of other alpha-olefins, in the presence of a catalyst which may comprise a cyclopentadienyl compound, represented by the 2 3 formula (Cp)MR'R R wherein (Cp) represents a cyclopentadienyl group, M represents titanium, vanadium, zirconium or hafnium, and 2 R', R and R are each an alkyl group having from 1 to δ carbon atoms, a cyclopentadienyl group, a halogen atom or a hydrogen atom, an alumoxane, which can be prepared by reacting trialkyl aluminum or di lkyl aluminum onohalide with water and a filler. Each of the above patents also teach that the polymerization process employing the homogeneous catalyst system is hydrogen sensitive thereby providing a means to control polymer molecular weight. As is well known in the prior, art, catalyst systems comprising a cyclopentadienyl compound, hereinafter frequently referred to as a metallocene or metallocene catalyst component, and an alumoxane offer several distinct advantages when compared to the more conventional Ziegler-type catalyst systems. For example, the cyclopentadienyl-transition metal/alumoxane catalyst systems, particularly those wherein the cyclopentadienyl compound contains at least one halogen atom, has demonstrated extremely high activity in the polymerization of alpha-olefins, particularly ethylene. Moreover, these catalyst systems produce relatively high yields of polymer product having a relatively narrow molecular weight distribution. Concomitant with the advantages, however, i.s the fact that at any given set of polymerization conditions heretofore contemplated for these catalyst systems, the molecular weight of the polymer product is generally lower than the molecular weight of the polymer product produced with a more conventional Ziεgler-type catalyst at the same conditions. Moreover, while relatively high molecular weight polymers can be produced with catalyst systems comprising a cyclopentadienyl-transition metal compound and an alumoxane compound at conditions heretofore contemplated for use thereof, however, polymerizations performed at higher temperatures result in the production of low molecular weight products, such as waxes and ologomers, rather than the desired high molecular weight products useful in the typical plastic applications. Each of German Patent Applications 2,608,933 and 2,608,863, European published Patent Application 35242, Ziegler-Natta Catalysis, by H. Sinn and . iaminsky, in Advances in Organo etallic Chemistry, IS, 99(1980), HaTogen-Free Soluble Zieqler Catalysis with Methyl lumoxane as Catalyst, by 3. Herwig and W. Kaminsky, in Polymer Bulletin, _, 464(1983) show that polymer product molecular 1 weight decreases to wax and oligo eric levels at elevated reaction 2 temperatures such as those described in the Examples 1n this patent 3 application. 4 A particular problem associated with the teachings of the 5 prior art relating to the catalyst systems comprising a 6 cyclopentadienyl-transition metal compound and an alumoxane 7 compound is that in order to obtain useful catalytic productivities 8 the ratio of alumoxane to metallocene must be very high. The prior 9 art exemplifies ratios of 2500:1 and greater as being useful and 10 clearly teaches that increasing catalytic productivity is obtained -* •••* with increasing alumoxane-metallocene ratio. See for example, 12 E. Giannetti et al . , Homogeneous Ziegler-Natta Catalysis. II 13 Ethylene Polymerization by IVB Transition Metal complexes/Methyl 14 Aluminoxane Catalyst Systems, J.Poly. Sci . 1_, 2117-2133 (1985). 15 Such an excess of alumoxane results in poor resin quality and high 16 costs associated with the deashing of polymer product. 7 Additionally, the cost of polymerization becomes excessive because 8 of the high cost of alumoxane. Erdolchemie German 3,150,270 Al 9 demonstrates that at high pressures and high temperatures one can 0 obtain high molecular weight polymers product, but nevertheless the 1 process as demonstrated employs the high ratio of alumoxane to 2 metallocene as suggested in the prior arts and obtains 3 productivities ranging from 90 to 250 g polymer/g catalyst. 4 The need, then, for an improved polymerization process 5 that both retains the several advantages heretofore achieved with 5 catalyst systems comprising a cyclopentadienyl-transition metal 7 compound and an alumoxane compound and which permits the efficient 8 and economically attractive production of high molecular weight 9 polymer products, i.e., at high productivity (1000 g polymer/g 0 catalyst or greater) is readily apparent. 1 SUMMARY OF THE INVENTION 2 It has now surprisingly been discovered that the 3 forementioned high molecular weight polymers can be obtained, while 4 the disadvantages of the prior art processes can be avoided or at * *-- least significantly reduced, with the method of the present 6 invention, while an improved process for polymerizing 7 alpha-olefins, either alone or in combination with other comonomers provided thereby. It is, therefore, an object of this Invention to provide an improved process for the polymerization and copolymerization of alpha-olefins, either alone or in combination with other comonomers. It 1s another object of this invention to provide such an improved process wherein relatively high molecular weight polymer products can be produced. It is still another object of this invention to provide such a process wherein the advantages normally associated with the use of a catalyst system comprising a cyclopentadienyl-transition metal compound and an alumoxane compound are retained. The foregoing and other objects and advantages will become apparent from the description, including the Examples, set forth hereinafter. In accordance with the present invention, the foregoing and other objects and advantages are accomplished by polymerizing ethylene, either alone or in combination with other monomers such as alpha-olefins having from 3-10 carbon atoms, i.e., butene-1, hexene-1, octene-1, 4-methylpentene-l, decene-1 and norbornene and d1-olefins having 4-10 carbon atoms, i.e., 1,3-butadiene, 1 ,4-hexadiene, 4-methyl-l,4-hexadiene, 5-methyl-l,4-hexadiene, 1,7-octadiene, ethylidiene norbornene and norbornadiene 1n the presence of a catalyst system comprising a cyclopentadienyl-transition metal compound and an alumoxane compound at elevated temperatures and pressures. As Indicated more fully hereinafter, it is important, in the process of this invention, that the polymerization temperature be above about 120 β C but below the decomposition temperature of said product and that the polymerization pressure be above about 500 bar (kg/cm ). In those situations wherein the molecular weight of the polymer product that would be produced at a given set of operating conditions is higher than desired, any of the techniques known 1n the prior art for control of molecular weight, such as the use of hydrogen, may be used in the process of this invention. DETAILED DESCRIPTION OF THE INVENTION As indicated, supra, the present invention relates to an improved process for polymerizing ethylene, either alone or in combination with other monomers such as.alpha-olefins and di-olefins in the presence of a catalyst comprising a cyclopentadienyl-transition metal compound and an alumoxane compound at elevated temperatures and pressures. As also indicated, supra, the polymerization will be accomplished at a temperature above the melting point of the polymer product but below the decomposition temperature of said polymer product and at a pressure equal to or above about 500 bar. In the process of the present Invention, ethylene, either alone or together with alpha-olefins having 3 or more carbon atoms or di-olefins having 4 or more carbon atoms, is polymerized in the presence of a catalyst system comprising at least one metallocene and an alumoxane. In accordance with this invention, one can also produce olefin copolymers particularly copolymers of ethylene and higher alpha-olefins having from 3-18 carbon atoms and copolymers of ethylene and di-olefins having from 4 to 18 carbon atoms. As indicated infra, the comonomer content can be controlled through the selection of metallocene catalyst component and by controlling the partial pressure of the various monomers. The metallocenes employed in the production of the reaction product are organometallic coordination compounds which are cyclopentadienyl derivatives of a Group 4b or Group 5b metal of the Periodic Table of the Elements (56th Edition of Handbook of Chemistry and Physics, CRC Press [1975]) and include mono, di and tricyclopentadienyls and their derivatives of the transition metals. Particularly desirable are the metallocene of a Group 4b and 5b metal such as titanium, zirconium, hafnium, and vanadium. The alumoxanes employed in forming the reaction product with the metallocenes are themselves the reaction products of an aluminum trialkyl with water. in general, the process of this invention employs at least one metallocene compound in the formation of the catalyst. As indicated, supra, metallocene is a metal derivative of a cyclopentadiene. The metallocenes usefully employed in accordance with this invention contain at least one cyclopentadiene ring. The metal is selected from the Group 4b and/or 5b metals, preferably titanium, zirconium, hafnium, and vanadium, and most preferably titanium and zirconium. The cyclopentadienyl ring can be unsubstituted or contain one or more substituents such as, for example, a hydrocarbyl substituent or other substituents such as, for example, a trialkyl silyl substituent. The metallocene can contain one, two, or three cyclopentadienyl rings however two rings are preferred. Useful metallocenes can be represented by the general formulas: I. (Cp) MR X r m n q wherein Cp is a cyclopentadienyl ring, M is a Group 4b or 5B transition metal, R is a hydrocarbyl group or hydrocarboxy having from 1 to 20 carbon atoms, X is a halogen, and is a whole number from 1 to 3, n is a whole number from 0 to 3, and q is a whole number from 0 to 3. II. (C 5-.'.)gR-'s(C5-.Vk MQ3-,- n g and III. R" s (C 5 R- k ) 2 MQ' wherein (CgR ) is a cyclopentadienyl or substituted cyclopentadienyl, each R' is the same or different and is hydrogen or a hydrocarbyl radical such as alkyl, alkenyl, aryl , alkylaryl, or aryl lkyl radical containing from 1 to 20 carbon atoms, a silicon containing hydrocarbyl radical, or hydrocarbyl radicals wherein two carbon atoms are joined together to form a C.-C 8 ring, R" is a C,-C. alkylene radical, a dialkyl germanium or silicon, or a alkyl phosphine or amine radical bridging two ^ ς ^'i ς -^ r i n 9 s > Q is a hydrocarbyl radical such as aryl, alkyl, alkenyl, alkylaryl, or aryl alkyl radical having from 1-20 carbon atoms, hydrocarboxy radical having from 1-20 carbon atoms or halogen and can be the same or different from each other, Q 1 is an alkylidene radical having from 1 to about 20 carbon atoms, s is 0 or 1, g is 0,1 or 2, s is 0 when g is 0, k is 4 when s is 1, and k is 5 when s is 0, and M is as defined above. Exemplary hydrocarbyl radicals are methyl, ethyl, propyl , butyl, amyl, isoamyl, hexyl , isobutyl, heptyl, octyl , nonyl , decyl , cetyl , 2-ethylhexyl , phenyl and the like. Exemplary silicon containing hydrocarbyl radicals are trimethylsilyl , triethylsilyl and triphenylsilyl . Exemplary halogen atoms include chlorine, bromine, fluorine and iodine and of these halogen atoms, chlorine is preferred. Exemplary hydrocarboxy radicals are ethoxy ethoxy, butoxy, amyloxy and the like. 1 Exemplary of the alkylidene radicals is ethylidene, ethyϋdene and propyϋdene. Illustrative, but non-limiting examples of the metallocenes 4 represented by formula I are dialkyl metallocenes such as bis(cyclo- 5 pentadienyDtitanium dimethyl, bis(cyclopentadienyl)titanium diphenyl, 6 bis(cyclopentadiεnyl)zirconium dimethyl, bis(cyclopentadienyl)- 7 zirconium diphenyl , bis(cycloρentadienyl)hafnium dimethyl and 8 diphenyl, bis(cyclopentadienyl)titanium di-neopentyl , b1s(cyclopenta- dienyl)zirconium di-neopentyl, bis(cyclopentadienyl)titanium dibenzyl, 10 bis(cyclopentadienyl)zirconium dibenzyl, bis(cyclopentadienyl)vanadium 1 dimethyl; the mono alkyl metallocenes such ' s bis(cyclopentadienyl)- titanium methyl chloride, bis(cyclopentadienyl) titanium ethyl 13 chloride bis(cyclopentadienyl)titanium phenyl chloride, bis(cyclo- pentadienyl)zirconium methyl chloride, bis(cyclopentadienyl)zirconium 1 ethyl chloride, bis(cyclopentadienyl)zirconium phenyl chloride, b.s- * 6 (cyclopentadienyl)titanium methyl bromide, bis(cyclopentadienyl)- 17 titanium methyl iodide, bis(cyclopentadienyl)titanium ethyl bromide, 18 bis(cyclopentadienyl) titanium ethyl iodide, bis(cyclopentadienyl) 19 titanium phenyl bromide, bis(cyclopentadienyl)titanium phenyl iodide, 20 bis(cyclopentadienyl)zirconium methyl bromide, bis(cyclopentadienyl)- 1 zirconium methyl iodide, bis(cyclopentadienyl)zirconium ethyl bromide, 2 bis(cyclopentadienyl)zirconium ethyl iodide, bis(cyclopentadienyl)- 3 .zirconium phenyl bromide, bis(cyclopentadienyl)zirconium phenyl 4 iodide; the trialkyl metallocenes such as cyclopentadienyltitanium ^ trimethyl, cyclopentadienyl zirconium triphenyl, and 6 cyclopentadienyl zirconium trineopentyl , cyclopentadienylzirconium 7 trimethyl, cyclopentadienylhafnium triphenyl , 8 cyclopentadienylhafnium trineopentyl , and cyclopentadienylhafnium 9 tri methyl . 0 Illustrative, but non-limiting examples of II and III 1 metallocenes which can be usefully employed in accordance with this 2 invention are monocyclopentadienyls titanocenes such as, penta- 3 methylcyclopentadienyl titanium trichloride, pentaethylcyclo- 4 pentadienyl titanium trichloride, bis(pentamethylcyclopentadienyl) 5 titanium diphenyl, the carbene represented by the formula bis(cyclopentadienyl)titaniuπv_CH 2 and derivatives of this reagent such as bis(cyclopentadienyl)T1»CH 2 * AKCH,),, (Cp 2 TiCH 2 ) 2 , Cp 2 TiCH 2 CH(CH 3 )CH £ , Cp 2 T1-CH 2 CH 2 CH 2 ; substituted bis(Cp)TKIV) compounds such as bis(indenyl)titanium diphenyl or di chloride, bis(methylcyclo- pentadi enyl )titanium diphenyl or dihalides; dialkyl, trialkyl, tetra-alkyl and penta-alkyl cyclopentadienyl titanium compounds such as bisd ,2-di methyl cyclopentadi enyl) titanium diphenyl or dichloride, bis(l ,2-diethylcyclopentadienyl)titanium diphenyl or dichloride and other dihalide complexes; silicon, phosphine, amine or carbon bridged cyclopentadiene complexes, such as di ethylsilyldicyclopentadienyl titanium diphenyl or dichloride, methyl phosphine di cyclopentadi nyl titanium diphenyl or dichloride, methyl enedi cyclopentadi enyl titanium diphenyl or dichloride and other complexes described by formulae II and III. Illustrative but non-limiting examples of the zirconocenes of Formula II and III which can be usefully employed in accordance with this invention are, pentamethyl cyclopentadi enyl zirconium trichloride, pentaethyl cyclopentadi enyl zirconium trichloride, the alkyl substituted cyclopentadi enes, such as bis(ethylcyclopenta- dienyDzi rconi um dimethyl, bis(β-phenylpropyl cyclopentadi enyl) zirconium dimethyl, bis (methyl cyclopentadi enyl )zi rconi um dimethyl, bis(n-butyl cyclopentadi enyl )zi rconi um dimethyl, bis(cyclohexyl- ethylcyclopentadi enyl )zi rconi um dimethyl, bis(n-octyl-cyclopenta- dienyDzi rconi um dimethyl, and haloalkyl and dihalide complexes of the above; dialkyl, trialkyl, tetra-alkyl, and penta-alkyl cyclopentadi enes, such as bis (pentamethyl cyclopentadi enyl )zi rconi um diphenyl, bis(pentamethylcyclopentadιenyl)zirconium dimethyl , bisd ,2-di methyl cyclopentadi enyl )zi rconi um dimethyl and mono and dihalide complexes of the above; silicon, phosphorus, and carbon bridged cyclopentadiene complexes such as di methyl silyl - di cyclopentadi enyl zirconium dimethyl, methyl halide or dihalide, and methyl ene di cyclopentadi enyl zirconium dimethyl, methyl halide, or dihalide. Mono, di and tri— silyl substituted cyclopentadienyl compounds such as b1s(trimethylsilylcyc1opentadienyDzirconium dichloride and dimethyl, bisd,3 di-trimethylsllyl- cyclopentadienyDzirconium dichloride and dimethyl and bisd ,2,4-tri-trimethylsilylcyclopentadienyDzirconium dichloride and dimethyl. Carbenes represented by the formulae Cp 2 Zr«CH 2 P(C-H 5 ) 2 CH 3 , and derivatives of these compounds such as Cp^rQ-LQ-KCH O . Bis(cyclopentadienyl)hafnium dichloride, b1s(cyclopenta- dienyDhafnium dimethyl, bis(cyclopentadienyl)vanadium dichloride and the like are illustrative of other metallocenes. Some preferred metallocenes are bis(cyclopentadienyl)zirconium dimethyl, bis(cyclopentadienyl)zirconium dichloride, bis(cyclopentadienyl)titanium dichloride, bis(methylcyclopentadienyl) zirconium dichloride, bis(methylcyclopentadienyl)titanium dichloride, b1s(n-butylcyclopentadienyl)zirconium dichloride, dimethylsilyldicyclopentadienyl zirconium dichloride, - ' ' bis(trimethylsilycyclopentadienyl)zirconium dichloride and dimethylsilyldicyclopentadienyl titanium dichloride. The alumoxane compounds useful in the process of this invention may be cyclic or linear. Cyclic alumoxanes may be represented by the general formula (R-A1-0) while linear alumoxanes may be represented by the general formula R(R-A1-0)_.A1R 2 . In the general formula R is a C ^ -C ς alkyl group such as, for example, methyl, ethyl, propyl, butyl and pentyl and n is an integer from 1 to about 20. Most preferably, R 1s methyl and n is about 4. Generally, 1n the preparation of alumoxanes from, for example, aluminum trimethyl and water, a mixture of the linear and cyclic compounds is obtained. The alumoxane can be prepared in various ways. Preferably, they are prepared by contacting water with a solution of aluminum trialkyl, such as, for examples, aluminum trimethyl, in a suitable organic solvent such as toluene or an aliphatic hydrocarbon. For example, the aluminum alkyl is treated with water in the form of a moist solvent. In an alternative method, the aluminum alkyl such as aluminum trimethyl can be desirably contacted with a hydrated salt such as hydrated copper sulfate or ferrous sulfate. Preferably, the alumoxane 1s prepared in trie presence of a hydrated ferrous sulfate. The method comprises treating a dilute solution of aluminum trimethyl in, for example, toluene, with ferrous sulfate represented by the general formula FeSO. " 7H 2 0. The ratio of ferrous sulfate to aluminum trimethyl is desirably about 1 mole of ferrous sulfate for 6 to 7 moles of aluminum trimethyl. The reaction is evidenced by the evolution of methane. " The ratio of aluminum in the alumoxane to total metal 1n the metallocenes which can be usefully employed can be in the range of about 0.5:1 to about 1000:1, and desirably about 1:1 to about 100:1. Preferably, the ratio will be in the range of 50:1 to about 5:1 and most preferably 20:1 to 5:1. In accordance with this invention, it has been discovered that not only can one obtain high molecular weight product while polymerizing at high temperatures, but that one can also obtain increasing: catalytic productivities with decreasing alumoxane-metallocene ratio to about 5:1. The solvents used in the preparation of the catalyst system are inert hydrocarbons, in particular a hydrocarbon that is inert with respect to the catalyst system. Such solvents are well known and include, for example, isobutane, butane, pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, toluene, xylene and the like. Since, in accordance with this invention, one can produce high molecular weight polymer product at relatively high temperature, temperature does not constitute a limiting parameter as with the prior art metallocene/alumoxane catalyst. The catalyst systems described herein, therefore, are suitable for the polymerization of olefins in solution over a wide range of temperatures and pressures. As indicated, supra, however, it is desirable that the the temperature be above about 150 β C to about 350°C, but below the decomposition temperature of said polymer product, typically from about 310 β C to about 325°C. Preferably, the polymerization will be completed at a temperature within the range from about 180 β C to about 280 β C. As also Indicated, supra, the polymerization will be completed at a pressure above about 500 bar, and generally at a pressure within the range from about 500 bar to about 3500 bar. Preferably, the polymerization will be completed at a pressure within the range from about 800 bar to about 1500 bar. After polymerization and deactivation of the catalyst, the product polymer can be recovered by processes well known in the art. Any excess reactants may be flashed off from the polymer and the polymer obtained extruded into water and cut into pellets or other suitable comminuted shapes. Pigments, antioxidants and other additives, as is known in the art, may be added to the polymer. The polymer product obtained in accordance with this invention will have a weight average molecular weight in the range of about 10,000 to about 1,500,000 and preferably 80,000 to about 1,000,000. The polydispersities (molecular weight distribution) expressed as Mw/Mn are typically from 1.5 to 3.0. The polymers may contain chain end unsaturation if no hydrogen is used during the polymerization. Broadened M can be obtained by employing two or more of the metal cyclopentadienyls in combination with the alumoxane as described in U.S. Patent Serial No. 4,530,914 entitled Process and Catalyst for Producing Polyethylene having a Broad Molecular Weight Distribution. The polymers produced by the process of this present invention are capable of being fabricated into a wide variety of articles, as 1s known for homopolymers of ethylene and copolymers of ethylene and higher alpha-olefins. EXAMPLES In the Examples following the alumoxane employed was prepared by adding 76.5 grams ferrous sulfate heptahydrate in 4 equally spaced increments over a 2 hour period to a rapidly stirred 2 liter round-bottom flask containing 1 liter of a 13.1 weight percent solution of trimethylaluminum (TMA) in,toluene. The flask was maintained at 50°C and under a nitrogen atmosphere. Methane produced was continuously vented. Upon completion of the addition of ferrous sulfate heptahydrate, the flask was continuously stirred and maintained at a temperature of 80 β C for δ hours. The reaction mixture was cooled to room temperature and was allowed to settle. The clear solution containing the alumoxane was separated by decantation from the insoluble solids. Molecular weights were determined on a Water's Associates Model No. 150C GPC (Gel Permeation Chromatography). The measurements were obtained by dissolving polymer samples in hot trichlorobenzene and filtered. The GPC runs are performed at 145*C in trichlorobenzene at 1.0 ml/ in flow using styragel columns from Perkin Elmer, Inc. 3.11 solutions (300 mlcrolitεrs of trichlorobenzene solution) were injected and the samples were run in duplicate. The integration parameters were obtained with a Hewlett-Packard Data Module. Example 1 In this example a stirred lOOcc steel autoclave reaction vessel which was equipped to perform Ziegler polymerization reactions at pressures up to 2500 bar and temperatures up to 300 β C was used. The reaction system was supplied with a thermocouple and pressure transducer to measure temperature and pressure continuously, and with means to supply purified compressed ethylene, nitrogen, hydrogen and any comonomer desired. Equipment for rapidly introducing premeasured volumes of catalyst, and equipment for rapidly venting the contents of the reactor and collecting the polymer product were also a part of the reaction system. In this Example, the polymerization was performed in pure ethylene without the addition of a solvent. In this Example 1, the temperature of the cleaned reactor containing ethylene at low pressure was equilibrated at the desired reaction temperature.of 150°C. The catalyst solution was prepared by mixing 0.180 mg of solid bis(n-butylcyclopentadienyl) zirconium dichloride with lO.Occ of 0.8M methylalumoxane solution in toluene in an inert atmosphere. A 0.40cc portion of this catalyst solution was transferred by low pressure nitrogen into the constant volume injection tube, which was held at 25 β C. During this run, ethylene was pressured into the autoclave at a total pressure of 1500 bar. The reactor contents were stirred at 1000 rp for one minute at which time the entire catalyst solution was rapidly Injected into " the stirring reactor with excess pressure. The temperature and pressure changes were recorded continuously for 120 seconds at which time the contents were rapidly vented yielding the polymer. The reactor was washed with xylene to collect any polymer remaining inside and all polymer was dried 1n vacuo. The yield was 3.54 g of polyethylene which had weight average molecular weight of 131,000, a polydispersity of 1.8 and a density of 0.955 g/cc. The conditions employed in this and the following Examples 2-25, as well as the results obtained, are summarized in Table I. Example 2 In this Example, the procedure used 1n Example 1 was repeated except that only 0.090 mg of bis(n-butylcyclopentadlenyl) zirconium were mixed with the lOcc solution methylalumoxane. The yield was 0.72 g of polyethylene having a weight average molecular weight of 185,000, a polydispersity of 1.9 and a density of 0.959 g/cc. Example 3 In this Example, the procedure used in Example 2 was repeated except that the autoclave was heated to a temperature of 230°C rather than 150°C. The yield was 1.71 g of polyethylene having a weight average molecular weight of 114,000, a polydisperisty of 2.0 and a density of 0.959 g/cc. Example 4 In this Example, the procedure of Example 2 was repeated except that 10.0 mole _. of 1-octene, based on ethylene, was injected into the autoclave with a syringe prior to the addition of ethylene. The yield was 0.25 g of an ethylene/octene copolymer having a weight average molecular weight of 182,000, a polydispersity of 1.9 and a density of 0.945 g/cc. Example 5 In this Example, the procedure of Example 4 was repeated except that 5.0 mole X of of 1-octene, based on ethylene, was injected into the autoclave with a syringe prior to the addition of ethylene rather than the 10.0 mole 1 used 1n Exasiple 4. The yield was 13.1 g of an ethylene/octene copolymer ha y ing a weight average molecular weight of 202,000, a polydispersity of 1.9 and a density of 0.950 g/cc. Example 6 In this Example, the procedure of Example 1 was repeated except that the autoclave was heated to 200 * C rather than 150 β C, 0.440 mg of bis(n-butylcyclopentadienyl) zirconium dichloride was added to just lcc of 0.8M methylalumoxane solution, rather than 0.180 mg added to lOcc of solution, and 9.0cc of toluene were added to the catalyst mixture. Again, 0.40cc of this catalyst mixture dO.Occ total volume) was transferred into the catalyst injection tube. The yield was 5.1 g of polyethylene having a weight average molecular weight of 119,000, a polydispersity of 2.4 and a density of 0.958 g/cc. Example 7 In this Example, the procedure of Example 6 was repeated except that 2.0cc 0.8M methylalumoxane solution was used, rather than 1.Occ, and only 8.0cc of toluene was added to the catalyst mixture rather than 9.Occ. The yield was 7.53 g of polyethylene having a weight average molecular weight of 98,000, a polydispersity of 1.9 and a density of 0.957 g/cc. Example 8 In this Exampl e, the procedure of Exampl e 1 was repeated except that the autoclave was heated to 200 β C, rather than 150 # C and only 0.110 mg of bi s(n-butyl cyclopentadi enyl ) zi rconi um di chloride was used, rather than 0.180 mg thereof as in Exampl e 1 . The yi eld was 3.70 g of polyethyl ene having a weight average mol ecular weight of 100,000, a polydi spersi ty of 2.0 and a densi ty of 0.958 g/cc. Example 9 In this Example, the procedure of Example 8 was repeated except that a nominal holding time of 40 seconds, rather than 120 seconds was used. The yield was 3.41 g of polyethylene having a weight average molecular weight of 96,000, a polydispersity of 1.9 and a density of 0.958 g/cc. Example 10 In this Example, the procedure of Example 8 was repeated except that a nominal holding time of 20 seconds, rather than 120 seconds, was used. The yield was 2.72 g of polyethylene having a weight average molecular weight of 94,200, a polydispersity of 1.9 and a density of 0.959 g/cc. Example 11 In this Example, the procedure of Example 8 was repeated except that only 5.Occ of a 0.8M solution of methylalumoxane was used, rather than lOcc thereof as in Example 8, and 5.Occ of toluene was added to the catalyst mixture. The yield was 4.00 g of polyethylene having a weight average molecular weight of 103,000, a polydispersity of 2.0 and a density of 0.958 g/cc. Example 12 In this Example, the procedure of Example 6 was repeated except that a nominal holding time of 40 seconds, rather than 120 seconds, was used. The yield was 2.87 g of polyethylene having a weight average molecular weight of 103,000, a polydispersity of 2.2 and a density of 0.958 g/cc. Example 13 In this Example, the procedure of Example 6 was repeated except that a nominal holding time of 20 seconds was used, rather than 120 seconds as was used in Example 6. The yield was 1.61 g of polyethylene having a weight average molecular weight of 126,000, a polydispersity of 2.1 and a density of 0.957 g/cc. Example 14 In this Example, the procedure of Example 8 was repeated except that the autoclave was heated only to 180 β C, rather than 200 β C as was used in Example 8 and the ethylene pressure was reduced from 1500 bar to 1000 bar. The yield was 4.00 g of polyethylene having a weight average molecular weight of 106,000, a polydispersity of 2.1 and a density of 0.958 g/cc. - - Exampl e 15 In this Example, the procedure of Example δ was repeated except that only 0.25cc of 0.8M methylalumoxane, rather than the l.Occ used in Example 6 and 9.75cc of toluene was added to the catalyst mixture, rather than the 9.0 cc used in example 6. The yield was 1.09 g of polyethylene having a weight average molecular weight of 129,000, a polydispersity of 2.2 and a density of 0.959 g/cc. Example 16 In this Example, the procedure of Example 6 was repeated except that only O.Scc of 0.8M solution of methylalumoxane was used, rather than the l.Occ used in Example 6, and 9.5cc of toluene was added to the catalyst mixture, rather than the 9.Occ which was added in Example 6. The yield was 3.18 g of polyethylene having a weight average molecular weight of 112,000, a polydispersity of 2.2 and density of 0.958 g/cc. Example 17 In this Example, the procedure of Example δ was repeated. The yield was 5.60 g of polyethylene, having a weight average molecular weight of 98,000, and a polydispersity of 1.9 and a density of 0.959 g/cc. Example 18 In this Example, the procedure of Example 8 was repeated except that the ethylene pressure was reduced from 1500 bar to 500 bar. The yield was 2.97 g of polyethylene having a weight average molecular weight of 100,000, a polydispersity of 2.1 and a density of 0.958 g/cc. Example 19 In this Example, the procedure of Example 8 was repeated except that the ethylene pressure was reduced from 1500 bar to 1000 bar. The yield was 5.70 g of polyethylene having a weight average molecular weight of 112,000, a polydispersity of 2.2 and a density of 0.957 g/cc. ISJ f\> IS3 IS) r_ r> (Jl __. t_> N> — ' O -o rr _ a_ * c •^ • «< 5 o o o o o o o o o o o o o o o o o o o o •< * o - i o o o o o o o f» a> IB o o o o o o o o o o o -~ o _ co _ _ IO a 3 -_ <o ... * s m * o o o o o o o o o o o £o_- £ £ o__ :o_ o:- o__ Λ. _. o o o — 0 < o o o o o o o — α. -o « 3 -! —- • < IB » — ' — - ^— ' α _ * . 3 -« •». _ a».• o r> o o o o o o o o iø vo vo o o o o o r> — ■ —x _r o c < — Ul «W •mm- φ t> o o tn o b b 3 φ r_ -- l-v) IS> IM 3 > o — • u u ω w u u w u> M ω - ω ^ ^ 9ι ω uι ω & >j ιo ιύ ιθ ιθ ιo ιθ ιo ιo ιo ιo ιθ ιs <o & M ia ιθ Jk & ιo ιo ιo ^ ji θ> - _ - _ o o o o o o o o o o o o o o o o o o o o o o o o o I I I I I I I I I I I I I I I I _- _. _r 1 o o 1 | o r> _r _r • r. Φ m O a. α. . — - 3 Φ _, O 3 23 ro ro o uι I I I I I I I I I o o (n ro o o X cr > o o o o ro vo o o o o o o o o o o o o o o o o o o -) o en 3 ui ui ut u ui tπ o u O O _. u O_i. u O_i u O _i. OO OUI UOI OUI UOI U O I UI U o o o o o o —UI _ —.I U—I _UI U._.I U-_I. UI βσ>* -o O O O O O O O O O O O O O O O O o _ oo oo oo oo oo oo oo oo IoM No No oN uι _. Jk _. M ^ ui N vι ω - _ _ _ _ _ i- ^ uι ω o Ul ^ φ ^ lO lC M IO Φ - O O Ol β O 'J Il in — . —4 u> _- _j oo > o o _ , o αo vo o — ' -J NJ — ' (-> o -_ —< © vo — - n _- uι ro o oo ro _. .t_ o o o o o o o o o σ o o o o o o o o © o o o o o o o o o ro r ro ro ιv> r ιs. ro -_ ro ro ro -s_ r ro — < _ M _ - . r w — « eseιo/z,8s.ι/i3d 6000/88 O Exampl 20 In this Example, t e procedure of Example 8 was repeated except that hydrogen, at a partial pressure of 9.δ bar, was introduced to the autoclave with the ethylene. The yield was 4.90 g of polyethylene having a weight ayerage molecular weight of 15,000 a polydispersity of 2.3 and a density of 0.961. Example 21 In this Example, the procedure of example 8 was repeated except that hydrogen, at a partial pressure of 32 bar, was introduced into the autocl y e with the ethylene. The yield was 7.93 g of polyethylene having a weight average molecular weight of 4,000, a polydispersity of 2.9 and a density of 0.965 g/cc. Example 22 In thi s Exampl e, the procedure of Exampl e 8 was repeated except that 20.0 mol e X, based on ethyl ene, of 1-hexene was i njected i nto the autoclave wi th a syri nge prior to the addi tion of ethyl ene. The yi eld was 4.78 g of a copolymer of ethyl ene/hexene having a weight average molecular weight of 85*000, a polydi spersi ty of 2.3 and a densi ty of 0.943 g/cc. Example 23 In this Example, the procedure of Example 22 was repeated except that 50.0 mole X of 1-hexene based on ethylene, was used rather than the 20.0 mole X of 1-hexene, used in Example 22. The yield was 4.93 g of a copolymer of ethylene/hexene having a weight average molecular weight of 76,000, a polydispersity of 2.1 and a density of 0.939 g/cc. Example 24 In this Example, the procedure of Example 22 was repeated except that 1 ,4-hexadiene was substituted for 1-hexene used in Example 22. The yield was 4.71 g of a copolymer of ethylene/hexadiene having a weight average molecular weight of 86,400, a polydispersity of 2.1 and a density of 0.945 g/cc. Example 25 In this Example, the procedure of Example 24 was repeated except that 50.0 mole X 1 ,4-hexadiene, based on ethylene, was used rather than the 20.0 mole X 1,4-hexadiene which was used in Example 24. The yield was 5.53 g of a copolymer of ethylβne/hexadlene having a weight average molecular weight of 83,400, a polydispersity of 2.2 and a density of 0.940 g/cc. Example 26 In this Example a stirred lOOOcc steel autoclave reaction vessel which was equipped to perform continuous Zlegler polymerization reactions at pressures up to 2500 bar and temperatures up to 300°C was used. The reaction system was supplied with a thermocouple and pressure transducer to measure temperature and pressure continuously, and with means to supply continuously purified compressed ethylene, hydrogen, and 1-hexene. Equipment for continuously introducing a measured flow of catalyst solution and equipment for rapidly venting and quenching the reaction and of collecting the polymer product were also a part of the reaction system. In this Example, the polymerization was performed with a molar ratio of ethylene to 1-hexene of 1.0 without the addition of a solvent. In this Example, the temperature of the cleaned reactor containing ethylene and 1-hexene was equilibrated at the desired reaction temperature of 180 β C. The catalyst solution was prepared by mixing 422.6 mg of solid b1s(n-butylcyclopentadienyl) zirconium dichloride with 1.0 liter of 0.8M methylalumoxane solution in 10 liters toluene in an inert atmosphere. This catalyst solution was continuously fed by a high pressure pump into the reactor at a rate of 660 cc/hour which resulted in a temperature of 180 β C in the reactor. During this run, ethylene and 1-hexene were pressured into the autoclave at a total pressure of 1000 bar at a mass flow rate of 50 kg/hour. The reactor contents were stirred at 1000 rpm. The yield of polymer product was 2.9 kg/hour of an ethylene-1-hexene copolymer which had weight average molecular weight of 57,718, a polydispersity of 2.3 and a density of 0.9244 g/cc. The conditions employed in this and the following Examples 27-41, as well as the results obtained, are summarized in Table II. Figure 1 visually demonstrates the increasing productivities obtained contrary to the teachings of the prior art by reducing the Al-metallocene ratio. Exampl 27 In this Example, the procedure used in Example 26 was repeated except that only 416.4 mg of bridged (dimethyl si lyldicyclo- pentadienyl) zirconium were substituted for the metallocene of Example 26. The yield was 3.3 kg/hour of ethyl ene-1-hexsne copolymer having a weight average molecular weight of 11,200, a polydispersity of 3.9 and a density of 0.9361 g/cc. Example 28 In this Example, the procedure used in Example 26 was repeated except that 456.3 mg of bis(cyclopentadienyl) zirconium dichloride was substituted for the metallocene of Example 26. The yield was 3.1 kg/hour of ethylene-1-hexene copolymer having a weight average molecular weight of 37,380, a polydisperisty of 2.1 and a density of 0.9312 g/cc. Example 29 In this Example, the procedure of Example 28 was repeated except that the total pressure was increased to 1500 bar. The yield was 2.9 kg/hour of an ethylene-1-hexene copolymer having a weight average molecular weight of 43,881, a polydispersity of 2.1 and a density of 0.9282 g/cc. Example 30 In this Example, the procedure of Example 29 was repeated except that the catalyst was prepared using 444.8 mg of bis (cyclopentadi enyl) zirconium dichloride, 0.25 liter methyl alumoxane solution and 5.0 liters of toluene. The yield was 2.8 kg/hour of an ethyl ene-1-hexene copolymer having a weight average molecular weight of 46,077, a polydispersity of 2.1 and a density of 0.9283 g/cc. Example 31 In this Example, the procedure of Example 29 was repeated except that the autoclave was pressurized to a total pressure of 2000 bar. The yield was 2.6 kg/hour of ethylene-1-hexene copolymer having a weight average molecular weight of 51,500, a polydispersity of 2.1 and a density of 0.9262 g/cc. Exampl e 32 In this Example, the procedure of Example 29 was repeated except that a total pressure of 2500 bar was used. The yield was 2.9 kg/hour of ethylene-1-hexene copolymer having a weight ayerage molecular weight of 50,200, a polydispersity of 2.0 and a density of 0.9243 g/cc. Example 33 In this Example, the procedure of Example 26 was repeated except that 804.3 mg of bis(n-butylcyciopentadienyl) zirconium dichloride, 0.50 liters of methylalumoxane solution, and 15.0 liters of toluene were used to prepare the catalyst. A total pressure of 2000 bar was used. The yield was 2.5 kg/hour of ethylene-1-hexene copolymer having a weight average molecular weight of 76,200, a polydispersity of 2.0 and a density of 0.9201 g/cc. Example 34 In this Example, the procedure of Example 33 was repeated except that a total pressure of 2500 bar was used. The yield was 2.9 kg/hour of ethylene-1-hexene copolymer having a weight average molecular weight of 77,200, a polydispersity of 1.9 and a density of 0.9180 g/cc. Example 35 In this Example, the procedure of Example 34 was repeated except that a 1-hexene to ethylene molar ratio of 1.6 rather than 1.0 was used. The yield was 3.0 kg/hour of ethylene-1-hexene copolymer having a weight average molecular weight of 59,400, a polydispersity of 1.9 and a density of 0.9084 g/cc. Example 36 In this Example, the procedure of Example 34 was repeated except that a temperature of 170°C rather than 130 β C was used. The yield was 1.9 kg/hour of ethylene-1-hexene copolymer having a weight average molecular weight of 72,900, a polydispersity of 1.8 and a density of 0.9107 g/cc. * ^ e - . c < , n ^ © -» *-_ -r> o ao m '- •T SO ι— _O CO vO T β «C «O O U * - O CM «J' «ϊ- N n n M N N ΛI N '- O '- O O O O N vι u l v Ov Ol Ol l Ol O OV wl Ol t l C - tt SI o -— o o o o o o o o o o o o o o o o (i| Bl ι- <- ι- ι- 0 0 _ βl - βl Ol O O -» N n N N r N -M N '- '- i- '- '- N N lM D O O O O O O O O O O O O O O O — © O O 0 0 0 0 O O 0 O 0 0 0 O p- M T CS «— m CII N N V OI N i- M N >- r- '- i- ci -O '- o iC σi N r 'T '-f in o ur> «— < ^ *^ iΛ -_ r- r- _rj -«. r- ιn -r. ιrt «n r -α_ . « •- σι <--> '— σv o _3 θ _. σι © ov o --- o σι ι_5 ..— e ^ n >- oc N n n N (n N t . N -<ι n τ- c. (>) -» (>i N ^^ • Φ « ε Φ O O O O O O O O O O O O O O O O u -«- -n _rj _n ιn _-j -_ --) --) u°> -r> _-> i- --) ir> u * ) --> _ c φ tn tc O O O O O O O O O O O O O f- O O lO O r- o -T -T O co 'T -- V-S * «T VO '<T CM C_> c - -o vo m σ» r_ r- ιΛ i_. -<f '»j- u. f--ι τ ι_J o o r_ m Φ (-> . a. & c o > t- « o o o o o o o o o o o o o o o o - * σ - φ 3 o o o o _- θ θ _-ι ιΛ _*> _. _. _*ι _n o o *» > "o O ^ — -u c ""*- c *α -> > « * Φ o o © o ■— _-) _. o o o o __ _. σι vo σx c r— O lO N '- - n n n o o o o β - i . '- <C E P- VO _rl in >— r— 4— CM CM CM CM <— ■— « * o _. § 3 -_• CM t- m o o o o o o o o o cM u-) c • C Φ o o o o cvi u- u. _- _- U- _. m in c. .— co w o o o o o o o o o © ϊ. o O ._* _. VI a F * » o *j n n o n n ιη n n (. β oi "r -f N -o — — ..- Ol c. i . iO io -r i-i w T ' . -r 'T N i o i-i T E <M _- _. _. τ v_3 »o c3 o o o ιn r- _. '--r ι— O v ε τ -<r τ '<τ -<r oo ao oo oo co oo co oo *>τ ^τ r_. _ « t N CM ^ .> ε ε - * o» e o © O O O O O O O O O O © O © O CO QO QO OO OO 03 CO CO O CO r- r» ?— r * . >_. ^— - --. σ * c « « ε ι_j r- eo σι o <— -M cn -jr «. <o r_ eo oi o »— N N !>j _i (n ιπ n ι η ι. n (. n n (η ^ ι •— «M CO Exampl e 37 In this Example, the procedure of Example 36 was repeated except that the catalyst was prepared using 857.8 mg of bis(n-butylcyclopentadienyl) zirconium dichloride. The yield was 3.0 kg/hour of ethylεne-1-hexene copolymer having a weight average molecular weight of 73,200, a polydispersity of 1.9 and a density of 0.9055 g/cc. Example 38 In this Example, the procedure of Example 36 was repeated except that the catalyst was prepared using 873.9 mg of bis(n-butylcyclopentadienyl) zirconium dichloride, and a 1-hexene to ethylene molar ratio of 2.0 was used rather than 1.6. The yield was 3.7 kg/hour of ethylene-1-hexene copolymer having a weight average molecular weight of 54,100, a polydispersity of 1.9 and a density of 0.9000 g/cc. Example 39 In this Example, the procedure of Example 38 was repeated except that the catalyst was prepared by mixing 2458.4 mg of bis(n-butylcyclopentadienyl) zirconium dichloride, 0.30 liters of methylalumoxane solution and 15.0 liters of toluene. The yield was 4.0 kg/hour of ethylene-1-hexene copolymer having a weight average molecular weight of 54,200, a polydispersity of 2.0 and a density of 0.9028 g/cc. Example 40 In this Example, the procedure of Example 38 was repeated except that the catalyst was prepared by mixing 2443.4 mg of bis(n-butylcyclopentadienyl) zirconium dichloride, 0.12 liters of methylalumoxane solution and 10.0 liters of toluene. The yield was 3.9 kg/hour of ethylene-1-hexene copolymer having a weight average molecular weight of 55,200, a polydispersity of 2.0 and a density of 0.9045 g/cc. Example 41 In this Example, the procedure of Example 36 was repeated except that the catalyst was prepared by mixing 4714.2 mg of bis(methylcyclopentadienyl)titanium dichloride, 0.85 liters of methylalumoxane solution and 10.0 liters of toluene. The yield was TABLE III Example No. Al/M (molar) Productivity (α Po 1 17960 190 2 35910 38 3 35910 92 4 35910 13 5 17960 705 6 740 2750 7 1470 2030 8 29390 200 9 29390 185 10 29390 150 11 14690 430 12 740 1550 13 740 870 14 29390 215 15 190 2350 16 370 3425 17 740 3020 18 29390 160 19 29390 310 20 29390 260 21 29390 425 22 29390 260 23 29390 265 24 29390 255 25 29390 300 26 760 940 27 670 470 28 510 850 29 510 885 30 131 1574 31 135 2000 32 135 2400 33 200 3630 34 200 4120 35 200 3665 36 200 3320 37 188 4280 38 185 3520 39 39 3522 40 16 4800 2.6 kg/hour of ethylene-1-hexene copolymer having a weight average molecular weight of 30,100, a polydispersity of 2.4 and density of 0.9241 g/cc. Table III demonstrates the relationship of Al/M ratio and producti vi ti es . The Examples demonstrate that at high pressures and temperatures high molecular weight polymer product can be obtained at productivities of 1000 and greater by employing catalyst systems having a relatively low Al/metal ratio. While the present invention has been described and illustrated by reference to particular embodiments thereof, it will be appreciated by those of ordinary skill in the art that the invention lends itself to variations not necessarily illustrated herein. For this reason, then, reference should be made solely to the appended claims for purposes of determining the true scope of the present invention.

Claims: WHAT IS CLAIMED IS 1. A process for polymerizing ethylene either alone or in combination with other olefins, comprising contacting said ethylene either alone or in combination with other olefins, with a catalyst comprising a cyclopentadienyl-transition metal compound and an alumoxane compound wherein the ratio of aluminum in the alumoxane to the total metal In the metallocene 1s in the range of 1000:1 to 0.5:1 at a temperature greater than 120 β C and a pressure of about 500 bar or greater. 2. The process of claim 1 wherein the ratio is in the range of 100:1 to 1:1. 3. The process of claim 2 wherein the ratio is in the range of 50:1 to 1:1. 4. The process of claim 1 wherein said pressure is above about 500 bar and the temperature is in the range of 150°C to 300'C. 5. The process of claim 1 wherein said pressure is within the range from about 500 bar to about 3500 bar. 6. The process of claim 5 wherein said pressure is in the range of 550 to about 3500 bar. 7. The process of claim 4 wherein the temperature is in the range of !80 β C to 280°. 8. The process of claim 1 wherein said transition metal is selected from the group of metals consisting of Groups IV and V of the Periodic Table Of Elements. 9. The process of claim 1 wherein said cyclopentadienyl-transition metal compound can be represented by one of the following general formulae: I. (Cp r )mMRnXq wherein Cp is a cyclopentadienyl ring, M is a Group 4b or 58 transition metal, R 1s a hydrocarbyl group or hydrocarboxy having from 1 to 20 carbon atoms, X is a halogen, and 1s a whole number from 1 to 3, n is a whole number from 0 to 3, and q 1s a whole number from 0 to 3. II. <C 5 R' k ) g R" $ (C 5 R' k )MQ 3 _ g and HI- R " s < 5 R, k 2 MQ ' wherein (C c is a cyclopentadienyl or substituted cyclopentadienyl, each R' is the same or different and 1s hydrogen or a hydrocarbyl radical such as alkyl, alkenyl, aryl, alkylaryl, or arylalkyl radical containing from 1 to 20 carbon atoms, silicon containing hydrocarbyl radicals, or a hydrocarbyl radical wherein two carbon atoms are joined together to form a C.-C 8 ring, R" is a C j -C. alkylene radical, a dialkyl germanium or silicon, or a alkyl phosphine or amine radical bridging two (C ς 'u) rings, Q is a hydrocarbyl radical such as aryl, alkyl, alkenyl, alkylaryl, or aryl alkyl radical having from 1-20 carbon atoms, hydrocarboxy radical having from 1-20 carbon atoms or halogen and can be the same or different from each other, Q 1 is an alkylidene radical having from 1 to about 20 carbon atoms, s is 0 or 1, g is 0,1 or 2, s is 0 when g is 0, k is 4 when s is 1, and k is 5 when s is 0, and M is as defined above. 10. The process of claim 9 wherein said alumoxane can be represented by one of the following formulae: I. (R-Al-0) n and II. R(R-A1-0) A1R. n 2 wherein R is a C,-C 5 alkyl group such as, for example, methyl, ethyl, propyl, butyl and pentyl and n is an integer from 2 to about 20. 11. The process of claim 10 wherein said transition metal is selected from the group of setaϊs consisting of titanium and zirconium. 12. The process of claim 11 wherein said transition metal is zirconium. 13. The process of claim 9 wherein said cyclopentadienyl compound may be represented by formula I and m is 2, n is 0 and q 1s 2. 14. The process of claim 13 wherein X is chlorine. 15. The process of claim 10 wherein R is methyl and n is greater than or equal 4. 16. The process of claim 9 wherein the cyclopentadi enyl - transition metal compound 1s selected from one of bis(cyclopεnta- di enyDzi rconi um dimethyl , bis(cyclopentadienyl) ziconium dichloride, bis(cyc1opentadieny1)titanium dichloride, bis (methyl cyclopentadi enyl) zirconium dichloride, bis (methyl cyclo- pentadi enyl) titanium dichloride, bis(n-buty1 cyclopentadi enyl) zirconium dichloride, dimethylsilyldicyclopentadienyl zirconium dichloride, bis(trimethylsily1cyclopentadienyl)zirconium dichloride, dimethyl si lyldi cyclopentadi enyl titanium dichloride or mixtures thereof. 17. The process of claim 10 where n is 4 or greater.

Inventors: SPEED CHARLES STANLEY, WELBORN HOWARD CURTIS JR, SPEED, CHARLES, STANLEY, WELBORN, HOWARD, CURTIS, JR.
Applicants: EXXON CHEMICAL PATENTS INC, EXXON CHEMICAL PATENTS, INC.
Application year: 1987
Main classification: C08F10
IPC codes: C08F4, C08F10, C08F210