2,956,993 United States Patent C Patented Oct. 18, 1960 2 corresponding to the formula M'M'Hy, wherein M' is an alkali metal, M' is a metal selected from the group 2,956,993 consisting of aluminum, gallium, indium and thallium, and y is equal to the sum of the valences of the two pROCESS AND CATALYST FOR PRODUCTION metals. OE OLEFN POLYMERS The improvement obtained when polymerizing an ole Gene Nowlin, Glen Burnie, Md., and Harold D. Lyons, fin in the presence of our novel catlayst is, firstly, that Bartlesville, Okla., assignors to Philips Petroena Com polymers of much higher molecular weight possessing pany, a corporation of Delaware very high impact strength and other desirable characteris O tics can be obtained than is true when certain of the prior No Drawing. Fied Dec. 22, 1955, Ser. No. 554,615 art catalysts have been employed, and secondly, the 16 Claims. (C. 260-94.9) polymerization reaction, particularly for ethylene, can be initiated and carried out at considerably lower ten peratures and pressures than are necessary when em This invention relates to the polymerization of olefins. 5 ploying the catalysts and the processes of the prior In one aspect, this invention relates to an improved art. method for polymerizing olefins and to a novel catalyst The metal halide component of our catalyst System therefor. comprises the halides of the metals titanium, zirconium, Reactions for polymerizing olefins are well known in hafnium and germanium. Examples of metal halides the art and are generally carried out in the presence of 20 which can be used include titanium dichloride, titanium catalysts. One class of catalysts which has been used in trichloride, titanium tetrachloride, titanium dibromide, the polymerization of monoolefins, particularly ethylene, titanium tribromide, titanium tetrabromide, titanium is organometal compounds, for example triethylalumi diiodide, titanium triiodide, titanium tetraiodide, titanium num, and the polymers which have been obtained in ac trifluoride, titanium tetrafluoride, zirconium dichloride, cordance with this method are generally liquid or low 25 zirconium trichloride, zirconium tetrachloride, zirconium molecular weight solid polymers. Frequently, the poly dibromide, zirconium tribromide, zirconium tetrabromide, mers obtained are dimers or trimers of the olefin charged. zirconium tetraiodide, zirconium tetrafluoride, hafnium However, it is often desirable to produce higher molecular trichloride, hafnium tetrachloride, hafnium triiodide, haf weight polymers which have desirable properties of heat nium tetraiodide, germanium dichloride, germanium tri stability and can be molded into vessels, pipes and tubing. 30 chioride, germanium tetrachloride, germanium dibromide, Such uses cannot be made of the lower molecular Weight germanium tetrabromide, germanium diiodide, germani polymers, for example, a polymer having a molecular um, tetraiodide, germanium difluoride, germanium tetra weight of about 1000, since a polymer of this molecular fluoride and the like. Mixtures of two or more of the weight is a wax-like material. metal halides can be used in the catalyst system of our in It is an object of this invention, therefore, to provide 35 vention. an improved process for the production of high molecular In admixture with one or more of the metal halides de weight olefin polymers. scribed above our novel catalyst comprises a compound A further object is to provide a novel catalyst for use corresponding to the formula M'(OR), wherein M’ in the production of olefin polymers. is one of the metals lithium, sodium, potassium, rubidium, A still further object is to produce high molecular 40 cesium, magnesium, calcium, zinc, strontium, cadmium, eight solid polymers of olefins, such as ethylene. barium, aluminum, gallium, indium, or thallium, R is an Other and further objects and advantages of this in alkyl, alkenyl, cycloalkyl, cycloalkenyl, or aryl radical, or vention will become apparent to those skilled in the art combinations of these radicals, e.g., an alkaryl or aralkyl upon consideration of the accompanying disclosure. radical, and x is an integer equal to the Valence of the it has now been discovered that an unexpected im 45 metal. Each of the aforementioned hydrocarbon radicals provement in the production of high molecular weight may contain up to about 20 carbon atoms, preferably polymer is obtained when an olefin, such as ethylene, is from 1 to 10, inclusive, carbon atoms with the total num polymerized in the presence of a catalyst composition ber of carbon atoms in the compound not exceeding 50. comprising (1) a metal halide selected from the group Mixtures of any two or more of these metal alkoxides can consisting of halides of titanium, zirconium, hafnium and 50 be employed in the practice of our invention. Examples germanium, (2) a compound corresponding to the for of these compounds which can be used include sodium mula M'(OR") wherein M' is a metal selected from the methoxide, aluminum ethoxide, potassium propoxide, group consisting of lithium, sodium, potassium, rubidium, rubidium isopropoxide, cesium n-butoxide, calcium Cesium, magnesium, calcim, zinc, strontium, cadmium, phenoxide, barium allyloxide Ba(OCH2CH=CH2)2), barium, aluminum, gallium, indium and thallium, R is gallium cyclohexoxide, magnesium tert-dodecoxide, cad Selected from the group consisting of alkyl alkenyl, cyclo 55 mium cyclohexeneoxide, indium isobutoxide, zinc alkyl, cycloalkenyl, and aryl radicals and combinations ecosoxide, methyoxyethoxyzinc, ethoxyphenoxymagnesi of these radicals, and x is equal to the valence of metal um, and the like. M, and (3) at least one component selected from the In admixture with at least one of the metal halides and following: (a) an organometal halide corresponding to 60 at least one of the Mi'(OR") compounds as set forth. the formula RMX, wherein R is a saturated acyclic above, our catalyst comprises at least one organometal hydrocarbon radical, a saturated cyclic hydrocarbon radi halide corresponding to the formula RMX, wherein R cal, an aromatic hydrocarbon radical, or combinations is a saturated acyclic hydrocarbon radical, a saturated of these radicals, M is a metal selected from the group cyclic hydrocarbon radical, an aromatic hydrocarbon consisting of aluminum, gallium, indium, thallium, and radical, or combinations of these radicals, wherein M is beryllium and X is a halogen, and wherein in and n are 65 a metal selected from the group consisting of aluminum, integers, the sum of m and n being equal to the valence gallium, indium, thallium and beryllium, and wherein X of the metal; (b) a mixture of an organic halide and at is a halogen. The m and n are integers and the sum of least one metal selected from the group consisting of m and n is equal to the valence of the metal M. X can sodium, potassium, lithium, rubidium, cesium, beryllium, be any of the halogens, including chlorine, bromine, magnesium, zinc, cadmium, mercury, aluminum, gal 70 iodine and fluorine. The saturated acyclic hydrocarbon lium, indium and thallium; and (c) a complex hydride radicals, saturated cyclic hydrocarbon radicals, and 2,956,998 3 4 aromatic hydrocarbon radicals which can be substituted hydride, lithium indium hydride, lithium gallium hydride, for R in the formula include hydrocarbon radicals having rubidium aluminum, and the like. The preferred mem up to about 20 carbon atoms each. Radicals having 10 ber of this class of compounds is lithium aluminum hy carbon atoms or less are preferred since the resulting dride. catalyst composition has a greater activity for initiating Among the catalyst compositions falling within the scope the polymerization of olefins. Mixtures of one or more of this disclosure which are preferred because their use of these organometal halide components, such as a mix in the process of this invention to catalyze the polymeri ture of ethylaluminum dichloride and diethylaluminum zation of olefins e.g., ethylene provides relatively high chloride, can be used in our catalyst composition. Specific molecular weight polymers and/or permits the use of examples of other organometal halides which are useful in relatively low reaction temperatures and pressures are the catalyst composition of this invention are the follow the following: a mixture of titanium tetrachloride and ing: CHAICl2 (CH3)2AlCl, C2H5A1Cl2 (C2H5)2AlCl, aluminum ethoxide with an approximately equimolar (C2H5)3A1Br, (CH3)2AlBr, Cahir Ala, (CH)2GaF, mixture of ethylaluminum dichloride and diethylalumi (C6H11)CaCl (cyclohexane derivative), (C6H5)GaBr2 num chloride; a mixture of titanium trichloride and alu (benzene derivative, C2H41GaBr2, (C14H29) aGaF, 5 minum ethoxide with an approximately equimolar mix (C6H5)2.InCl (benzene derivative), CH1. In F3, ture of ethylaluminum dichloride and diethylaluminum (C6H11)In Bra (cyclohexane derivative), C17H35Be, chloride; a mixture of titanium tetrachloride, aluminum CHBeBr, 3-methylcyclohexylaluminum dichloride, 2 ethoxide and lithium aluminum hydride; a mixture of Zir cyclohexylethylgallium dichloride, p-tolylberyllium iodide, conium tetrachloride and sodium propoxide with an ap di-(3-phenyl-1-methylpropyl)indium fluoride, 2-(3-iso 20 proximately equimolar mixture of ethylaluminum dichlo propylcyclohexyl)ethylthallium dibromide, and the like. ride and diethylaluminum chloride; and a mixture of Zir Alternatively, or in addition to the RMX compounds conium tetrachloride and calcium phenoxide with an ap set forth above, our catalyst comprises a mixture of one proximately