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United States Patent Office Patented Jan 3,074,98 United States Patent Office Patented Jan. 22, 1963 2 3,074,918 pressure, at elevated hydrogen pressures or at partial pres POLYMERIZATION OF CYCLEC OLEFENS sures of hydrogen. Herbert Sousa Eletterio, Wilmington, Dei, assignor to The reactive catalyst is formed by treating the Sup E. I. du Poné de Nemours and Company, Willanaiagio R, ported metal oxide with a metal hydride wherein the De., a corporation of Delaware 5 metal is selected from groups I, II and III of the periodic No Drawing. Fied June 20, 1957, Ser. No. 667,018. table of elements in the presence of an inert, liquid 7 Caians. (C. 260-93.1) hydrocarbon solvent in which the metal hydride is either The present invention relates to the polymerization of dissolved or dispersed. The metal hydrides employed are cyclic olefins and to novel polymeric products obtained the hydrides of alkali metals, alkaline earth metals and therefrom, 10 boron and aluminum. This treatment may be carried out It was heretofore known that metal oxides selected over a wide range of temperatures from room tempera from group VI-B of the periodic table of elements when ture to 300° C. The treatment may further be carried supported on inert carriers on activation by treatment out prior to polymerization or in the presence of the with a reducing gas would give rise to active catalysts monomer to be polymerized at polymerization condi capable of polymerizing ethylene to high molecular weight 15 tions. The quantity of the metal hydride added to the solid polymers. The activity of these catalysts is further supported group VI-B metal oxide may be greatly varied increased by the addition of a promoter in the form of a from about 0.01 to 1 parts of metal hydride per part of metal hydride selected from groups I to II of the periodic the solid catalyst. The catalysts can be employed in vari ous forms and sizes, e.g., powders, granules or shaped table of elements. The preparation of these catalysts is 20 pellets. illustrated in U.S. Patents 2,691,647, 2,726,231, 2,728,758, The polymerization of the cyclic olefins according to 2,731,452 and 2,731,453, among others. the present invention is preferably carried out in the pres The activity of these catalysts has heretofore been be ence of a hydrocarbon solvent, liquid at polymerization lieved to be limited to the polymerization of terminally conditions. The polymerization may also be carried out pylene.unsaturated gaseous monomers such as ethylene and pro 25 in bulk where the monomer is liquid at polymerization conditions. It is, however, generally preferred to employ In accordance with the present invention it was dis sufficient solvent to maintain the polymer-formed in solu covered that supported group VI-B metal oxide catalysts, tion since such conditions greatly facilitate the separation preferably activated by treatment with a reducing gas, of catalyst from polymer. The polymerization tempera when reacted with a group I to III metal hydride will 30 ture can be varied from room temperature to 250° C. and . polymerize cyclic olefins to high molecular weight poly above. The polymerization pressure is not critical. Gen mers. It was furthermore discovered that the polymer erally, the monomers employed in the present invention ization of the cyclic olefins does not proceed, as would be are liquids and are polymerized under autogenous pres expected through the opening of the double bond, but sure. However, it is quite feasible to carry out the proc through the breaking of the ring. Consequently, the 35 ess of the present invention at elevated pressures up to polymerization of monocyclic olefins such as cyclopen 200 atmospheres, and above, if such can be obtained with tene gives rise to linear polymers, the polymerization of the liquid monomers employed. The quantity of the bicyclic olefins gives rise to polymers containing recur catalyst may vary depending on such process conditions ring single ring structures and in general polycyclic ole as temperature and physical form, of the catalyst. In fins gives rise to polymers containing recurring units in 40 which the unit has one ring structure less than the origi general, the catalyst is employed in quantities varying nal monomer. from 0.01 to 10% of the monomer, The olefins employed in the present invention are cyclic lowingThe examples:present invention is further illustrated by the fol olefins having at least one unsubstituted ring double bond Example I and not more than one double bond in each ring. Thus representative examples of monocyclic, bicyclic and tri A sample of 7.5% molybdena on gamma-alumina cyclic olefins employed in the present invention are cyclo (commercially available from the Oronite Co.) was pentene, cyclohexene, cyclobutene, cyclooctene, bicyclo heated in a stream of hydrogen at atmospheric pressure (2,2,1)-heptene-2, , substituted bicyclo-(2,2,1)-heptene-2, for 16 hours at 480 C. Into a 250 ml, flask was charged bicyclopentadiene, substituted bicyclopentadienes, 1,2-di 50 under an atmosphere of nitrogen 100 ml. of benzene hav hydrobicyclopentadiene, etc. - ing therein dispersed 6 g. of the hydrogen treated molyb The catalyst employed in the present invention and its dena on alumina. To the dispersion was added under preparation have been illustrated in the prior art. The agitation 1.5 g. of lithium aluminum hydride and 50 ml. group VI-B metal oxides employed in the present inven of bicyclo-(2,2,1)-heptene-2. The reaction mixture was tion comprise the metal oxides of chromium, molybde 55 allowed to stand for a period of 12 hours at room tem num, tungsten and uranium. These metals are listed in perature. The resulting polymer catalyst mixture was group VI-B of the periodic table of elements as illustrated filtered, and the polymer was extracted by refluxing with in "The Handbook of Chemistry and Physics,” Chemical xylene and precipitated with methanol. A solid poly Rubber. Publishing Company, 37th edition, page 392. meric material weighing 2 g. Was obtained. The polymer 60 was molded into a film and subjected to infrared analysis. The preferred metal oxide is molybdenum oxide. The and X-ray analysis. The polymer was found to be amor carriers employed to support the catalyst are difficultly phous in structure- and was found to contain trans reducible metal oxides such as titania, Zirconia and alu unsaturation and a considerable amount of cis-unsatura mina. The ratio of the group. VI-B metal oxide to the tion. The polymer was dissolved in carbon tetrachloride support may be varied from 1:20 to 1:1, but is preferably and ozonized. A solid acid was obtained. The p-bromo in the range of 1:10. Although the treatment of the sup 65 phenacyl derivative of the acid was found to have a melt ported metal oxide, when employed in combination with ing point at 166-168 C. A mixed melting point deter a metal hydride, with a reducing gas is not absolutely mination with an authentic sample of di-p-bromophenacyl essential, it is generally preferred to treat the supported ester of cis-1,3-cyclopentanedicarboxylic acid showed no catalyst with hydrogen at a temperature of 350° C. to 70 depression. An infrared scan of the ester prepared from 850 C. The treatment may be carried out at atmospheric, the acid obtained from ozonization of the polymer was found to be identical to the infrared scan of the dip. 8,074,916 A. 3. of 12 hours. Methanol was added to the reaction mixture bromophenacyl ester of cis-1,3-cyclopentane dicarboxylic to precipitate the polymer catalyst mixture. The mix acid. The polymer thus corresponds to the structural ture was filtered and the polymer was extracted from the formula: catalyst with boiling xylene. A solid polymer weighing 10 g. was obtained. The polymer could be molded into stiff films, the infrared scan of which showed cis- and (tie) trans-unsaturation in the polymer. Example II Example VII Into a 330 ml. stainless steel autoclave was charged O Into a reaction flask was charged under nitrogen 5 g. under nitrogen 6 g. of hydrogen treated moybdena on of hydrogen reduced molybdena on alumina (prepared alumina (prepared as described in Example ) dispersed as described in Example :) dispersed in 50 ml. of ben in 100 ml. of benzene, 1.5 g. of lithium aluminum hydride zene, 1.5 g. of lithium aluminum hydride and 25 ml. of and 50 g. of bicyclo-(2,2,1)-heptene-2. The reactor was 1,2-dihydrobicyclopentadiene. The reaction mixture was heated to 100° C. and agitated at that temperature under 5 mildly agitated at room temperature for a period of 36 autogenous pressure for a period of 4 hours. The re hours. The polymer was obtained in the form of a gel sulting polymer solution was filtered to remove the cata in the solvent. The polymer and catalyst residues weighed iyst and the polymer was precipitated by the addition of 15 g. A sample of extracted polymer, obtained by ex methanol. The dried washed solid polymer weighed 2 g. traction with benzene followed by precipitation, could be The polymer could be molded into tough rubbery films. 20 molded into tough, clear, rigid films. Infrared analysis The infrared scan of the films was similar to the one ob of the film showed the presence of cis- and trans-unsatu tained from the polyner prepared in Example I. ration in the polymer in accordance with the following Example III polymer structure: H. into a reaction flask was charged under nitrogen 5 g. of hydrogen reduced chromia on gamma-alumina (com -- mercially available) which had been reduced by the treatment described in Example I.
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