Patent GB-786014-A (GB)
Title: Improvements in or relating to polymerization of normally gaseous mono-olefins
IPC: B01J23/22
Filed: 1956-03-07
Abstract: Polymerization catalysts comprise an oxide of a Group 5A metal and/or a supported oxide of a Group 6A metal, in conjunction with a co-catalyst AIR3, wherein R is selected from hydrogen and hydrocarbon radicals.  The oxides may be used in admixture with each other or with the oxides of copper, tin, zinc, nickel, cobalt, titanium and zirconium, e.g. the mixtures obtained by calcining Group 5A or 6A metal salts of metavanadic or molybdic acids.  The oxides may be pre-reduced before use.  In examples, the aluminium compounds used are the trimethyl, triethyl and triphenyl compounds, but many others are specified.  The supports listed, which may also be used for Group 5A metal oxides, are activated carbon, alumina, activated and tabular alumina, magnesia, titania, zirconia, silica, aluminosilicates, clays, fused silicates, silicon carbide, diatomaceous earths, metals (such as iron or steel) preferably treated to produce a film of the corresponding oxide (e.g. anodized aluminium), kaolin, iron oxide, carbon block, and fluorides of alkali metals, alkaline earth metals, aluminium, gallium and indium.  The catalyst may be in the form of a film of oxide on the inner surface of the reactor, e.g. V2O5 coated on a calcined aluminium surface.  Example 13 also illustrates the use of unsupported 6A metal oxide catalyst.  Relative proportions for catalyst, co-catalyst and support are given.ALSO:C2 to C4 mono-olefines are polymerized at low pressure and temperature using a catalyst comprising an oxide of a Group 5A metal and/or a supported oxide of a Group 6A metal, in conjunction with a cocatalyst of formula AlR3 wherein R is selected from hydrogen and hydrocarbon radicals.  Ethylene, which may contain oxygen as impurity, propylene and 1-butene are specified olefines and these may be copolymerized with t-butyl-ethylene, butadiene, isoprene, styrene, aryl alkyl styrenes, tetrafluoroethylene and trifluoromonochloroethylene. Oxides disclosed are V2O5, Cb2O5, Ta2O5, Vo2, V2O3, VO, CbO2, CbO, TaO2, MoO3, Cr3O3, WO3 and mixtures with each other or with oxides of copper, tin, zinc, nickel, cobalt, titanium and zirconium, e.g. the mixtures obtained by calcining Group 5A or 6A metal salts of metavanadic or molybdic acids.  The oxides may be calcined or pre-reduced before use.  In examples the aluminium compounds used are the trimethyl, triethyl and triphenyl compounds, but many others are specified. The supports listed, which may also be used for Group 5A metal oxides, are activated carbon, alumina, activated alumina, tabular alumina, magnesia, titania, zirconia, silica, aluminosilicates, clays, fused silicates, silicon carbide, diatomaceous earths, metals (such as iron or steel) preferably treated to produce a film of the corresponding oxide (e.g. anodized aluminium), kaolin, iron oxide, carbon black and fluorides of alkali metals, alkaline earth metals, aluminium, gallium and indium.  The catalyst may be in the form of a film of oxide on the inner surface of the reactor, e.g. V2O5 coated on a calcined aluminium surface. Example 13 also illustrates the use of unsupported 6A metal oxide catalysts.  Relative proportions of catalyst, cocatalyst and support are given and preferred space velocities are stated.  The polymerization may be carried out in the gas phase, the catalyst being treated from time to time to remove polymer and to be reactivated, but preferably in an inert liquid hydrocarbon medium of which many aliphatic, aromatic and olefinic examples are given.  The catalyst may be in a fixed bed and olefine may be led continuously into and out of contact with the catalyst.  In order to avoid reaction of contaminants in the olefinic feed with the aluminium compound the liquid medium should be purified, e.g. by treatment with p-toluene-sulphonic acid, sulphuric acid, Friedel-Crafts catalysts, maleic anhydride, calcium, calcium hydride, sodium or other alkali metals, alkali metal hydrides, lithium aluminium hydride, hydrogen, hydrogenation catalysts or filtration through grains of copper or Group 8 metal. High density, crystalline polymers may be obtained. The products may be mixed with anti-oxidants, stabilizers, fillers, extenders, plasticizers, pigments, insecticides, fungicides, lower molecular weight polyethylene, hydrocarbon oils, lubricating oils, xylene, paraffin, petrolatum and ester waxes, and high molecular weight polybutylenes, and may be used in the manufacture of carboys, plastic pipe, gas barriers, packaging and coating materials and binders.  The polymers may be milled, halogenated, halogenated followed by dehalogenation, sulphohalogenated, sulphonated and irradiated with X-rays or radioactive materials to effect cross-linking, and may be converted into sponges or latices. Specification 713,081 is referred to.