Patent GB-832209-A (GB)
Title: Chemical product and process
IPC: C08F2/00
Filed: 1956-05-02
Abstract: Catalysts suitable for the polymerization of aliphatic 1-olefins comprise (1) one or more oxyhalides, hydroxyhalides or oxyhydroxyhalides of metals of Group VI of the Periodic Table after Mendel<\>aeeff or complex salts of the halides or oxyhalides thereof with sodium, potassium, lithium, rubidium, caesium or ammonium halides, and (2) one or more of (a) compounds of sodium, potassium, lithium, rubidium, caesium, beryllium, magnesium, zinc, cadmium, mercury, aluminium, gallium, indium or thallium having valencies thereof bound to hydrogen, saturated acyclic hydrocarbon radicals, saturated cyclic hydrocarbon radicals or aromatic hydrocarbon radicals, and ether, thioether, amine, alkali metal hydride, alkyl or aryl complexes thereof; (b) organometallic halides of formula RxMXy where R is at least one saturated acyclic, saturated cyclic or aromatic hydrocarbon radical, M is aluminium, gallium, indium, thallium or beryllium, X is a halogen and x and y are integers, the sum of x and y being equal to the valence of the metal; (c) at least one free metal which is sodium, potassium, lithium, rubidium, caesium, beryllium, magnesium, zinc, cadmium, mercury, aluminium, gallium, indium or thallium; and (d) a mixture of said free metal and an organic halide.  Many suitable catalyst components are listed, and the use of mixtures of diethyl aluminium chloride and ethyl aluminium dichloride with potassium molybdenum hexachloride (I), molybdenum oxydihydroxydichloride (II), and chromyl chloride (III); and of triethylaluminium with chromyl chloride is exemplified.ALSO:Aliphatic 1-olefins are polymerized in the presence of catalysts comprising (1) one or more oxyhalides, hydroxyhalides and oxyhydroxyhalides of Group VI metals and the complex salts of the halides and oxyhalides thereof with sodium, potassium, lithium, rubidium, caesium and ammonium halides, and (2) one or more of (a) compounds of sodium, potassium, lithium, rubidium, caesium, beryllium, magnesium, zinc, cadmium, mercury, aluminium, gallium, indium, and thallium having valencies thereof bound to hydrogen, saturated acyclic hydrocarbon radicals, saturated cyclic hydrocarbon radicals and aromatic hydrocarbon radicals, and ether, thioether, amine, alkali-metal hydride, alkali metal alkyl and alkali metal aryl complexes thereof; (b) organo-metal halides of the form RxMXy, where R is a saturated acyclic hydrocarbon radical, a saturated cyclic hydrocarbon radical or an aromatic hydrocarbon radical, M is aluminium, gallium, indium, thallium or beryllium, X is a halogen and x and y are integers, their sum being the valency of the metal; (c) an organic halide and one or more of sodium, potassium, lithium, rubidium, caesium, beryllium, magnesium, zinc, cadmium, mercury, aluminium, gallium, indium and thallium; and (d) one or more metals listed under (c). Specified polymerizable hydrocarbons are ethylene, propylene, 1-butene, 1-hexene, 1-octene, isobutylene, 2-methyl butene-1, 2-methyl hexene-1, 2-ethyl heptene-1, cyclohexene, mixtures of ethylene and propylene, ethylene and 1-butene, propylene and 1-butene, and propylene and pentenes.  Many suitable catalyst components are listed and the use of mixtures of diethyl aluminium chloride and ethyl aluminium dichloride with potassium molybdenum hexachloride (I), molybdenum oxydihydroxy dichloride (II), and chromyl chloride (III), and of triethylaluminium with chromyl chloride (IV), is exemplified.  The polymerization may be effected in the gaseous phase or in the presence of inert diluents, e.g. propane, butane, pentane, iso-octane, cyclohexane, methylcyclohexane, chlorobenzene, benzene and toluene, in a continuous process or batchwise.  The olefin feed may be freed from contaminants, e.g. carbon dioxide, water and oxygen, by treating with pyrogallol solution, sodium hydroxide and a drying agent, and catalyst residues in the product may be deactivated by treating with an alcohol, e.g. methanol.