Patent GB-798447-A (GB)
Title: Improvements in the production of polymerisation products from olefinically-unsaturated hydrocarbons
IPC: C08F2/00
Filed: 1956-09-03
Abstract: Catalysts used in the polymerization of olefins (see Group IV (a)) comprise: (1) a compound of a metal or semi-metal of Group IVb or Vb containing a hydrocarbon radical; (2) a halide of a metal of Group II or III; and (3) a halogen-containing compound of a Group IVa, Va or VIa metal.  Specified catalyst components are: (1) the ethyl, propyl, butyl, hexyl, octyl, allyl, cycloalkyl, methylcycloalkyl, aromatic and alkyl-aromatic derivatives of germanium, tin, lead, arsenic, antimony and bismuth; e.g. germanium tetraethyl; diethyl-, tetraethyl-, tetrahexyl-, and tetraallyl-tin; hexaphenyl distannane, tetraethyl lead, arsenic triphenyl, antimony tricyclohexyl and bismuth triethyl; and halogen, hydroxy and metal carbonyl derivatives thereof such as triethyl lead chloride and diethyl lead mono (iron carbonyl); (2) beryllium, magnesium, zinc, aluminium and gallium chlorides, zinc bromide and iodide, boron fluoride and aluminium bromide; and (3) titanium halides such as the tetra- and tri-chlorides, vanadium halides such as the tetrachloride, zirconium tetrabromide, thorium tetrachloride, vanadium oxytrichloride, chromium trichloride, chromyl chloride, and tungsten and molybdenum hexachlorides.  The catalyst components are preferably mixed in an inert medium such as pentane, heptane, octane, petroleum ether, gasoline, gasoline fractions, cyclohexane, tetrahydronaphthalene, decahydronaphthalene, benzene, xylene, toluene and dichlorobenzene. After polymerization the catalyst may be destroyed with alcohols (methanol) and ethers, optionally containing acids such as hydrochloric or oxalic, aqueous organic or inorganic acids, and complex forming acids such as tartaric, citric or nitrilotriacetic. A wetting agent may be present during the catalyst deactivation.ALSO:Olefins are polymerized with a catalyst comprising, (1) a compound of a metal or semimetal of Group IVb or Vb containing a hydrocarbon radical, (2) a halogen containing compound of a metal of Group IVa, Va or VIa, and (3) a halide of a Group II or III metal. Olefins specified are ethylene, propylene, butylene, isobutylene, butadiene, isoprene, styrene and its derivatives such as the alkyl compounds, and mixtures thereof, and the monomer is preferably purified with materials such as silica gel, alkali metals, copper or organometallic compounds, such as those of the Group IVb and Vb metals.  Specified catalyst components are: (1) the ethyl, propyl, butyl, hexyl, octyl, allyl, cycloalkyl, methylcycloalkyl, aromatic and alkyl aromatic derivatives of germanium, tin, lead, arsenic, antimony and bismuth; e.g. germanium tetraethyl; diethyl-, tetraethyl-, tetrahexyl- and tetra-allyl-tin; hexaphenyl distannane, tetraethyl lead, arsenic triphenyl, antimony tricyclohexyl and bismuth triethyl; and halogen, hydroxy and metal carbonyl derivatives thereof, such as triethyl lead chloride and diethyl lead mono (iron carbonyl); (2) beryllium, magnesium, zinc, aluminium and gallium chlorides, zinc bromide and iodide, boron fluoride and aluminium bromide; and (3) titanium halides such as the tetra- and trichlorides, vanadium halides such as the tetrachloride, zirconium tetrabromide, thorium tetrachloride, vanadium oxytrichloride, chromium trichloride, chromyl chloride, tungsten hexachloride and molybdenum hexachloride.  The polymerization is preferably effected in an inert medium such as pentane, heptane, octane, petroleum ether, gasoline, gasoline fractions, cyclohexane, tetrahydronaphthalene, decahydronaphthalene, benzene, xylene, toluene and dichlorobenzene, and these may be previously purified with silica gel, active carbon or sodium.  In Examples, it is said that polymerization may be continuous with ethylene, catalyst and/or solvent being added continuously.  The products may be purified and the catalyst decomposed by addition of ethers or alcohols (methanol specified) which may contain acids such as hydrochloric or oxalic, or by the addition of aqueous organic or inorganic acids or complex forming acids such as tartaric, citric or nitrilotriacetic.  A wetting agent may be included during purification.  The polyolefine obtained may be used to produce injection mouldings, films, foils, fibres or threads.