Patent GB-785314-A (GB)
Title: Improvements in and relating to the polymerisation of olefines
Inventor: VINCENT MERVYN FREDERICK
IPC: C08F2/00
Filed: 1954-12-24
Abstract: Catalysts for the polymerization of olefines (see Group IV (a)) are obtained by reaction of a Group 4A, 5A or 6A metal compound with an organo-compound of a non-transition metal of Groups 1, 2 or 3, said organo-compound containing at least one hydrocarbon radical attached to the metal and any remaining valencies being satisfied by hydrogen or halogen.  The Group 4A, 5A or 6A metal compound may be a halide, oxyhalide, complex halide, alcoholate, acetate, benzoate or acetylacetonate, e.g. the chlorides of titanium, vanadium, molybdenum, tungsten, tantalum, niobium and zirconium.  Organo compounds of Groups 1 to 3 disclosed are aluminium trimethyl, triethyl, tripropyl, tributyl and triphenyl; alkyl and aryl aluminium halides, e.g. phenyl aluminium sesquiiodide; complex alkyls of an alkali metal and aluminium, gallium, indium or thallium, e.g. lithium aluminium tetraethyl and sodium aluminium tetrapropyl; alkali metal alkyls and aryls, e.g. lithium butyl, sodium phenyl and amyl, and zinc dibutyl and diethyl; alkyl hydrides such as aluminium ethyl dihydride and aluminium diethyl hydride; complex compounds such as sodium aluminium tetraphenyl or triethyl hydride, lithium aluminium propyl trihydride and potassium aluminium trimethyl fluoride; and molecular complexes thereof with ethers, thio ethers and amines. Optionally promoters such as ethyl aluminium sesquichloride and aluminium chloride may be included.  In examples methanol, ethanol, acetone, ether, water, pentane, bromine water, caustic soda and hydrochloric acid are materials used for destroying the catalyst and purifying the product.  Specifications 757,524 and 762,200, [both in Group IV (b)], are referred to.ALSO:Ethylene and a -olefines are polymerized in a medium comprising the reaction product of a Group 4A, 5A or 6A metal compound with an organo-compound of a non-transition metal of Groups 1, 2 or 3, said organo-compound containing at least one hydrocarbon radical attached to the metal and any remaining valencies being satisfied by hydrogen or halogen. Olefines specified are propylene, butene-1, isobutylene and styrene and may be pure or diluted with hydrogen or hydrocarbons, e.g. butene-2.  The Group 4A, 5A or 6A metal compound may be a halide, oxyhalide, complex halide, alcoholate, acetate, benzoate or acetylacetonate, e.g. the chlorides of titanium, vanadium, molybdenum, tungsten, tantalum, niobium and zirconium.  Organo compounds of Groups 1 to 3 disclosed are aluminium triethyl, trimethyl, tripropyl, tributyl and triphenyl; alkyl and aryl aluminium halides, e.g. phenyl aluminium sesquiiodide; complex alkyls of an alkali metal and aluminium, gallium, indium or thallium, e.g. lithium aluminium tetraethyl and sodium aluminium tetrapropyl; alkali metal alkyls and aryls, e.g. lithium butyl, sodium phenyl and amyl, and zinc dibutyl and diethyl; alkyl hydrides such as aluminium ethyl dihydride and aluminium diethyl hydride; complex compounds such as sodium aluminium tetraphenyl or triethyl hydride, lithium aluminium propyl tri-hydride and potassium aluminium trimethyl fluoride; and molecular complexes thereof with ethers, thio-ethers or amines. Optionally promoters, such as ethyl aluminium sesquichloride and aluminium chloride, may be included.  The olefin may be polymerized in the vapour or liquid phase or may be passed into contact with the surface of an inert solvent such as butane, pentane, hexane, petroleum ether, cyclohexane, methyl cyclohexane or decahydronaphthalene.  The polymerization is preferably carried out in the absence of water and oxygen and, optionally, in the presence of an anti-oxidant such as bis-(2-hydroxy - 3 - alpha - methylcyclohexyl - 5 - methyl-phenyl) methane.  Preferred molar ratios of catalyst components are specified.  Further catalyst components may be added during the reaction and in examples ethylene or styrene and/or solvent are added continuously.  In examples methanol, ethanol, acetone, ether, water, pentane, bromine water, caustic soda and hydrochloric acid may be used for stopping the reaction and purifying the polymers.  In Example 11 the polymerization is carried out at - 70 DEG  C.  The products may be highly crystalline and are useful in the manufacture of filaments, foils, sheets, tubes and chemical intermediates.  Crystalline and oily polymers may be separated by fractionation with solvents. Specifications 757,524 and 762,200, [both in Group IV (b)], are referred to.