Patent GB-859696-A (GB)
Title: Improvements in or relating to composite metal-polymer compositions
IPC: C09D5/00
Filed: 1959-06-26
Abstract: The invention comprises a composition consisting of a metal, including boron, partly or wholly encapsulated by a polymer formed by polymerization of an olefinically unsaturated polymerizable hydrocarbon in situ on the surface of the metal.  The composition may be made by treating a metal of Group Ib, II, III, IV, Va, VIa, VII or VIII with a catalyst representable (i) by the formula Rn\TiXm or (ii) the reaction product of catalytic mixtures of compounds representable by the formulae MX1p + R1 (z-x) M1Yx, wherein R is an alkyl or aryl radical which is linked to titanium by a C-Ti bond, X is an alkoxide or halide radical, n is 1 or 2 an m is 1, 2 or 3, the sum of m + n being 2, 3 or 4, M is a metal of Group IVa, Va, VIa, VIIa or VIII, X1 is a halide or alkoxide radical, p is the valency of M, R1 is an alkyl or aryl radical, Y is a halide radical, M1 is a metal or Group Ia, IIa, IIb or IIIb, x is 0, 1 or 2 and z is the valency of M1, and further treating the thustreated metal with an olefinically unsaturated polymerizable hydrocarbon comprising styrene, an alkyl-substituted styrene, ethylene, propylene, butadiene or isoprene.  Exemplary of such metals which may be encapsulated are copper, magnesium, barium, mercury, boron, aluminium, yttrium, titanium, germanium, lead, tin, vanadium, chromium, molybdenum, manganese, iron, cobalt and nickel.  The polymerization may be carried out in an inert diluent such as toluene.  Catalysts of type (i) include dimethyltitanium dichloride, methyltitanium trichloride, dimethyltitanium monochloride, isopropyltitanium dichloride, phenyltitanium triisopropoxide, alphanaphthyl-titanium tributoxide, p-tolyltitanium tributoxide, p-anisyltitanium tributoxide, diphenyltitanium dibutoxide, isopropyltitanium tributoxide, dimethyltitanium diisopropoxide, methyltitanium monochloride, phenyltitanium monochloride and methyltitanium dibutoxide.  Catalysts of type (ii) may comprise a compound such as zirconium tetrachloride, titanium tetrachloride, titanium trichloride, van adium dichloride, vanadium oxychloride, vanadium trifluoride, vanadium trichloride, vanadium oxydichloride, tantalum pentachloride, molybdenum trichloride, molybdenum pentachlordie, chromium trichloride, chromium difluoride, ferric chloride, manganese dichloride, vanadium oxyacetylacetonate, iron acetylacetonate, cobalt acetylacetonate, chromium acetylacetonate, manganese acetylacetonate, an alkyl vandate or an alkyl titanate together with an organometallic compound such as triethyl aluminium, butyl-lithium, amylsodium and phenylsodium, dimethylmagnesium, diethylmagnesium, diethylzinc, methylmagnesium bromide, butylmagnesium bromide, phenylmagnesium chloride, trimethylaluminium, triisobutylaluminium, tetraphenyltin and tetraphenyl-lead, trioctylaluminium tridodecylaluminium, dimethylaluminium bromide, diethylaluminium chloride, ethylaluminium dibromide, isobutylaluminium sesquichloride, dipropyl-aluminium iodide, diisobutylaluminium fluoride, diisobutylaluminium bromide, diethylaluminium hydride, diisobutylaluminium hydride, and complexes of such organometallic compounds, as for example, sodium aluminium tetrabutyl, lithium aluminium tetraoctyl and sodium aluminium triethylchloride.ALSO:A process for producing a metal-polymer composition comprises treating a metal of Group Ib, II, III, IV, Va, VIa, VII or VIII with a catalyst representable by the formula RnTiXm or with the reaction product of catalytic mixtures of compounds representable by the formulae MX1p + R1(z-x)M1Yx, wherein R is an alkyl or aryl radical which is linked to titanium by a C-Ti bond, X is an alkoxide or halide radical, n is 1 or 2 and m is 1, 2 or 3, the sum of m + n being 2, 3 or 4, M is a metal of Group IVa, Va, VIa, VIIa or VIII, X1 is a halide or alkoxide radical, p is the valency of M, R1 is an alkyl or aryl radical, Y is a halide radical, M1 is a metal of Group Ia, IIa, IIb or IIIb, x is 0, 1 or 2 and z is the valency of M1, and further treating the thus-treated metal with an olefinically unsaturated polymerizable hydrocarbon comprising styrene, an alkyl-substituted styrene, ethylene, propylene, butadiene or isoprene.  Exemplary of such metals which may be encapsulated by the polymer, are copper, magnesium, barium, mercury, boron, aluminium, yttrium, titanium, germanium, lead, tin, vanadium, chromium, molybdenum, manganese, iron, cobalt and nickel.  The polymerization may be carried out in an inert diluent such as toluene.  The catalyst components which are specified and which are added to the metal include dimethyltitanium dichloride, methyltitanium trichloride, dimethyltitanium monochloride, isopropyltitanium dichloride, phenyltitanium triisopropoxide, alphanaphthyltitanium tributoxide, p-tolyltitanium tributoxide, p-anisyltitanium tributoxide, diphenyltitanium dibutoxide, isopropyltitanium tributoxide, dimethyltitanium diisopropoxide, methyltitanium monochloride, phenyltitanium monochloride, methyltitanium dibutoxide, zirconium tetrachloride, titanium tetrachloride, titanium trichloride, vanadium dichloride, vanadium oxychloride, vanadium trifluoride, vanadium trichloride, vanadium oxydichloride, tantalum pentachloride, molybdenum trichloride, molybdenum pentachloride, chromium trichloride, chromium difluoride, ferric chloride, manganese dichloride, vanadium oxyacetylacetonate, iron acetylacetonate, cobalt acetylacetonate, chromium acetylacetonate, manganese acetylacetonate, alkyl vanadates and alkyl titanates, the alkali metal alkyls or aryls such as butyllithium, amylsodium and phenylsodium, dimethylmagnesium, diethylmagnesium, diethylzinc, methylmagnesium bromide, butylmagnesium bromide, phenylmagnesium chloride, trimethylaluminium, triisobutylaluminium, tetraphenyltin and tetraphenyllead, trioctylaluminium, tridodecylaluminium, dimethylaluminium bromide, diethylaluminium chloride, triethylaluminium, ethylaluminium dibromide, isobutylaluminium sesquichloride, dipropylaluminium iodide, diisobutylaluminium fluoride, diisobutylaluminium bromide, diethylaluminium hydride, diisobutylaluminium hydride, and complexes of such organometallic compounds, as for example, sodium aluminium tetrabutyl, lithium aluminium tetraoctyl and sodium aluminium triethylchloride.