Patent GB-1036574-A (GB)
Title: New epoxide-containing metal chelates process for their preparation and their use
IPC: C07D303/24
Filed: 1963-06-06
Abstract: Metal chelates containing epoxide groups are prepared by reacting an acetoacetic ester of the formula <F\1> where R1 and R2 each represents a hydrogen atom or alkyl radical with 1 to 4 carbon atoms, Z is an aliphatic, cyclo-aliphatic or araliphatic radical containing at least one 1,2-epoxide group or a radical differing from such a radical as aforesaid by containing in place or a methylene radical, a divalent functional radical and n is an integer, with a metal compound capable of forming stable chelate compounds with b -dicarbonyl compounds.  Metal compounds specified are the halides, sulphates, nitrates and acetates, which may be hydrated, of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Zn, Cu, Al, Be, Ga, Mg, Ca, Sr, Ba, Y, Zr, Nb, Mo, Rb, Re, Pd, Hf, Ta, W, Rh, Os, In, Pt, Ce, Hg, Pb, Th, Sn, Bi and U; vanadyl, uranyl, copper-, nickel- and cobaltammines; aluminium ethylate, isopropylate and butylate; tetrabutyl titanate; tetraethylene glycol ortho-titanate; bis-(tributoxytitanoxy) ethane; chromium trisacetylacetonate; copper bisacetylacetonate; vanadyl bisacetylacetonate, copper ethyl acetoacetate and chromium ethyl acetoacetate.  The acetoacetic esters containing epoxide groups are the reaction products of hydroxyepoxy compounds and diketeness. In the examples, the adducts of ketene with the indicated epoxides are reacted with the indicated metal compounds; (6) glycidol, tetrabutyl titanate; (7) ethylene glycol monoglycidyl ether, aluminium ethylate; (8) 3,4epoxyhexahydrobenzal glycerol, 1,2-bis-(tributoxytitanoxy) ethane; (9) 3,4 - epoxyhexahydrobenzal glycerol, MgCl2.6H2O; (10) 3,4epoxytetrahydrodicyclopentadienol - 8, 1,2-bis(tributyoxytitanoxy) ethane; (11) and (12) 3,4epoxytetrahydrodicyclopentadienol - 8, MgCl2. 6H2O; and (16) 3,4-epoxytetrahydicyclopentdienol-8, aluminium isopropylate.  The preparation of the above mentioned ketene adducts, of ethylene glycol monoglycidyl ether, and of 1,2-bis-(tributoxytitanoxy) ethane are also described.ALSO:Metal chelates containing epoxide groups are prepared by reacting an acetoacetic ester of the formula <FORM:1036574/C3/1> where R1 and R2 each represents a hydrogen atom or an alkyl radical with 1 to 4 carbon atoms, Z stands for an aliphatic, cycloaliphatic or araliphatic radical containing at least one 1,2-epoxide group or a radical differing from such a radical as aforesaid by containing, in place of a methylene radical, a divalent functional radical and n is an integer, with a metal compound capable of forming stable chelate compounds with b -dicarbonyl compounds.  Metal compounds specified are the halides, sulphates, nitrates and acetates which may be hydrated, of scandium titanium, vanadium, chromium, manganese, iron, cabalt, nickel, zinc, copper, aluminium, beryllium, gallium, magnesium, calcium, strontium, barium, yttrium, zirconium, niobium, molybdenum, rubidium, rhenium, palladium, hafnium, tantalum, tungsten, rhodium, osmium, indium, platinum, cerium, mercury, lead, thorium, tin, bismuth and uranium; vanadyl, uranyl, copper-, nickel- and cobalt-amines; aluminium ethylate, isopropylate and butylate; tetrabutyl titanate; tetraethylene glycol ortho-titanate; bis(tributoxy titanoxy)ethane; chromium trisacetylacetonate; copper bisacetylacetonate; vanadyl bis-acetylacetonate; copper ethyl acetoacetate and chromium ethyl acetoacetate.  The acetoacetic esters containing epoxide groups are the reaction products of hydroxy-epoxy compounds and diketenes.  The hydroxy-epoxy compounds may be polyepoxides or epoxy resins containing one or more hydroxyl groups which may have been introduced by the hydrolysis of epoxide groups; many such compounds are specified.  The metal chelates formed may be cross-linked or cured by the conventional epoxy resin curing agents, many of which are specified, or they may be used as accelerators for the conventional epoxy resin curing agents in the curing of epoxy resins, many of which are specified. Curable mixtures containing the metal chelates may also contain asphalt, bitumen, glass fibres, mica, quartz meal, cellulose, kaolin, ground dolomite, colloidal silica, metal powder and solvents. They may be used as laminating resins, paints, lacquers, dipping and casting resins, moulding compositions, pore fillers, putties, floorings, potting and insulating materials for electrical components and as adhesives.