Patent GB-413728-A (GB)
Title: Manufacture of new oil-soluble metal salts of organic acids
IPC: C09F9/00
Filed: 1933-01-20
Abstract: Oil soluble metal salts, useful in the preparation of coating compositions are obtained from metals other than alkali metals and organic acids having the formula ROCH2COOH in which R is an alkyl radicle having more than five carbon atoms, a hydroaromatic radicle or an aryl group having at least one normal alkyl chain of at least five carbon atoms.  The salt formation is effected by treating an oxide, hydroxide or carbonate of the heavy metals with the acid or reacting an alkali salt of the acid with a heavy metal salt.  In examples: (1) capryloxyacetic acid is neutralized with sodium hydrate and treated with lead nitrate to give lead capryloxyacetate which is a resin soluble in petroleum naphtha; such a solution is dispersed in drying oils, alkyd resins, paints and varnishes and acts as a siccative; the lead salt dissolves in warm linseed oil without discolouration; (2) capryloxyacetic acid is boiled with bismuth hydroxide in xylene and the solvent removed; the resulting bismuth capryloxyacetate is a pale waxy mass soluble in warm olive oil; salts derived from cobalt, manganese and aluminium and capryloxyacetic, hexyloxyacetic, heptyloxyacetic, n-octyloxyacetic, nonyloxyacetic and decyloxyacetic acids are prepared in a similar manner; the acid obtained from chloracetic acid and the mixture of alcohols derived as a by-product in the synthesis of methanol from carbon monoxide and hydrogen is also mentioned; (3) the lead, cobalt, manganese, aluminium, zinc and bismuth salts of p-sec-hexylphenoxyacetic acid and the lead, cobalt, manganese, aluminium, zinc, nickel, iron, chromium and mercury salts of p-caprylphenoxyacetic acid are prepared by the methods of examples (1) and (2); (4) cobalt sulphate, manganous chloride and lead nitrate are added in slight excess to the neutral sodium salt of terpinoxyacetic acid to form the corresponding heavy metal salts of terpinoxyacetic acid; they act as siccatives for tung oil, alkyd resins and printing oils; (5) the lead, cobalt, manganese, aluminium, zinc, barium, nickel and iron salts of fenchyloxyacetic acid and bornyloxyacetic acid and the lead salt of cyclohexyloxyacetic acid are prepared by the above methods.  The aluminium, zinc, calcium and barium salts are colourless resins soluble in a mixture of butyl acetate and toluene and may be blended with nitrocellulose lacquers.  The following acids are also mentioned: p-amylphenoxyacetic acid, p - sec - octylphenoxyacetic acid, octylcresoxyacetic acid, sec-amylnaphthoxyacetic acid and methyl cyclohexyloxyacetic acid and the following metals; cerium, thallium, tin, uranium, strontium, vanadium, copper, titanium, antimony, silver, and gold.  The salts may be used with solutions of phenol aldehyde resins and resins derived from polyhydric alcohols and polybasic acids.ALSO:Oil-soluble metal salts, useful in the preparation of coating-compositions, salves for destroying micro-organisms, and waterproofing-agents for textiles are obtained from metals other than alkali metals and organic acids having the formula ROCH2COOH in which R is an alkyl radicle having more than five carbon atoms, a hydroaromatic radicle or an aryl group having at least one normal alkyl chain of at least five carbon atoms. The salt formation is effected by treating an oxide, hydroxide or carbonate of the heavy metals with the acid or reacting an alkali salt of the acid with a heavy metal salt.  The acids may be obtained by oxidation of the corresponding alcohols.  In examples: (1) capryloxyacetic acid (obtained from sodium caprylate and chloracetic acid) is neutralized with sodium hydrate and treated with lead nitrate to give lead capryloxyacetate which is a resin soluble in petroleum naphtha; such a solution is dispersed in drying oils, alkyd resins, paints and varnishes and acts as a siccative; the lead salt dissolves in warm linseed oil without discoloration; (2) capryloxyacetic acid is boiled with bismuth hydroxide in xylene and the solvent removed; the resulting bismuth capryloxyacetate is a pale waxy mass soluble in warm olive oil; salts derived from cobalt, manganese and aluminium and capryloxyacetic, hexyloxyacetic, heptyloxyacetic, n-octyloxyacetic, nonyloxyacetic and decyloxyacetic acids are prepared in a similar manner; the acid obtained from chloracetic acid and the mixture of alcohols derived as a by-product in the synthesis of methanol from carbon monoxide and hydrogen is also mentioned; (3) the lead, cobalt, manganese, aluminium, zinc, and bismuth salts of p-sec-hexylphenoxyacetic acid (obtained by condensing phenol with sec-hexyl alcohol and reacting the product with chloracetic acid) and the lead, cobalt, manganese, aluminium, zinc, nickel, iron, chromium, and mercury salts of p-caprylphenoxyacetic acid are prepared by the methods of examples (1) and (2); (4) cobalt sulphate, manganous chloride and lead nitrate are added in slight excess to the neutral sodium salt of terpinoxyacetic acid (obtained from chloracetic acid and commercial a -terpineol) to form the corresponding heavy metal salts of terpinoxyacetic acid; they act as siccatives for tung oil, alkyd resins, and printing-oils; (5) the lead, cobalt manganese, aluminium, zinc, barium, nickel and iron salts of fenchyloxyacetic acid (obtained from fenchylalcohol and chloracetic acid) and bornyloxyacetic acid and the lead salt of cyclohexyloxyacetic acid are prepared by the above methods.  The aluminium zinc, calcium and barium salts are colourless resins soluble in a mixture of butyl acetate and toluene and may be blended with nitrocellulose lacquers. The bismuth, mercury, lead, copper, antimony, silver and gold salts are soluble in warm olive oil to give bactericidal and fungicidal solutions.  The aluminium, barium, calcium, magnesium, strontium, titanium and zinc salts are useful as water-proofing agents.  The following acids are mentioned: p-amylphenoxyacetic acid, p-sec-octylphenoxyacetic acid, octylcresoxyacetic acid, sec-amylnaphthoxyacetic acid and methyl cyclohexyloxyacetic acid and also the following metals: cerium, thallium, tin, uranium, and vanadium.  The salts may be used with solutions of phenol aldehyde resins and resins derived from polyhydric alcohols and polybasic acids.  Specification 414,121 is referred to.ALSO:Toxic metal salts soluble in oils or petrolatum and capable of destroying micro-organisms are obtained from metals other than alkali metals and organic acids having the formula ROCH2 COOH in which R is an alkyl radicle having more than five carbon atoms, a hydroaromatic radicle or an aryl group having at least one normal alkyl chain of at least five carbon atoms.  Salts of the said acids with bismuth, mercury, lead, copper, antimony, silver and gold may be used in salves or ointments or they may be dissolved in olive oil to obtain bactericides or fungicides.  In examples, (1) capryloxyacetic acid is neutralized with sodium hydrate and treated with lead nitrate to give lead capryloxyacetate which is a resin soluble in petroleum naphtha; (2) capryloxyacetic acid is boiled with bismuth hydroxide in xylene and the solvent removed; the resulting bismuth capryloxyacetate is a pale waxy mass soluble in warm olive oil; salts derived from cobalt, manganese and aluminium and capryloxyacetic, hexyloxyacetic, heptyloxyacetic, n-octyloxyacetic, nonyloxyacetic and decyloxyacetic acids are prepared in a similar manner; the acid obtained from chloracetic acid and the mixture of alcohols derived as a by-product in the synthesis of methanol from carbon monoxide and hydrogen is also mentioned: (3) the lead, cobalt, manganese, aluminium, zinc and bismuth salts of p-sec-hexylphenoxyacetic acid and the lead, cobalt, manganese, aluminium, zinc, nickel, iron, chromium and mercury salts of p-caprylphenoxyacetic acid are prepared by the p  methods of examples (1) and (2): (4) cobalt sulphate, manganous chloride and lead nitrate are added in slight excess to the neutral sodium salt of terpinoxyacetic acid to form the corresponding heavy metal salts of terpinoxyacetic acid; (5) the lead, cobalt, manganese, aluminium, zinc, barium, nickel and iron salts of fenchyloxyacetic acid and bornyloxyacetic acid and the lead salt of cyclohexyloxyacetic acid are prepared by the above methods.  The following acids are also mentioned: p-amylphenoxyacetic acid, p-sec-octylphenoxyacetic acid, octylcresoxyacetic acid, sec-amylnaphthoxyacetic acid and methylcyclohexyloxyacetic acid, and the following metals: cerium, calcium, magnesium, strontium, titanium, thallium, tin, uranium and vanadium.