Patent GB-365038-A (GB)
Title: Acids and salts from petroleum hydrocarbons and method of producing same
IPC: C07C65/32
Filed: 1930-10-01
Abstract: Keto-acids, obtained by condensing non-aromatic petroleum hydrocarbons with the anhydrides of polybasic acids, are converted to heavy metal salts by treatment of their alkali metal or ammonium salts with solutions of heavy-metal salts, the precipitate being purified by washing with warm water or by solution in a volatile organic solvent.  Salts of aluminium, cadmium, chromium, cobalt, copper, iron, lead, manganese, mercury, cerium, nickel, silver, thallium, thorium, tin, uranium, vanadium, zinc, calcium, barium, strontium, magnesium, and other metals may be obtained in this way. These salts are insoluble in water, but soluble in toluene, drying oils and hot turpentine, and accelerate the drying of linseed oil, china wood oil and varnishes made therefrom.  They may also be used as resins for nitrocellulose lacquers and other coating compositions. The copper and mercury salts are toxic towards marine organisms and may be used for impregnating marine piling and for varnishes on ships' bottoms. The esters of these acids may be used as plasticizers for nitrocellulose.ALSO:Non-aromatic petroleum hydrocarbons are condensed with the anhydride of polybasic acid in the presence of a catalyst of the Friedal-Crafts type, and the complex salt formed is hydrolysed to give a mixture of monobasic ketonic acids.  Suitable hydrocarbons are crude petroleum oil, or any of its thermal decomposition products or other derivatives, such as kerosene, gasoline, petroleum naphtha, varnish-maker's naphtha, petrolatum, paraffin oil, and paraffin wax; suitable anhydrides are phthalic, succinic, maleic, and camphoric anhydrides, and the catalyst may be aluminium, ferric or stannic chloride, or mixtures such as aluminium and ferric chlorides or aluminium and sodium chlorides. The temperature may be between 70-125 DEG  C., and the pressure may be above or below atmospheric pressure.  Solvents may be added to keep the mixture liquid during the condensation.  The hydrolysis of the reaction product may be effected by means of water, dilute sulphuric acid, or sodium carbonate solution; the last gives a soap solution from which the acid is precipitated on addition of dilute sulphuric acid.  These ketonic acids are readily soluble in caustic alkalies and ammonia and in various organic solvents.  By treatment of these water-soluble salts with solutions of heavy metal salts, the corresponding heavy-metal salt of the keto-acid is precipitated, and may be purified by washing with warm water or by solution in a volatile organic solvent.  These salts are soluble in toluene, hot turpentine, and drying oils, and improve the drying, hardening, and gloss formation of linseed and china wood oil and varnishes made therefrom.  They may also be used as waterproofing agents for textiles or as resins for nitrocellulose lacquers and other coating compositions.  The copper and mercury salts are toxic towards marine organisms and may be used for impregnating marine piling and for varnishes on ships' bottoms. Esters of the keto-acids may be prepared by heating the acids with excess of an alcohol in the presence of sulphuric acid or hydrogen chloride.  The methyl and ethyl esters are oily liquids, and the ethyl, butyl, bornyl, and isobornyl esters are suitable as solvents or as plasticizers for cellulose derivatives, especially for nitrocellulose.  The bornyl and isobornyl esters may be prepared by heating pinene or oil of turpentine with the keto-acid mixture, and are soluble in various organic solvents.  They are readily compatible with nitrocellulose giving therewith clear films of excellent flexibility, adhesion and gloss.  On boiling with strong alkalies, soaps together with borneol are formed.  The borneol may be isolated by steam distillation.