Patent GB-791285-A (GB)
Title: Epoxidation of unsaturated fatty acid esters
Inventor: MCHENRY BEAVERS ELLINGTON
IPC: C07D303/42
Filed: 1955-02-02
Abstract: An ester of a water-insoluble olefinically unsaturated aliphatic acid, or a mixture of such esters, is epoxidized by reacting the ester or ester mixture with an aqueous solution which has a pH of 0 to -1.5 and which contains hydrogen peroxide, formic acid, and an ionizable acidic agent other than formic acid and other than one which under the reaction conditions employed is such as to cause decomposition of more than 35 per cent of the epoxy groups formed in the reaction, the hydrogen peroxide being employed in an amount equivalent to at least one mol. for each olefinic bond in each mol. of ester present and the formic acid being employed in an amount equivalent to 0.02 to 1 mol. for each olefinic bond in each mole of ester present.  It is preferred to use from 1 to 2 mols. of hydrogen peroxide and from 0.05 to 0.5 mol. of formic acid per mol. of unsaturation.  Specified ionizable acidic agents are inorganic acids such as phosphoric, sulphuric, hydrochloric, nitric, and boric acids; acid-forming salts such as sodium or potassium acid sulphate, potassium persulphate, and zinc chloride; organic sulphonic acids such as p-toluene sulphonic and methane sulphonic acids, strong carboxylic acids such as maleic, fumaric, and oxalic acids and acidic esters such as ethyl di-acid phosphate, n-propyl di-acid phosphate, and monomethyl sulphate. It is preferred to use an inorganic acidic agent, e.g. phosphoric or sulphuric acid.  The reaction may be carried out between 10 DEG  and 100 DEG  C. and preferably at 50-80 DEG  C.  The esters to be epoxidized are preferably esters of oleic, linoleic, or linolenic acids but esters of undecylenic, myristoleic, palmitoleic, petroselenic and erucic acids may also be used.  The esters may be derived from monohydric or polyhydric alcohols, e.g. ethyl, isopropyl, n-butyl, sec-butyl, tert-butyl, tert-amyl, n-octyl, 2-ethyl hexyl, octadecyl, lauryl, cyclohexyl, and benzyl alcohols, ethylene glycol, 1,2-propylene glycol, 2-ethylhexanediol, 1,3; butanediol-1,2 (-1,3 or -1,4), dodecanediol-1,12, di- and tri-ethylene glycols, glycerol, and pentaerythritol.  Specified mixed esters are mixtures of ethyl and butyl oleates, benzyl and cyclohexyl linoleates, octyl oleate and dodecyl linoleate and of octyl linolenate and dodecyl linolenate.  Mixed esters of polyhydric alcohols may also be used, e.g. semi-drying and drying vegetable oils, specified vegetable oils being soybean, corn, cottonseed, safflower, sunflower, sesame, poppyseed, walnut, peanut, linseed and perilla oils.  In carrying out the process it is preferred to make an aqueous dispersion of hydrogen peroxide, formic acid, and the acidic agent, e.g. phosphoric acid, having a pH value of 0 to -1.5 and then adding about one-tenth of the mixture to the stirred unsaturated ester heated to between 50 DEG  and 80 DEG  C.  Portions of the peroxidic mixture are then added periodically, e.g. nine aliquot portions may be added at intervals of thirty minutes.  The reaction mixture is then stirred at the elevated temperature until epoxidation is complete.  The reaction mixture is separated into an aqueous phase and an organic phase comprising the epoxidized ester and the rate of separation can be increased by adding a water-immiscible liquid, e.g. toluene which is a solvent for the epoxidized ester.  The process may also be operated by adding the hydrogen peroxide, formic acid, and acidic agent individually and simultaneously. Examples are given for the epoxidation of soybean oil, butyl oleate, 2-ethylhexyl linoleate, cottonseed oil, safflower seed oil and linseed oil respectively using phosphoric acid in each case as the ionizable acidic agent.  An example is also given for the epoxidation of soybean oil using H2SO4, HNO3, HBF4, butyl di-acid phosphate, methane sulphonic acid, H3BO3, K2S2O8, and oxalic acid respectively as the acidic agent and comparative examples are given for the epoxidation of soyabean oil in which the additional acidic agent is omitted.