Patent GB-423919-A (GB)
Title: Improvements in or relating to the production of esters and compositions containing same
IPC: C07C59/185
Filed: 1933-05-08
Abstract: Esters of levulinic acid are manufactured by esterifying the acid with a modified polyhydric alcohol, i.e. a compound consisting of a polyhydric alcohol, (other than a carbohydrate), in which the hydrogen of at least one hydroxyl group is replaced by an organic radicle, the said compound containing at least one free hydroxyl group.  The esterification may be carried out at a temperature sufficiently high for the water to be removed as formed, e.g. 80--250 DEG  C., and/or by employing a catalyst, e.g. hydrochloric or sulphuric acid, arylsulphonic acids, e.g. p-toluenesulphonic acid, alcoholates, e.g. sodium alcoholate, or zinc chloride, and/or a solvent, e.g. benzene or toluene, to aid in the removal of the water. An inert gas, e.g. carbon dioxide, may be passed through the mixture. The products are employed as plasticizers for cellulose derivatives, e.g. cellulose nitrate, cellulose acetate, crotyl cellulose, benzyl cellulose, ethyl cellulose or cellulose propionate, in the manufacture of lacquers for coating metal and wood, dopes for coating fabrics, plastic compositions for the preparation of toilet ware, novelties, sheeting, rods or tubes, and in blasting powders. Examples describe the esterification of levulinic acid with: (1) ethoxyethanol; (2) butoxyethanol; (3) coconut oil diglyceride; (4) coconut oil monoglyceride; (5) hydrogenated castor oil; (6) lauroxyethanol; (7) phenoxyethanol; (8) ethoxyethoxyethanol; (9) butoxyethoxyethanol.  Other modified polyhydric alcohols specified are: tetrahydrofurfuryl alcohol, tetrahydrofurfuryloxyethyl alcohol, dimethylin, dibutylin, cyclohexyloxyethyl alcohol, ethoxycyclohexyl alcohol, stearoxyethyl alcohol, glycol monoacetate, monoethylin, monobenzylin, glycerin chlorhydrin, monoacetin, linseed oil and chinawood oil monoglycerides, coconut oil and chinawood oil glycolides, chinawood oil diglyceride, di-, tri- and p tetraethylsorbitol, sorbitol triacetate, benzyl sorbitol, castor oil, glycol dilactate, diethylene glycol, glycol monolaurate, methoxypropyl alcohol and benzyloxyethyl alcohol.  In examples of coating compositions, the following mixtures are dissolved in a solvent mixture consisting of butyl and ethyl acetate and alcohols and toluene for the cellulose nitrate compositions, of acetone, ethyl alcohol and acetate, acetone oils, toluene, methoxyethanol and diacetone alcohol for the cellulose acetate compositions, or of ethyl alcohol and toluene for the cellulose ether composition: (10) cellulose nitrate, hydrogenated castor oil trilevulinate, damar and castor oil; (11) cellulose nitrate, damar and lauroxyethyl levulinate; (12) cellulose acetate and butoxyethyl levulinate; (13) cellulose nitrate, pigment, damar, castor oil and coconut oil monoglyceride dilevulinate; (14) ethyl cellulose and butoxyethoxyethyl levulinate; (15) cellulose nitrate and acetate and butoxyethoxyethyl levulinate.  The following examples of plastic compositions are given: (16) cellulose acetate and butoxyethyl levulinate; (17) cellulose nitrate and hydrogenated castor oil trilevulinate; (18) ethyl cellulose and butoxyethoxyethyl levulinate; (19) cellulose acetate, butoxyethyl levulinate and a filler; (20) cellulose nitrate, lauroxyethyl levulinate and a filler; (21) cellulose acetate and nitrate and ethoxyethoxyethyl levulinate.  Part of the plasticizer may be replaced by one or more known plasticizers, e.g. triacetin, dimethyl phthalate, acetanilide or triphenyl phosphate in the cellulose acetate compositions, or camphor, dibutyl phthalate or tricresyl phosphate in the cellulose nitrate compositions.  Resins other than damar, e.g. ester gum, synthetic resins, e.g. of the polyhydric alcohol-polybasic acid type, pigments or fillers may be added.