Patent GB-395340-A (GB)
Title: Improvements in the manufacture and production of softening and gelatinising agents
IPC: C08K5/11
Filed: 1932-01-04
Abstract: Esters suitable for plasticizing and softening agents for lacquers, films and plastics containing cellulose derivatives, such as the nitrate and acetate, urea-aldehyde and other resins or other organic film-forming substances, are made by esterifying all the carbonyl groups of polycarboxylic acids produced by oxidation of aliphatic hydrocarbons or their oxygen derivatives of high molecular weight by means of nitric acid or oxides of nitrogen, such oxidation being effected at temperatures not exceeding 110 DEG  C.  The esterification is effected with monohydric alcohols or phenols or with one hydroxy group of polyhydric alcohols or hydroxyl bearing ethers of polyhydric alcohols.  The oxidation products may be prepared as described in Specification 324,492, [Class 2 (iii), Dyes &c.]; or fats or their acids or residues obtained in their working-up may be oxidized with 45 per cent aqueous nitric acid at 85 DEG  C. Monocarboxylic acids may be separated from the products by fractional distillation or fractional crystallization, and from the fraction of high acid value the constituents insoluble in petroleum ether and difficulty soluble in cold water but soluble in hot water may be separated; these constituents are a -o -dicarboxylic acids of 8-20 carbon atoms.  The polycarboxylic acids may be purified by dissolving in the alcohol intended for the esterification and separating the insoluble matter.  Suitable alcohols are methyl, ethyl, propyl, isopropyl, butyl, lauryl and octodecyl alcohols, ethylene, propylene, 1-3 butylene, and diethylene glycols, glycerin, monoalkyl ethers of glycols such as ethylene glycol, monoethyl ether, cyclohexanol and its homologues, benzyl alcohol and phenols.  In using polyhydric alcohols the conditions are so chosen that only one hydroxyl group of the alcohol reacts, for instance by reacting an alkali salt of the polycarboxylic acid with the corresponding chlorhydrin or the acids may be reacted with an alkylene oxide.  Any non-esterified alcohol may be left in the product; for instance butyl or isobutyl alcohol which have solvent action for the compositions to be produced.  In examples, (1) an oxidation product of paraffin wax with nitric acid at 90 DEG  C. is esterified with butyl alcohol, the ester being distilled off at 170-230 DEG  C. at 1-2 mm. pressure; it may be added to a solution of low-viscosity cellulose nitrate in a mixture of equal parts of normal or isobutyl acetate, normal or isobutyl alcohol, and toluene to form an elastic lacquer.  (3) An oxidation product of paraffin wax with nitric acid at 100 DEG  C. is esterified with glycol monoethyl ether, the ester being distilled off at 190-230 DEG  C. at 1-2 mm. pressure and may be treated with bone black; it is suitable for a camphor substitute for shaped articles of cellulose nitrate.  (4) An oxidation product of paraffin wax with nitric acid at 80 DEG  C. is esterified with p-methyl cyclohexanol, the ester being suitable for a softening agent for solutions of cellulose nitrate or synthetic resins such as urea-formaldehyde resins for making non-splintering glass.  (5) An oxidation product of waste fat with 45 per cent nitric acid at 85 DEG  C. is esterified with isopropyl alcohol, the ester being added to a solution of low viscosity cellulose nitrate in butyl acetate, butyl alcohol and toluene to produce an elastic lacquer.  (6) An oxidation product of train oil with 45-50 per cent nitric acid at 90 DEG  C. while maintaining the acid concentration, by adding nitrous gases, is esterified with glycol monoethyl ether; the product is suitable for a gelatinizing agent for celluloid articles.  (7) An oxidation product of "sulphur olive oil" (an oil extracted from olive husks by carbon disulphide) with nitric acid as in the preceding example, is esterified with cyclohexanol; the product is stirred with calcium hydroxide, ground in a ball-mill with benzine, filtering off the calcium soaps, distilling off the benzene, and distilling the ester in vacuo.  (8) An oxidation product of paraffin wax with nitric acid at 80 DEG  C. is esterified with mainly n-hexylene oxide obtained from olefines from the cracking of paraffin, and the free hydroxyl groups may be acylated if desired. (9) The anhydrides of the acids used in the preceding example (obtained by the reaction of acetic anhydride in the acids) are heated with phenol at 130-140 DEG  C., the product being a soft mass melting at 40 DEG  C.  Specifications 12806/84, [Class 15, Bleaching &c.], 213,267, [Class 32, Distilling &c.], 320,854, 322,496, 327,162, [all in Class 2 (iii), Dyes &c.], and 377,265 also are referred to.