Patent GB-786543-A (GB)
Title: Improvements in or relating to stable ketene dimer-emulsifier mixtures and their preparation
IPC: C09K23/00
Filed: 1955-10-24
Abstract: A non-ionic emulsifier, for ketene dimers (see Group III) is made by reacting ethylene oxide with a hexitol in a mole ratio of from 30 to 75 moles of ethylene oxide per mole of the hexitol to form a polyoxyethylene ether of the hexitol, reacting the polyoxyethylene ether of the hexitol with a 12 to 20 carbon atom fatty acid in a ratio from 0.5 to 0.85 moles of fatty acid per hydroxyl equivalent of the polyoxyethylene ether to form an ester, treating the ester with either an acylating, alkylating or etherifying agent, to reduce the hydroxyl number below about 10. The reaction of the polyoxyethylene ether with the fatty acid may be carried out in the presence of a small proportion of a catalyst, preferably in an atmosphere of carbon dioxide.  The reduction of the hydroxyl group may be accomplished preferably by acylation but numerous other methods are described. (1) Acylation with anhydrides or acid chlorides of lower fatty acids such as acetic acid and propionic acid.  (2) Ketenes such as ketene and methyl ketene may be used.  (3) Carbamate esters may be formed with isocyanates.  (4) Etherification with dimethyl sulphate and alkali or alkyl iodide and a sodium derivative of the hydroxyl material.  (5) Condensation with olefine (isobutylene) in presence of acid catalyst.  (6) Cyanoethylation with acrylonitrile and a tertiary amine.  Specifically exemplified are the preparation of (1) acetylated polyoxyethylene sorbitol esters, of oleic acid with an acid number 0.66, 3.04 and 1.4, saponification numbers 126, 128 and 137, and hydroxyl numbers 4, 2 and 4 respectively; (2) acetylated polyoxyethylene sorbitol ester of stearic acid with acid number 1.6, saponification number 130 and hydroxyl number 2; (3) acetylated polyoxyethylene sorbitol esters from refined tall oil acids with acid numbers 23.8 and 14, saponification numbers 118 and 132 and hydroxyl numbers 4 and 5 respectively.  Ketene dimers mentioned are those prepared from montanic acid, naphthenic acid, D 9,10-decylenic acid, D 9,10-dodecylenic acid, palmitoleic acid, oleic acid, ricinoleic acid, petroselinic acid, vaccenic acid, linoleic acid, linolenic acid, eleostearic acid, licanic acid, parinaric acid, tariric acid, gadoleic acid, arachidonic acid, cetoleic acid, erucic acid and selacholeic acid, as well as ketene dimers prepared from naturally occurring mixtures of fatty acids such as found in coconut oil, babassu oil, palm kernel oil, palm oil, olive oil, peanut oil, rape oil, beef tallow, lard (leaf) and whale blubber. Exemplified is the preparation of mixed hexadecyl-hexadecenyl-ketene dimers by forming the acid chlorides of a mixture of 45 per cent stearic, 55 per cent palmitic acids and reacting with a tertiary amine.  U.S.A. Specification 2,627,477 is referred to.ALSO:A composition, which is emulsified by the addition of warm water, comprises a ketene dimer and an emulsifier comprising an ester of a C12-C20 fatty acid and polyoxyethylene ether of a hexitol, preferably sorbitol, of 30-75 oxyethylene groups per mole., with a fatty acid/ether ratio of 0.5-0.85 per hydroxyl equivalent of the ether and the hydroxyl number of the ether ester having been reduced to less than 10 e.g. by acylation, alkylation, acetylation or etherification.  U.S.A. Specification 2,627,477 is referred to.ALSO:A non-ionic emulsifier, for ketene dimers (see Group III), is made by reacting ethylene oxide with a hexitol in a mole. ratio of from 30 to 75 moles. of ethylene oxide per mole. of the hexitol to form a polyoxyethylene ether of the hexitol, reacting the polyoxyethylene ether of the hexitol with a 12 to 20 carbon atom fatty acid in a ratio from 0.5 to 0.85 moles. of fatty acid per hydroxyl equivalent of the polyoxyethylene ether to form an ester, treating the ester with either an acylating, alkylating or etherifying agent, to reduce the hydroxyl number below about 10.  Ketene dimers which may be emulsified are phenyl ketene, benzyl ketene, decyl ketene, octyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl, tetracosyl, -naphthyl, and cyclohexyl ketene dimers, those prepared from montanic acid, naphthenic acid, D 9, 10-decylenic acid, D 9, 10-dodecylenic acid, palmitoleic acid, oleic acid, ricinoleic acid, petroselinic acid, vaccenic acid, linoleic acid, linolenic acid, eleostearic acid, licanic acid, parinaric acid, tariric acid, gadoleic acid, arachidonic acid, cetoleic acid, erucic acid and selacholeic acid, as well as ketene dimers prepared from naturally occurring mixtures of fatty acids such as found in coconut oil, babassu oil, palm kernel oil, palm oil, olive oil, peanut oil, rape oil, beef tallow, lard (leaf) and whale blubber.  The reaction of the polyoxyethylene ether with the fatty acid may be carried out in the presence of a small porportion of a catalyst, preferably in an atmosphere of carbon dioxide.  The reduction of the hydroxyl group may be accomplished preferably by acylation, but numerous other methods are described.  Specifically exemplified are the preparation of (1) acetylated polyoxyethylene sorbitol esters, of oleic acid with an acid number 0.66, 3.04 and 1.4 respectively, saponification numbers 126, 128 and 137 respectively and hydroxyl numbers 4, 2 and 4; (2) acetylated polyoxyethylene sorbitol ester of stearic acid with acetyl 1.6, saponification number 130 and hydroxyl number 2; (3) acetylated polyoxyethylene sorbitol esters from refined tall oil acids with acid numbers 23.8 and 14, saponification numbers 118 and 132 and hydroxy numbers 4 and 5. U.S.A. Specification 2,627,477 is referred to.