Patent GB-375842-A (GB)
Title: Improvements in the manufacture and production of derivatives of polyhydric alcohols
IPC: C07C43/13
Filed: 1931-03-26
Abstract: Emulsions, making.--As emulsifying agents may be employed derivatives of polyhydric alcohols manufactured by etherifying or esterifying part of the hydroxyl groups in hydroxyalkyl ethers of aliphatic polyhydric alcohols free from carbonyl groups, which alcohols contain at least three carbon atoms in the molecule, e.g. the hexa- and pentahydroxyethyl ethers of sorbitol, the tetrahydroxyethyl ether of pentaerythritol and the trihydroxyethyl ether of glycerol, with aliphatic substances which contain at least six, preferably from ten to eighteen carbon atoms in the molecule, the final product containing at least two free hydroxyl groups.  The aliphatic substances containing at least six carbon atoms may include alkyl halides, e.g. decyl bromide, halogenhydrins, e.g. dodecylene chlorhydrin, aliphatic halogen carboxylic acids, e.g. chlorostearic, chlorolauric or chlorohydroxystearic acids, alkylene oxides, e.g. hexylene or dodecylene oxides, alcohols, mono- or polybasic aliphatic open chain or cycloaliphatic acids, e.g. lauric, stearic, palmitic, or linoleic acids, coco nut oil fatty acids, fatty acids obtained by oxidation of paraffin hydrocarbons or naphthenic acid, aliphatic carboxylic sulphonic acids, e.g. palmitic sulphonic acid, and sulphuric or phosphoric esters of aliphatic alcohols or of other hydroxyl-bearing aliphatic compounds, e.g. Turkey red oils.  In an example, olive oil is emulsified in water with the aid of the mono-ester from coco nut fatty acids and sorbitol hexahydroxyethyl ether.  The Provisional Specification describes also the products of partial etherification or esterification of polyhydric alcohols themselves or their derivatives or substitution products, including derivatives containing carbonyl groups, e.g. pentaerythritol, hexitols, sugars or carbohydrates or their hydrogenation products.ALSO:Derivatives of polyhydric alcohols are manufactured by etherifying or esterifying part of the hydroxyl groups in hydroxyalkyl ethers of aliphatic polyhydric alcohols free from carbonyl groups, which alcohols contain at least three carbon atoms in the molecule, with aliphatic substances which contain at least six, preferably from ten to eighteen carbon atoms in the molecule, the final product containing at least two free hydroxyl groups.  The hydroxyalkyl ethers are obtainable by the action of alkylene oxides on the said polyhydric alcohols, e.g. glycerol, pentaerythritol or sorbitol.  For the etherification or esterification there may be employed alkyl halides, halogenhydrins, aliphatic halogen carboxylic acids, e.g. chlorostearic, chlorolauric or chlorohydroxystearic acids, alkylene oxides, e.g. hexylene or dodecylene oxides, alcohols, mono- or polybasic aliphatic open chain or cycloaliphatic carboxylic acids, aliphatic carboxylic sulphonic acids, e.g. palmitic sulphonic acid, acid sulphuric or phosphoric esters of aliphatic alcohols or of other hydroxyl-bearing aliphatic compounds, e.g. Turkey red oils, or derivatives of the said acids. e.g. acid chlorides or anhydrides. The partial esterification may be carried out by heating the hydroxyalkyl ethers with an amount of acid less than is necessary for complete esterification or by allowing the corresponding acid chlorides or anhydrides to act on a solution of the ethers, e.g. in pyridine.  The components may be simply heated together, and the reaction may be accelerated by the addition of small quantities of catalysts assisting esterification such as boric, sulphuric, or phosphoric acids.  The reaction may be performed in inert solvents such as hydrocarbons or ethers. The procedure is analogous for the partial etherification.  The products are valuable wetting, cleansing, and dispersing agents. They may be employed in the textile industry in washing, carbonizing, dyeing, printing, rendering fibres soft and flexible, in spinning artificial threads as additions to the precipitating baths or to the spinning solutions, in the leather industry, e.g. in soaking hides, in the cleaning industry for the preparation of cleaning agents of all kinds, also for the preparation of drilling greases and lubricants.  In examples: (1) sorbitol hexahydroxyethyl ether is heated with one or two molecular proportions of coco nut oil fatty acids with the addition of boric acid; (2) a mixture of sorbitol hexa- and pentahydroxyethyl ethers is heated with a mixture of fatty acids containing 8-11 carbon atoms in the molecule obtained by the oxidation of paraffin wax; the product which consists mainly of the mono-esters, has excellent wetting and foaming action making it suitable for use as an auxiliary agent in the textile industry; (3) an aqueous solution of the mono-ester obtained from sorbitol hexahydroxyethyl ether and a mixture of fatty acids having an average of 10 carbon atoms in the molecule obtained by the oxidation of paraffin wax, or of the ether obtained from equimolecular proportions of sorbitol hexahydroxyethyl ether and decyl bromide, is employed as a wetting agent for textiles, e.g. cotton; (4) glycerol trihydroxyethyl ether is esterified with the fatty acid mixture employed in (2), the product consisting mainly of the mono esters; (5) glycerol trihydroxyethyl ether is heated with lauric acid to produce the mono-laurate; (6) a mixture of sorbitol hexa- and penta-hydroxyethyl ethers is esterified with lauric acid to produce mainly the monolaurates; (7) sorbitol hexahydroxyethyl ether is treated with sodium ethylate to produce its sodium derivative, which is heated with 1 : 2-dodecylene chlorhydrin (prepared by splitting off water from n-dodecyl alcohol and treating the 1 : 2-dodecylene obtained with sodium hypochlorite and carbon dioxide); the product, which is probably the monohydroxydodecyl ether of sorbitol hexahydroxyethyl ether, has a strong wetting action even in the presence of alkaline or acid agents or of calcium compounds and may thus be employed in the presence of hard water; the monohydroxydecyl ether of pentaerythritol tetrahydroxyethyl ether may be similarly employed; the sorbitol hexahydroxyethyl ether may also be replaced by polyhydroxyethyl ethers of sorbitol in which several polyethylene ether groups (-O-C2H4-O-C2 H4-O-C2 H4 O H) are connected to one or more hydroxyl groups of the original sorbitol; (8) the sodium derivative of sorbitol hexahydroxyethyl ether is heated with the sodium salt of hydroxychlorostearic acid (obtainable by adding on hypochlorous acid to oleic acid); the product consists mainly of a 9 : 10-dihydroxystearic acid in which one of the hydroxyl groups is etherified with sorbitol hexahydroxyethyl ether; (9) sorbitol hexahydroxyethyl ether is heated with 2 molecular proportions of linoleic acid to produce the di-linoleic ester; the product is valuable for sizing textiles, especially those from artificial silk; the mono-and tri-esters are similarly prepared; (10) sorbitol pentahydroxyethyl ether is heated with naphthenic acid to produce the naphthenic ester; the product may be employed for wetting out woollen goods; the monopalmitic esters of sorbitol penta- and hexa-hydroxyethyl ethers are similarly prepared; the products are useful for preventing the precipitation of calcium soaps from solutions of soaps in hard water and may be used for this purpose in washing or otherwise treating textiles; (11) viscose silk is treated with an aqueous solution of sorbitol hexahydroxyethyl ether monostearic ester, giving it a soft touch; the process may be combined with dyeing by adding the ester to the dyebath; (12) olive oil is emulsified in water with the aid of the mono-ester from coconut fatty acids and sorbitol hexahydroxyethyl ether; the emulsion may be employed for softening textiles; if olein be employed instead of olive oil the preparation may be employed for oiling textiles. Specifications 313,892, 329,266, [both in Class 2 (iii), Dyes &c.], 359,399, 360,493, and 361,865 are referred to.  The Provisional Specification describes also the partial etherification or esterification of polyhydric alcohols themselves or their derivatives or substitution products, including derivatives containing carbonyl groups, e.g. pentaerythritol, hexitols, sugars, or carbohydrates or their hydrogenation products.  Additional examples describe the preparation of sorbitol monolaurate by heating sorbitol with lauric acid chloride in pyridine and of esters of polyhydroxyethyl ethers of sugars with carboxylic acids.