| 摘要 |
New salts of polyesters of aliphatic sulphodicarboxylic acids are prepared by condensing (A) one or more fatty acid monoof di-glycerides, wherein the fatty acid component contains at least 8 carbon atoms, with (B) an esterification product of (a) a polyalkylene glycol and (b) one or more ethylenically unsaturated aliphatic dicarboxylic acids or anhydrides thereof wherein the ethylenically unsaturated grouping is alpha to a carbonyl group, the reactants of (A) and (B) being employed in a molar ratio of about 2 moles. of the former to 1 mole. of the latter and the reactants of (a) and (b) being employed in a molar ratio of 1 of the former to about 2 of the latter, and reacting the resulting polyester condensation product with a bisulphite or metabisulphite containing an inorganic or organic cationic salt-forming substituent. In the sulphonation step, one or two sulphonate groups may be introduced at the double bonds of the polyester condensation product by adjustment of the amount of bisulphite or meta-bisulphite reactant. The preferred products have the general formula <FORM:0745412/IV(a)/1> wherein R represents an aliphatic radical having at least 7 carbon atoms, R1 represents the residue of a polyalkylene glycol and M is a salt-forming cation e.g. an alkali metal, NH4, a polyvalent metal, methyl-, ethyl-, propyl- and butyl-amines and the corresponding dialkyl amines, mono-, di- and tri-ethanolamines, guanylurea, guanidine, hydroxyethyl guanidine, biguanide, aryl amines such as aniline, alkaryl and aralkyl amines such as toluidine and benzyl amine, and nicotine, pyridine, quinoline and alkaloids. The bis-esters of (B) may be prepared from poly alkylene glycols which may be high polymers of the lower glycols, e.g. the carbo-waxes of molar weights of up to 7,500, and such unsaturated dibasic aliphatic acids as maleic, fumaric, citraconic, itaconic and mesaconic acids and their anhydrides. These bisesters are preferably reacted with fatty acid mono-glycerides such as those derived from caprylic, myristic, stearic, behenic, carnaubic, montanic, oleic, elaidic, isooleic, rapic, brassidic and melissic acids and like acids obtained from animal and vegetable oils and fats, including dehydrated castor oil and tall oil. Sulphonation is normally effected by heating the reactants in water or a mixture of water and a miscible solvent, e.g. ethanol. The sulphonates are obtained in salt form, normally the alkali metal, NH4 or amine salts and these may be acidified, e.g. in alcoholic solution and the liberated sulphonic acid then reacted with other bases to form salts, e.g. the calcium, barium, lead or cadmium salts. The products are useful as dispersing agents in the textile and other industries (see Group IV (c)) and as emulsifying agents (see Group III). In typical examples: (5) polyethylene glycol 400 is reacted with maleic anhydride and the resulting ester condensed with glyceryl mono-stearate as in (1) yielding a polyester which is refluxed with ethanolamine bisulphite in aqueous ethanol, whereupon the excess bisulphite is oxidized with H2O2 to bisulphate, ethanolamine is added in amount equivalent to the bisulphate and the mixture is stripped to yield a waxy paste; (7) Carbo wax 1500 replaces the glycol used in (4); (9) polypropylene glycol 400 replaces the glycol used in (4); (13) maleic anhydride is esterified with polyethylene glycol 400, and the dimaleate ester is condensed with tallow diglyceride and the resulting polyester sulphonated as in (4).ALSO:New salts of polyesters of aliphatic sulphodicarboxylic acids are prepared by condensing (A) one or more fatty acid mono- or diglycerides, wherein the fatty acid component contains at least 8 carbon atoms, with (B) an esterification product of (a) one or more alkylene or polyalkylene glycols, and (b) one or more ethyleni cally unsaturated aliphatic dicarboxylic acids or anhydrides thereof wherein the ethylenically unsaturated grouping is alpha to a carbonyl group, the reactants of (A) and (B) being employed in a molar ratio of about 2 mols. of the former to 1 mol. of the latter and the reactants of (a) and (b) being employed in a molar ratio of 1 of the former to about 2 of the latter, and reacting the resulting polyester condensation product with a bisulphite or metabisulphite containing an inorganic or organic cationic salt-forming substituent. In the sulphonation step, one or two sulphonate groups may be introduced at the double bonds of the polyester condensation product by adjustment of the amount of bisulphite or meta-bisulphite reactant. The preferred products have the general formula <FORM:0745412/IV(a)/1> wherein R represents an aliphatic radical having at least 7 carbon atoms, R1 represents the residue of an alkylene or polyalkylene glycol having at least 2 carbon atoms and M is a salt-forming cation, e.g. an alkali metal, NH4, a polyvalent metal, methyl-, ethyl-, propyl- and butyl-amines and the corresponding dialkyl amines, mono-, di - and tri - ethanolamines, guanylurea, guanidine, hydroxyethyl guanidine, biguanide, aryl amines such as aniline, alkaryl and aralkyl amines such as toluidine and benzyl amine, and nicotine, pyridine, quinoline and alkaloids. The bis-esters of (B) may be prepared from the various glycols, e.g. from ethylene glycol up to octylene glycol and poly alkylene glycols ranging from di- and tri-ethylene glycols up to high polymers of the lower glycols, e.g. the carbowaxes of molar weights of up to 7500, and such unsaturated dibasic aliphatic acids as maleic, fumaric, citraconic, itaconic and mesaconic acids and their anhydrides. These bis-esters are preferably reacted wth fatty acid mono glycerides such as those derived from caprylic, myristic, stearic, behenic, carnaubic, montanic, oleic, elaidic, iso-oleic, rapic, brassidic and melissic acids and like acids obtained from animal and vegetable oils and fats, including dehydrated castor oil and tall oil. Sulphonation is normally effected by heating the reactants in water or a mixture of water and a miscible solvent, e.g. ethanol. The sulphonates are obtained in salt form, normally the alkali metal, NH4 or amine salts and these may be acidified, e.g. in alcoholic solution and the liberated sulphonic acid then reacted with other bases to form salts, e.g. the calcium, barium, lead or cadmium salts. The products are useful as dispersing agents in the textile and other industries (see Group IV (c)) and as emulsifying agents (see Group III). In typical examples (1) ethylene glycol and maleic anhydride are heated to 148 DEG C. and the resulting dimaleate glycol ester is heated with 2 mols. of glyceryl monostearate in xylene whereby the water of reaction is distilled off as formed yielding a polyester which is heated under reflux in aqueous alcohol with a mixture of Na2SO3 and Na2S2O5 whereupon excess bisulphite is oxidized with H2O2, the pH adjusted to 6.5 with aqueous NaOH and the product then stripped of solvent to yield a white waxy solid; (4) nonaethylene glycol is reacted with maleic anhydride, the resulting di-maleate ester of the glycol is condensed with two mols. of mono-stearyl glyceride and the polyester formed is refluxed in aqueous ethanol first with Na2SO3 and then with Na2S2O5 and the sulphonate worked up as in (1); (5) polyethylene glycol 400 is reacted with maleic anhydride and the resulting ester condensed with glyceryl monostearate as in (1) yielding a polyester which is refluxed with ethanolamine bisulphite in aqueous ethanol, whereupon the excess bisulphite is oxidized with H2O2 to bisulphate, ethanolamine is added in amount equivalent to the bisulphate and the mixture is stripped to yield a waxy paste; (7) carbo wax 1500 replaces the glycol used in (4); (9) polypropylene glycol 400 replaces the glycol used in (4); (13) maleic anhydride is esterified with polyethylene glycol 400, and the dimaleate ester is condensed with tallow diglyceride and the resulting polyester sulphonated as in (4). The sodium sulphite used in some of the above examples serves to neutralize free acid contained in the polyester, thereby yielding also sodium bisulphite, and circumventing waste of bisulphite or metabisulphite due to decomposition thereof by such free acid.ALSO:Surface-active salts of polyesters of aliphatic sulpho-dicarboxylic acids are prepared by condensing (A) one or more fatty acid mono- or di-glycerides, wherein the fatty acid component contains at least 8 carbon atoms, with (B) an esterification product of (a) one or more alkylene or polyalkylene glycols and (b) one or more ethylenically unsaturated aliphatic dicarboxylic acids or anhydrides thereof wherein the ethylenically unsaturated grouping is alpha to a carbonyl group, the reactants (A) and (B) being employed in a molar ratio of about 2 moles of the former to 1 mole of the latter and the reactants (a) and (b) being employed in a molar ratio of 1 of the former to about 2 of the latter, and reacting the resulting polyester condensation product with a bisulphite or metabisulphite containing an inorganic or organic cationic salt-forming substituent. The products may be used as softening agents and as antistatic agents, especially in conjunction with other antistatic agents, in treating textile materials of various kinds e.g. cellulose esters, rayon, nylon or polyacrylonitrile. The salts may also be used as detergents or as dispersants, e.g. of dyes and inks. In the sulphonation step, one or two sulphonate groups may be introduced at the double bonds of the polyester condensation product by adjustment of the amount of bisulphite or meta-bisulphite reactant. The preferred products have the general formula:- <FORM:0745412/IV(c)/1> wherein R represents an aliphatic radical having at least 7 carbon atoms, R1 represents the residue of an alkylene or polyalkylene glycol having at least 2 carbon atoms and M is a salt-forming cation, e.g. an a
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