Patent GB-748570-A (GB)
Title: Process for the preparation of sulphonated polyethers
IPC: C07C303/24
Filed: 1953-09-15
Abstract: A process for the production of addition products of polyethers comprises contacting sulphonating agents which act more strongly than concentrated sulphuric acid with polyethers containing at least 3 ether oxygen atoms in one polyether chain, in such quantity that per molecule of polyether at least one and preferably at least three molecules of sulphonating agent are available for addition product formation with the ether oxygen, but that per atom of ether oxygen not more than one molecule of sulphonating agent is available for addition product formation. Suitable starting materials are reaction products of alkylene oxides, polyethers or their hydrogen halide esters with organic compounds having reaction-capable hydrogen atoms, such as phenols, alcohols, carboxylic acids, amines, amides, sulphonamides, mercaptans or sulphonic acids, and may contain aromatic, aliphatic and cycloaliphatic groups and hetero-atoms. Mixed reaction products, containing, for example, both ethylene and propylene oxide residues, can be used.  The sulphonating agents to be employed are chlorosulphonic acid, oleum, sulphur trioxide and mixtures of these compounds.  The polyethers may contain hydroxyl, amino or amido groups which react preferentially with the sulphonating agent and only after such reaction is the excess available for addition compound formation.  The addition reaction can be effected in the presence of solvents such as sulphur dioxide, carbon disulphide and chlorinated and/or fluorinated hydrocarbons, e.g. trichlorethylene, at temperatures between - 50 DEG  and +60 DEG C.  On contact with water the addition compounds decompose to form sulphuric acid solutions which can be used as pickling or cleaning liquids for metals, the polyethers improving the viscosity, dirt-carrying capacity and wetting power of the solution.  In examples: (1) a polyethylene oxide of the formula HO.CH2CH2O(CH2 CH2O)nCH2CH2OH, where n is an integer, of average molecular weight 300, is reacted at below 30 DEG  C. with excess chlorosulphonic acid to form an oily product; (2) an oil addition product is formed by the reaction of excess chlorosulphonic acid with a compound of the average molecular weight 360 and the formula CH3O (CH2CH2O)nCH2CH2OH (obtained by the reaction of ethylene oxide with glycol monomethyl ether).  On introduction into water a sulphuric and hydrochloric acid solution of the sulphonated polyglycol ether is obtained, which is suitable for use as a pickling or metal-cleaning agent; (3) viscous oils containing sulphur trioxide in bound form are obtained by reacting sulphur trioxide at - 15 DEG  C. with a polyethylene oxide of average molecular weight 5000 dissolved in liquid sulphur dioxide. A similar product is obtained by the reaction at 40 DEG  C. of a polyethylene oxide of average molecular weight 9000 with excess chlorosulphonic acid; (4) a reaction product of 8 to 9 mols. of ethylene oxide with a mixture of fatty alcohols of chain length C12 to C13 (from the reduction of coconut fat acid) is reacted with excess chlorosulphonic acid to give an oily product, which on addition to water forms a hydrochloric and sulphuric acid solution of the sulphonated ethylene oxide derivative having capillary active properties; (5) an addition product is formed by reacting an end methylated reaction product of 10 mols. of ethylene oxide with the alcohol referred to in Example (4).  The product is split on dissolving in water, to give the polyether again; (6) an addition product is formed by reacting in liquid sulphur dioxide an addition product of 5 to 6 mols. of ethylene oxide with one mol. of an alkylbenzene sulphamide formed from a technical alkylbenzene mixture with 14 to 18 carbon atoms in the alkyl residue; (7) a reaction product of about 10 mols. of ethylene oxide with one mol. of a coconut fatty acid amide with a chain length C12 to C18 is reacted with chlorosulphonic acid at temperatures up to 40 DEG  C.  After expelling hydrochloric acid formed in the esterification of the end groups an oil containing 90 per cent of the chlorosulphonic acid bound in the manner of an addition product is obtained; (8) a reaction product of about 12 mols. of ethylene oxide with one mol. of dodecylmercaptan is reacted in liquid sulphur dioxide at - 15 DEG  C. with chlorosulphonic acid to give an addition product containing 90 per cent of the chlorosulphonic acid in a form which can easily be split off.