Patent GB-583118-A (GB)
Title: Production of high-molecular weight organic compounds containing sulphonic groups
IPC: C07C309/04
Filed: 1943-12-08
Abstract: Water soluble salts of alkane sulphonic acids and the free acids, obtained by reacting ethylene or propylene with an aqueous solution of a salt of sulphurous acid at temperatures between 90 DEG  C. and 200 DEG  C. and at pressures above 400 atmospheres (see Group IV), may be used in emulsifying processes.  A typical product has the formula H (CH2 CH2)n SO3 Na where n is greater than one, obtained from ethylene and sodium bisulphite. The salts include metal salts, preferably of the alkali metals, and ammonium and amine salts.  In typical examples are described: (1) an alkane sulphonic acid of neutral equivalent 120 and the sodium salt, from sodium bisulphite and ethylene; (4) an alkane sulphonic acid of neutral equivalent 195 and the sodium salt, from sodium sulphite and ethylene; (5) mixed alkane sulphonic acids of neutral equivalent 132 and the potassium salts, from potassium meta-bisulphite and ethylene; (6) magnesium alkane sulphonates, from magnesium sulphite and ethylene, whose aqueous solution on acidification is surface active; (7) alkane sulphonic acids of neutral equivalent 138 and the sodium salts, from sodium bisulphite and propylene.ALSO:Salts of alkane sulphonic acids are prepared by subjecting ethylene or propylene, or mixtures thereof, with a water-soluble salt of sulphurous acid to a temperature between 90 DEG  and 200 DEG  C., preferably 115 DEG  to 125 DEG  C., and a pressure of at least 400 atmospheres, preferably 700 to 1000 atmospheres, and preferably for a time between one half and ten hours.  The free sulphonic acids may be obtained by treating the salts with concentrated hydrochloric acid.  The process is one of telomerization and, for example, when sodium bisulphite and ethylene are used, the products are of the type H(CH2CH2)nSO3Na, where n is greater than one.  The ethylene or propylene need not be pure and may contain other gaseous mono-olefines such as the butylenes; mixtures of gaseous mono-olefines derived from the cracking of petroleum may be employed provided the di-olefine content is small.  The reaction is preferably carried out in the presence of water or a mixture thereof with an inert organic liquid.  Any water-soluble sulphite or bisulphite may be used, the metallic or alkali-metal salts being preferred, but the ammonium and amine salts are included.  Peroxygen compounds such as benzoyl peroxide, ascaridole, sodium peroxide, hydrogen peroxide and persulphates and molecular oxygen may be present as catalysts, but are not essential.  The reaction may be carried out in the presence of polyhalogenated hydrocarbons such as carbon tetrachloride, chloroform, hexachlorethane, and hexachlorbenzene; these compounds which appear to act as promoters, may also react with the olefines by the process claimed in Specification 5858/43, but the alkane sulphonates are readily separated from the products of such a reaction as the latter are insoluble in water. The products of this invention may be used wetting, dispersing, penetrating, deterging, emulsifying (see Group III) and frothing processes (see Group II).  The free acids may be converted by known methods into the corresponding sulphonyl halides, esters and amides which are useful as chemical intermediates, solvents, softening agents and plasticisers.  In typical examples: (1) sodium bisulphite, water and carbon tetrachloride are reacted under an ethylene pressure of 720-790 atmospheres at 107-124 DEG  C., a solid ethylene-carbon tetrachloride product is filtered off and the filtrate evaporated to dryness yielding a salt-like residue which on treatment with hydrochloric acid yields an oil having a neutral equivalent of 120 corresponding with the formula H(C2H4)nSO3H, where n is greater than 1 and giving a foaming solution in water; (2) sodium bisulphite, water and iso-octane are heated similarly under ethylene pressure yielding a white solid containing the sodium salts of alkyl sulphonic acids which on acidification yield the free acids as a brown grease-like residue of neutral equivalent 154 forming a foaming solution in water; (3) sodium bisulphite, water, carbon tetrachloride and isooctane are reacted with ethylene as in (1) above, the free sulphonic acid obtained having a neutral equivalent of 173; (4) sodium sulphite, water and ethylene are heated as above in the presence of ascaridole as catalyst and carbon dioxide as a diluent, the free sulphonic acid obtained having a neutral equivalent of 195, and yielding a foaming solution in water, while polythene is isolated from the crude reaction mixture on filtration; (5) potassium meta-bisulphite, water, carbon tetrachloride and ethylene are heated under pressure and the products worked up as above, yielding free sulphonic acids of a neutral equivalent of 132 which foam in aqueous solution; (6) magnesium sulphite hexahydrate, water, iso-octane and carbon tetrachloride are heated under ethylene pressure, a white solid filtered off and magnesium alkyl sulphonates isolated from the filtrate whose aqueous solutions on acidification are surface active; (7) sodium bisulphite, carbon tetrachloride and water are heated under propylene pressure in the presence of ascaridole yielding a white insoluble solid and alkane sulphonic acids of neutral equivalent 138 as the sodium salts.ALSO:Water soluble salts of alkane sulphonic acids, and the free acids, obtained by reacting ethylene or propylene with an aqueous solution of a salt of sulphurous acid at temperatures between 90 DEG C. and 200 DEG  C. and at pressures above 400 atmospheres (see Group IV) may be used in frothing processes.  A typical product, from ethylene and sodium bisulphite, has the formula H(CH2CH2)n SO3Na where n is greater than one. The salts include metal salts, particularly of the alkali metals, and ammonium and amine salts.  In typical examples are described: (1) an alkane sulphonic acid of neutral equivalent 120 and its sodium salt, from sodium bisulphite and ethylene; (4) an alkane sulphonic acid of neutral equivalent 195 and its sodium salt, from sodium sulphite and ethylene; (5) mixed alkane sulphonic acids of neutral equivalent 132 and the potassium salts, from potassium meta-bisulphite and ethylene; (6) magnesium alkane sulphonates, from magnesium sulphite and ethylene, whose aqueous solution on acidification is surface active; (7) alkane sulphonic acids of neutral equivalent 138 and the sodium salts, from sodium bisulphite and ethylene.