Patent GB-1082179-A (GB)
Title: Unsaturated carboxylic salt materials and derivatives thereof
Inventor: SMEETS FRED
IPC: C08G65/334
Filed: 1965-07-19
Abstract: A surface-active composition comprises a builder and/or filler and a salt derivative of a sulphonated ester material obtained by esterification with one or more C1- 22 monohydric alcohols of the reaction product obtained by contacting bisulphite ions under acid conditions with an organic unsaturated ester material prepared by esterifying with one or more alcohols the unsaturated organic acid material obtained by hydrolysis of the unsaturated organic salt material prepared by heating an alkaline earth metal salt of citric acid for a period of time until an increase in titratable alkalinity of the reaction mixture is obtained (see Division C2). The bisulphite ion may also be reacted directly with the unsaturated organic salt material by omitting the steps of hydrolysing and subsequently esterifying the latter. The surface-active agent may be in powder form and other detergents may be present.  The composition may also comprise a liquid carrier, e.g. an aqueous or organic medium, to form gels, solutions or disperse compositions such as emulsions, pastes or creams.ALSO:A surface active condensation polymer comprises a salt derivative of the reaction product of a monohydric alcohol, one or more polyhydric alcohols or a mixture thereof, and a sulphonated organic acid material obtained by contacting bisulphite ions under acid conditions with an organic unsaturated ester material prepared by esterifying with one or more alcohols the unsaturated organic acid material obtained by hydrolysis of the unsaturated organic salt material prepared by heating an alkaline earth metal salt of citric acid for a period of time until an increase in titratable alkalinity of the reaction mixture is obtained.  The bisulphite ion may also be reacted directly with the unsaturated organic salt material by omitting the steps of hydrolysing and subsequently esterifying the latter.  To prepare an unsaturated polyester the unsaturated organic salt material may be hydrolysed to the corresponding acid derivative which may then be reacted with the alcohol and/or polyol component. In Example 13 a sulpho-acid material is reacted with glycerol and in Example 14 the unsaturated organic acid material is reacted with diethylene glycol.ALSO:An unsaturated organic salt material is obtained by heating an alkaline earth metal salt of citric acid for a period until an increase in titratable alkalinity of the reaction mixture is obtained.  The citric acid salt is preferably heated to a temperature not less than 230 DEG  C. and the pyrolysis (which may be effected by employing conventional techniques) continued until the concentration of citrate starting material in the reaction mixture is 5% by weight or less.  The reaction product is of undetermined composition but may contain more than 3 carboxylic acid groups per mol.; aconitic acid may also be formed.  The product may be hydrolysed to give an unsaturated organic acid material and one or more acids containing less than 4 carboxylic acid groups may be separated from the said acid material (or from the corresponding sulpho-acid, ester or sulpho-ester materials described below). The acid material may be converted to the corresponding sodium salt and it may also be esterified with one or more alcohols to give an unsaturated organic ester material.  The salt, acid and ester materials may be reacted with bisulphite ion to produce a sulphonated organic material which may contain both sulphonic and carboxylic acid groups; the bisulphite ion may be derived from an alkali-metal bisulphite, an alkali metal or ammonium sulphite which may be converted to the corresponding bisulphite in situ or the bisulphite ions may be provided in situ by injecting SO2 into an acid solution of said organic material.  Unsaturated organic sulphoacid material may be obtained by hydrolysis of the corresponding salt or ester derivative. The sulphonated materials may be esterified or partially esterified, e.g. with one or more C1- 22 monohydric alcohols, with polyhydric alcohols or with a mixture thereof and any acidity remaining after esterification may be neutralized with a suitable base.  The esterified, sulphonated materials possess surface active properties.