Patent GB-581339-A (GB)
Title: Manufacture of condensation products
IPC: C08G12/22
Filed: 1943-11-18
Abstract: A process for the preparation of condensation products stated to be an improvement in or modification of the invention described in Specification 533,219, comprises the reaction of a carboxylic acid methylolamide having at least 7 carbon atoms or a mixture of a carboxylic acid amide having at least 6 carbon atoms and formaldehyde with an aliphatic mercaptan, conducted by causing at least one sparingly soluble reaction component, desirably, the methylolamide, to react in a state of aqueous dispersion, preferably at 60-100 DEG C.  Aliphatic, aromatic, aliphatic-aromatic, or cycloaliphatic amides, especially those containing at least twelve carbon atoms, for example, the amides of lauric acid, palmitic acid, stearic acid and oleic acid, also the amides of hardened train oil fatty acids or of resin acids or naphthenic acids may be used, as well as benzoic acid amide, chloromethyl-benzoic acid amide or salicylic acid amide; urethanes, having at least 6 atoms, for example, those of the higher fatty alcohols may also be used.  As aliphatic mercaptans there may be used ethyl and hexadecyl mercaptans, and mercaptans containing a group imparting solubility in water such as oxyethyl-mercaptan, thioglycerine, thioglycollic acid, b -mercapto-ethane sulphonic acid or their salts.  A fine dispersion of the reaction component used in aqueous dispersion may be obtained, for example, by grinding, precipitating or emulsifying it in a molten condition.  Strong acids such as hydrochloric acid may be present.  An acid reaction may also be produced by using the free mercapto acid.  The reaction may also be carried out in a medium having a pH greater than 6.9.  The preferred proportions employed are 2 mols. or less of the mercaptan to 2 mols. of the methylolamide or corresponding mixture of amide and formaldehyde.  The products which are water-soluble and contain an aliphatic radical of high molecular weight may be used as textile assistants, especially as softening or washing agents either alone or with other substances usually employed with textile assistants.  In examples: (1) finely-divided stearic acid methylol amide suspended in water is agitated with thioglycollic acid for 20 hours at 55-60 DEG C. and then at 75-80 DEG  C. and the product isolated by filtration and neutralized with caustic soda to give a colourless powder.  This sodium salt, alone, or admixed with a dispersing agent which is resistant to hard water, for example a mixture consisting of 70 parts of the above sodium salt and 30 parts of the disodium salt of m -heptadecyl-N-benzyl-benzimidazole disulphonic acid, is a useful softening agent; (2) stearic acid methylolamide is suspended in aqueous thioglycollate solution, hydrochloric acid is added and the stirred mixture heated for 20 hours at 55-60 DEG  C. and then at 78-80 DEG  C., the resulting product being recovered as in (1); the sodium glycollate is prepared by heating sodium chloracetate with thiourea in aqueous sodium hydroxide solution; (3) a mixture of stearic acid methylolamide and aqueous sodium thioglycollate solution is fused by heating and additional thioglycollate solution and then hydrochloric acid added with stirring at 90-95 DEG  C., the product obtained being worked up as in (1); stearic acid methyolamide is prepared by reacting the amide with paraformaldehyde in presence of triethanolamine; (4) a mixture of stearic and oleic acid methylolamides are reacted as in (3); (5) the mixture of condensation product and dispersing agent described in (1) above is added to aqueous dimethylolurea solution for use p  in rendering textiles resistant to creasing; fabric so treated handles softer than when treated in absence of said mixture.  A sample has been furnished under Sect. 2 (5) of a product obtained by reacting benzoic acid N-methylolamide suspended in an aqueous solution of thioglycollic acid.  The Specification as open to inspection under Sect. 91 includes the use, generally of amides of carboxylic acids and mercaptans, reference being made to heterocyclic amides in addition to those specified above.  This subject-matter does not appear in the Specification as accepted.