Patent GB-984742-A (GB)
Title: Improvements in method of effecting substitution in polymeric compounds containing active hydrogen
IPC: C07C305/06
Filed: 1962-04-02
Abstract: Cyanoethyl thiosulphate sodium salt may be prepared by adding acrylonitrile to a buffered aqueous solution of sodium thiosulphate at 60 DEG  C., or by refluxing a mixture of sodium thiosulphate dissolved in water with b -chloropropionitrile dissolved in ethanol. Cyanoethyl pyridinium chloride may be prepared by mixing ethanol solutions of acrylonitrile and pyridine hydrochloride in the presence of triethylamine as catalyst, or by refluxing pyridine and b -chloropropionitrile in butanol.  Cyanoethyl acetate may be prepared by refluxing ethylene cyanohydrin with acetic acid in benzene in the presence of sulphuric acid as catalyst.  Cyanoethyl sulphate ammonium salt may be prepared by reacting ethylene cyanohydrin with sulphamic acid in the presence of urea; the product may be converted to acid form by treating with an ion exchange resin and neutralized with sodium hydroxide to give the corresponding sodium salt.  Carbamoethyl thiosulphate sodium salt may be prepared by refluxing a mixture of an aqueous solution of sodium thiosulphate and an ethanol solution of b -chloropropionamide.  Carboxyethyl thiosulphate sodium salt may be prepared by refluxing aqueous solutions of sodium thiosulphate and sodium b -chloropropionate.  Aldehydoethyl thiosulphate sodium salt may be prepared by adding acrolein to a buffered aqueous solution of sodium thiosulphate.  Bis - b  - sodium thiosulphato propionate of ethylene glycol may be prepared by refluxing a mixture of aqueous sodium thiosulphate solution and an ethanol solution of ethylene glycol bis-b -chloropropionate.  Acetylethyl thiosulphate sodium salt may be prepared by adding methyl vinyl ketone to a buffered aqueous solution of sodium thiosulphate.  Carboxyethyl pyridinium chloride may be prepared by dissolving acrylic acid and an ethanol solution of pyridine hydrochloride in acetone in the presence of triethylamine as catalyst, or by refluxing pyridine with b -chloropropionic acid in petroleum ether. ALSO:A method of improving the physical and chemical properties of polymeric materials containing active hydrogen atoms comprises reacting the polymeric materials under alkaline conditions with compounds having the molecular structure X(CHR1-CHR2Y)n where X is an electronegative activating group attached to the remainder of the molecule by carbon to carbon bonds, R1 is hydrogen or an alkyl group containing 1 to 5 carbon atoms, R2 is hydrogen, an alkyl group containing 1 to 5 carbon atoms or X, Y is a polar residue derived from a reagent of weak nucleophilic character and n is the valence of X and has a value 1 or 2. Specified polymers are cellulose, proteins, starches, polyvinyl alcohol, polyamines and polyamides, which may be treated in solution or dispersion, in the form of shaped articles, e.g. films, fibres and sheets, or textile structures, e.g. yarn, fabrics and webs.  Specified activating groups X are -COOR, -COR, -CN, -CONHR and -CSNHR where R is hydrogen or alkyl; -CF3; and -CF2R and -CH2SiR3 where R is alkyl.  Specified polar residues Y are -OSO3M, -SSO3M and -OCOCH3 where M is alkali metal or ammonium, -NC9H7 and -NC6H8.  Many suitable compounds are listed.  The alkali may be provided by the phosphates, carbonates, hydroxides, alkoxides and silicates of alkali metals, and the quaternary ammonium hydroxides.  Examples describe the treatment of cotton fabric with (14) ammonium cyanoethyl sulphate, (15) sodium cyanoethyl sulphate, (16) cyanoethyl thiosulphate, and (21) the reaction product of ethylene glycol bis-chloropropionate and sodium thiosulphate; the treatment of rayon fabric with (17) cyanoethyl thiosulphate and cyanoethyl sulphate; the treatment of corn starch with (18) ammonium cyanoethyl sulphate; the treatment of regenerated cellulose film with (19) ammonium cyanoethyl sulphate; and the treatment of polyvinyl alcohol with ammonium cyanoethyl sulphate.ALSO:The physical and chemical properties of fabrics made of polymeric materials containing active hydrogen atoms are improved by reacting under alkaline conditions with compounds having the structure X (CHR1-CHR2Y)n where X is an electronegative activating group attached to the remainder of the molecule by carbon to carbon bonds, R1 is hydrogen or an alkyl group containing 1 to 5 carbon atoms, R2 is hydrogen, an alkyl group containing 1 to 5 carbon atoms or X, Y is a polar residue derived from a reagent of weak nucleophilic character and n is the valence of X and has a value 1 or 2.  Specified polymeric materials are cellulose, proteins, polyvinyl alcohol, polyamines and polyamides. Specified activating groups are -COOR, -COR, -CN, -CONHR and -CSNHR where R is hydrogen or alkyl.  Specified polar residues are -OSO3M, -SSO3M and -OCOCH3 where M is alkali metal or ammonium, and -NC5H5, -N(CH3)2 CH2 C6H5, -NC9H7 and -NC6H8, many suitable being listed. The alkali may be provided by the phosphates, carbonates, hydroxides, alkoxides and silicates of alkali metals, and quaternary ammonium hydroxides.  Examples describe the treatment of cotton fabrics with (14) ammonium cyanoethyl sulphate, (15) sodium cyanoethyl sulphate, (16) cyanoethyl thiosulphate and (21) the reaction product of ethylene glycol bischloropropionate and sodium thiosulphate; and the treatment of rayon fabric with (17) cyanoethyl thiosulphate and cyanoethyl sulphate.