Patent GB-461354-A (GB)
Title: Improvements in the manufacture and production of valuable polymerisation products
IPC: C08G73/04
Filed: 1935-07-15
Abstract: A catalyst promoting polymerization is caused to act on ethylene imine itself or on ethylene imine C-- or N-- substituted by a hydrocarbon radicle, such catalyst, when of acid character, being used only in such amount as is less than an equivalent proportion.  A preliminary polymerization under mild conditions may be followed by further polymerization under stronger conditions.  The substituted ethylene imines are obtainable by the process described in Specification 460,888.  Specified catalysts are acids, e.g. hydrochloric or sulphuric acid, acid salts, e.g. sodium bisulphate, surface-active substances, e.g. bleaching earths, active carbon or silica gel, especially such as retain small amounts of acid, chloramines, ethanolamine sulphuric acid ester, boron fluoride and peroxides, e.g. hydrogen peroxide.  In addition to the catalysts there may be present amines of high molecular weight, ethylene oxide or reaction products from ethylene oxide and organic compounds.  The products, which are colourless and viscous to waxy, are applicable as levelling agents in dyeing, as impregnating agents, as additions to rubber, for the preparation of mixed polymerization products from acrylic acid and its derivatives and for improving the fastness of dyeings to washing and to water.  They may be employed together with other substances, e.g. turkey red oil, aromatic or aliphatic sulphonic acids, polymerization products of ethylene oxide, reaction products of ethylene oxide with hydroxy, carboxy or amino compounds, solvents such as cyclohexanol, cyclohexanone, carbon tetrachloride, benzine, glycol ethers or alkylolamines and inorganic salts such as sodium phosphates or perborate.  In examples: (1) a 10 per cent aqueous solution of ethylene imine containing a small amount of b -chlorethylamine is allowed to stand for 12 hours at room temperature to obtain a colourless viscous mass soluble in water; anhydrous ethylene imine may be used instead of the aqueous solution; the polymerization may be accelerated by adding sodium bisulphate; the polymerization may also be effected upon material such as cellulose; (2) ethylene imine is stirred at 50--100 DEG  C. with addition of small amounts of 30 per cent aqueous hydrochloric acid; (3) an aqueous suspension of N-phenylethyleneimine is warmed while stirring and either leading in air or a very slow current of hydrogen chloride or adding a small amount of hydrochloric or sulphuric acid to obtain a white water-insoluble powder; (4) N-propylethylene-imine is stirred while leading in a very small amount of hydrogen chloride, raising the temperature to the boil and continuously adding more of the imine; (5) N-cyclohexylethylene imine or C-ethylethylene imine containing 0,1 to 0,5 per cent of b -chlorethylamine or its hydrochloride is heated to about 100 DEG  C. to obtain a water-insoluble wax-like mass; (6) ethylene imine or the polymerization product therefrom obtained as in (1) is heated under pressure with ethanolamine sulphuric acid ester to obtain a rubber-like product suitable for making shaped articles or artificial leather; (7) an aqueous suspension of N-phenylethylene imine containing 1 per cent or less of hydrogen peroxide is heated with stirring; an emulsion of the product may be used for treating natural fibres.  N-propylethylene imine is obtainable from N-propylethanolamine sulphuric acid ester by the process described in Specification 460,888.ALSO:Colourless viscous to waxy products obtainable by the action of catalysts promoting polymerization on ethylene imine itself or on ethylene-imine C- or N- substituted by a hydrocarbon radicle are employed as additions to rubber.