Patent GB-797175-A (GB)
Title: Improvements in addition products of polyamines
IPC: D06M13/372
Filed: 1956-08-02
Abstract: Amines H2N-R-NH2 are reacted with polyglycol derivatives XCH2CH2(OCH2CH2) m-O-Z-O-(CH2CH2O)nCH2CH2X to give water-water-soluble products which can be further reacted to yield cross-linked material (see Group IV (a)); R represents a chain of methylene groups (e.g. 2-10) which may be substituted or may be interrupted by N or O; Z is a hydrocarbon residue (e.g. ethylene) or may be -CO-A-CO-or -CO-NH-A-NH-CO-, where A is e.g. phenylene or hexamethylene; X is a halide or ester group, e.g. chloride, bromide, iodide, sulphate or sulphonate; m and n are 3-40.  The water-soluble products are obtained by using the amine in excess at a temperature of 10-150 DEG  C., in the presence or absence of a solvent.  Examples are given of the reaction between diethylene triamine and polyethylene glycol 600 dichloride in butanol.  Other specified amines are hexamethylene diamine, triethylene tetramine, tetraethylene pentamine, bis-(2-aminopropyl) - amine, bis - (3 - aminopropyl)-amine and di-(3-aminopropyl)-ether.  Starting materials.-Polyglycol dichlorides, di-methanesulphonates and di-toluene-p-sulphonates are made by reacting the polyglycols with thionyl chloride, methanesulphonyl chloride or toluene-p-sulphonyl chloride respectively, in the presence of pyridine or other base. Polyglycol disulphates are obtained as ammonium salts by reaction of the polyglycols with sulphamic acid.  The di-iodides are prepared from the dichlorides by treatment with sodium iodide in the absence of a solvent, or in a solvent in which sodium chloride is insoluble, e.g. acetone.  The polyglycol halides in which Z is -CO-A-CO- or -CO-NH-A-NH-CO- are made by reacting the glycol halohydrins with a dibasic acid (or anhydride) or di-isocyanate respectively.ALSO:The reaction products of amines H2N-R-NH2 with polyglycol derivatives XCH2CH2-(OCH2CH2) m-O-Z-O-(CH2CH2O)m\t CH2-CH2X are applied to textiles (particularly of hydrophobic or cellulose fibres) to give an antistatic finish that is fast to cleaning and laundering and to improve their receptivity for acid dyes.  In the formul  R represents a chain of methylene groups (e.g. 2-10) which may be substituted or may be interrupted by N or O; Z is a hydrocarbon residue (e.g. ethylene) or may be -CO-A-CO- or -CO-NH-A-NH-CO-, where A is, e.g., phenylene or hexamethylene; X is a halide or ester group, e.g. chloride, bromide, iodide, sulphate or sulphonate; m and n are 3-40. The products obtained by using an excess of the amine reactant are water-soluble but are cross-linked and rendered insoluble on the fabric by further heating, with or without further amounts of the polyglycol derivative.  Instead of preparing the reaction product first, the fabric may be impregnated with solutions of the amine and the polyglycol derivative and the whole reaction carried out on the fibre.  In the examples: (1) a bleached polyester taffeta fabric is padded with a solution of the product from diethylene triamine and polyethylene glycol 600 dichloride, and also polyethylene glycol 600 di-iodide, dried and cured; (2) a bleached nylon taffeta fabric is padded with a solution containing diethylene triamine and polyethylene glycol di-iodide, dried and cured; (3) the fabric of (1) is treated as in (2); (4) the process of (1) is repeated without the additional di-iodide; (5) the di-iodide of (1) is replaced by a mixture of the corresponding dichloride and sodium iodide, the latter acting also as curing catalyst.  The process may also be applied to fabrics of cellulose triacetate, polyacrylonitrile, and acrylonitrile-vinylchloride copolymers. Other suitable amines besides diethylene triamine are specified.ALSO:Products are obtained by reacting amines H2N-R-NH2\t with polyglycol derivatives <FORM:0797175/IV (a)/1> at temperatures between 10 DEG  and 150 DEG C.  When the reactants are taken in 1 : 1 proportions the products are polymeric and cross-linked, but by using excess of amine water-soluble compounds are obtained which can be cross-linked by reaction with further quantities of the polyglycol derivative.  In the formul  R represents a chain of methylene groups (e.g. 2-10) which may be substituted or may be interrupted by N or O; Z is an hydrocarbon residue (e.g. ethylene) or may be-CO-A-CO-or -CO-NH-A-NH-CO-, where A is e.g. phenylene or hexamethylene; X is an halide or ester group, e.g. chloride, bromide, iodide, sulphate or sulphonate; m and n are 3-40.  It is desirable to use conditions such that the reaction takes place only partially, e.g. to the extent of 70-95 per cent.  The halide ions in the product can be exchanged for nitrate by allowing it to stand with aqueous sodium nitrate.  The products may be used for treating textiles (see Group IV (c)) or as ion-exchange materials, especially when formed on an inert carrier such as silica gel or alumina. Examples show the reaction of diethylene triamine with polyethylene glycol 600 dichloride and di-iodide, the latter in the presence of silica gel to give an ion-exchange material. Other specified amines are hexamethylene diamine, triethylene tetramine, tetraethylene pentamine, bis - (2 - aminopropyl) - amine, bis-(3 - aminopropyl) - amine and di - (3 - aminopropyl)-ether.