Patent GB-645138-A (GB)
Title: Improvements in or relating to the manufacture of textile treatment agents
IPC: D06M13/322
Filed: 1947-10-07
Abstract: Compounds of the formula <FORM:0645138/IV (b)/1> where R is a hydrocarbon radical, substituted or not, A is a tertiary amine residue, X is a monovalent anion, m is zero or an integer, n is an integer and the sum of m and n is greater than one, are made by treating a polycarbamate R(OCONH2)m+n with formaldehyde or a formaldehyde-yielding substance and an aliphatic or heterocyclic tertiary amine salt and/or an addition compound of an aliphatic or heterocyclic tertiary amine with an inorganic acid anhydride.  The reaction may occur in stages, the polycarbamate with formaldehyde or formaldehyde-yielding substance giving a polymethylol derivative which is then treated with the tertiary amine; a solvent or diluent may be present, e.g. free tertiary amine, chloroform or hydrocarbons. The quaternary group may also be introduced by stages, the mixture of polycarbamate and formaldehyde or formaldehyde-yielding substances (or the preformed poly-methylol derivative) being treated with a secondary amine and the resulting polytertiary amine then reacted with an alkylating agent.  The reaction with the secondary amine may be carried out in a solvent (e.g. dioxane, ethyl acetate, ethanol, methanol) and any water that separates is preferably removed before alkylating, which step may also be effected in a solvent or diluent such as acetone.  The polycarbamates used as starting materials may be obtained from compounds R(OH)m+n by (1) conversion into chloroformio esters with phosgene and treatment with ammonia, or (2) treatment with carbamyl chloride.  The compound R(OH)m+n may be ethylene glycol, octadecane-1 : 12-diol, glycerol, N : N1ethylene-bis-ricinoleamide, or mixtures such as castor oil and hydrogenated castor oil. Specified polycarbamates are ethylene-1 : 2-bis-carbamate, hexamethylene - bis - carbamate, octadecane - 1 : 12-diol-bis-carbamate, triolein-11 : 111 : 1111-triol - tris - carbamate, tristearin - 11 : 111 : 1111 - triol-tris-carbamate and terephthalyl-bis-(oxyethylene carbamate).  Specified tertiary amines are trimethylamine, triethylamine, N : N1-tetramethyl - ethylene diamine, methyldiethylamine, dimethylcyclohexylamine, diethylcyclohexylamine, N-methylpiperidine, pyridine, a -picoline and hexamethylene tetramine.  For two-stage formation of the quaternary salt, specified secondary amines are dimethylamine, diethylamine, piperidine and diethanolamine; the alkylating agent may be dimethyl sulphate, diethyl sulphate, benzyl chloride, stearamidomethyl chloride, methylene-bis-(N : N1-dichlormethyl-stearamide) or glycerol trichlormethyl ether.  The products of the invention are easily hydrolysed, one or more of the groups -OCONHCH2AX being converted into -OCONHCH2OH.  On heating above 100 DEG  C. they yield water-insoluble resins.  Examples show the preparation of typical substances according to the invention.  Specifications 615,838 and 622,967 are referred to.ALSO:Compounds of the formula <FORM:0645138/IV (c)/1> where R is a hydrocarbon radical, substituted or not, A is a tertiary amine residue, X is a monovalent anion, m is zero or an integer, n is an integer and the sum of m and n is greater than one, are applied to textile materials of animal or vegetable origin or of regenerated cellulose or cellulose esters or ethers to confer improved shrink-resistance, water-repellance and softness; they may also be applied in conjunction with crease-resisting agents in the same bath or separately.  The materials are impregnated with a solution or suspension of the agent, preferably below 60 DEG  C., dried and heated to about 150 DEG  C. to convert the compounds into insoluble resinous bodies.  In the case of cellulose and its derivatives, an acid-binding agent such as sodium acetate may be added to minimise tendering.  Other textile-finishing agents may be added, e.g. other water-repellent agents.  Examples show the application of typical compounds to confer improved shrink-resistance: (1) the condensation product of cetyl alcohol with 17 mols. of ethylene oxide is emulsified in water with tristearin-11 : 111 : 1111 - triol - tris - (carbamatomethylpyridinium) trichloride and hydrochloric acid. Wool flannel is padded with this dispersion, squeezed, dried at 50 DEG  C. and baked at 150 DEG  C.; (2) viscose staple is impregnated with an aqueous solution of ethylene glycol-1 : 2-bis-(carbamatomethylpyridinium) dichloride, squeezed, dried and baked at 150 DEG  C; (3) wool flannel is padded with an aqueous solution of trimethylene - bis - (carbamatomethylpyridinium) dichloride, squeezed, dried and baked; (4) viscose staple is padded with an aqueous solution of octadecane-1 : 12-diol-bis-(carbamatomethylpyridinium) dichloride, squeezed, dried and baked at 150 DEG  C.; (5) wool flannel is padded with an aqueous solution of tristearin-11 : 111 : 1111 - triol - tris - (carbamatomethyl-diethylammonium) tri - (methylsulphate), squeezed, dried and baked at 110 DEG  C; it is then washed with aqueous oleyl sodium sulphate and sulphuric acid and dried; (6) tristearin - 11 : 111 - dihydroxymethylcarbamate - 1111 - carbamatomethyl - diethyl-methyl ammonium methylsulphate is pasted with ethanol and diluted with warm water; a wool flannel is impregnated with this emulsion, dried and baked at 150 DEG  C.  Crease-resisting additives may be phenol-formaldehyde or urea-formaldehyde resins. Water-repellent additives may be methylolstearamide, methylenedistearamide, methylol - octadecylcarbamate, methylene distearate, methylol and alkoxymethyl derivatives of polycarbamates, polyvalent metal salts such as aluminium acetate, paraffin wax, montan wax, carnauba wax or beeswax.  Specifications 615,838, [Group IV (b)], and 622,697 are referred to.