Patent GB-828903-A (GB)
Title: Process for the improvement of shaped articles composed of high-melting polymers containing ester groups in the chain
IPC: D06M13/405
Filed: 1956-02-21
Abstract: Two-dimensional shaped structures composed of hydrophobic fibre-forming linear polyesters are partially hydrolysed with an aqueous solution of an inorganic alkaline splitting agent in the presence of a promoter, as defined below, the promoter being present in an amount not in itself sufficient to bring about the desired hydrolysis.  Specified polyesters are polyethylene terephthalate, the polycondensate of 4-[o -hydroxy butoxy] benzoic acid, the polycondensates of aminoethanol and sebacic acid and of hexamethylene diamine, hexamethylene glycol and sebacic acid, polyurethanes, e.g. those derived from hexamethylene di-isocyanate and hexamethylene glycol or from butanediol-1 : 4 bis chloroformate and hexamethylene diamine, and the polyester from hydroxypivalic acid.  Specified splitting agents are sodium and potassium hydroxide and sodium sulphide.  The promoters are quaternary ammonium hydroxides or their salts which are stable in aqueous solution, organic phosphonium or sulphonium compounds, and also guanides and biguanides, the basicity of which equals or approaches the basicity of the quaternary bases. Specified promoters include N-methyl-N-dodecyl - N - dihydroxyethyl ammonium hydroxide, N - trimethyl - N - (4 - isopropylbenzyl) ammonium hydroxide, N-trimethyl-N-[xenyl - 1 - methyl] ammonium hydroxide, N-trimethyl - N - p - phenoxy butyl ammonium hydroxide, N - dimethyl - N - octadecyl - N - hydroxyethyl ammonium hydroxide, mixed N-dimethyl-N-palm kernel fatty alkyl N-benzyl ammonium hydroxides, mixed palm kernel fatty acid amides of the general formula <FORM:0828903/IV(c)/1> where RCO- represents the palm kernel fatty acid radical R1 and R2 represent two alkyl radicals or a cycloalkyl radical, R3 represents a b -hydroxyethyl radical and x is an integer greater than 1, dodecyl guanidine, N-dodecyl-N1-N11 ethylene guanidine, pentadecyl biguanide and pentadecyl-dimethyl sulphonium hydroxide.  Fibres or fabrics composed wholly of linear polyesters or partly of cellulosic or polyamide fibres may be passed through or printed or padded with a solution of alkaline splitting agent and promoter, optionally in the presence of a thickening agent, e.g. methyl cellulose, hydroxyethyl cellulose or polyvinyl alcohol, or a swelling agent, e.g. diethylene glycol, diphenyl - 1 - polyglycol ether, N-methyl - N - hydroxyethyl - N - [xenylmethyl]-amine, N-methyl butyrolactam, phenyl methyl carbinol or benzyl alcohol.  Alternatively, promoter bases or their salts, e.g. of p-methoxybenzoic or salicylic acid, may first be applied to the polyester goods by padding, printing or spraying with solutions in organic solvents and the promoters fixed by steaming or dry heating, whereafter the alkaline splitting agent is caused to act upon the goods either in a bath or as a padding.  Special effects can be achieved by application to the goods of a resist, e.g. a film-forming polyamide containing basic groups, or a pigment, e.g. a zinc sulphide dispersion.  The treatment may result in an improved "handle," a lesser tendency to "pill," crease proofing, greater tensile strength and development of a roughened surface.  In one example, a polyethylene terephthalate fabric is printed with a paste containing sodium hydroxide, hydroxyethyl cellulose, dodecyl-trihydroxyethylammonium glycollate and trimethyl-[xenyl-methyl] ammonium glycollate; steaming under pressure at 140 DEG  C. then produces a dull effect on the etched portion, which may be subsequently dyed with Alizarine Direct Blue A and other water-soluble acetate rayon dyestuffs.  German Specification 912,863 is referred to.ALSO:Two-dimensional shaped structures composed of hydrophobic fibre-forming polyesters are partially hydrolysed with an aqueous solution of an inorganic alkaline splitting agent in the presence of a promoter, as defined below, the promoter being present in an amount not in itself sufficient to bring about the desired hydrolysis.  The polyesters which may be treated are those containing ester groups within the main polymeric chain, as opposed to cellulose or polyacrylic esters.  Specified polyesters are polyethylene terephthalate, the polycondensate of 4-(o -hydroxy-butoxy)-benzoic acid, the polycondensates of aminoethanol and sebacic acid and of hexamethylene diamine, hexamethylene glycol and sebacic acid, polyurethanes, e.g. those derived from hexamethylene diisocyanate and hexamethylene glycol or from butanediol - 1 : 4 - bis-chloroformate and hexamethylene diamine, and the polyester from hydroxypivalic acid.  The promoters are quaternary ammonium hydroxides or their salts which are stable in aqueous solution, organic sulphonium and phosphonium compounds and also guanides and biguanides, the basicity of which equals or approaches the basicity of the quaternary bases. Specified promoters include N-methyl-N-dodecyl-N-dihydroxy-ethyl ammonium hydroxide, N-trimethyl - N - (4 - isopropylbenzyl) - ammonium hydroxide, N - trimethyl - N - (xenyl - 1 - methyl)-ammonium hydroxide, N-trimethyl-N-p-phenoxybenzyl ammonium hydroxide, N-di-methyl - N - octadecyl - N - hydroxyethyl ammonium hydroxide, mixed N-dimethyl-N-palm kernel fatty alkyl N-benzyl ammonium hydroxides, mixed palm kernel fatty acid amides of the general formula <FORM:0828903/IV (a)/1> where RCO- represents the palm kernel fatty acid radical, R1 and R2 represent two alkyl radicals or a cycloalkyl radical, R3 represents a b -hydroxyethyl radical and x is an integer greater than 1, dodecyl guanidine, N-dodecyl-N1:N11-ethylene guanidine, pentadecyl biguanide and pentadecyl-dimethyl sulphonium hydroxide. p  Specified splitting agents are sodium and potassium hydroxides and sodium sulphide.  The process may be carried out by treating fibres or fabrics composed wholly of linear polyesters, or of blends of linear polyesters with cellulosic fibres or polyamide fibres, in a bath by passage therethrough or by conventional printing or padding in the presence of thickening agents, e.g. methyl cellulose, hydroxyethyl cellulose or polyvinyl alcohol, and, if desired, in the presence of swelling agents, e.g. diethylene glycol, diphenyl-1-polyglycol ether, N-methyl-N - hydroxyethyl - N - (xenylmethyl) - amine, N-methyl butyrolactam, phenyl methyl carbinol or benzyl alcohol.  Promoter bases or their salts, e.g. of p-methoxybenzoic or salicylic acid, may be first applied to the materials by padding, printing or spraying with solutions in organic solvents and the promoters may be fixed by steaming or dry heating.  Finally the alkaline splitting agent may be caused to act upon the materials either in a bath or as a padding solution.  Special hydrolysing effects can be achieved by application to the materials of a resist, e.g. a film-forming polyamide containing basic groups, or a pigment, e.g. a zinc sulphide dispersion.  Examples are given.  German Specification 912,863 is referred to.