Improved shaped articles made from fibre forming synthetic polyesters

摘要

The dye receptivity of oriented synthetic polyester filamentary materials, especially polyethylene terephthalate, is enhanced by treatment under anhydrous conditions and in the absence of any hydroxylating agent with a covalent compound which is capable of penetrating the shaped and oriented polyester and which can be changed in situ into an acid or a base by the subsequent application of a hydroxylating agent (treatment with boron trifluoride and vapours of sulphuric acid, sulphur trioxide and chlorsulphonic acid being specifically excluded), until up to 5% by weight of the covalent compound is incorporated into the polyester. Preferably, the covalent compound is capable of reacting with water within five minutes at room temperature. The covalent compound may be used in its liquid or vapour phase, diluted with a diluent, or as a molecular complex, e.g. with dioxane, trimethylamine or pyridine. Treatment may be effected between room temperature and the decomposition temperature of the shaped polyester. Specified compounds include phosphorus containing compounds defined by:- or by where X and Y are any of Cl, NCO, NCS, alkoxy or aryloxy and Z is Cl, NCO or NCS, for example chlorides of phosphorus oxyacids, e.g. phosphorus oxychloride, alkyl and aryl phosphoryl chlorides, for example O-O-dialkyl and O-O-diaryl phosphoromonochloridates and O-alkyl and O-aryl phosphorodichloridates (e.g. diphenyl phosphorochloridate, diethyl phosphorochloridate, phenyl-phosphorodichloridate, and methyl phosphoric acid dichloride) and phosphorus isocyanates, e.g. phosphorus triisocyanate and phosphorus oxyisocyanate. Other suitable compounds include chloracetyl chloride, sulphonyl chloride, a mixture of propyl sulphonyl chloride and propane disulphonyl chloride, methionic acid dichloride, alkane monosulphonyl chlorides, e.g. methyl sulphonyl chloride, alkane sulphonic anhydrides, alkane polysulphonyl chlorides, silicon tetrachloride, tin tetrachloride, ferric chloride, aluminium chloride and zinc chloride. The shaped polyesters may be exposed to ammonia, an amine, for example mono-, di-, and trisubstituted amines, e.g. dimethylamine, or ethylene diamine, or to a heterocyclic base, e.g. pyridine, before, during, or after the treatment. Amines or heterocyclic bases may be applied in the liquid or vapour phase, with or without a diluent. The treated shaped polyesters may be washed with water prior to dyeing. In a preferred method filamentary materials are continuously fed through a contacting zone held at or near the boiling point of the covalent compound, excess liquid picked up in the zone being stripped by a current of hot air, washed with water and dried. Desirably, the filamentary materials pass through the vapour of the covalent compound which is held at or near the boil under reflux conditions and do not dip below the level of the boiling compound.ALSO:The receptivity to acid, basic and disperse dyes of oriented synthetic polyester filamentary materials, especially polyethylene terephthalate, is enhanced by treatment under anhydrous conditions and in the absence of any hydroxylating agent with a covalent compound which is capable of penetrating the shaped and oriented polyester and which can be changed in situ into an acid or a base by the subsequent application of a hydroxylating agent (treatment with boron trifluoride and with vapours of sulphuric acid, sulphur trioxide and chlorosulphonic acid being specifically excluded), until up to 5% by weight of the covalent compound is incorporated into the polyester. Preferably, the covalent compound is capable of reacting with water within five minutes at room temperature. The covalent compound may be used in its liquid or vapour phase, diluted with a diluent, or as a molecular complex, e.g. with dioxane, trimethylamine or pyridine. Treatment may be effected between room temperature and the decomposition temperature of the shaped polyester. Specified compounds include phosphoruscontaining compounds defined by:- where X and Y are any of Cl, NCO, NCS, alkoxy or aryloxy and Z is Cl, NCO or NCS, for example chlorides of phosphorus oxyacids, e.g. phosphorus oxychloride, alkyl and aryl phosphoryl chlorides, for example, O-O-dialkyl and O-O-diaryl phosphoromonochloridates and O-alkyl and O-aryl phosphorodichloridates (e.g. diphenyl phosphorochloridate, diethyl phosphorochloridate, phenyl-phosphorodichloridate, and methyl phosphoric acid dichloride) and phosphorus isocyanates, e.g. phosphorus triisocyanate and phosphorus oxyisocyanate. Other suitable compounds include chloracetyl chloride, sulphonyl chloride, a mixture of propyl sulphonyl chloride and propane disulphonyl chloride, methionic acid dichloride, alkane monosulphonyl chlorides, e.g. methyl sulphonyl chloride, alkane sulphonic anhydrides, alkane polysulphonyl chlorides, silicon tetrachloride, tin tetrachloride, ferric chloride, aluminium chloride and zinc chloride. The shaped polyesters may be exposed to ammonia, an amine, for example mono-, di-, and trisubstituted amines, e.g. dimethylamine, or ethylene diamine, or to a heterocyclic base, e.g. pyridine, before, during, or after the treatment. Amines or heterocyclic bases may be applied in the liquid or vapour phase, with or without a diluent. The treated shaped polyesters may be washed with water prior to dyeing. In a preferred method filamentary materials are continuously fed through a contacting zone held at or near the boiling point of the covalent compound, excess liquid picked up in the zone being stripped by a current of hot air, washed with water and dried. Desirably, the filamentary materials pass through the vapour of the covalent compound which is held at or near the boil under reflux conditions and do not dip below the level of the boiling compound. In examples, the receptivity of polyethylene terephthalate filamentary materials to these types of dyestuff is enhanced by treatment as follows:- (a) disperse dyes:- (1) phosphorus oxychloride and pyridine, followed by soaking in aqueous ammonia, (2) phosphorus oxychloride, (3) diphenyl phosphorochloridate, (4) diethyl phosphorochloridate, (5) phenyl phosphorodichloridate, (6) phosphorus triisocyanate, (7) methionic acid dichloride, (11) a mixture of propyl sulphonyl chloride and propane disulphonyl chloride made by passing chlorine, sulphur dioxide and propane into boiling carbon tetrachloride while irradicating with ultra-violet light, (13) methyl phosphoric acid dichloride, (b) basic dyes:- (8), (12) methionic acid dichloride, (10) methyl sulphonyl chloride, (13) methyl phosphoric acid dichloride, (c) acid dyes:- (14) phosphorus oxychloride followed by ammonia, (15) sulphonyl chloride followed by ethylene diamine.