GB613817A - Improvements in the production or treatment of cellulose derivative or synthetic resin materials - Google Patents

Abstract

Hydrophobe cellulose derivative or synthetic resin fibres, films, and like articles, of modified dyeing affinities, are obtained by incorporating in them or in the solutions or compositions from which they are formed a proportion of a polyamine of a molecular weight less than 1000 and containing at least three basic amino groups, at least one of which is attached only to aliphatic carbon. The amount of polyamine incorporated may be such as to give a basic nitrogen content of at least 0.02 per cent. The treatment also improves the resistance to burnt gas fumes of colourations which are loose to such fumes. A large number of polyamines is specified, including diethylene triamine, triethylene tetramine, 1.13 - diamino - 7 - aza - tridecane, 1.16-diamino-3.7.10.14-tetra-aza-hexadecane, 1.30 - diamino - 3.14.17.28 - tetra - aza - triacontane, C.C.C.-tri-g -aminopropyl-methylamine, 1.16-di-(benzylamino)-7.10-diaza-hexadecane, and N.N1-bis-g -aminopropyl-p-phenylene diamine. The polyamines may contain substituents other than hydrocarbon radicals, e.g. compounds obtained by reacting polyamines with acrylonitrile. Partially acidylated amines may be used, e.g. mono-acetyl triethylene tetramine, or the product obtained by reaction of 2 moles. of diethylene triamine with 1 mole. of a dicarboxylic acid or ester, e.g. ethyl oxalate. The treated materials may be dyed with acid wool dyes or amino-anthraquinone dyes. The polyamines used may be in a pure or crude state, e.g. a crude amine obtained by reacting 1 mole. of ethylene dibromide with 2 moles. of hexamethylene diamine, or 1 mole. of 4.41-bis-o -brom-methyl diphenyl or 1.4-bis-o -brom-methyl benzene with 2 moles. of hexamethylene diamine. The cellulose acetate or other materials may be impregnated with an aqueous or organic solution or dispersion of the polyamine at room or raised temperature. This may be followed by a simple drying or by a heat treatment at 100-140 DEG C. The fastness of the polyamine on the materials may be improved by an after-treatment with formaldehyde, glyoxal, ethyl oxalate, a di- or polyisocyanate or isothiocyanate, or an adduct formed from 1 mole. of hexamethylene diisocyanate and 2 moles. of acetoacetic ester. The process may be applied to fibres, films, or other materials made of cellulose esters or ethers, vinyl polymers such as vinyl chloridevinyl acetate copolymers, acrylonitrile polymers, or polyamides (nylons), e.g. a nylon from hexamethylene diamine and adipic acid. Animalized fibres of the nylon type may be obtained by spinning from a melt containing a poly-tertiary amine. A suitable amine for this purpose can be obtained by condensation of 2 moles. of N-diethylamino ethyl chloride with N.N1-dimethyl hexamethylene diamine. In an example, a crude polyamine is obtained by refluxing 2 moles. of hexamethylene diamine with 1 mole. of ethylene dibromide in ethanol, taking up the product in ethanol and water, adding caustic potash in ethanol, filtering off the potassium bromide, and evaporating the solution to dryness. A 5 per cent aqueous solution of the product is used for impregnating cellulose acetate fabric, which is subsequently dyed with Azo Geranine 2GS, or with 1.4-dimethylamino-anthraquinone. In another example, 1.16-diamino-7.10-diaza-hexadecane is incorporated in a cellulose acetate solution in acetone. The solution is spun into fibres which are then dyed with Solway Ultra Blue BS or Azo Geranine 2 GS. The fibres may be treated with formaldehyde to improve the fastness of the polyamine. Specifications 581,153, 586,549, 597,253, 610,311, 613,807, [Group IV (b)], and 613,818 are referred to.ALSO:Polyamines of a molecular weight less than 1000 and containing at least three basic amino groups, at least one of which is attached only to aliphatic carbon are used for treating synthetic resins and cellulose derivatives and include the following: 1.12-diamino-3.10-diazadodecane, prepared by condensing 1.6-dibromohexane with a large excess of ethylene diamine, C.C.C.-tri-g -aminopropyl-methylamine prepared by hydrogenation of tri-b -cyanoethyl-nitromethane and N.N1-bis-g -aminopropyl-p-phenylene diamine prepared by addition of 2 molecules of acrylonitrile to p-phenylene diamine and hydrogenation of the product. The polyamines may contain substituents other than hydrocarbon radicals, e.g. compounds obtained by reacting polyamines with acrylonitrile. Partially acidylated amines may be used, e.g. the product obtained by reaction of 2 moles. of diethylenetriamine with 1 mole. of a dicarboxylic acid ester, e.g. ethyl oxalate. Crude amines obtained by reacting 1 mole. of ethylenedibromide with 2 moles. of hexamethylene diamine and 1 mole. of 4.41-bis-o -brom-methyl diphenyl or 1.4-bis-o -brom-methyl benzene with 2 moles. of hexamethylene diamine are mentioned. A suitable amine for incorporation in a nylon melt spinning composition can be obtained by condensation of 2 moles. of N-diethylaminoethylchloride with N.N1-dimethylhexamethylenediamine. In an example, a crude polyamine is obtained by refluxing 2 moles. of hexamethylenediamine with 1 mole. of ethylenedibromide in ethanol, taking up the product in ethanol and water, adding caustic potash in ethanol, filtering off the potassium bromide, and evaporating the solution to dryness. Specifications 581,153, 586,549, 597,253, 610,311, 613,807 and 613,818 are referred to.ALSO:Hydrophobe cellulose derivative or synthetic resin fibres, films, and like articles, of modified dyeing affinities, are obtained by incorporating in them or in the solutions or compositions from which they are formed a proportion of a polyamine of a molecular weight less than 1000 and containing at least three basic amino groups, at least one of which is attached only to aliphatic carbon. The amount of polyamine incorporated may be such as to give a basic nitrogen content of at least 0.02 per cent. The treatment, applied before or after dyeing, also improves the resistance to burnt gas fumes of colourations which are loose to such fumes. A large number of polyamines is specified, including diethylene triamine, triethylene tetramine, 1.13-diamino-7 - aza - tridecane, 1.16 - diamino - 3.7.10.14 - tetra - aza - hexadecane, 1.30 - diamino - 3.14.17.28 - tetra - aza - triacontane, C.C.C.tri - g - aminopropyl - methylamine, 1.16 - di - (benzylamino) - 7.10 - diaza - hexadecane, and N.N1-bis - g - aminopropyl - p - phenylene diamine. The polyamines may contain substituents other than hydrocarbon radicals, e.g. compounds obtained by reacting polyamines with acrylonitrile. Partially acidylated amines may be used, e.g. mono-acetyl triethylene tetramine, or the product obtained by reaction of 2 moles of diethylene triamine with 1 mole of a dicarboxylic acid ester, e.g. ethyl oxalate. The treated materials may be dyed with acid wool dyes or amino-anthraquinone dyes. The polyamines used may be in a pure or crude state, e.g. a crude amine obtained by reacting 1 mole of ethylene dibromide with 2 moles of hexamethylene diamine, or 1 mole of 4.41-bis-o -brom - methyl diphenyl or 1.4 - bis - o - brommethyl benzene with 2 moles of hexamethylene diamine. The cellulose acetate or other materials may be impregnated with an aqueous or organic solution or dispersion of the polyamine at room or raised temperature. This may be followed by a simple drying or by a heat treatment at 100-140 DEG C. Acid wool dyes and dispersed water-insoluble dyes may be incorporated in the treated materials by substantive absorption, by padding, or by printing methods. Acid wool dyes may be applied from organic media, e.g. aqueous ethanol, having a swelling action on the materials. The fastness of the polyamine on the materials may be improved by an aftertreatment with formaldehyde, glyoxal, ethyl oxalate, a di- or polyisocyanate or isothiocyanate, or an adduct formed from 1 mole of hexamethylene diisocyanate and 2 moles of aceto-acetic ester. The fibres, films, or other materials may be made of cellulose esters or ethers, vinyl polymers such as vinyl chloride-vinyl acetate copolymers, acrylonitrile polymers, or polyamides. In an example, a crude polyamine is obtained by refluxing 2 moles of hexamethylene diamine with 1 mole of ethylene dibromide in ethanol, taking up the product in ethanol and water, adding caustic potash in ethanol, filtering off the potassium bromide, and evaporating the solution to dryness. A 5 per cent aqueous solution of the product is used for impregnating cellulose acetate fabric, which is subsequently dyed with Azo Geranine 2GS, or with 1.4-dimethylamino-anthraquinone. The fibres may be treated with formaldehyde to improve the fastness of the polyamine. Specifications 581,153, 586,549, 597,253; 610,311, 613,807, [both in Group IV (b)], and 613,818 are referred to.