Patent GB-473266-A (GB)
Title: Process for saponifying and alkylating shaped materials made from cellulose esters or artificial resins
IPC: C08B13/00
Filed: 1936-01-08
Abstract: Shaped materials of cellulose esters or highly polymeric artificial resins containing saponifiable groups, are subjected to treatment with an alkylene oxide or analogue thereof in the presence of a substance of alkaline reaction, the conditions of treatment being such that the materials retain their structure. The materials undergo alkylation and saponification during the treatment.  Ethylene oxide, propylene, butylene cyclohexene, phenoxypropene, and morpholino propene oxide or butadiene dioxide, epichlorhydrin, propylene sulphide, ethylene imine, butylethylene imine, or cyclohexyl ethylene imine, are specified alkylene oxides or analogues.  The materials treated may be in the form of suspensions of flocks or fibres, including cotton linters acetylated with retention of the fibrous structure, threads, bristles, sheets, films, spun goods, or fabrics. Materials of cellulose acetate, formate, acetate-formate, or other mixed ester or ether-ester of cellulose, or polyvinyl esters, poly-acid esters, lactones, amides, or imides, may be subjected to the treatment.  The treatment changes the dyeing properties of the materials; affinity for water-insoluble acetate dyestuffs, acid dyes, and substantive dyes may be increased.  Treatment is preferably conducted in presence of moisture at raised temperature.  Swelling agents may be present.  Instead of using a free base or basic salt, a neutral salt which reacts with alkylene oxides with liberation of a base, may be used.  Chlorides, and thiocyanates are specified.  The use of a separate alkali may be dispensed with if the alkylene oxide or imide is itself of basic character.  The treatment of cellulose ester or artificial resin material containing free hydroxyl groups with alkylene oxides containing basic nitrogen is excluded.  Gaseous reagents may be used and treatment carried out under pressure either constant or oscillating.  Treatment may be conducted with the alkylene oxide in liquid or dissolved form.  Water-insoluble solvents containing water dispersed with the aid of lecithin, oleyl-polyglycol, salts of naphthene sulphonic acids or other dispersing agent may be used.  The basic substances may be incorporated in the cellulose esters or polyvinyl esters before or subsequently to the shaping operation.  Methylamine, N - butyl-amine, cyclohexylamine, morpholine, ethylene diamine, tetramethyl ethylene diamine, 1.3-dicyclohexylamino isopropanol, oxyethyl morpholine, dodecyl trimethyl ammonium chloride, guanidine sulphocyanide, guanidine lactate, triethanolamine acetate, isohexyl guanidine acetate, 4-dimethyl aminomethyl-1-oxybenzene, potassium sulphocyanide, potassium acetate, calcium chloride, calcium saccharate, sodium iodide, ammonium chloride, or magnesium perchlorate are specified alkaline substances or substances giving alkaline substances by reaction with the alkylene oxides.  Halogen alkylamines, mercaptans, and sulphides such as iso-thio-urea ethers, benzyl mercaptan, chloroethyl methyl sulphide, and chlor-oxypropyl methyl sulphide may also be used.  When the basic substance is incorporated in a solution of the cellulose ester or synthetic resin before the shaping operation it may be dissolved, finely dispersed, or emulsified therein.  The proportion of alkylene oxide required may be reduced if alcohols are present.  Primary and secondary amines may be present in the form of easily split condensation products with formaldehyde, chloral, acetyl acetone or acetoacetic ester.  If desired, the fibres or like materials may be first treated with the alkylene oxide, or this reagent may be incorporated in the solutions before shaping, and then the materials are treated with the basic substance, e.g. ammonia, or strong organic bases such as cyclohexylamine or b -amino ethyl aniline.  After the treatment with basic substance, the materials may be further treated with alkylene oxides.  The process is applicable to mixtures of wool and cellulose acetate fibres, and dyeing of the wool with acid dyes is facilitated. The alkylation may be conducted in the presence of other alkylating agents together with the alkylene oxides, or treatment with other alkylating agents may be carried out prior to treatment with alkylene oxides.  In an example, cellulose tri-acetate artificial fibres are immersed in a solution of cyclohexylamine, hydroextracted in a cloth and dried.  The material is then heated in a closed vessel with propylene oxide vapour.  The treated material may easily be dyed with the dye from diazotized 6-bromo-2 : 4-dinitro-1-aminobenzene and 1-butyl - oxethylamino - 3 - methyl - 6 - methoxybenzene.  In another example, cellulose acetate solution containing cyclohexylimino-crotonic acid-ethyl ester is spun to form fibres which are stapled and then heated with propylene oxide.  Cellulose acetate solution containing a sulphocyanide is spun to form artificial silk which is then heated with ethylene oxide.  The material may be dyed with water-soluble dyestuffs.  Cellulose acetate yarns made from solutions containing calcium chloride are treated with propylene oxide vapour mixed with air.  The treated material strongly absorbs acid dyestuffs, and the affinity for substantive dyes is increased.  Cellulose acetate filaments are swollen in acetic acid solution, centrifuged, suspended above n-butylamine, and then heated with propylene or ethylene oxide.  Cellulose acetate artificial silk is treated with an aqueous solution of chloro-phenoxypropene oxide, centrifuged, and suspended in a humid atmosphere containing ethylene diamine vapour.  Cellulose acetate solution containing ethylene-bis-imino-crotonic acid-ethyl ester is spun to form filaments which are then treated with propylene oxide vapour.  Cellulose triacetate fibres are immersed in cyclohexylamine solution, centrifuged, dried, and suspended in presence of saturated common salt solution above a solution of 1.2-propylene sulphide and methanol.  The yellow tint is removed by treatment with an acid dispersion of p-toluene sulpho-dichloramide.  Cellulose acetate material is treated with p-chlorphenoxypropene oxide dispersed with oleylpoly-glycol, Glauber's salt being added to the bath. Cyclo-hexylamine is then added.  The material may be dyed with water-soluble dyes such as Orange II, dyes such as Pyramine Orange 3G, or many indigosol dyes.  Cellulose acetate satin is heated with ethylene imine vapour mixed with humid air.  The material may be dyed with acid dyes such as Quinoline Yellow N extra.  Cellulose acetate material containing polyvinyl acetate is impregnated with cyclohexylamine and then heated with propylene oxide and methanol. Cellulose acetate solution containing tetrachlor-oxypropyl ammonium chloride is spun to form filaments which are heated with ethylene imine in a humid atmosphere.  The material may be dyed with water-soluble dyes with acid groups such as Orange II, Metanil Yellow, and Alizarin cyanine green G extra.  Specifications 463,043, 465,105, and 467,173 are referred to.