Patent GB-489668-A (GB)
Title: Improvements in or relating to amino-derivatives of cellulose
IPC: F01L7/04
Filed: 1937-02-01
Abstract: Amino-alkyl cellulose ethers obtained by reacting a secondary amine with an aryl sulphonate of a hydroxy alkyl cellulose are employed as dispersing, emulsifying, or fixing agents for oils, waxes, pigments, or other materials.  The dispersions may contain mould or mildew inhibitors, wetting agents, anti-oxidants, plasticizers, adhesives, insecticides, film-formers, or thickeners.  They may be applied to metals, wood, stone, plaster, paper, asbestos, felt, cotton, wool, or regenerated cellulose materials.  Coating compositions which are aqueous dispersions of a wax such as paraffin wax and a fixing agent such as aluminium acetate, having as emulsifying agent a salt of an amino-alkyl cellulose ether, may be used for sizing and waterproofing textiles, and for fixing acid dyes to paper.  With or without a fixing agent the compositions may be used for sizing paper. Aqueous dispersions of titanium oxide or other solid, including mildew inhibitors such as salicylanilide, with a wetting agent, a softener, and as dispersing agent, b -aminoethoxyethyl cellulose acetate may be used for sizing and delustring fabrics, and fixing water-insoluble solids thereto.  Dibutylaminopropyl or ethyl cellulose, and N-dihydroxyethylamino-ethyl cellulose, are also specified.  The cellulose ether may contain methyl, ethyl, propyl, butyl, dodecyl, or benzyl radicles.  In its formation there may be used alkyl hydroxy-alkyl, cycloalkyl, aryl, or aralkyl secondary amines.  The cellulose ether may be used in the form of a salt with an acid such as acetic, formic, propionic, butyric, lactic, benzoic, phosphoric, sulphuric, or hydrochloric acid.  The Specification as open to inspection under Sect. 91 comprises also the use of aminoalkyl celluloses produced by other methods, e.g. by treating cellulose or a cellulose derivative with alkali metal in presence of liquid ammonia, and then treating the cellulosate with a monohalogen amine or salt thereof.  This subject-matter does not appear in the Specification as accepted.ALSO:Amino-alkyl cellulose compounds soluble in dilute acids are obtained by reacting a secondary amine with an aryl sulphonate of a hydroxy alkyl cellulose in solution in an organic solvent, the aryl sulphonate having been obtained by reacting an aromatic sulphonyl halide with a cellulose derivative containing at least one molecular proportion of a hydroxy alkyl substituent per glucose unit.  The hydroxy alkyl cellulose may contain methyl, ethyl, propyl, butyl, dodecyl, or benzyl radicles.  In an example, glycol cellulose is obtained by treatment of alkali cellulose with ethylene oxide until a water-soluble product is obtained.  The product is dissolved in pyridine and heated with p-toluene sulphonyl chloride.  The aryl sulphonate obtained is dissolved in benzyl alcohol and heated with dibutylamine and the product is precipitated by pouring the solution into ether.  Dibutylamino - ethyl cellulose soluble in aqueous acetic acid is obtained.  In another example, dibutylamino-propyl cellulose is obtained by using b -hydroxypropyl cellulose instead of glycol cellulose. Benzene sulphonyl chloride, or b -naphthalene sulphonyl chloride may be used as sulphonating agent.  Alkyl, hydroxy-alkyl, cycloalkyl, aryl or aralkyl secondary amines may be used.  The products form addition salts with acids, including the acetate, formate, propionate, butyrate, lactate, benzoate, phosphate, sulphate, and hydrochloride.  The products may be formed into filaments, bristles, and self-supporting films.  Films cast from a N-dihydroxyethylaminoethyl cellulose prepared from diethanolamine and glycol cellulose p-toluene sulphonate are clear, tough, and pliable. The products may be employed in coating compositions which are essentially solutions of the products in aqueous acids or organic solvents such as methanol, dioxane, or chloroform, or in coating compositions in which the amino-alkyl cellulose is present as a dispersing, emulsifying, or fixing agent for an oil, wax, or pigment. The coating compositions may contain mould or mildew inhibitors, wetting agents, antioxidants, plasticizers, adhesives, insecticides, film-formers, or thickeners.  They may be applied to metals, wood, stone, brick, plaster, paper, paper pulp, asbestos, felt, cotton, wool, or regenerated cellulose.  The coated materials may be caused to adhere to themselves or to one another by application of heat. Solutions of the aminoalkyl celluloses in acids may be used as sizes for rayon tyre cord to improve its adhesion to rubber, as sizes for regenerated cellulose sheets to improve the anchorage thereto of printing inks and lacquers, and as waterproof adhesive in the manufacture of veneers.  Coating compositions which are aqueous emulsions of a wax such as paraffin and a fixing agent such as aluminium acetate, having as emulsifying agent a salt of one of the amino-alkyl celluloses, may be used for sizing and waterproofing textiles and for fixing acid dyes to paper.  With or without the fixing agent these compositions may be used for sizing paper, especially as beater size in the production of chalk-filled paper. Aqueous dispersions of titanium oxide or other solid, including mildew inhibitors such as salicylanilide, with a wetting agent, a softener, and as dispersing agent, b -aminoethoxyethyl cellulose acetate or other aminoalkyl cellulose salt made according to the process described, may be used for sizing and delustring fabrics and fixing the water-insoluble solid thereto.  Films made from solutions of the amino - alkyl celluloses are rendered insoluble by a short baking at elevated temperatures.  The Specification as open to inspection under Sect. 91 comprises also the production of amino-alkyl celluloses by treating cellulose or a cellulose derivative containing hydroxyl groups with an alkali metal in presence of liquid ammonia, and treating the alkali metal cellulosate with a monohalogen amine or salt thereof.  In examples, cellulose or glycol cellulose is mixed with dry liquid ammonia and sodium, and the solution or mixture is then treated with bromo-propyl-dimethyl amine hydrobromide or bromo-ethyl-amine hydrobromide.  This subject-matter does not appear in the Specification as accepted.