Patent GB-390518-A (GB)
Title: Manufacture of new cellulosic materials and artificial materials therefrom
IPC: C08B15/06
Filed: 1931-07-04
Abstract: Cellulose xanthate is contacted with an organic compound containing at least one nitrogen atom attached to carbon, at least one oxygen atom attached to carbon, and at least one halogen atom attached to a carbon atom.  Each of the three different elements may be contained more than once in the molecule of the organic compound, but in all cases there must be within the molecule at least one arrangement of these different elements, in which not more than two of them are attached to the same carbon atom.  The organic compound may contain an amino-group, a hydroxyl-group and a halogen atom, and may be a halogen derivative of an amino-propanol.  It may contain sulphur, selenium, or tellurium, in addition to the characteristic elements. If desired the cellulose xanthate may be treated with substances which react to produce a compound of the type specified.  The product of the cellulose xanthate and the organic compound is converted into artificial threads, films, coatings, dressings, sizings, book p cloth, artificial leather, adhesives, cements, plates, plastic compositions, or thickening agents for pigments, by bringing a solution or paste of the product into the appropriate shape or form and acting thereon with a coagulating agent and if desired with a plasticizing agent.  The reaction between viscose and the reagent may be carried out at room temperature or at raised temperatures, and in the presence of diluents such as acetone and water.  Instead of cellulose xanthate, other cellulose compounds containing CSS-groups such as cellulose xantho-fatty acids, cellulose dixanthate, a cellulose xanthic ester, or a xanthate as described in Specifications 335,994, [Class 2 (ii), Cellulose &c.], 357,167, 357,527, 357,595, or 368,288 may be used.  There may be added to the viscose or the reagent or the product, any additions known in the viscose art such as glycerine, glucose, sulphates, sulphites, silicates, aluminates, phosphates, blue colouring matter, peroxides, sulphonated oils, sulphur, proteins, proteids, phenols, naphthols, aldehydes, or ketones.  The product of viscose and a reagent of the type specified may be further esterified or etherified either with the CSS-group still present or after it has been split off by acid treatment and the further reaction may be performed on the artificial silk or other material which is obtained.  For coagulation, all baths known in the viscose art or the art of coagulating solutions of other alkali-soluble cellulose compounds may be used.  For plasticizing, baths containing not less than 20 per cent of sulphuric acid or an equivalent amount of another mineral acid, or other plasticizing reagents such as zinc chloride solution, aliphatic or aromatic esters of polybasic inorganic acids, e.g. glycerophosphoric acid, glycerosulphuric acid, methyl or ethyl sulphuric acid; sulphonic acids of aliphatic or aromatic hydrocarbons; carboxy-organo-mineral acids; aromatic sulpho-acids containing nitrogen; or sulphuric acid containing bisulphates, formaldehyde or pyridine, may be used. Glycerine, glucose, alcohol, aniline, pyridine, an aldehyde, or organic acid may be added to the plasticizing agent.  In the production of artificial threads stretching may be effected by means of rods, rollers, or by providing an extended air path, or by a high speed of spinning. The products may be treated with shrinking agents. In an example, viscose made from wood pulp or cotton linters is mixed with a substance formed by the reaction between ammonia and a -dichlorhydrine; after ageing and filtering, the solution is extruded through fine orifices into strong sulphuric acid, the thread being wound upon a bobbin which dips into water so as to dilute the sulphuric acid carried by the thread.  The thread may be desulphurized by hot pyridine, alcoholic or aqueous phenol, or by hot or strong alkali sulphide solution.  The sulphuric acid bath may contain sulphates up to saturation.  In other examples, epichloramine as free base or in the form of oxalate or hydrochloride, tris-(chlor-oxypropyl)-amine as free base or as hydrochloride or its syrupy transformation product formed by heating a solution of the base, or the product obtained by treating epichlorhydrin with aqueous ammonia, are employed for reaction with viscose.  In other examples viscose is treated with ammonia and immediately afterwards with a -dichlorhydrine; plasticizing treatment is carried out on the materials subsequently to coagulation; viscose is prepared from high viscosity wood pulp or cotton linters; films are produced by extruding solutions of the xanthate compounds through slits into a coagulating or plasticizing bath; cotton fabric is impregnated filled or coated with a solution of the xanthate compound to which china clay, lampblack, talc, mica, dyestuff or pigment has been added, and the material with or without drying, if desired under tension, is passed through a coagulating or plasticizing bath and washed.  In other examples, a paste of the xanthate compound is employed for securing sheets of cardboard or thick cloth together, and the material after calendering is introduced into a coagulating or plasticizing bath and subsequently washed and dried; a paste of the xanthate compound is freed from bubbles by vacuum treatment and formed into a thick plate which is introduced into cooled strong sulphuric acid and subsequently washed; a solution of the xanthate compound is mixed with zinc white, mica, or soot, and printed in a roller printing-machine on a cotton fabric which is then introduced into a coagulating or plasticizing bath.  Other substances which may be used for reaction with viscose are :--2-chloro-2 - nitro-propanol-1, 1-bromo-1-nitro-propanol-2, 3.3.3.-trichloro-1-nitro-propanol, acet-imido-b -chloro-ethyl ether, dibromo-acetic acid dimethylamide, N-methyl-N-chloro-acetylurea, oxalic acid ethyl ester-(b -bromo-ethylamide), N-(b g -dibromo propyl)-urea, acetic acid (b g -dibromo-propylamide), trimethyl-(iodoxy-propyl)-ammonium hydroxide, chloracetyl-amino-acetic acid ethyl ester, chloracetyldiglycine-amide, a b -dibromo-propionyl-aminoacetic acid, b -chlor-a -amino-propionic acid, 2-acetamino-benzyl chloride, chlorallyl-phenylurea, (2-bromo-methyl-benzyl)-o-anisidine, 2-(g -chlor-b -oxy-propylamino)-benzyl alcohol, 1<2>- or 1<3>-chlor-5-amino-4-oxy-3 methoxy-1-propyl-benzene, dichloro acetic acid ethylamide, chlorpropyl-ethoxy-phenyl-urea.  In addition to one of the reagents of the type specified, the viscose may be treated simultaneously with a halogen derivative of a polyhydric alcohol, a halogen fatty acid, a trithiocarbonic acid ester, or a reagent described in Specifications 357,121, 357,154, 357,526, or 385,979 for being contacted with viscose.  Threads, films, coatings and other materials containing hollow spaces may be obtained by incorporating in the solutions a gas, or substance which evolves gas during the coagulating step, or finely divided liquids or solids which may subsequently be removed by evaporation or extraction with solvents. Delustred effects may be obtained by incorporating oils, fats, soaps, aromatic hydrocarbons, aniline, or inorganic pigments. Specifications 281,352, 312,197, 323,731, 323,732, [all in Class 2 (ii), Cellulose &c.], 341,899, 357,551, 385,980, 390,516, and 390,523 are also referred to.ALSO:Cellulose xanthate is contacted with an organic compound containing at least one nitrogen atom attached to carbon, at least one oxygen atom attached to carbon, and at least one halogen atom attached to a carbon atom.  Each of the three different elements may be contained more than once in the molecule of the organic compound, but in all cases there must be within the molecule at least one arrangement of these different elements, in which not more than two of them are attached to the same carbon atom.  The organic compound may contain an amino-group, a hydroxyl-group and a halogen atom, and may be a halogen derivative of an amino-propanol. It may contain sulphur, selenium, or tellurium, in addition to the characteristic elements.  If desired, the cellulose xanthate may be treated with substances which react to produce a compound of the type specified.  The product of the cellulose xanthate and the organic compound is converted into artificial threads, films, coatings, dressings, sizings, book cloth, artificial leather, adhesives, cements, plates, plastic compositions, or thickening agents for pigments, by bringing a solution or paste of the product into the appropriate shape or form and acting thereon with a coagulating agent and if desired with a plasticizing agent.  The reaction between viscose and the reagent may be carried out at room temperature or at raised temperatures, and in the presence of diluents such as acetone and water.  Instead of cellulose xanthate, other cellulose compounds containing CSS-groups such as cellulose xantho-fatty acids, cellulose dixanthate, a cellulose xanthic ester, or a xanthate as described in Specifications 335,994, [Class 2 (ii), Cellulose &c.], 357,167, 357,527, 357,595, or 368,288, [all in Group IV], may be used.  There may be added to the viscose or the reagent or the product, any additions known in the viscose art such as glycerine, glucose, sulphates, sulphites, silicates, aluminates, phosphates, blue colouring matter, peroxides, sulphonated oils, sulphur, proteins, proteids, phenols, naphthols, aldehydes, or ketones.  The product of viscose and a reagent of the type specified may be further esterified or etherified either with the CSS-group still present or after it as been split off by acid treatment and the further reaction may be performed on the artificial silk or other material which is obtained. For coagulation, all baths known in the viscose art or the art of coagulating solutions of other alkali-soluble cellulose compounds may be used.  For plasticizing, baths containing not less th