Patent GB-385979-A (GB)
Title: Manufacture of cellulose xanthate derivatives and artificial materials therefrom
IPC: C08B13/02
Filed: 1931-03-31
Abstract: Cellulose xanthate or other cellulose compound containing a -CSS group is contacted with an organic compound containing at least one sulphur atom attached to a carbon atom and at least one halogen atom attached to a carbon atom.  The organic compound may be a halogen derivative of a sulphur analogue of a di- or polyhydric alcohol or a sulphur derivative of a halogen derivative of a di- or polyhydric alcohol.  Instead of sulphur, the compound may contain selenium or tellurium.  Solutions or pastes of the product are converted into artificial silk, films, plates, coatings, dressings for textiles, paper or leather, sizings for yarns, book cloth, artificial leather, adhesives, cements, plastic compositions, and thickening-agents for pigments in textile printing, by bringing them into the desired shape or form and then treating with a coagulating agent.  The coagulated structure may be treated with a plasticizing agent or the coagulating agent may be one that also has a plasticizing effect. Substances containing sulphur and halogen may be obtained by treating a chlorhydrin with less than the molecular proportion of an alkali sulphide or sulpho - hydrate.  Instead of halogenated mercaptans of glycerine, other reagents may be used such as the methyl iodide addition product of diethylene disulphide, ethanedithiolethyl - b  - chloro - ethyl ether, ethylb -chloro-ethyl sulphide, b  b <1>-dichloro-diethyl sulphide or disulphide, b  b <1>-dichloro-a -ethoxydiethyl-sulphide, chlorosulphonal, a -sulphydrylo -chlorostyrol xanthic ester, a -bromo-b -oxythionaphthene, a -dibromo-b -ketodihydrothionaphthene, or the substances <FORM:0385979/IV/1> or <FORM:0385979/IV/2>  The cellulose xanthate employed may be prepared from ripened or unripened alkali cellulose. Instead of cellulose xanthate, a cellulose xantho-ffatty acid, cellulose dixanthate or a cellulose xanthate derivative, as described in Specifications 335,994, [Class 2 (ii), Cellulose &c.], 357,167, 357,527, 357,595, and 368,288, may be used.  During the manufacture there may be added glycerine, glucose, inorganic salts, silicates, aluminates, phosphates, blue colouring matter, peroxides, sulphonated oils, finely divided sulphur, proteins, proteids, phenols, naphthols, aldehydes, ketones, or ammonia.  Cellulose xanthate may be caused to react with other substances such as halogenated di- or poly-hydric alcohols, halogenated fatty acids, or trithiocarbonic esters in addition to one or more of the substances characteristic of the process.  Coagulating baths as known in the viscose artificial silk art and containing dilute mineral acids or salts may be used during the conversion of the products into artificial silk, films, coatings, and other structures.  For plasticizing baths, strong sulphuric, hydrochloric, nitric, phosphoric, or other strong mineral acid may be used either alone or mixed with inorganic salts, organic acids, glycerine, glucose, alcohol, aniline, pyridine, or an aldehyde. Other plasticizing agents may be used such as methyl or ethyl sulphuric acid, glycerophosphoric acid, glycerosulphuric acid, methionic acid, oxymethyl sulphonic acid, ethyl sulphonic acid, benzene sulphonic acid, phenol sulphonic acid, a mineral oil sulphonic acid, sulphonic acid, sulphono diacetic acid, acid, a sulphonic acid of an aromatic compound containing nitrogen, or zinc chloride with or without the addition of acid.  In examples, viscose is mixed with a crude or purified compound formed by the action of an alkali sulphide or sulphydrate on a dichlorhydrin, and the solution is spun into dilute or strong sulphuric acid which may be saturated with sodium, magnesium, or ammonium sulphate, the resulting threads being stretched if desired by high rate of spinning, or by passing round rods or rollers.  The threads are washed and desulphurized with sodium sulphide, or hot pyridine, or alcoholic or aqueous solution of phenol.  The solution of the viscose compound may be extruded through a slit to form a film which is passed through a coagulating or plasticizing bath.  Cotton fabric is impregnated, filled, or coated on a padding, backfilling or spreading machine with a solution of the viscose compound to which talc, clay, dyestuff, or pigment such as mica or lampblack is added and the material with or without drying is passed through a coagulating or plasticizing bath, washed and dried. The viscose compound in the form of a paste is used for pasting sheets of cardboard or thick cloth together.  The material is pressed, calendered, treated with a coagulating or plasticizing bath, washed and dried.  The paste may be formed into thick plates which are treated with coagulating or plasticizing baths, washed and dried. A solution of the viscose compound is mixed with zinc white, mica, or soot and printed in a roller printing machine on a cotton fabric, which is then passed through a coagulating or plasticizing bath, washed and dried.  Threads and other structures containing hollow spaces may be obtained by incorporating in the solutions substances capable of evolving gases during coagulation, or by incorporating solids or liquids which are removed after coagulation.  Substances for producing diminished lustre may also be incorporated in the solutions.  Specifications 281,352, 312,197, 323,731, 323,732, [all in Class 2 (ii), Cellulose &c.], 341,899, 357,121, 357,154, 357,526, 357,551 and 385,980 also are referred to.  The Provisional Specification also specifies the following substances which may be added to cellulose xanthate: trimethyl-thiosinamine-dibromide, b  - g - dibrompropyl-isothiocyanate, thiopropionic acid b - g -dibromo propylamide, N- (b -chloro-allyl)-thiourea, bis-chloroacetylcystin, and dichloralethylene-dithio-glycol.ALSO:Cellulose xanthate or other cellulose compound containing a \CSS group is contacted with an organic compound containing at least one sulphur atom attached to a carbon atom and at least one halogen atom attached to a carbon atom. The organic compound may be a halogen derivative of a sulphur analogue of a di- or polyhydric alcohol or a sulphur derivative of a halogen derivative of a di- or polyhydric alcohol.  Instead of sulphur, the compound may contain selenium or tellurium.  Solutions or pastes of the product are converted into artificial silk, films, plates, coatings, dressings, for textiles, paper, or leather, sizings for yarns, book cloth, artificial leather, adhesives, cements, plastic compositions, and thickening agents for pigments in textile printing, by bringing them into the desired shape or form and then treating with a coagulating agent.  The coagulated structure may be treated with a plasticizing agent or the coagulating agent may be one that also has a plasticizing effect. Substances containing sulphur and halogen may be obtained by treating a chlorhydrin with less than the molecular proportion of an alkali sulphide or sulpho-hydrate. Instead of halogenated mercaptans of glycerine, other reagents may be used such as the methyl iodide addition product of diethylene disulphide, ethane-dithiolethyl-b -chloro-ethyl ether, ethyl-b -chloro-ethyl sulphide, b b 1-dichloro-diethyl sulphide or disulphide, b b 1-dichloro - a  - ethoxy-diethyl-sulphide, chlorsulphonal, a -sulphydryl-o -chlorostyrol xanthic ester, a -bromo-b -oxy-thionaphthene, a -dibromo-b -ketodihydrothionaphthene, or the substances <FORM:0385979/V/1> The cellulose xanthate employed may be prepared from ripened or unripened alkali cellulose.  Instead of cellulose xanthate, a cellulose xantho-fatty acid, cellulose dixanthate, or a cellulose xanthate derivative as described in Specifications 335,994, [Class 2 (ii), Cellulose &c.], 357,167, 357,527, 357,595, and 368,288, [all in Group IV], may be used. During the manufacture there may be added glycerine, glucose, inorganic salts, silicates, aluminates, phosphates, blue colouring matter, peroxides, sulphonated oils, finely divided sulphur, proteins, proteids, phenols, naphthols, aldehydes, ketones or ammonia.  Cellulose xanthate may be caused to react with other substances such as halogenated di- or polyhydric alcohols, halogenated fatty acids, or trithiocarbonic esters in addition to one or more of the substances characteristic of the process.  Coagulating baths as known in the viscose artificial silk art and containing dilute mineral acids or salts may be used during the conversion of the products into artificial silk, films, coatings, and other structures.  For plasticizing baths, strong sulphuric, hydrochloric, nitric, phosphoric, or other strong mineral acid may be used either alone or mixed with inorganic salts, organic acids, glycerine, glucose, alcohol, aniline, pyridine, or an aldehyde.  Other plasticizing agents may be used such as methyl or ethyl sulphuric acid, glycerophosphoric acid, glycerosulphuric acid, methionic acid, oxymethyl sulphonic acid, ethyl sulphonic acid, benzene sulphonic acid, phenol sulphonic acid, a mineral oil, sulphonic acid, sulphoacetic acid, sulphono diacetic acid, a sulphonic acid of an aromatic compound containing nitrogen, or zinc chloride with or without the addition of acid.  In examples, viscose is mixed with a crude or purified compound formed by the action of an alkali sulphide or sulphydrate on a dichlorohydrine. The solution of the viscose compound may be extruded through a slit to form a film which is passed through a coagulating or plasticizing bath.  Cotton fabric is impregnated, filled or coated on a padding, backfilling or spreading machine with a solution of p  the viscose compound to which talc, clay, dyestuff, or pigment such as mica or lampblack is added and the material with or without drying is passed through a coagulating or plasticizing bath, washed and dried.  The viscose compound in the form of a paste is used for pasting sheets of cardboard or thick cloth together.  The material is pressed, calendered, treated with a