Patent GB-404331-A (GB)
Title: Improvements in or relating to the manufacture or treatment of products or articles having a basis of cellulose derivatives
IPC: C08K5/151
Filed: 1932-06-02
Abstract: Dopes, varnishes, and the like are made from cellulose esters or ethers using cyclic oxo-ketones, other than oxanones (cyclic tetramethylene oxo-ketones), as solvents or plasticizers for the cellulose derivatives.  The cyclic oxo-ketone may constitute the low, medium, or high boiling solvent present, and may be used in conjunction with other low, medium, or high boiling solvents, and/or diluents, as well as dyestuffs, pigments, resins and the like.  The solvent power of the cyclic oxo-ketones may be reduced by the presence of suitable substituent groups, e.g. alkyl groups, or by mixing the oxo-ketones with suitable diluents such as hydrocarbons, ethers, alcohols, and water.  The following examples are given, (1) A cellulose acetate coating composition containing the ethyl ester of cumaranone-2, carboxylic acid-1; (2) a cellulose acetate coating composition containing ethylene methylene oxo-ketone; (3) a nitro cellulose lacquer containing the ethyl ester of cumaranone-2, carboxylic acid-1; and (4) a cellulose acetate composition for coating rubber insulated cables, containing ethylene methylene oxo-ketone.  The preparation of a number of oxo-ketones is described.ALSO:Dopes, varnishes, plastic materials, insulating-materials for electric conductors, artificial filaments, ribbons, films, and the like are made from cellulose esters or ethers using cyclic oxo-ketones, other than oxanones (cyclic tetramethylene oxo-ketones), as solvents or plasticizers for the cellulose derivatives.  For example, in the manufacture of dopes, varnishes or the like, the cyclic oxoketone may constitute the low, medium, or high boiling solvent present, and may be used in conjunction with other low, medium, or high boiling solvents, and/or diluents, as well as dyestuffs, pigments, resins and the like.  In the production of artificial filaments, the solvents may be present in the spinning solution itself, or in the coagulating or subsequent treatment bath, as described in Specifications 179,234, [Class 2 (ii), Cellulose &c.], 340,324, 340,325, and 340,437.  The cyclic oxo-ketones are also applicable in the treatment of already formed filaments, yarns, fabrics, films, and the like, for example, they may be employed to diminish the tendency of woven fabrics to slip, split, or ladder, as in Specification 280,990, [Class 2 (ii), Cellulose &c.], to improve the pliability or extension by shrinking processes as described in Specification 389,823, and to improve the tenacity of filaments or other products by stretching processes during or subsequent to softening with cyclic oxo-ketones, for example, as is described in Specifications 370,430 and 371,461.  Again, the solvents of the invention may be used to make up sizes for filaments and yarns.  A further application is in the treatment of cellulose derivative yarns prior to the application of substances adapted to dye, print, discharge, load, mordant, or delustre the materials, in order to facilitate the absorption of these agents by the materials.  The solvents may also be employed to relustre, either uniformly or locally, fabrics which have been delustred by the action of hot aqueous media or moist steam, as is described in Specification 259,265, [Class 2 (ii), Cellulose &c.].  In any of the above applications, the solvent power of the cyclic oxo-ketones may be reduced by the presence of suitable substituent groups, e.g. alkyl groups, or by mixing with suitable diluents such as hydrocarbons, ethers, alcohols, and water.  The following examples are given. (1) A cellulose acetate plastic composition containing the ethyl ester of cumaranone-2, carboxylic acid -1; (2) a cellulose acetate coating composition containing the ethyl ester of cumaranone-2, carboxylic acid-1; (3) a cellulose acetate coating composition containing ethylene methylene oxo-ketone; (4) a nitro cellulose lacquer containing the ethyl ester of cumaranone-2, carboxylic acid-1; (5) a cellulose acetate composition for coating rubber insulated cables, containing ethylene methylene oxo-ketone; (6) a spinning solution containing acetone and ethylene methylene oxo-ketone.  In further examples, (7) an acetone solution of cellulose acetate which may contain, e.g. 10 per cent of ethylene methylene oxo-ketone, is spun into a 30--40 per cent solution of ethylene methylene oxo-ketone, and the filaments drawn out; (8) cellulose acetate yarns are soaked in a 30--40 per cent solution of ethylene methylene oxo-ketone and stretched; and (9) a cellulose acetate fabric, delustred or not, is printed with a paste containing dyestuff or pigment, di-ethylene glycol, water, ethylene methylene oxo-ketone, and gum arabic, is dried, washed in warm water, soaped at 50 DEG  C., and rinsed. Cyclic oxo-ketones may be prepared by any of the following methods. (1) Dehydration of dioxy-ketones, for example dioxy-acetone and 1,3-dioxy-2-butanone, by simple heating, or by means of dehydrating agents, or dehydrating catalysts.  (2) Ketonisation of an ether di-carboxylic acid, e.g. by heating the alkaline earth metal salt of the ether dicarboxylic acid, or by acting on the dry ester of the ether dicarboxylic acid, e.g. the methyl ethyl ether-a b <1>-dicarboxylic acid diethyl ester, with sodium under the conditions of the Claisen synthesis. Examples of suitable starting materials are dimethyl ether-a a <1>-dicarboxylic acid, methyl ethyl ether-a a <1>-dicarboxylic acid, diethyl ethera a <1>-dicarboxylic acid, diethyl ether-b b <1>-dicarboxylic acid, ethyl propyl ether-a a <1>-dicarboxylic acid, ethyl iso-propyl ether-a a <1>-dicarboxylic acid, dipropyl ether-a a <1>-dicarboxylic acid, di-isopropyl ether-a a <1>-dicarboxylic acid, and sym-dimethyl-diethyl diglycollic acid. (3) Removal of hydrogen and halogen from halogen alkyl oxy-alkyl ketones, or from alkyl ethers of oxy-carboxylic acid halides by means of alkalies or condensing agents such as the chlorides of aluminium, antimony, iron, and copper.  Suitable starting materials are g -chlor-b -keto-a -oxypropane, d -chlor-g -keto-b -oxy-b -methyl butane, the ethyl ether of glycollic acid chloride, the isobutyl ether of glycollic acid chloride, and a -ethoxy-n-valeric acid chloride.  (4) Treatment of poly-halogenated ketones, in which one halogen atom is present on each side of the keto group, with agents which remove halogen and substitute oxygen therefor, such as silver oxide, cupric oxide, litharge, mercuric oxide, and other agents, according to Specification 374,134.  Examples of suitable polyhalogenated ketones are a a <1>-dichloracetone, a g -dichlor - b - keto - butane, a g  - dibrom - b  - keto-butane, b d  - dichlor - g - keto - b  - methyl-butane, b d  - dibrom - g  - keto - b  - methyl-butane, and b d  - dibrom - g  - keto - pentane.  In an example, cumaranone-3, keto-2, carboxylic acid ethyl ester is prepared by condensing ethyl salicylate with ethyl chloracetate by means of sodium in alcohol, and treating a solution of the product with more sodium.ALSO:Dopes, plastic materials, films, and the like are made from cellulose esters or ethers using cyclic oxo-ketones, other than oxanones (cyclic tetramethylene oxo-ketones), as solvents or plasticizers for the cellulose derivatives.  For example, in the manufacture of dopes, or the like, the cyclic oxo-ketone may constitute the low, medium, or high boiling solvent present, and may be used in conjunction with other low, medium, or high boiling solvents, and/or diluents, as well as dyestuffs, pigments, resins and the like.  The solvents of the invention may be used to make up sizes for filaments and yarns.  In any of the above applications, the solvent power of the cyclic oxo-ketones may be reduced by the presence of suitable substituent groups, e.g. alkyl groups, or by mixing the oxo-ketones with suitable diluents such as hydrocarbons, ethers, alcohols, and water.  The following examples are given: (1) a cellulose acetate plastic composition containing the ethyl ester of cumaranone-2, carboxylic acid-1; (2) a cellulose acetate coating composition containing the ethyl ester of cumaranone-2 carboxylic acid-1; (3) a cellulose acetate coating composition containing ethylene methylene oxo-ketone; (4) a nitro cellulose lacquer containing the ethyl ester of cumaranone-2, carboxylic acid-1; and (5) a cellulose acetate composition for coating rubber insulated cables, containing ethylene methylene oxo-ketone.  The preparation of a number of oxo-ketones is described.