Patent GB-714701-A (GB)
Title: Improvements in or relating to a process for the production of starch derivatives and the resulting product
IPC: D06M15/11
Filed: 1951-08-02
Abstract: Starch ethers made by treating starch or modified starch with epoxyalkanes or substituted epoxyalkanes in the presence of certain tertiary amines or quaternary ammonium compounds (see Group IV (b)) may, where the etherifying agent contains unsaturated carbon bonds as in butadiene monoxide (vinylethylene oxide) or glycidyl allyl ether, polymerize on further heating due to cross-linking (examples 9 and 10).  Where epichlorhydrin is the etherifying agent, cross-linking similarly appears to occur through reaction of the chlorine with free hydroxyl of other starch molecules (example 11).  The ethers may be dispersed in water and applied as adhesives or sizes to paper and textiles, extruded into fibres or applied as films and then polymerized by heat.ALSO:Substantially dry starch, i.e. starch having a moisture content not above that of commercial dry starch, viz. 10-20 per cent or less, is etherified with an epoxyalkane, substituted epoxyalkane or mixture thereof in the presence as catalyst of tetraethanolammonium hydroxide, triethanolamine, tri(hydroxyethyl)hydroxyisopropylammonium hydroxide, triethylamine, trimethylamine, trimethylbenzylammonium hydroxide or mixtures thereof.  Any native starch, starch modified by acids, alkalis, enzymes or oxidizing agents, dextrins, roll-dried starches or solubilized starch products may be used.  Etherifying agents include alkylene oxides, epichlorhydrin, styrene oxide, butadiene monoxide, glycidol and its derivatives, e.g. ethers or halogen derivatives.  A volatile solvent for the catalyst, e.g. alcohols or water, generally about 5-15 per cent by weight of the starch, if desired with traces of surface-active agents, may be present.  The amount of etherifying agent is equivalent to the degree of substitution required, e.g. 0.05-1.5 mols. per glucose unit of starch.  With a tertiary amine as catalyst, an excess equivalent to that necessary to form the quaternary base is required.  Temperatures from about 18-70 DEG  C. or above, preferably 40-70 DEG  C. with a reaction time of 3-10 hours, are used.  The amount of catalyst is preferably 0.0075-0.015 mol. per 0.1 mol. etherifying agent but a wider range is suitable. The product is purified by volatilization of impurities by increase of temperature, reduction of pressure, and/or sweeping with inert gas.  Preferably the starch is agitated, wetted by a spray of an alcohol or solution of wetting agent, followed by a spray of catalyst, and then heated with the etherifying agent as gas or liquid.  The products are of use as adhesives and sizes for textiles and paper.  They may be blended to give pudding powders or modified as by roll-drying to gelatinize, and ground. Unsaturated starch ethers become insoluble on heating due to polymerization and may thus be dispersed as a sol in water, applied as coatings or films or extruded into fibres, and made insoluble by heating.  Examples describe the treatment of corn starch with propylene oxide, isopropanol, and various concentrations of tetraethanolammonium hydroxide as catalyst; the use of ethylene oxide, butadiene monoxide, and glycidyl allyl ether instead of propylene oxide, the last two giving non-gelatinizable products on prolonged reaction owing to polymerization; the use of epichlorhydrin, when hydroxypropylene diether cross-linkages cause the product to be non-gelatinizable; and the use of triethanolamine, triethyl (or methyl) amine, and trimethylbenzyl ammonium hydroxide as alternative catalysts and water containing a wetting agent in place of isopropanol.  Corn starch oxidized with NaOCl, and tapioca starch are also treated.ALSO:Starch ethers prepared by treating substantially dry starch or modified starch with epoxyalkanes or substituted epoxyalkanes in the presence of certain tertiary amines or quaternary ammonium compounds (see Group IV (b)) are used in making adhesives and sizes for paper and textiles.  Where the etherifying agent contains unsaturated carbon bonds, the ethers may be applied dispersed in water and then polymerized by heat.ALSO:Starch ethers prepared by treating substantially dry starch or modified starch with epoxyalkanes or substituted expoxyalkanes in the presence of certain tertiary amines or quaternary ammonium compounds (see Group IV(b)) are mixed with sugar and flavouring materials and roll dried to give pudding powders forming puddings on mixing with cold liquid, e.g. cold milk.  In an example, hydroxypropyl starch, cane sugar and cocoa in proportions of 100 : 50 : 21 by weight and water are mixed and roll dried, and the product ground and blended with salt, dextrose and cane sugar in proportions of 0.5 : 15 : 35.