Patent GB-945207-A (GB)
Title: Method of preparing homogeneous gelatinized starch product
IPC: C08B30/12
Filed: 1962-03-30
Abstract: A mixture of starch raw material and starch swelling agent is worked in a confining chamber at 125 DEG C. to 250 DEG C. for 0.5 to 5 minutes at a pressure substantially above the autogenous vapour pressure of the mixture at the reaction temperature to form a hot fluid homogenised mass, and immediately thereafter transferred into a region of substantially lower temperature and pressure. The proportion of starch swelling agent is 22% to 67% by weight of starch raw material dry substance, and the working is sufficient to provide an adiabatic temperature rise of at least 50 DEG C. in the worked mass. In a further embodiment, 0.01% to 50% by weight of starch dry substance, of a starch modifying agent may be present in the mixture. The starch raw material may be any native starch, a dextrin or thin-boiling starch, or a starch derivative such as starch acetate and propionate and starch ethers e.g. hydroxyethyl, carboxymethyl and cyanoethyl starch.  The starch swelling agent or plasticizer is preferably water, but may be e.g. formamide, ethylene diamine dimethyl sulphoxide, pyrrolidine, urea, piperazine, glycerol, ethylene glycol, sorbitol, propylene glycol, chloral hydrate, dimethyl formamide and mixtures or solutions thereof. The starch modifying agent may be a hydrolytic or oxidising agent e.g. hydrochloric, sulphuric phosphoric, acetic, oxalic, benzoic, and levulinic acids; sodium and calcium hypochlorite, potassium permanganate, potassium persulphate, sodium perborate, hydrogen peroxide, benzoyl peroxide and hypochlorous acid; or may be a starch-derivatizing reagent such as anhydrides of acetic, n-butyric, succinic, isatoic, quinolinic and phthalic acids; n-butyryl chloride, benzene sulphonyl chloride, phosphorus oxychloride, beta-propiolactone, phenylisocyanate, vinyl acetate, vinyl n-butyrate, ketene, monochloroacetic acid, alpha-bromopropionic acid, ethylene chlorohydrin, propylene chlorohydrin, glyceryl alpha-chlorohydrin, ethylene oxide, propylene oxide, 3-diethylamino -1, 2-epoxypropane, 3-dibutylamino 1, 2-epoxypropane, N-(2, 3-epoxypropyl)- piperidine, N,N-(2,3-epoxypropyl) methylaniline, cyclohexane oxide, styrene oxide, methyl chloride, ethyl chloride, beta-diethylamino ethyl chloride, betadimethylamino ethyl chloride, beta-methylamino isopropyl chloride, dimethyl sulphate, diethyl sulphate, triisopropyl borate, tributyl phosphate, tetraethyl orthosilicate, triethyl phosphite, ethylene imine, propylene imine, methacrylamide, acrolein, ethyl acrylate, methyl acrylate, n-butyl acrylate, epichlorohydrin, ethylene dibromide, and butadiene diepoxide. The mixture may also include a catalyst such as sodium and calcium hydroxides, potassium carbonate, sodium silicate, sodium aluminate, sulphuric acid, sodium chloride, or a tertiary amine or quaternary ammonium hydroxides. The hot fluid mass is preferably transferred to the zone of lower pressure through an orifice or die which shapes the mass into thin strands, filaments or ribbons. A suitable form of apparatus for carrying out the process is a conventional screw-type plastics extruder, through the barrel of which the mixture is forced while maintaining the required temperature and pressure. The pressure in the zone of lower pressure is preferably atmospheric and the temperature therein preferably no greater than that provided by the flashing of plasticizer from the extruded material. If water or other low-boiling plasticizer is used, sufficient is flashed off from the mixture in the lower pressure zone to provide a porous, friable solid which may be easily ground.  If a high-boiling plasticizer is used, the extruded plastic material may be vacuum-dried or extracted with a solvent such as methanol or acetone.  Preferably, the final product contains 10-15% by weight of plasticizer. The combination of intense shearing in the working zone, and elevated temperature and pressure accelerates the gelatinisation and also the reaction of the starch with the modifying agent when used. If the adiabatic rise in temperature is greater than required, the apparatus may be externally cooled. U.S.A. Specifications 2,516,633 and 2,516,634 are referred to.