Starch nitrate production

Nitrotoluenes, Van No strand, NY(1918) 2)M.Kostevitch, "Tarry Matter of Alpha Trinitrotoluene, Part II, Imprd Art Vol-taire,P aris( 1927), 8 3)Sidgwick( 19 37), 259 et seq 4)Davis(1943), 136-7, 147, 149-51 170-1 5>negering( 1950), 139 seq 6) Dept of the Army TM 9-1910( 1955), 146 Alkalies, Action on Nitric Esters. Organic nitrates in general are readily saponified by alkaline solns. A simple metathetical reaction to yield the alkali nitrate and alcohol does not take place instead, as a result of simultaneous oxidation and reduction, alkali nitrite and a variety of products are formed depending on the conditions of the reaction. The resistance of different nitric esters to alkalies varies considerably. Thus, starch nitrate is decomposed much more slowly than cellulose nitrate and amylopectin nitrate still more alowly... 

The most extensive of the researches carried out in the nineteenth century were those of Miihlhauser [14], who dissolved starch in a ten-fold quantity of nitric acid, sp. gr. 1.50 and precipitated the product with thirty times as much sulphuric acid. In this way he introduced 13.5% N, but the nitration product was unstable. 

On account of such strong degradation, the viscosity of nitrostarch solutions is low whatever the preparative method applied. Likewise large differences in the viscosities of starch before nitration exert practically no influence on the viscosity of the nitrated product. Experiments carried out by T. Urbanski and Golofit [34] provided the data needed to determine the viscosity of starch (in Parlow degrees) and the viscosity of nitrostarch obtained by nitration with nitric acid, sp. gr. 1.50, followed by precipitation with water. The results are collected in Table 105. 

The nitration product of starch is a non-homogeneous substance. Nitrostarch may be divided into fractions by adding water to its solution in acetone as demonstrated by T. Urbanski and Cieslak [38], The individual fractions vary slightly in respect of nitrogen content, whereas their viscosity is almost identical. 

A further factor that causes the non-homogeneity of nitrostarch is the presence of the two components, amylose and amylopectin in starch. It has been demonstrated by nitrating each of these starch components separately that the nitration products differ from one another. Berl and Kunze [37] detected that amylopectin yields a product of a considerably higher viscosity than that resulting from the nitration of amylose. This effect may be attributable to the higher molecular weight of amylopectin. 

Braconnot, " in 1833, prepared the first starch nitrate by dissolving potato starch in cool, concentrated nitric acid and precipitating the product by the addition of water. He designated his product xyldidine. Since then, a large number of investigations of starch nitration have been reported in the scientific and patent literature. A concise review of the older work is given by Kesseler and Rohm.""... 

Although early preparations of starch nitrates were unstable and hazardous to handle, stabilizing treatments have been developed which have made the compounds relatively safe. Production of stable products requires the use of purihed starches and the thorough washing of the starch nitrate to remove all traces of acid. The nitrate may be washed in hot water or with water containing neutralizing agents such as carbonates" or other alkaline solutions. The nitrate may also be stabilized by the addition of aniline or methanol." ... 

Recently, in addition to nitrated celluloses, starch nitrate, etc., various nitrated products of other polysaccharides have received attention, r.g. nitrated inulin, nitrated lichenin. The foUowii is an example of the preparation of one of these products on a small scale ... 

Perhaps the first of the numerous patents for mixtures of starch nitrate with oxidants, and the like, was assigned to W. Schiickher in 1889 for the production of a smokeless gunpowder. His mix included ammonium, barium, potassium, sodium and starch nitrates, together with potassium chlorate, picric acid salts, nitronaphthalene, and carbon. The starch nitrate used was probably defective in stability. 

Another (and the best) patent of this period, covering the production of starch nitrate, was issued to F. B. Holmes of Woodbury, New Jersey, and assigned to the Eastern Dynamite Corporation of Wilmington, Delaware. He treated starch with mixed acids (in a preferred proportion of nitric acid, 32.5% sulfuric acid, 64.5% water, 3%), using 25 parts of dried starch to 100 parts of the mixed acids. He stabilized the product by boiling it for 75-100 hours in water containing calcium carbonate. Later patents covered a wide variety of ammonium compounds as stabilizers. Millions of pounds of starch nitrate were made by Holmes patents. 

At about the same time, Saposchnikoff attempted a molecular-weight determination on starch nitrate produced by dissolution in nitric acid, and arrived at the figure of 1845— agreeing best with the formula C36H430is-(N03)i7. This formula, wherein the DP is 6, is not unlikely, as the conditions used probably effected degradation. In Britain, Arnold and his associates were granted patents for the nitration of potato starch in mixed acids. The product was probably worthless, owing to the naive assumption that it was freed of acids by currents of fresh water. ... 

Starch nitrate is a fascinating product, as anyone who has ever made it will enthusiastically agree. 

Derivatives of starch. The esters and ethers of starch do not find the wide field of uses of their cellulose counterparts. Starch nitrate is used as a high explosive. Slight derivatization of starch yields a number of commercially useful products. 

The yield was highest with starch or dextrin, intermediate and about the same with sucrose, glucose, maltose and lactose and poorest with glycerol. Kanamycin was produced by media containing soybean meal, peanut meal, cottonseed meal, corn steep liquor, peptone, yeast extract or meat extract, with or without sodium nitrate. Commercially available soybean meal was recognized to be one of the best nitrogen sources. The addition of corn steep liquor, peptone, yeast extract or nitrate to the soybean meal promoted the production of kanamycin. 

Nitrostarch (NS) is a nitrate ester (more properly a mixt of several nitrate esters) of starch, which is a plant-product polysaccharide of the general formula (CgHujOj) The general molecular formula for NS is [C6H7(OH)x-(0NO2)y]n where x + y - 3, The following empirical relation, similar to that used for NC... 

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