Cellulose, explosives Nitration

The first successhil attempt to make textile fibers from plant cellulose can be traced to George Audemars (1). In 1855 he dissolved the nitrated form of cellulose in ether and alcohol and discovered that fibers were formed as the dope was drawn into the air. These soft strong nitrocellulose fibers could be woven into fabrics but had a serious drawback they were explosive, nitrated cellulose being the basis of gun-cotton (see Cellulose esters, inorganic esters). 

Cellulose nitrate (pyroxylin) [9004-70-0], made from cellulose and a mixture of nitric and sulfuric acids, is called gun cotton and is used in explosives. Nitrates of lower DS find some appHcation in coatings and adhesives. 

Cellulose Explosives.—The explosives made from cellulose are of two kinds, viz., cellulose nitrates alone, as in gun cotton, and mixtures of cellulose nitrates and nitro-glycerol which constitute the smokeless powders made from cellulose nitrates. 

An essential characteristic of cellulose nitrates is their capability of undergoing thermally breaking to give nitrogen, nitrogen oxides, carbon dioxide, carbon monoxide, and water. This spontaneous reaction requires a high activation energy and is self-catalyzed by the decomposition products. The manufacture of explosives (nitrated cotton) is based on this property. 

E. Dodgen, "Continuous Nitration of Cellulose SNIA Viscosa Process," in Symposium on Processing Propellants, Explosives and Ingredients, ADPA, Washington, D.C., 1977, p. 4.2-1. 

In explosives, diphenylamine stabilizes cellulose nitrate by reacting with nitrogen oxides (see Explosives and propellants). The products formed include /V-nitrosodiphenylamine and mono andpolynitro derivatives. 

The principal chemical iadustry based on wood is pulp and paper. In 1995, 114.5 x 10 metric tons of wood were converted iato - 60 x 10 metric tons of fiber products ranging from newsptint to pure cellulose ia the United States (1,76). Pure cellulose is the raw material for a number of products, eg, rayon, cellulose acetate film base, cellulose nitrate explosives, cellophane, celluloid, carboxymethylceUulose, and chemically modified ceUulosic material. 

Group 1 Chlorate and metal perchlorate report or whistling compositions Dry non-gelatinized cellulose nitrates Barium peroxide/zirconium compositions Burn very violently Flash shells (maroons) Casings containing flash compositions Sealed hail-preventing rockets Mass explosion risk... 

Cellulose nitrate is inflammable and explosive when dry, but when soaked in water it is considered entirely safe if reasonable care is taken in handling. 

Is there a possibility of nitrating a compound Many of the explosions in chemical processing are the result of nitrating be it cellulose, tributylphosphate (to form red oil), or ammonia to form fertilizer. 

Nature uses cellulose primarily as a structural material to impart strength and rigidity to plants. Leaves, grasses, and cotton, for instance, are primarily cellulose. Cellulose also serves as raw material for the manufacture of cellulose acetate, known commercially as acetate rayon, and cellulose nitrate, known as guncotton. Guncotton is the major ingredient in smokeless powder, the explosive propellant used in artillery shells and in ammunition for firearms. 

I) cellulose nitrate to which the Explosives Act 1875 applies or (ii) solutions of cellulose nitrate where the nitrogen content of the cellulose nitrate 12.3 /n by weight and the solution contains 55 parts of cellulose nitrate per 100 parts by weight of solution. 

Nitrocellulose is usually handled wet and containing approximately 30% of water. Under these conditions it can be considered as a nonexplosive material when the nitrogen content does not exceed 12-6%. More highly nitrated cellulose is known as guncotton and is explosive even when moderately wet. When dry, nitrocellulose of all types is an extremely sensitive and dangerous explosive. Dry nitrocellulose is required for use in certain types of explosives and is then prepared by slow drying of the wet material in a current of warm air. 

During preparation of an oxidising agent on a larger scale than described [1], addition of warm sodium hydroxide solution to warm ammoniacal silver nitrate with stirring caused immediate precipitation of black silver nitride which exploded [2], Similar incidents had been reported previously [3], including one where explosion appeared to be initiated by addition of Devarda s alloy (Al—Cu—Zn) [4], The explosive species separates at pH values above 12.9, only produced when alkali is added to ammoniacal silver solutions, or when silver oxide is dissolved with ammonia [5], The Sommer Market reagent mixture used to identify cellulose derivatives led to a severe explosion [6],... 

Reactivity of benzoyl nitrate towards moisture is so great that attempted filtration through an undried filter paper causes explosive decomposition (possibly involving cellulose nitrate ). 

The analytical use of cellulose fibre to absorb uranyl nitrate solution prior to ignition has led to explosions dining ignition, owing to formation of cellulose nitrate. An alternative method is described. 

Cellulose nitrate is very easily ignited and bums very rapidly or explosively, depending on the degree of confinement, degree of nitration and state of subdivision. Unless very pure and stabilised, it deteriorates in storage and may ignite... 

Subsequent tests in which small portions of these undiluted liquid amines and dried cellulose nitrate linters were contacted (with a little added butyl acetate for the solid phenol) under various conditions, gave ignition with the first 3 amines, and exotherms to 110°C with foaming decomposition for the remaining 4. Other amine resin components showed slight or no exotherms in either test [2], Contact of cellulose nitrate with a little butylamine caused explosive reaction [3]. 

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