Nitrate lignin

Miihlhaeuser (Ref 2) nitrated jute previously purified by boiling in a 1% Na2C03 soln followed by a water rinse. By using lp dry jute 15 parts of acid, 2/1 coned H2S04/concd HNOj, a product with 12.26% N and 132% yield was obtd. The props of Nitrojute are similar to those of nitrated lignocellulosses (See Lignin Nitrate in this Vol)... 

Lignin Nitrate (Nitrolignin). A general term employed to designate nitrated products contg lignin, such as wood, straws, jute, esparto grass, flax and hemp fibers (Ref 1)... 

Schuitze s Explosives and Powders. Schultze, an artillery captain in the Ger army, in 1867 patented a series of propints based on Nitro-lignin (nitrated woodmeal or sawdust). The smokeless powders antedated by at least 20 years colloidal smokeless powders developed independently by P. Vieille in Fr and M. Dutton-hoffer. Two examples of Schuitze s powders are given by Daniel (Ref, p 707) as follows ... 

The aromatic nature of lignin contrasts with the aliphatic stmcture of the carbohydrates and permits the selective use of electrophilic substitution reactions, eg, chlorination, sulfonation, or nitration. A portion of the phenoUc hydroxyl units, which are estimated to comprise 30 wt % of softwood lignin, are unsubstituted. In alkaline systems the ionized hydroxyl group is highly susceptible to oxidative reactions. 

The viscosity range of CN products can be adjusted in advance by choosing the starting cellulose with an appropriate degree of polymerization (DP). A study of the different celluloses examined the impact of various cellulose properties, such as morphological factors (percent crystallinity, fiber length, and distribution), chemical composition (DP, ash content), and hemiceUulose and lignin content, on the nitration behaviors of cellulose (55). 

Graft polymerization of methylmethacrylate monomer onto pulps of different residual lignin contents using ceric ammonium nitrate as the initiator was carried out to study the influence of this residual lignin on the graft-ability of these pulps (Fig. 3). From this figure one can... 

Miner s Friend. A lignin Dynamite, formerly manufd in the USA by the Hecla Powder Co. It contd varying amts of NG together with lignin and Na nitrate... 

In the case of liq expls and propints, Myrol (methyl nitrate plus methanol) was used either by itself or in mixts with liqs such as benz, MNB, etc. For use as a plastic expl or propint, Myrol was treated with small quantities of NC to form a soft jelly. As a solid expl or propint, it was treated with 25-30% NC to form a hard jelly, or was mixed with the usual sol ingredients of dynamites, sUch as kieselguhr, sawdust, inorganic nitrates, lignin, etc... 

Plastomenites. Propints, patented in Ger by Guttler in 1889—90, consisting of NC, Nitro-lignine, Nitrosugar, Nitrostarch, etc, gelatinized by the addition of nitrated aromatic compds such as benz, toluene, phenol, naphthalene, etc. Inorganic nitrates, chlorates, chromates, picrates, etc, could be added to the mixt... 

The inclusion of nitrate may lead to various complications, which have been discussed in Chapter 2. In addition, the nitrogen status of the growth medium determines the levels of lignin peroxidases and manganese-dependent peroxidases that are synthesized in Phanerochaete chrysosporium. The role of Mn concentration is noted later and in Chapter 3, Part 5. 

Solubilized lignin solutions are easily oxidized and the presence of the aromatic units containing electron-withdrawing ether and alcohol moieties makes it available for electrophilic substitution reactions, such as nitration, halogenation, hydroxylation, etc. 

Imperial Schultz Powder. It consists of Nitro-lignin 80.1, Ba nitrate 10.2, vaseline 7.9 volatile matter 1.8%. Its props are reported as... 

Lignin is removed from wood by both the sulfate and soda paper pulp processes, and limited amts have been recovered from these sources and other wood waste. It has been used as a component of Dynamites, and has been nitrated... 

The earliest expts devoted to the nitration of lignin, previously isolated from woodpulp by means of HC1, were reported by Hagglund (Ref 3). Lignin mixed with fuming nitric acid... 

In order to separate lignin from carbohydrates, stronger reagents were used in the expts of Friese et al ( Refs 9 12) for the nitration of wood pulp, namely normal mixed acids. In this way nitrolignin with a higher N content was obtained. When nitric-sulfuric acids (1 2 ratio) were used, a prod contg 8.45% N was obtained with a yield of 55%... 

Lignin Dynamitas. Mixts prepd by impregnating sawdust with NG were known by this name. They sometimes contd metallic nitrates Ref Daniel (1902), 408... 

This treatment does not remove the lignin. The fibers are dark in color and very stiff. They are not used in paper manuf nor for the nitration of NC, but can be pressed into a product of extreme durability hardness, known as "Masonite Presswood ... 

Giant Powder. Under the title Gdante ( Poudre), Daniel (Ref 1) called this an older Amer name for Dynamite, manufd in Calif under the name Dynamite-Lignine, which contd Na nitrate. 

Vulcain Dynamite. One of the varieties of so-called lignin dynamites . It contained NG, lignin (such as sawdust) and Na nitrate Ref Daniel (1902), 408 797... 

No. Material for nitrating Cellulose content % Copper number Pentosans content % Lignin content % Fats, waxes content 0/ /o Ash content %... 

An appreciable part of the lignin molecule is aromatic in character. Hence it would be expected to take part readily in the reaction of nitration. It has been found, however, that the capacity of lignin to undergo oxidation predominates especially in the presence of dilute nitric acid. This can be explained by the fact that the aromatic part of the lignin molecule derives from pyrocatechol. The reaction of lignin with nitric acid forms the basis of a method of separating cellulose from wood pulp, that consists in treating this mass with dilute nitric acid (3-10%). 

The earliest experiments devoted to the nitration of lignin, previously isolated... 

Powell and Whittaker [61] nitrated lignin with mixed nitric and sulphuric acid at —5°C. The nitration product was isolated by precipitation with water and ice. 

A property of the nitration product of lignin which attracted attention was its failure to form detectable amino groups on reduction. The product of reduction... 

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