Cellulose trinitrate

There are a variety of reaction systems that allow the formation of cellulose trinitrate [9046-47-3]. HNO in methylene chloride, CH2CI2, yields a trinitrate with essentially no degradation of the cellulose chain (53). The HNO /acetic acid/acetic anhydride system is also used to obtain the trinitrate product with the fiber stmcture largely intact (51,52). Another polymer analogous reaction utilises a 1 1 mixture of HNO and H PO with 2.5% P2O5 to achieve an almost completely nitrated product (54). 

Cellulose triesters, moisture properties of selected, 5 416t Cellulose trinitrate, 5 396 Cellulose valerate(s), 5 419 moisture properties, 5 416t Cellulose x, 5 373, 378-379 8 21 Cellulose xanthate, 4 716 5 383 20 559 Cellulosic-acrylic fibers, dyeing, 9 201-202 Cellulosic fiber blends, dyeing, 9 199-202 Cellulosic fiber—nylon blends, dyeing, 9 202 Cellulosic fibers, 18 96... 

Meyerhoff (14-16) has also observed similar blocking of the gel column using cellulose trinitrate fractions with molecular weight above 1.4 x 10, while fractions with molecular weight 4.2 X 10° could not be separated. It is obvious from these results that he did not, however, realize the presence of the hemlcellulose derivatives in the wood-pulp based cellulose nitrate and its role in blocking of the high porosity column as shown in this study. 

Gunpowder Potassium chlorate Nitrated cellulose Gun cotton Cellulose trinitrate Smokeless powder... 

Fig. 83. X-Ray diagrams (according to Miles and Craik [13]) (a) ramie cellulose, (b) ramie cellulose dinitrate, (c) ramie cellulose trinitrate.

A plane projection of the crystal cell of cellulose (a) and of cellulose trinitrate b) is outlined by the schemes in Fig. 84. Much interest was aroused in the results... 

Fig. 84. X-Ray fibre diagrams (a, b and c), cell projections of cellulose (d) and cellulose trinitrate...

Mathieu [18] has shown that X-ray diagrams taken at frequent intervals during nitration of cellulose with N205 vapour indicate that the structure progresses through all the stages from cellulose to cellulose trinitrate. 

Taking into account both their own X-ray investigations and those of other workers, Meyer and Mark [17] came to the conclusion that indistinct pictures of cellulose nitrates having a lower nitrogen content than cellulose trinitrate and hence containing free hydroxyl groups, occur due to the statistically irregular distribution... 

If all or nearly all the hydroxyl groups are esterified (as in cellulose trinitrate), then the long-chain-molecules again possess a regular structure, and under the influence of forces of adhesion (van der Waals bonds) close mutual contact may be maintained (Fig. 89a). Here again the solvent may be too weak as to push aside... 

Fig. 98. Relation between n2je and surface tension a of aliphatic liquids on their ability to dissolve cellulose trinitrate (Moll [53]).

The graph concerns cellulose trinitrate and aliphatic solvents including alcohols, ketones, esters, nitroparaffins, chloroderivatives of hydrocarbons. The liquids are ranged in respect of their fi2/s values and of surface tension a. 

Other liquids capable of dissolving trinitrate give less viscous solutions. The constants fi2/e and a for those substances are situated in an area enclosed by the curve B. Values of both constants that lie outside the curve B, in the area C, indicate solvents which are merely able to cause cellulose trinitrate to swell (Fig. 99). 

Cellulose trinitrate, 13.8% N, undergoes rapid denitration at room temperature when treated with dry pyridine. Segall and Purves [55a] have stated that in the presence of hydroxylamine the course of the reaction is changed one molecule of N2 is produced and a highly polymerized fibre-like dinitrate with a number of nitro groups 1.7 is formed. During this reaction denitration without degradation takes place. 

The hydrolytic activity of sulphuric acid is one of reasons why efforts to obtain cellulose trinitrate by treatment with mixtures composed of nitric acid and sulphuric acid were a failure. The maximum percentage of nitrogen combined in ester form was not higher than 13.96%. 

It has been established (Bouchonnet, Trombe and Petitpas [35]) that cellulose trinitrate with 14.14% N can be obtained as result of nitrating linters with a mixture composed of 50% of nitrig acid, 25% of acetic acid and 25% of acetic anhydride for 5 hr at 15°C. The product was stabilized by alcohol extraction. 

Thus, Bouchonnet [48] nitrated cellulose in a solution of nitrogen pentoxide in carbon tetrachloride, to obtain a stable cellulose trinitrate of 14.1% N. Similar... 

Dalmon [72] reacted the fibre of Chinese nettle (ramie) with nitric anhydride in a stream of dry air. Nitrocellulose containing as much as 14.12% N, i.e. cellulose trinitrate (within the limits of analytical error), was obtained. T. Urban-ski and Janiszewski [56] obtained a nitrogen content of 13.90-13.95% on repeating these experiments with cotton (linters) at 25°C. 

The accessibility of the OH groups in cellulose is 96-99% when nitrated with mixed acids. The accessibility of 0N02 in cellulose trinitrate on denitration is only ca. 70%. The latter value is much lower than the former because of the much higher crystallinity of the trinitrate compared with that of the lower substituted cellulose nitrates. The difference may explain why the rate of nitration is higher than that of denitration. The inaccessible regions in the nitration are to be attributed to cellulose junction points and in the denitration of cellulose trinitrate to trinitrate junction points . 

Lab investigation of multiphase nitration of cellulose) 243)P-Lhoste, MP 40, 77-81(1958) CA 55, 3055(196l)(Sulfuric acid impurity in cellulose trinitrate prepd by mixed acids) -244) P.Lhoste O.Naud, MP 40, 83 92(1958) CA 55, 3053(196l)(Stability of cellulose trinitrate... 

Holtzer, A. M., H. Benoit and P. Doty The molecular configuration and hydrodynamic behavior of cellulose trinitrate. J. Phys. Chem. 58, 624 (1954). 

H 9 Hunt, M. L., S. Newman, H. A. Scheraga and P. J. Flory Dimensions and hydrodynamic properties of cellulose trinitrate molecules in dilute solutions. J. Phys. Chem. 60, 1278 (1956). 

The classic example of the extended cellulose chain is, of course, cellulose trinitrate, to which we now turn. The most extensive viscosity measurements include those of Immergut, Ranby and Mark 131) and of Harland (5). These data are plotted in Fig. 20. Although the molecular weight ranges from 3 104 to about 106, the points scatter to a considerable extent, as the difficulty of working with this material is well known. 

As with so many significant discoveries, serendipity smiled on Christan Schonbem when he accidentally synthesized cellulose trinitrate by using his... 

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