Poly nitration

This change in editorial leadership has resulted, perhaps inevitably, in a change in editorial policy which is reflected in the contents of Volume 8. There has been a marked de-emphasis on the inclusion of organic parent compounds followed by an exhaustive and voluminous cataloging of azide, azido, azo, diazido, diazonium, diazo, nitro, dinitro, polynitro, hitr amine, nitrate (esters and salts), dinitrate, poly nitrate, nitroso, polynitroso, chlorate, perchlorate, peroxide, picrate, etc, derivatives — regardless of whether any of these derivatives exhibit documented explosive or energetic properties. Only those materials having such properties have been included in this volume... 

The crude mixture of 4- and 5-nitroindanes produced by mixed acid nitration of indane following a literature method [1] is hazardous to purify by distillation. The warm residue from distillation of 15 mmol at 80°C/1.3 mbar exploded on admission of air, and a 1.3 mol batch exploded as distillation began under the same conditions. Removal of higher-boiling poly-nitrated material before distillation is recommended. 

Fluoranthene (Called 1,2-benzo-acenaphthy-len or 1,8-o-phenylen-naphthylen in Ger), C16H10(Thought to be ClaH10in early literature), mw 202.24, colorless ndls, sp gr 1.158 at 20°, nD 1.739 at 20°, bp 393°, 217°(30mm Hg), mp 109.5-110.5°, sol In benz, chlf, eth, HAc hot ale. A tetracyclic fused ring aromatic hydrocarbon, this material is found in some coal tars. It forms definite complexes with many poly nitrated aromatics (Refs 1 to 6) Refs 1) Beil 5, 685, (340, 344), [609] 2276 2) J. vonBraun E. Anton, Ber... 

The reported improvement in yields and selectivities in both mono- and poly-nitration of aromatic compounds using Claycop with acetic anhydride (and if necessary nitric acid) in tetrachloromethane has been investigated.28 The reagent system is found to be modestly catalytic and regioselective in the mononitration of toluene but is neither catalytic nor regioselective in the nitration of 2-nitrotoluene. 

Triple-base + non-vol plasticizers nitroxy-alkyl nitramines (See under Amines), poly-nitrate esters of poly(hydroxymethyl) cyclo-alkanones poly(hydroxymethyl) cyclo-alkanols... 

CA 72, 57361) (1970) [Gelling polyol poly-nitrate—NC expls prepd hy using nitroparaffin solvents. Polynitrates (I) were not good solvents for NC (11) and, as such, were not ca-... 

Nitration, like halogenations, occurs preferentially at the 4- or 5 position in A/ -unsubstituted and A/-substituted imidazoles. As with all nitrations, poly-nitration can occur, and there is the potential for subsequent thermal hazards or runaway reactions. Despite its lack of reactivity, polynitration products have been reported. 

There have been many studies of the orientation of nitration in di- and poly-substituted derivatives of benzene, but in very few cases have... 

Nitration and aromatic reactivity D The nitration of hi- and poly-cyclic compounds... 

Cellulose nitrate resin Poly(aryl ether)... 

Cellulosics. CeUulosic adhesives are obtained by modification of cellulose [9004-34-6] (qv) which comes from cotton linters and wood pulp. Cellulose can be nitrated to provide cellulose nitrate [9004-70-0] which is soluble in organic solvents. When cellulose nitrate is dissolved in amyl acetate [628-63-7] for example, a general purpose solvent-based adhesive which is both waterproof and flexible is formed. Cellulose esterification leads to materials such as cellulose acetate [9004-35-7], which has been used as a pressure-sensitive adhesive tape backing. Cellulose can also be ethoxylated, providing hydroxyethylceUulose which is useful as a thickening agent for poly(vinyl acetate) emulsion adhesives. Etherification leads to materials such as methylceUulose [9004-67-5] which are soluble in water and can be modified with glyceral [56-81-5] to produce adhesives used as wallpaper paste (see Cellulose esters Cellulose ethers). 

By sulfonation of the appropriate naphthaleneamine or aminonaphthalenesulfonic acid. By nitration/reduction of the appropriate naphthalene (poly) sulfonic acid. 

Poly(phenylene oxide)s undergo many substitution reactions (25). Reactions involving the aromatic rings and the methyl groups of DMPPO include bromination (26), displacement of the resultant bromine with phosphoms or amines (27), lithiation (28), and maleic anhydride grafting (29). Additional reactions at the open 3-position on the ring include nitration, alkylation (30), and amidation with isocyanates (31). 

Poly(vinyl nitrate) has been prepared and studied for use in explosives and rocket fuel (104,105). Poly(vinyl alcohol) and sulfur trioxide react to produce poly(vinyl sulfate) (106—111). Poly(vinyl alkane sulfonate)s have been prepared from poly(vinyl alcohol) and alkanesulfonyl chlorides (112—114). In the presence of urea, poly(vinyl alcohol) and phosphoms pentoxide (115) or phosphoric acid (116,117) yield poly(vinyl phosphate)s. 

Citric acid esters are used as plasticizers ia plastics such as poly(viayl chloride), poly(vinhdene chloride), poly(viQyl acetate), poly(viQyl butyral), polypropylene, chlorinated rubber, ethylceUulose, and cellulose nitrate. Most citrate esters are nontoxic and are acceptable by the FDA for use in food-contact packaging and for flavor in certain foods. As a plasticizer, citrate esters provide good heat and light stabiUty and excellent flexibiUty at low temperatures. Triethyl citrate, tri- -butyl citrate, isopropyl citrate, and stearyl citrate are considered GRAS for use as food ingredients (224—228). 

Silver [7440-22-4]—The coloi additive silvei (EEC No. E 174) is a crystaUine powdei of high purity silver prepared by die reaction of silver nitrate with ferrous sulfate in the presence of nitric, phosphoric, and sulfuric acids. Poly(vinyl alcohol) is used to prevent the agglomeration of crystals and the formation of amorphous silver. 

Chisso-Asahi Fertilizer Company, Ltd. This company utilizes thermoplastic resins, such as polyolefins, poly(vinyhdene chloride), and copolymers, as their coating materials. The coatings are dissolved in fast-drying chlorinated hydrocarbon solvents and are appHed to a variety of substrates including urea, diammonium phosphate [7783-28-0] potassium sulfate [7778-80-3], potassium chloride [7447-40-7], and ammonium nitrate/potassium sulfate-based N—P—K fertilizers. 

Comparison of Table 5.4 and 5.7 allows the prediction that aromatic oils will be plasticisers for natural rubber, that dibutyl phthalate will plasticise poly(methyl methacrylate), that tritolyl phosphate will plasticise nitrile rubbers, that dibenzyl ether will plasticise poly(vinylidene chloride) and that dimethyl phthalate will plasticise cellulose diacetate. These predictions are found to be correct. What is not predictable is that camphor should be an effective plasticiser for cellulose nitrate. It would seem that this crystalline material, which has to be dispersed into the polymer with the aid of liquids such as ethyl alcohol, is only compatible with the polymer because of some specific interaction between the carbonyl group present in the camphor with some group in the cellulose nitrate. 

Commercial grades of PVP, K-15, K-30, K-90, and K-120 and the quaternized copolymer of vinylpyrrolidone and dimthylaminoethylmethacrylate (poly-VP/ DMAEMA) made by International Specialty Products (ISP) were used in this study. PEO standard calibration kits were purchased from Polymer Laboratories Ltd. (PL), American Polymer Standards Corporation (APSC), Polymer Standards Service (PSS), and Tosoh Corporation (TSK). In addition, two narrow NIST standards, 1923 and 1924, were used to evaluate commercial PEO standards. Deionized, filtered water, and high-performance liquid chromatography grade methanol purchased from Aldrich or Fischer Scientific were used in this study. Lithium nitrate (LiN03) from Aldrich was the salt added to the mobile phases to control for polyelectrolyte effects. 

The quaternized copolymer of vinylpyrrolidone and dimethylaminoethylmetha-crylate (poly-VP/DMAEMA) has been analyzed successfully with Ultrahydrogel columns and a mobile phase of a 0.1 M Tris pH 7 buffer with 0.3 or 0.5 M lithium nitrate (14). In this study, poor recovery of a poly-VP/DMAEMA sample was noticed when 0.2 M lithium nitrate was used for KB-80M, SB806-MHQ, and TSK GM-PWxl columns. Good recovery was achieved with 0.4 M lithium nitrate, and M of the poly-VP/DMAEMA were found to be 290,000, 300,000, and 320,000 for the respective columns. This demonstrates the equivalence of these columns for SEC of cationic polymers. 

Generation of radicals by redox reactions has also been applied for synthesizing block copolymers. As was mentioned in Section II. D. (see Scheme 23), Ce(IV) is able to form radical sites in hydroxyl-terminated compounds. Thus, Erim et al. [116] produced a hydroxyl-terminated poly(acrylamid) by thermal polymerization using 4,4-azobis(4-cyano pentanol). The polymer formed was in a second step treated with ceric (IV) ammonium nitrate, hence generating oxygen centered radicals capable of starting a second free radical polymeriza-... 

Cordes et al995 carried out alkaline hydrolyses of p-nitrophenylhexanoate 55 (PNPH) in the presence of poly-4-vinylpyridine partially quaternized with dodecyl-bromide and ethylbromide (QPVP). They also found that the polyelectrolytes are increasingly effective as catalysts with an increasing ratio of dodecyl to ethyl groups, and the hydrophobic interactions are important in determining the catalytic efficiency. They observed the inhibitory effects of several gegen-anions fluoride ions are the weakest inhibitor, and nitrate is the strongest (F- < Cl < S04 [Pg.159]

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