Esters of cellulose

In order to find a safer non-flammable alternative to nitrocellulose, cellulose esters of lower organic acids have been developed and commercialized. 

Cellulose acetate is prepared by reacting cellulose with acetic acid or acetic anhydride in the presence of a catalyst. Cellulose acetate has low flammability and better weathering resistance, but is of little interest as a binder for coatings due to its limited solubility and sensitivity to hydrolysis. 

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Eor two different esters of cellulose, 1q values are listed here in two different temperature regions, 30 and 130-140°C ... 

Fig. 1. Acetyl value and combined acetic acid for acetate esters of cellulose. Designations are as follows CA = acetate(DS = 2.4) CELL = cellulose(DS = 0) CTA = triacetate(DS = 3.0). Combined acetic acid (%) = 6005(DS)/( 159.1 + 43.04(DS)) acetyl value...

Cellulose esters of aromatic acids, aUphatic acids containing more than four carbon atoms and aUphatic diacids are difficult and expensive to prepare because of the poor reactivity of the corresponding anhydrides with cellulose Httle commercial interest has been shown in these esters. Of notable exception, however, is the recent interest in the mixed esters of cellulose succinates, prepared by the sodium acetate catalyzed reaction of cellulose with succinic anhydride. The additional expense incurred in manufacturing succinate esters is compensated by the improved film properties observed in waterborne coatings (5). 

Mixed esters containing the dicarboxylate moiety, eg, cellulose acetate phthalate, are usually prepared from the partially hydroly2ed lower aUphatic acid ester of cellulose in acetic acid solvent by using the corresponding dicarboxyhc acid anhydride and a basic catalyst such as sodium acetate (41,42). Cellulose acetate succinate and cellulose acetate butyrate succinate are manufactured by similar methods as described in reference 43. 

Other inorganic esters of cellulose have been frequendy described and investigated. However, only CN has achieved any commercial significance. 

CN is the oldest and most important inorganic ester of cellulose. It is a white, ododess, and tasteless substance. It has found uses in plastics, lacquers, and explosives. CN is manufactured by treating cellulose with nitric acid in the presence of sulfuric acid and water. The amount of water determines the DS attained (11,48,49). 

Nitro-filter cloths are composed of cellulose nitrate, which is an ester of cellulose. Any chemical compound that will saponify the ester will destroy the cloth. Caustic soda or potash in strengths of 2% at 70° C or over alkali sulfides, polysulfides and sulfohydrates or mixtures of ethyl alcohol and ether, ethyl, amyl and butyl acetates, pyridine, ferrous sulfates, and other reducing agents are detrimental to the cloth. 

Nitrocellulose, of the resins used in these end uses and in car refinishing, is the nitrate ester of cellulose. The structure is linear and a wide range of (high) molecular weights is available as well as various degrees of nitration ... 

In 1833 Braconnot obtained nitric esters of cellulose and starch by acting with nitric acid on plant fibres and starch, at low temperature. 

Several review articles are available on the synthesis, physico-chemical properties, and bio degradability of natural-based polymers, and their composites [6-9]. The same aspects have been the subjects of recent books [10-12]. In the following account, we concentrate on organic esters of cellulose. 

Schemes are available, however, that start from the free carboxylic acid, plus an activator . Dicyclohexylcarbodiimide, DCC, has been extensively employed as a promoter in esterification reactions, and in protein chemistry for peptide bond formation [187]. Although the reagent is toxic, and a stoichiometric concentration or more is necessary, this procedure is very useful, especially when a new derivative is targeted. The reaction usually proceeds at room temperature, is not subject to steric hindrance, and the conditions are mild, so that several types of functional groups can be employed, including acid-sensitive unsaturated acyl groups. In combination with 4-pyrrolidinonepyridine, this reagent has been employed for the preparation of long-chain fatty esters of cellulose from carboxylic acids, as depicted in Fig. 5 [166,185,188] ...

Contact of cellulose acetate with 1200 1 of uncooled anhydrous acid in acetic anhydride led to a particularly disastrous explosion [1], and interaction of benzyl cellulose with boiling 72% acid was also explosive [3], Perchlorate esters of cellulose may have been involved in all these incidents. 

The most widely used inorganic ester of cellulose is cellulose nitrate (CN), also called nitrocellulose or gun cotton. Celluloid is produced from a mixture of CN and camphor. It was first made in 1833 when cellulose-containing linen, paper, or sawdust was reacted with concentrated nitric acid. It was the first synthetic cellulose product that was recognized. Initially, CN was used as a military explosive and improvements allowed the manufacture of smokeless powder. A representation of CN is given in structure 9.7. 

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