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Acetate, mixed acetate propionate and acetate butyrate, and nitrate esters of cellulose are produced commercially [Brewer and Boagan, 1985; Heinze and Liebert, 2001]. Most products fall into either of two categories about 2.4 or close to 3 ester groups per repeat unit. As a result of decreased hydrogen bonding and crystallinity relative to cellulose, these esters are thermoplastic (i.e., they ow when heated) and can be manufactured into products by extrusion, molding, and similar processes. All cellulose esters except the triacetate generally require plasticization to achieve the required ow behavior. Plasticization is insuf cient for the triacetate and processing is usually carried out in solutions of methylene chloride methanol. Cellulose acetate is the most important ester derivative of cellulose. It is produced by acetylation of cellulose using acetic anhydride in acetic acid in the presence of a strong acid catalyst (usually sulfuric acid). In Eq. 9-29 the symbol is a general means of repreP senting a polymer molecule minus the functional group of interest and P OH speci cally

9-29

The Federal Reserve Banks raised their rediscount rates to 7% and held them there throughout the year of heavy deflation that followed Commercial paper averaged 750% for the year, its highest annual average until 1969 Call money touched 25% and averaged 774% The Treasury issued six-month certificates at 575% and twelve-month certificates at 6%, and these sold to yield as much as 775% The yield curve became sharply negative: the shorter the maturity, the higher the yield From January to May of 1920, the average of prime corporate bond yields rose from 495 to 556%, the highest yield of the century until 1967 Market liquidation, however, was centered in Liberty Bonds It is estimated that of 18 million original subscribers to Liberty Bonds, 14 million sold out (515) Price fluctuations of as much as 111 2% occurred in thirty days.

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represents the cellulose molecule, although it could also represent poly(vinyl alcohol) or any other polymer containing a hydroxyl group. Partially acetylated cellulose (i.e., cellulose with less than three ester groups per repeat unit) is produced by an indirect route. Direct synthesis yields an inhomogeneous product due to insolubility of cellulose in the reaction mixture. Some chains are completely acetylated while others may be completely unreacted. A partially acetylated product is usually produced by controlled hydrolysis of the triacetate. The triacetate is soluble in the reaction mixture and complete solubility ensures that the nal product will be more homogeneous. Hydrolysis of the triacetate is carried out by controlled reversal of the esteri cation reaction by the addition of water or dilute acetic acid. Cellulose acetate and other esters are tough, strong materials with good optical clarity. The acetate has the best strength and hardness while the acetate butyrate is better in weatherability, dimensional stability, and low-temperature impact strength. The acetate propionate has properties in between the other two materials. The largest-volume application of cellulose acetate is as a ber for textiles (clothes, draperies, and bedspreads) and cigarette lters. Plastic applications for cellulose acetate and the mixed ester derivatives include eyeglass frames, photographic lm, combs, brush handles, lm and sheet for decorative signs, and lacquers and protective coatings for automobiles and wood furniture. Cellulose nitrate is used for lacquer nishes (automobiles, wood furniture), explosives, and propellants.

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Various ether derivatives of cellulose, including some that are water-soluble, are important [Heinz and Liebert, 2001; Just and Majewicz, 1985; Zhang, 2001]. Methyl cellulose and carboxymethyl cellulose (R CH3 and CH2 COOH, respectively) are synthesized by reaction of cellulose with sodium hydroxide followed by the appropriate alkyl halide:

9-30

The first 31 2s of 1947 declined from 100 to 891 8, to yield 418%, taxexempt; the comparatively short-term Third 41 4s of 1928 declined from 95 to 855 8, to yield 658%, PTE; and the longer Fourth 41 4s of 1938 declined from 94 to 82, to yield 582%, PTE A representative group of high-grade corporate bond issues at their low prices of this decade are shown in the table below..

Hydroxyethyl cellulose is produced by using ethylene oxide in place of the halide. Applications for these products include lacquers, additives for detergents, food, drilling muds, and paints. 9-3d Chitin

Chitin is a polysaccharide similar to cellulose except that the OH at C 2 is replaced by an acetamido group (CH3 CONH). Chitin is the main component of the hard external covering (exoskeleton) of crustaceans such as lobsters, crabs, and shrimp. Like cellulose, the processing of chitin into polymeric products is limited by its insolubility and decomposition without melting. The availability in huge quantities has encouraged many attempts to nd commercial applications of chitin, but very few have been found to be economically feasible. 9-4 REACTIONS OF POLY(VINYL ACETATE) In addition to its use as a plastic, poly(vinyl acetate) is used to produce two polymers that cannot be synthesized directly since their monomers do not exist. Poly(vinyl alcohol) is obtained by alcoholysis of poly(vinyl acetate) with methanol:

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