Polymer degradation cellulose

Boron also reacts with hydroxyl-containing polymers such as cellulose. When exposed to a flame the boron and hydroxyl groups form a glassy ester that coats the substrate and reduces polymer degradation. A similar type of action has been observed in the boron—alumina tfihydrate system. 

Acid anhydrides have been employed with, and without the use of a base catalyst. For example, acetates, propionates, butyrates, and their mixed esters, DS of 1 to ca. 3, have been obtained by reaction of activated cellulose with the corresponding anhydride, or two anhydrides, starting with the one with the smaller volume. In all cases, the distribution of both ester groups was almost statistic. Activation has been carried out by partial solvent distillation, and later by heat activation, under reduced pressure, of the native cellulose (bagasse, sisal), or the mercerized one (cotton linters). No catalyst has been employed the anhydride/AGU ratio was stoichiometric for microcrystalhne cellulose. Alternatively, 50% excess of anhydride (relative to targeted DS) has been employed for fibrous celluloses. In all cases, polymer degradation was minimum, and functionalization occurs preferentially at Ce ( C NMR spectroscopic analysis [52,56,57]). 

In principle, some of these problems may be avoided if the carboxylic acid proper is employed for cellulose esterification. This approach, however, is not attractive because low yield, and polymer degradation are expected. The rea-... 

Scarcely had the covalent chain concept of the structure of high polymers found root when theoretical chemists began to invade the field. In 1930 Kuhn o published the first application of the methods of statistics to a polymer problem he derived formulas expressing the molecular weight distribution in degraded cellulose on the assumption that splitting of interunit bonds occurs at random. 

Cholesteric lyotropic mesophases of cellulose in LiCl-DMAC solutions at 1(>-15% (w/w) concentration have been observed by Ciferri and coworkers (19.59.61.62) and McCormick et al. (63). LiCl/DMAC ratios between 3/97 and 11/89 (w/w) were used. LiCl-DMAC does not degrade cellulose and does not react with the polymer (59). It does form a complex with the OH CToups on cellulose which is believed to result in dissolution (62). Optical rotary dispersions are negative, indicating the superhelicoidal structure has a left-handed twist. 

Cellulose Cellulose is a straight-chain polymer of glucose units linked by (31-4 bonds. The polysaccharide chains are aligned to form fibrils that have great tensile strength. Cellulases, enzymes that degrade cellulose, are absent in mammals but are produced by some bacteria, fungi and protozoa. 

A second and distinct era in the development of branched macromolecular architecture encompasses the time between 1940 to 1978, or approximately the next four decades. Kuhn 151 published the first report of the use of statistical methods for analysis of a polymer problem in 1930. Equations were derived for molecular weight distributions of degraded cellulose. Thereafter, mathematical analyses of polymer properties and interactions flourished. Perhaps no single person has affected linear and non-linear polymer chemistry as profoundly as P. J. Flory. His contributions were rewarded by receipt of the Nobel Prize for Chemistry in 1974. 

A.A. Faroq, D. Price, G.J. Milnes, and A.R. Horrocks, Use of GC analysis of volatile products to investigate the mechanisms underlying the influence of flame retardants on the pyrolysis of cellulose in air. Polym. Degrad. Stab., 33, 155-170 (1991). 

A condensation polymer is one in which the repeating unit lacks certain atoms which were present in the monomer(s) from which the polymer was formed or to which it can be degraded by chemical means. Condensation polymers are formed from bi- or polyfunctional monomers by reactions which involve elimination of some smaller molecule. Polyesters (e.g., 1-5) and polyamides like 1-6 are examples of such thermoplastic polymers. Phenol-formaldehyde resins (Fig. 5-1) are thermosetting condensation polymers. All these polymers are directly synthesized by condensation reactions. Other condensation polymers like cellulose (1-11) or starches can be hydrolyzed to glucose units. Their chemical structure indicates that their repealing units consist of linked glucose entities which lack the elements of water. They are also considered to be condensation polymers although they have not been synthesized yet in the laboratory. 

Cellulosic materials such as wood flour, paper, and rayon improve biodegradation of poly(lactic acid) in aerobic soil (Figure 11.19). The polymer degrades at a rate similar to... 

Zou X, Gurnagul N. Uesaka T and Bouchard J (1994), Accelarated aging of papers of pure cellulose, mechanism of cellulose degradation and paper embritlement . Polymer Degradation and Stabilization, 43(3), 393 02. 

The major causes of instability of cellulose nitrate are due to the products of hydrolytic, thermal and photochemical reactions. Degradation of the polymer is autocatalytic, that is, the products of breakdown tend to catalyse a faster and more extensive degradation reaction than the primary processes, if allowed to remain in contact with degraded cellulose nitrate. 

Paetau, L C.Z. Chen J.L. Jane. Effects of crosslinking and cellulose incorporation on mechanical properties and water absorption./. Environ. Polym. Degrad. 1994b, A 211-217. 

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