Cellulose insolubility

Question Why is cellulose insoluble, while starch, which appears to have a very similar structure, is soluble ... 

Qualification of different cellulose sources for the various end use applications is determined on the basis of purity, molecular size, and a-cellulose content, a-cellulose refers to the portion of cellulose insoluble in 18% aqueous sodium hydroxide. Whereas the content of noncellulosic polysaccharides has proven to be a hindrance to the clarity of cellulose esters (determined as haze in otherwise clear films), a-cellulose content is important for the spinnability of cellulose solutions into regenerated fibers, and for viscosity characteristics of cellulose ethers. Molecular weights play an important role in various cellulose ethers. 

Ethyl cellulose Insoluble in water, regardless of pH soluble in some organic solvents Controlled-release coatings Aqueous dispersions (20-30% solids)... 

The cellulose chains do not form coils like amylose but are aligned in parallel rows that are held in place by hydrogen bonds between hydroxyl groups in adjacent chains, making cellulose insoluble in water. This gives a rigid structnre to the cell walls in wood and fiber that is more resistant to hydrolysis than are the starches (see Fignre 13.12). 

Cellulose. This is insoluble in water, hot and cold. It dissolves in a solution of Schweitzer s reagent (precipitated cupric hydroxide is washed free from salts and then dissolved in concentrated ammonia solution), from which it is precipitated by the addition of dilute acids. Cellulose is not hydrolysed by dilute hydrochloric acid. 

Sodium carboxymethyl cellulose [9004-32-4] (CMC) and hydroxyethyl cellulose [9004-62-0] (HEC) are the ceUulosics most widely used in drilling fluids (43). CMC is manufactured by carboxymethylation of cellulose which changes the water-insoluble cellulose into the water-soluble CMC (44). Hydroxyethyl cellulose and carboxymethyl hydroxyethyl cellulose (CMHEC) are made by a similar process. The viscosity grade of the material is determined by the degree of substitution and the molecular weight of the finished product. 

Emulsion polymerizations of vinyl acetate in the presence of ethylene oxide- or propylene oxide-based surfactants and protective coUoids also are characterized by the formation of graft copolymers of vinyl acetate on these materials. This was also observed in mixed systems of hydroxyethyl cellulose and nonylphenol ethoxylates. The oxyethylene chain groups supply the specific site of transfer (111). The concentration of insoluble (grafted) polymer decreases with increase in surfactant ratio, and (max) is observed at an ethoxylation degree of 8 (112). 

Commercial Disperse Azo Dyes. The first proposal to use insoluble dyes in suspension in an aqueous foam bath, ie, disperse dyes, to dye cellulose acetate was in 1921 (60). Commercialization of disperse dyes began in 1924 with the introduction of the Duranol dyes by British Dyestuffs Corporation (61) and the SRA dyes by British Celanese Company (62). In contrast to the acid monoazo dyes, derivatives of benzene rather than of naphthalene are of the greatest importance as coupling components. Among these components mono- and dialkylariifines (especially A/-P-hydroxyethyl-and A/-(3-acetoxyethylanifine derivatives) are widely used couplers. Nitrodiazobenzenes are widely used as diazo components. A typical example is CeUiton Scarlet B [2872-52-8] (91) (Cl Disperse Red 1 Cl 11110). 

Since polysaccharides are the most abundant of the carbohydrates, it is not surprising that they comprise the greatest part of industrial utiliza tion (9,22). Most of the low molecular weight carbohydrates of commerce are produced by depolymerization of starch. Polysaccharide materials of commerce can be thought of as falling into three classes cellulose, a water-insoluble material starches, which are not water-soluble until cooked and water-soluble gums. 

In one process to produce highly activated cellulose for acetylation, cellulose is treated with NaOH (mercerization) followed by a hydroxyalkylating agent, eg, ethylene oxide or propylene oxide, to give a cellulose hydroxyalkyl ether with a DS of 0.05—0.3 (76). The resulting water-insoluble material is highly reactive to conventional acetic anhydride—sulfuric acid acetylation. 

CP can also be prepared by the reaction of cellulose with phosphoms oxychloride in pyridine (37) or ether in the presence of sodium hydroxide (38). For the most part these methods yield insoluble, cross-linked, CP with a low DS. A newer method based on reaction of cellulose with molten urea—H PO is claimed to give water soluble CP (39). The action of H PO and P2 5 cellulose in an alcohol diluent gives a stable, water-soluble CP with a high DS (>5% P) (40). These esters are dame resistant and have viscosities up to 6000 mPa-s(=cP) in 5 wt % solution. Cellulose dissolved in mixtures of DMF—N2O4 can be treated with PCl to give cellulose phosphite [37264-91-8] (41) containing 11.5% P and only 0.8% Cl. Cellulose phosphinate [67357-37-5] and cellulose phosphonate [37264-91 -8] h.a.ve been prepared (42). 

Unlike HEC and CMC, which are purified by washing with aqueous organic solvents, methylceUulose and its hydroxyalkyl modifications are purified in hot water where they are insoluble. As with other cellulose ethers, drying and grinding complete the process. 

Detergent Methods. The neutral detergent fiber (NDF) and acid detergent fiber (ADF) methods (2), later modified for human foods (13), measure total insoluble plant cell wall material (NDF) and the cellulose—lignin complex (ADF). The easily solubilized pectins and some associated polysaccharides, galactomaimans of legume seeds, various plant gums, and seaweed polysaccharides are extracted away from the NDF. They caimot be recovered easily from the extract, and therefore the soluble fiber fraction is lost. 

Because of the insolubility of cellulose it is not possible to carry out uniform esterification with the lower organic acids (acetic acid, propionic acid etc.) and in those cases where incompletely substituted derivatives are required a two-stage reaction is employed. This involves total esterification in a medium in... 

Nitration of cellulose followed by plasticisation of the product with camphor has the effect of reducing the orderly close packing of the cellulose molecules. Hence whereas cellulose is insoluble in solvents, except in certain cases where there is chemical reaction, celluloid is soluble in solvents such as acetone and amyl acetate. In addition the camphor present may be dissolved out by chloroform and similar solvents which do not dissolve the cellulose nitrate. 

The cellulose molecule is rigid and forms strong hydrogen bonds with adjacent molecules. It is thus insoluble and decomposes before softening on heating. Partial replacement of hydroxyl groups by acetyl groups has a number of effects ... 

Because of high interchain bonding, cellulose is insoluble in solvents and is incapable of flow on heating, the degradation temperature being reached before the material starts to flow. It is thus somewhat intractable in its native form. Cellulose, however, may be chemically treated so that the modified products may... 

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