Solubility cellulosics

Cellulose Deriva.tives, Cellulose can be derivatized to make both water-soluble gums and hydrophobic polymers. The preparation of the hydrophobic cellulose esters (qv), cellulose acetates and cellulose nitrates, has already been mentioned. The water-soluble cellulose derivatives are cellulose ethers (qv). 

Cellulose acetate [9004-35-7] is the most important organic ester because of its broad appHcation in fibers and plastics it is prepared in multi-ton quantities with degrees of substitution (DS) ranging from that of hydrolyzed, water-soluble monoacetates to those of fully substituted triacetate (Table 1). Soluble cellulose acetate was first prepared in 1865 by heating cotton and acetic anhydride at 180°C (1). Using sulfuric acid as a catalyst permitted preparation at lower temperatures (2), and later, partial hydrolysis of the triacetate gave an acetone-soluble cellulose acetate (3). The solubiUty of partially hydrolyzed (secondary) cellulose acetate in less expensive and less toxic solvents such as acetone aided substantially in its subsequent commercial development. 

Several derivatives of cellulose, including cellulose acetate, can be prepared in solution in dimethylacetamide—lithium chloride (65). Reportedly, this combination does not react with the hydroxy groups, thus leaving them free for esterification or etherification reactions. In another homogeneous-solution method, cellulose is treated with dinitrogen tetroxide in DMF to form the soluble cellulose nitrite ester this is then ester-interchanged with acetic anhydride (66). With pyridine as the catalyst, this method yields cellulose acetate with DS < 2.0. 

An alcohol-soluble cellulose acetate butyrate containing ca 50% butyryl and ca 4.5% hydroxyls available commercially. 

Table 14. Flexographic Ink Formulation Containing Alcohol-Soluble Cellulose Acetate Propionate...

Soluble Cellulose Nitrate, ASTM D301-72, American Society for Testing and Materials, Philadelphia, Pa., 1983. 

An example of the first type is the emulsion stabiliser as exemplified by sodium oleyl sulphate, cetyl pyridinium chloride and poly(ethylene oxide) derivatives. For a number of applications it is desirable that the latex be thickened before use, in which case thickening agents such as water-soluble cellulose ethers or certain alginates or methacrylates may be employed. Antifoams such as silicone oils are occasionally required. 

Although acetylation thus renders the cellulosic structure soluble, cellulose acetate will still decompose below its softening point. It is thus necessary to compound cellulose acetate with plasticisers in order to obtain plastics materials of suitable flow properties. Other ingredients are also added at the same time. 

A number of water-soluble cellulose ethers are marketed." Methyl cellulose is prepared by a method similar to that used for ethyl cellulose. A degree of substitution of 1.6-1.8 is usual since the resultant ether is soluble in cold water but not in hot. It is used as a thickening agent and emulsifier in cosmetics, as a paper size, in pharmaceuticals, in ceramics and in leather tanning operations. 

The heat exchanger fins from aluminum or its alloy are coated with aqueous solution containing a water-soluble cellulose resin or polyvinyl alcohol and a surfactant to form a hydrophilic film. Phosphoric acid ester was used as anionic surfactant (0.05-4.5%) in aqueous solution to form a hydrophilic film showing contact angle with water of 5-32° [288]. 

Barth, H. G. and Regnier, F. E., High-performance gel permeation chromatography of water-soluble cellulosics, /. Chromatogr., 192, 275, 1980. 

Barth, H.G. and Regnier, F.E. "High Performance Gel Permeation Chromatography of Water-Soluble Cellulosics." J. Chromatog.(19801 192, 275 293. 

Unmodified and anionically modified starches, soluble cellulose derivatives such as carboxymethylcellulose, polyvinyl alcohol, latex and other polymers are also used in some specialised applications. Starch, however, because of its cost, is by far the most common dry strength additive, about twenty times more being used than, for example, polyacrylamide. 

Surface sizes are usually solutions of water-soluble polymers. The most important of which, because of its commercial cheapness, is starch. Other more costly but more specialised film-forming polymers such as soluble cellulose derivatives (particularly carboxy-methyl cellulose), polyvinyl alcohol and alginates are also used. 

Other water-soluble polymers which do not tend to suffer from problems of retrogradation are sometimes used when different properties are required. Soluble cellulose derivatives, particularly car-boxymethyl cellulose, which is prepared by reaction of high purity cellulose with chloroacetic acid in the presence of alkali (equation 8.1), is popular for surface sizing base papers which are subsequently to be coated, because it assists in water removal when the coating mix is applied. 

Previous work by us has led to the synthesis of silicon, germanium and tin polyethers utilizing Interfacial systems (for instance 5-9). The tin-cotton products should possess an analogous structure from previously reported similarities in reactivity of soluble cellulosic hydroxyls with organic acid chlorides... 

Emulsion as an Explosive. D.R. Wiggam (USP 1999828 CA 29, 4180(1935) prepd an emulsion suitable as an explosive by rapidly agitating NG with a water-soluble cellulose ether, such as methyl cellulose Ref Clift Fedoroff, Vol 2(1943), p El... 

Refs l)Hercules Powder Co, "CMC. A Water-Soluble Cellulose Gum , Wilmington,... 

Acetone-soluble cellulose acetate is prepared by deacetylating cellulose triacetate. The product formed directly is unsatisfactory. Thus the distribution of free hydroxyls and acetate groupings is of primary importance. Cramer and Purves118(b) studied the distribution by tosylation and found that the acetyl removal from primary and secondary hydroxyl groups occurs at approximately the same rate, but that the number of... 

Different water-soluble cellulose derivatives have been used for the determination of endocellulase activities. Carboxymethylcellulose (CMC) has been proposed as substrate and recently Almin et al. (3) have improved their method for the calculation of endocellulase activities, using a medium-molecular-weight CMC (Mv = 299,000 and Mw = 142,000) with well-defined physicochemical properties. No corrections... 

Most experiments were performed with cotton or cotton linters as highly crystalline celluloses. Table I shows conditions leading to complete dissolution. A minimum amount of an acid which forms a cellulose ester (sulfuric or trifluoromethylsulfuric acid) (Entries 5 7-14) is necessary for the reaction. The dissolution is accelerated by a temperature increase (Entries 10-12 13, 14) and leads to water-soluble cellulose acetate hydrogensulfate. Whereas this primary hydrolysis can be achieved within 1-5 min, the deesterification and complete hydrolysis of the soluble cellulose derivative proved to be much more difficult. This is in contrast to the generally accepted view that the main resistance to the hydrolysis of cellulose lies in the crystalline nature or low accessibility determining the heterogeneous first step of the reaction. 

The complete hydrolysis of the soluble cellulose derivative required gradual addition of water and, preferably, acid. Water can act on cellulose acetate hydrogensulfate in three ways (a) saponification of sulfate groups, (b) saponification of acetate groups, and (c) hydrolysis of glycosidic bonds. Reaction (a) is most rapid and occurs under the mildest conditions. As Table II shows, the product is not any more water soluble (Entries 1-4). Under more severe conditions, the deacetylation (b) has proceeded to water-soluble products, the total amount of dissolved carbohydrates corresponding to theory (Entries 5-10). How-... 

Figure 9. Effect of enzyme components from T. koningii cellulose on the formation of alkali-soluble cellulose from cotton fiber. A reaction mixture consisting of 200 mg of cotton, 2 mL of 0.2 M acetate buffer, pH 4.5, enzyme, water, and NaNs solution to give a total volume of 10 mL, was incubated at 50°C for various times. Percentage hydrolysis was calculated from the loss in weight determined on weighed crucibles. The fraction soluble in alkali (10% NaOH) was determined in a similar fashion after incubating for 3 hr at 25°C. Ct ( - 0) Cx + /3-glucosidase ( - ) ...

---