Cellulose, esterification

Cellulosics. CeUulosic adhesives are obtained by modification of cellulose [9004-34-6] (qv) which comes from cotton linters and wood pulp. Cellulose can be nitrated to provide cellulose nitrate [9004-70-0] which is soluble in organic solvents. When cellulose nitrate is dissolved in amyl acetate [628-63-7] for example, a general purpose solvent-based adhesive which is both waterproof and flexible is formed. Cellulose esterification leads to materials such as cellulose acetate [9004-35-7], which has been used as a pressure-sensitive adhesive tape backing. Cellulose can also be ethoxylated, providing hydroxyethylceUulose which is useful as a thickening agent for poly(vinyl acetate) emulsion adhesives. Etherification leads to materials such as methylceUulose [9004-67-5] which are soluble in water and can be modified with glyceral [56-81-5] to produce adhesives used as wallpaper paste (see Cellulose esters Cellulose ethers). 

Zinc chloride is a Lewis acid catalyst that promotes cellulose esterification. However, because of the large quantities required, this type of catalyst would be uneconomical for commercial use. Other compounds such as titanium alkoxides, eg, tetrabutoxytitanium (80), sulfate salts containing cadmium, aluminum, and ammonium ions (81), sulfamic acid, and ammonium sulfate (82) have been reported as catalysts for cellulose acetate production. In general, they require reaction temperatures above 50°C for complete esterification. Relatively small amounts (<0.5%) of sulfuric acid combined with phosphoric acid (83), sulfonic acids, eg, methanesulfonic, or alkyl phosphites (84) have been reported as good acetylation catalysts, especially at reaction temperatures above 90°C. 

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-... 

In applying cellulose esterification methods to starch, it must be remembered that starch is much more easily hydrolyzed than cellulose. Many esterification procedures for cellulose are too drastic to be applied to starch unless milder reaction conditions are provided. 

Starch has been acetylated by Barnett s mixture, W hich is composed of acetic acid, acetic anhydride, and a catalyst consisting of equal parts of sulfur dioxide and chlorine. This mixture, originally developed for cellulose esterification," readily acetylates starch at 55 , the acetyl content reaching the theoretical value of 44.8% in about four hours. A critical evaluation of the reaction by Hassid and Dore, and particularly by Higginbotham and Richardson, has shown that the acetates prepared have the viscosity, reducing power, and solubility characteristics indicative of a partially degraded starch. 

Esterification and Hydrolysis. In the course of the production of organic esters of cellulose, esterification is performed by mixing cellulose with the appropriate organic acids, anhydrides, and catalysts. Normally, the reaction of this mixture proceeds rapidly and is permitted to continue until the three hydroxyl groups on each anhydroglucose unit have been replaced with the acyl group of the organic acid or mixture of acids. 

Figure 17.8 Mechanism of the cellulose esterification with octyl anhydride.

Table 3. Cellulose esterification at 19S°C with octanoic acid in the presence of different...

Table 4. Cellulose esterification at 19S C with different fetty acids in the presence of...

Cellulose esterification does not basically differ from the path shown in Figure 21.8. In fact, the esterification reaction is occurred by the primary and secondary hydroxyl groups of cellulose instead of alcohols. A U.S. patent for the preparation of cellulose ester was issued to Kuo and Leonard in 1984 [28]. 

Cellulose triacetate is obtained by the esterification of cellulose (qv) with acetic anhydride (see Cellulose esters). Commercial triacetate is not quite the precise chemical entity depicted as (1) because acetylation does not quite reach the maximum 3.0 acetyl groups per glucose unit. Secondary cellulose acetate is obtained by hydrolysis of the triacetate to an average degree of substitution (DS) of 2.4 acetyl groups per glucose unit. There is no satisfactory commercial means to acetylate direcdy to the 2.4 acetyl level and obtain a secondary acetate that has the desired solubiUty needed for fiber preparation. 

Alcohols and glycerols are nitrated by esterification ia a mixture of concentrated nitric and sulfuric acids. This reaction is of importance ia the production of nitroglycerin from glycerol and nitrocellulose from cellulose. 

Every polysaccharide contains glycosyl units with unsubstituted hydroxyl groups available for esterification or etherification. Polysaccharide derivatives are described by their degree of substitution (DS), which is the average number of substituent groups per glycosyl unit. Because each monomeric unit of cellulose molecules has free hydroxyl groups at C-2, C-3, and C-6, the maximum DS for cellulose, and all polysaccharides composed exclusively of neutral hexosyl units, the majority of polysaccharides, is 3.0. 

Cellulose activated with ethylenediarnine [107-15-3] is used to prepare high molecular-weight cellulose butyrate (23). Cellulose so activated has a larger measured surface area (120 m /g) than cellulose activated with acetic acid (4.8 m /g). The diamine is removed with water, followed by solvent exchange with acetic acid and butyric acid before esterification. 

Fig. 5. Composition of cellulose acetate butyrate (propionate) as a function of butyryl (propionyl) content of esterification bath.

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. 

Ethylenediamine (70,71), benzyl alcohol and acetone (72), ethylene glycol (73) and C2—C g carboxyUc acids (74) are claimed to increase the reactivity of cellulose toward acetylation. Sodium hydroxide and Hquid ammonia (71) are excellent swelling agents and have been used to activate cellulose before esterification. Ultrasonic treatment of cellulose slurries (75) reportedly swells the fibers and improves reactivity. 

Determining the degree of substitution using standard proton nmr refles on the integral ratio between the ceUulosic ring protons ( i 5.0-2.96) and the ester alkyl protons ( i 1.26 for butyryl and propionyl and i 2.06 for acetyl methyl groups). This simple procedure is used extensively to determine the extent of esterification and is currently the fastest, easiest way for determining the DS of mixed cellulose esters. 

Etherification. The accessible, available hydroxyl groups on the 2, 3, and 6 positions of the anhydroglucose residue are quite reactive (40) and provide sites for much of the current modification of cotton ceUulose to impart special or value-added properties. The two most common classes into which modifications fall include etherification and esterification of the cotton ceUulose hydroxyls as weU as addition reactions with certain unsaturated compounds to produce ceUulose ethers (see Cellulose, ethers). One large class of ceUulose-reactive dyestuffs in commercial use attaches to the ceUulose through an alkaH-catalyzed etherification by nucleophilic attack of the chlorotriazine moiety of the dyestuff ... 

However, this method is appHed only when esterification cannot be effected by the usual acid—alcohol reaction because of the higher cost of the anhydrides. The production of cellulose acetate (see Fibers, cellulose esters), phenyl acetate (used in acetaminophen production), and aspirin (acetylsahcyhc acid) (see Salicylic acid) are examples of the large-scale use of acetic anhydride. The speed of acylation is greatiy increased by the use of catalysts (68) such as sulfuric acid, perchloric acid, trifluoroacetic acid, phosphoms pentoxide, 2inc chloride, ferric chloride, sodium acetate, and tertiary amines, eg, 4-dimethylaminopyridine. 

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... 

Esterification is complete in 5-6 hours and the product at this stage is known as primary cellulose acetate. 

---