Sulfuric acid catalysts cellulose

Cellulose valerates have been synthesized by conventional methods using valeric anhydride and sulfuric acid catalyst (25,26). Alternatively, the cellulose is activated by soaking in water, which is then displaced by methylene chloride or valeric acid the temperature is maintained at <38° C to minimize degradation. 

Solution Process. With the exception of fibrous triacetate, practically all cellulose acetate is manufactured by a solution process using sulfuric acid catalyst with acetic anhydride in an acetic acid solvent. An excellent description of this process is given (85). In the process (Fig. 8), cellulose (ca 400 kg) is treated with ca 1200 kg acetic anhydride in 1600 kg acetic acid solvent and 28—40 kg sulfuric acid (7—10% based on cellulose) as catalyst. During the exothermic reaction, the temperature is controlled at 40—45°C to minimize cellulose degradation. After the reaction solution becomes clear and fiber-free and the desired viscosity has been achieved, sufficient aqueous acetic acid (60—70% acid) is added to destroy the excess anhydride and provide 10—15% free water for hydrolysis. At this point, the sulfuric acid catalyst may be partially neutralized with calcium, magnesium, or sodium salts for better control of product molecular weight. 

Most commercial preparations of cellulose esters still follow, basically, the methods described by Franchimom and Miles—esterification with sulfuric acid catalyst followed by hydrolysis. The principal steps in this process are shown in Fig. I. 

The shredded pulp is treated with glacial acetic acid which may contain part or all of the sulfuric acid catalyst. This prctreatmenl" swells the cellulose libers and increases the accessibility of the acetylatine agent. Ratios of acetic acid to cellulose may be I I to 3 1 and the treatment time may vary from one-half to several hours, depending upon temperature. 

The observation of Blume and Swezey (5) that cellulose dissolves extremely rapidly in acetic anhydride-dimethylformamide, containing sulfuric acid catalyst, suggested that we investigate the possibilities of this reaction for hydrolyzing celluloses. The cellulose acetate formed was not degraded, whereas our purpose was complete degradation. Accordingly, the depolymerization of the cellulose derivative in solution had to be examined. 

The first organic ester of cellulose was cellulose acetate, prepared by Schutzenberger in 1865 by heating cotton and acetic anhydride to about 180 °C in a sealed tube until the cotton dissolved (J ). In 1879, Franchimont acetylated cotton at lower temperatures with the aid of a sulfuric acid catalyst (2). Miles, in 1903, described the preparation of partially hydrolyzed cellulose acetate, which was easily distinguished from the fully acetylated... 

Sulfuric add acts as a catalyst by initially reacting witii the cellulose, preferentially at the primary hydroxyl groups. Then reaction with the acetic anhydride replaces the combined sulfuric acid, and cellulose triace-... 

Excess acetic anhydride is then killed by adding stop acid (aqueous acetic acid). It is important to note that the addition of the stop acid has three purposes it kills excess anhydride it helps to desulfate the residual sulfate linkages, especially when added slowly [6] and it provides some water in the reaction mixture so that the latter is no longer anhydrous. This last item is important because chain degradation of the cellulose triacetate is much slower in an aqueous acetic acid system than it is in an anhydrous acetic acid system, especially at elevated temperatures. Therefore, stop acid helps to maintain the target viscosity because in many processes not all of the sulfuric acid catalyst is neutralized at this point. 

In the manufacture of cellulose triacetate using sulfuric acid catalyst in the batch process, there is a stabilization step following the acetylation. The residual sulfate groups are hydrolyzed (called desulfation) at an elevated temperature by slow addition of dilute aqueous acetic acid solution containing magnesium or sodium acetate or other suitable base to neutralize the liberated sulfuric acid [26,27]. 

Cellulose-based natural fiber can be oxidized using oxidizing agent with acidic catalyst. Oxidation reactions applied to cellulose in fiber for chemical modifications [43]. Oxidation reactions occur on cellulose selectively at particular position. The reaction of sodium metaperiodate with cellulose in wood fiber in the presence of sulfuric acid catalyst at 120°C and 85 KPa pressure yielded the oxidized product. Sodium metaperiodate reacts with hydroxyl groups of cellulose and produce 2,3-dialdehyde cellulose which improved the physical and mechanical properties of polymer composites [44]. 

Benzimldazo(l,2-c)qmnazolm-5-yl]-2H-chromene-2-one (57) 3-[benzothiadiazoleimidazo(l,2-c)quinazolin-5-yl]-2H-chromene-2-one (58) Cellulose sulfuric acid (Catalyst)/ DMF MWl (5-6 min, 91-97%) Antibacterial and antifungal [66]... 

Most cellulose acetate is manufactured by a solution process, ie, the cellulose acetate dissolves as it is produced. The cellulose is acetylated with acetic anhydride acetic acid is the solvent and sulfuric acid the catalyst. The latter can be present at 10—15 wt % based on cellulose (high catalyst process) or at ca 7 wt % (low catalyst process). In the second most common process, the solvent process, methylene chloride replaces the acetic acid as solvent, and perchloric acid is frequentiy the catalyst. There is also a seldom used heterogeneous process that employs an organic solvent as the medium, and the cellulose acetate produced never dissolves. More detailed information on these processes can be found in Reference 28. 

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. 

Other mixed esters, eg, cellulose acetate valerate [55962-79-3] cellulose propionate valerate [67351-41-17, and cellulose butyrate valerate [53568-56-2] have been prepared by the conventional anhydride sulfuric acid methods (25). Cellulose acetate isobutyrate [67351-38-6] (44) and cellulose propionate isobutyrate [67351-40-0] (45) have been prepared with a 2inc chloride catalyst. Large amounts of catalyst and anhydride are required to provide a soluble product, and special methods of delayed anhydride addition are necessary to produce mixed esters containing the acetate moiety. Mixtures of sulfuric acid and perchloric acid are claimed to be effective catalysts for the preparation of cellulose acetate propionate in dichi oromethane solution at relatively low temperatures (46) however, such acid mixtures are considered too corrosive for large-scale productions. 

Ca.ta.lysts for Acetylation. Sulfuric acid is the preferred catalyst for esterifying cellulose and is the only known catalyst used commercially for this function. The role of sulfuric acid during acetylation has been discussed (77,78). In the presence of acetic anhydride, sulfuric acid rapidly and almost quantitatively forms the cellulose sulfate acid ester (77). Even in the absence of anhydride, the sulfuric acid is physically or mechanically retained (sorbed) on the cellulose. The degree of absorption is a measure of the reactivity or accessibiUty of different celluloses. 

Perchloric acid is a weU-known acetylation catalyst, especially in the fibrous method of preparing cellulose triacetate. Unlike sulfuric acid, perchloric acid does not combine with cellulose (78), ie, it does not form esters, and therefore virtually complete acetylation (DS 3.0, 44.8% acetyl) occurs. However, the extremely corrosive nature of perchloric acid and explosive nature of its salts have precluded its use industrially as an acetylation catalyst. 

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. 

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. 

There are several schemes for the synthesis of cellulose formates (slow) reaction of the polymer with formic acid faster reaction in the presence of a mineral acid catalyst, e.g., sulfuric or phosphoric acid. The latter route is usually associated with extensive degradation of the polymer chain. Reaction of SOCI2 with DMF produces the Vilsmeier-Haack adduct (HC(Cl) = N (CH3)2C1 ) [145]. In the presence of base, cellulose reacts with this adduct to form the unstable intermediate (Cell - O - CH = N" (CH3)2C1 ) from which cellulose formate is obtained by hydrolysis. The DS ranges from 1.2 to 2.5 and the order of reactivity is 5 > C2 > C3 [140-143,146]. 

Acetate A general name for processes for making cellulose acetate fibers. Cellulose is acetylated, dissolved in acetone, and spun into fibers by injecting through orifices into heated chambers. Cellulose mono-acetate is made by acetylating with a mixture of acetic acid, acetic anhydride, and sulfuric acid as the catalyst. Cellulose tri-acetate is made in a similar fashion, but using perchloric acid as the catalyst, and dry-spinning from a solution in ethanol/ methylene chloride. Cellulose tri-acetate fibers were first made commercially by Courtaulds in London in 1950. 

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 representing a polymer molecule minus the functional group of interest and —OH specifically... 

These carbonaceous catalysts can be obtained by the sulfonation of incompletely carbonized organic compounds [42]. Note that starch and cellulose can be used as carbon precursor [43, 44]. After the incomplete pyrolysis of the carbon precursor, the SO3H groups have been introduced by sulfonation with sulfuric acid (Scheme 3). After this treatment, the presence of phenolic hydroxyl, carboxylic acid, and sulfonic groups at the surface of these amorphous carbonaceous materials has been demonstrated. 

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