Cellulose acetate, acetic anhydride

Cellulose acetate, 4 716 5 368, 422-427 15 839-840. See also Cellulose acetates acetic anhydride used in production of, 1 157... 

A recent interesting example of the use of alkane feedstocks to develop more sustainable processes is the direct conversion of ethane into acetic acid developed by Sabic. Acetic acid is the raw material for many key petrochemical intermediates and products, including vinyl acetate monomer (VAM), purified terephthalic acid (PTA), acetate esters, cellulose acetate, acetic anhydride, monochloroacetic acid (MCA), and so on. Acetic acid is produced commercially from several feedstocks and by several different technologies. 

Aluminium alloys have an excellent resistance to the action of reagents used for the fabrication of cellulose acetate acetic anhydride, concentrated acetic acid, butyric anhydride, and cotton. Many pieces of equipment in various aluminium alloys are used in production units for cellulose esters 3003, 5052, A-S13 (44100), etc., for storage tanks, reaction vessels, dryers, evaporators, and valves. 

Acetic acid is a two-carbon monocarboxylic acid with many applications in food and as a building block for a wide range of industrial chemicals (Table 7.1). While much of the industrial acetic acid production is used directly for applications such as solvents, its primary use by volume is as a feedstock for the production of other chemicals such as vinyl acetate, which is used in plastics, adhesives and paints. Other products include cellulose acetate, acetic anhydride and acetate esters. The synthetic production route has been the dominant process since 1950 [31] using either hydrocarbon-derived ethylene or methanol as the feedstock. The 10% currently produced by microbial conversion is directed towards food applications. 

Cellulose acetate [9004-35-7], prepared by reaction of cellulose with acetic anhydride, acetic acid, and sulfuric acid, is spun into acetate rayon fibers by dissolving it in acetone and spinning the solution into a column of warm air that evaporates the acetone. Cellulose acetate is also shaped into a variety of plastic products, and its solutions are used as coating dopes. Cellulose acetate butyrate [9004-36-8], made from cellulose, acetic anhydride, and butyric anhydride in the presence of sulfuric acid, is a shock-resistant plastic. 

Preparation (acetylation) Cellulose + Acetic anhydride, Cellulose acetate -H2O (1)... 

Perchloric acid Acetic acid, acetic anhydride, alcohols, antimony compounds, azo pigments, bismuth and its alloys, methanol, carbonaceous materials, carbon tetrachloride, cellulose, dehydrating agents, diethyl ether, glycols and glycolethers, HCl, HI, hypophosphites, ketones, nitric acid, pyridine, steel, sulfoxides, sulfuric acid... 

The cellulose molecule contains three hydroxyl groups which can react and leave the chain backbone intact. These alcohol groups can be esterified with acetic anhydride to form cellulose acetate. This polymer is spun into the fiber acetate rayon. Similarly, the alcohol groups in cellulose react with CS2 in the presence of strong base to produce cellulose xanthates. When extruded into fibers, this material is called viscose rayon, and when extruded into sheets, cellophane. In both the acetate and xanthate formation, some chain degradation also occurs, so the resulting polymer chains are shorter than those in the starting cellulose. 

Figure 3 shows the production of acetaldehyde in the years 1969 through 1987 as well as an estimate of 1989—1995 production. The year 1969 was a peak year for acetaldehyde with a reported production of 748,000 t. Acetaldehyde production is linked with the demand for acetic acid, acetic anhydride, cellulose acetate, vinyl acetate resins, acetate esters, pentaerythritol, synthetic pyridine derivatives, terephthaHc acid, and peracetic acid. In 1976 acetic acid production represented 60% of the acetaldehyde demand. That demand has diminished as a result of the rising cost of ethylene as feedstock and methanol carbonylation as the preferred route to acetic acid (qv). 

Most of the acetic acid is produced in the United States, Germany, Great Britain, Japan, France, Canada, and Mexico. Total annual production in these countries is close to four million tons. Uses include the manufacture of vinyl acetate [108-05-4] and acetic anhydride [108-24-7]. Vinyl acetate is used to make latex emulsion resins for paints, adhesives, paper coatings, and textile finishing agents. Acetic anhydride is used in making cellulose acetate fibers, cigarette filter tow, and ceUulosic plastics. 

About half of the wodd production comes from methanol carbonylation and about one-third from acetaldehyde oxidation. Another tenth of the wodd capacity can be attributed to butane—naphtha Hquid-phase oxidation. Appreciable quantities of acetic acid are recovered from reactions involving peracetic acid. Precise statistics on acetic acid production are compHcated by recycling of acid from cellulose acetate and poly(vinyl alcohol) production. Acetic acid that is by-product from peracetic acid [79-21-0] is normally designated as virgin acid, yet acid from hydrolysis of cellulose acetate or poly(vinyl acetate) is designated recycle acid. Indeterrninate quantities of acetic acid are coproduced with acetic anhydride from coal-based carbon monoxide and unknown amounts are bartered or exchanged between corporations as a device to lessen transport costs. 

By-product acetic acid is obtained chiefly from partial hydrolysis of cellulose acetate [9004-35-7]. Lesser amounts are obtained through the reaction of acetic anhydride and cellulose. Acetylation of saHcyHc acid [69-72-7] produces one mole of acetic acid per mole of product and the oxidation of allyl alcohol using peracetic acid to yield glycerol furnishes by-product acid, but the net yield is low. 

Eastman Goal Chemicals. In 1983 Eastman Chemical Co. became the first chemical producer in the United States to return to coal as a raw material for large-scale manufacture of industrial chemicals (35). In that year, Eastman started manufacturing acetic anhydride from coal. Acetic anhydride is a key intermediate for production of coatings, ceUulosic plastics, and cellulose acetate fibers. Acetic anhydride from other sources also is used in the manufacture of pharmaceuticals, starches and sweeteners, and flavors and fragrances. 

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. 

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. 

When the acetylation is completed, microscopic examination of the solution should reveal no undissolved residues. The reaction is terrninated by adding water to destroy the excess anhydride and provide a water concentration of 5—10% for hydrolysis. A 10—25% cellulose acetate concentration is typical. 

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. 

Cellulose esters of aromatic acids, aUphatic acids containing more than four carbon atoms and aUphatic diacids are difficult and expensive to prepare because of the poor reactivity of the corresponding anhydrides with cellulose Httle commercial interest has been shown in these esters. Of notable exception, however, is the recent interest in the mixed esters of cellulose succinates, prepared by the sodium acetate catalyzed reaction of cellulose with succinic anhydride. The additional expense incurred in manufacturing succinate esters is compensated by the improved film properties observed in waterborne coatings (5). 

Mixed cellulose esters containing the dicarboxylate moiety, eg, cellulose acetate phthalate, have commercially useful properties such as alkaline solubihty and excellent film-forming characteristics. These esters can be prepared by the reaction of hydrolyzed cellulose acetate with a dicarboxyhc anhydride in a pyridine or, preferably, an acetic acid solvent with sodium acetate catalyst. Cellulose acetate phthalate [9004-38-0] for pharmaceutical and photographic uses is produced commercially via the acetic acid—sodium acetate method. 

Cellulose chloroacetates (30) and aminoacetates (30,31), acetate sorbates (32), and acetate maleates (33) have been prepared but are not commercially important. These esters are made from hydrolyzed cellulose acetate with the appropriate anhydride or acid chloride in pyridine. 

Mixed esters containing the dicarboxylate moiety, eg, cellulose acetate phthalate, are usually prepared from the partially hydroly2ed lower aUphatic acid ester of cellulose in acetic acid solvent by using the corresponding dicarboxyhc acid anhydride and a basic catalyst such as sodium acetate (41,42). Cellulose acetate succinate and cellulose acetate butyrate succinate are manufactured by similar methods as described in reference 43. 

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. 

Cellulose dissolved in suitable solvents, however, can be acetylated in a totally homogeneous manner, and several such methods have been suggested. Treatment in dimethyl sulfoxide (DMSO) with paraformaldehyde gives a soluble methylol derivative that reacts with glacial acetic acid, acetic anhydride, or acetyl chloride to form the acetate (63). The maximum degree of substitution obtained by this method is 2.0 some oxidation also occurs. Similarly, cellulose can be acetylated in solution with dimethylacetamide—paraformaldehyde and dimethylformamide-paraformaldehyde with a potassium acetate catalyst (64) to provide an almost quantitative yield of hydroxymethylceUulose acetate. 

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. 

In the fibrous acetylation process, part or all of the acetic acid solvent is replaced with an inert dilutent, such as toluene, benzene, or hexane, to maintain the fibrous stmcture of cellulose throughout the reaction. Perchloric acid is often the catalyst of choice because of its high activity and because it does not react with cellulose to form acid esters. Fibrous acetylation also occurs upon treatment with acetic anhydride vapors after impregnation with a suitable catalyst such as zinc chloride (67). 

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. 

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. 

Sulfuric acid reacts with acetic anhydride to form acetylsulfuric acid (79). This reaction is favored by low temperature and high anhydride concentration. In cellulose acetylation, probably both sulfuric acid and acetylsulfuric acid exist and react with cellulose to form cellulose sulfate acid ester. 

Fig. 7. Combined sulfur during preparation of cellulose acetate hydrolysis of sulfate and esters (6). Acetylation schedule A, mixer charged with linters and acetic acid B, minor portion of catalyst added C, began cooling to 18°C D, acetic anhydride added and continued cooling to 16°C E, significant portion...

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. 

Recent Developments. A considerable amount of cellulose acetate is manufactured by the batch process, as described previously. In order to reduce production costs, efforts have been made to develop a continuous process that includes continuous activation, acetylation, hydrolysis, and precipitation. In this process, the reaction mixture, ie, cellulose, anhydride, catalyst, and solvent, pass continuously through a number of successive reaction zones, each of which is agitated (92,93). In a similar process, the reaction mass is passed through tubular zones in which the mixture is forced through screens of successively small openings to homogenize the mixture effectively (94). Other similar methods for continuous acetylation of cellulose have been described (95,96). 

In an integrated continuous process, cellulose reacts with acetic anhydride prepared from the carbonylation of methyl acetate with carbon monoxide. The acetic acid Hberated reacts further with methanol to give methyl acetate, which is then carbonylated to give additional acetic anhydride (100,101). 

High temperature acetylation of cellulose above 50°C produces cellulose acetate from low purity wood pulp cellulose in shorter reaction times. In a high temperature method recently disclosed (102), cellulose reacts with 200—400% acetic anhydride in the presence of <5% acid catalyst at 68—85°C for 3—20 min. After the acid catalyst is neutralized with magnesium acetate, the cellulose acetate is hydrolyzed at 120°C for two hours (103). Several modified catalyst systems have been developed for acetylation of cellulose above 90°C (89,90). 

With the takeover of the American Celanese Corp. in mid-1986, the new Hoechst Celanese Corp., with Eastman Chemical Co. are the world leaders in cellulose acetate tow and flake production as of this writing. With confidence in both the acetate market and acetic anhydride supply (105), Hoechst... 

There are a variety of reaction systems that allow the formation of cellulose trinitrate [9046-47-3]. HNO in methylene chloride, CH2CI2, yields a trinitrate with essentially no degradation of the cellulose chain (53). The HNO /acetic acid/acetic anhydride system is also used to obtain the trinitrate product with the fiber stmcture largely intact (51,52). Another polymer analogous reaction utilises a 1 1 mixture of HNO and H PO with 2.5% P2O5 to achieve an almost completely nitrated product (54). 

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. 

The earliest preparation of cellulose acetate is credited to Schiitzenberger in 1865. The method used was to heat the cotton with acetic anhydride in sealed tubes at 130-140°C. The severe reaction conditions led to a white amorphous polymer but the product would have been severely degraded and the process difficult to control. Subsequent studies made by Liebermann, Francimont, Miles, the Bayer Company and by other workers led to techniques for controlled acetylation under less severe conditions. 

In a typical process for manufacture on a commercial scale bleached wood pulp or cotton linters are pretreated for 12 hours with 40-50% sulphuric acid and then, after drying, with acetic acid. Esterification of the treated cellulose is then carried out using a mixture of butyric acid and acetic anhydride, with a trace of sulphuric acid as catalyst. Commercial products vary extensively in the acetate/ butyrate ratios employed. 

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