2.1. Cellulose Acetate 2.1.1.

Chemistry of Cellulose Esterification The esterification reaction of the primary and secondary hydroxyl groups of cell ulose does not basically differ from that of other alcohols. The peculiarities l ie in the macromolecular structure of the cellulose molecule. The splitting of t he molecule chain competes with the catalyzed esterification, but can be fairly well controlled under appropriate conditions. The speed and completeness of the reaction is dependent on the quality of the cellulose, whereas the different rea ctivities of the primary and secondary hydroxyl groups [83], [86] have little in fluence on industrial processes. Acids, acid chlorides, and acid anhydrides are possible esterification reagents for the three hydroxyl groups in each glucose unit. Esterification with free acids, with the exception of formic acid [87], whose es ters are not stable, requires such high temperatures and catalyst concentrations that only low molecular mass products are obtained. Acid chlorides in pyridine, however, were suggested for use in the production of esters from higher fatty a cids (lauric acid, stearic acid, and palmitic acid), without ever having attaine d any industrial significance. Attempt was made to manufacture cellulose acetate industrially with acetyl chloride and catalysts, but the process proved to be u seless. All industrial processes in current use, therefore, are based on acetic acid anh ydride as a reactant, whereby theoretically 3 mol of anhydride per unit of gluco se are used and 3 mol of acetic acid are formed. Attempts to use ketene, which could be directly accumulated without incurring ac etic acid, which must again be processed, did not lead to any results [88]. Numerous catalysts were suggested to accelerate the reaction. Only sulfuric acid and perchloric acid are of any practical importance. Zinc chloride, which is re quired in large amounts of 0.5 1 part per part of cellulose, is no longer used t oday because of the high reprocessing costs. Other mineral acids, however, are n ot sufficiently acidic in the water-free acetic acid acetic acid anhydride syste m. The catalytic effect of sulfuric acid is primarily in the rapid and quantitat ive formation of acidic cellulose sulfuric acid esters (sulfoesters) [89], which are substituted by acetyl groups as the reaction progresses and the temperature rises. Due to the topochemical character of the reaction, soluble cellulose esters with low acetic acid content can be obtained only from the triester stage by way of hydrolysis. Incompletely esterized and insoluble derivatives are found in additi on to the triester before completion of the reaction. Cellulose esters with low acetic acid content are produced by subsequent hydroly sis in a homogeneous system by adding water or dilute acetic acid to destroy the excess anhydride and possibly by adding sulfuric acid for acceleration and then again split off under controlled conditions (temperature, water content, and ti me) a certain number of acetyl groups without further breakdown of the cellulose chain. 2.1.2. Raw Materials Cellulose. The production of high-quality cellulose esters requires that special attention be paid to the selection of the starting materials. The cellulose bas es generally consist of highly purified cotton linters with an a-cellulose conte nt of over 99 % and celluloses from wood pulp which contain between 90 and 97 % a-cellulose. After the long layered spinnable cotton has been freed of the cotton seed by gin ning, the remaining shorter fibers on the seed pod are usually removed with two cuts before the seeds go to the oil presses for further processing. The first cu

t gives about 4 % longer linters relative to the entire cotton flower, which are preferentially processed to medicinal cotton, felt, paper, etc. The second cut gives about 8 % shorter layered linters, which are best suited for further chemi cal processing. The raw linters undergo mechanical cleaning by means of screening, pressure boil ing in a 3 5 % sodium hydroxide solution, and finally acid alkaline bleaching. S pecial care should be taken during drying, since local overdrying of cellulose, the water content of which should lie between 3 and 8 %, impairs the reactivity considerably. Table (9) shows analytical values of good linters [90]. For a long time, cellulose from wood pulp could only be used for the manufacture of lower-quality cellulose esters because of the 90 95 % a-cellulose content. C elluloses with an a-cellulose content of 96 % have been available for about 20 y ears. Due to special processing techniques, they give cellulose esters comparabl e to those produced from linters as far as tensile strength, color, clarity of t he solutions, and light stability as well as thermal stability are concerned. Acetic Acid Anhydride. Most manufacturers of cellulose acetate convert the resul ting acetic acid to anhydride directly on the premises and adjust the concentrat ions as required for their process, generally between 90 and 95 %. 2.1.3. Industrial Processes Only a few of the proposed industrial processes for the manufacture of cellulose esters have attained industrial significance. Even when the fact that no two ma nufacturers use identical processes is taken into consideration, the following c ategories can be distinguished: 1) Acetylation in a homogeneous system (solution acetate) Use of glacial acetic acid as a solvent (glacial acetic acid process) Use of methylene chloride as a solvent (methylene chloride process) 2) Acetylation in a heterogeneous system (fiber acetate) Whereas the triester that is formed during esterification according to the solut ion acetate process goes into solution and can subsequently be hydrolyzed to sec ondary acetate, fiber acetate is formed in the presence of nonsolvents, similar to the nitration of cellulose. This method does not permit hydrolysis. A flow diagram of the entire process is shown in Figure (7). 2.1.3.1. Pretreatment 7 %. Too little m The cellulose is first dried to obtain a moisture content of 4 oisture would lower the reactivity of the cellulose, and too much moisture would lead to a higher acetic acid consumption and an extremely violent reaction star t. Acetic acid is generally used as a pretreatment reagent, which for some processe s can contain small amounts of sulfuric acid to further improve the diffusion of the acetylating reagents. It is believed that the pretreatment process causes a partial swelling of the cellulose by splitting the hydrogen bonds so that the acetylating reagents can enter the fibers more rapidly. A ratio of 30 100 parts of glacial acetic acid per 100 parts of cellulose, which is sprayed into the thoroughly mixed cellulose at temperatures of up to 50 ?C i n appropriate equipment such as mixing vats, is usually sufficient for the pretr eatment process. Pretreatment, depending on the process and temperatures, takes from one to several hours. 2.1.3.2. Esterification Acetic Acid Process. The acetylation mixture consists of glacial acetic acid as a solvent for triacetate, an excess of 10 40 % glacial acetic acid anhydride and , depending on the process, 2 15 % sulfuric acid with respect to the cellulose.

Esterification begins after the initial spontaneous reaction of the water contai ned in the cellulose with part of the anhydride; the semiliquid mass uniformly s aturated with acetylation mixture forms a fiber pulp while developing temperatur es of up to 50 ?C and ultimately a highly viscous solution. A decomposition of the cellulose chain takes place parallel to the strongly exot hermic esterification. The chain degradation can be controlled by controlling th e reaction temperature, e.g., by adding cooled solution portionwise and cooling the reaction vessel down to the desired temperature range. The use of glacial ac etic acid as a solvent, in which the highly esterified triacetate is poorly diss olved, results in gel formation and precipitation of the triacetate. This is due to the formation of sulfate acetate, which is formed as an intermediate during the reaction. It is reesterified to pure acetic acid esters especially at higher temperatures. After the reaction solution is free of fibers, the degradation of the cellulose ester molecule can continue until the desired viscosity is attained. The reactio n is then stopped by adding water or dilute acetic acid, which destroys the exce ss anhydride. Cooled kneaders are suitable reaction vessels in that they allow a rapid and uni form mixture and catalyst distribution through intensive mixing. This is importa nt for controlling the reaction (Fig. (8)). Methylene Chloride Process. Using methylene chloride (bp 41 ?C) as a solvent pre sents several advantages over acetic acid. Due to the fact that methylene chlori de is such an excellent solvent for primary triacetate, lower catalyst concentra tions (1 % sulfuric acid) are required at higher esterification temperatures. Fu rthermore, due to its low boiling point, the heat of reaction can be removed by means of vaporization and return of the cooled methylene chloride. The reaction of highly viscous solutions can, thus, be better controlled. Finally, only a hal f to a third as much dilute acetic acid must be recycled compared with the glaci al acetic acid process. Table (10) shows typical examples for acetylation according to the glacial aceti c acid and methylene chloride processes. Figure (9) shows a sceme for the produc tion of cellulose acetate according to the methylene chloride process. Acetylation according to the methylene chloride process is carried out largely i n rotating drums (roll vats) or in horizontal containers with shovel-like stirre rs on both sides. The problem of corrosion, which arises during esterification a nd especially during hydrolysis, has only been partially solved by using equipme nt constructed of bronze, high-alloy steels, or plates containing metals such a s silver, titanium, or tantalum. Fiber Acetate. Cellulose can be esterified maintaining its fiber structure by ad ding sufficient amounts of nonsolvents to the triacetate during acetylation. Car bon tetrachloride, benzene, or toluene can be used as nonsolvents [94], [95]. Temperature and catalyst concentrations are similar to those required for the so lvation process. A large amount of liquid is required to keep the loose volumino us cellulose in suspension. Perchloric acid is preferred as a catalyst because o f the great difficulty with which the sulfuric acid ester is split in this syste m. The hydrolysis of fiber acetate to acetone-soluble esters is not possible in a h eterogeneous system. Its utilization is limited to special applications, such as the manufacture of foils and films from triacetate. As shown in Figure (10), fiber acetate is produced by rotation in various direct ions and at various speeds in a perforated drum enclosed in a metal casing. The shaft of the drum is hollow so that liquid may be added during rotation [96]. Continuous Processes. In spite of numerous attempts, continuous acetylation and hydrolysis processes have achieved only limited industrial applications and are not used in the production of high-quality esters for, among others, plastic mas ses. Due to the varying reactivities of the different celluloses, considerable v ariations between batches are possible so that the development of a continuous p rocess is seriously impeded.

2.1.3.3. Hydrolysis After the esterification is completed, the process is interrupted by adding wate r or dilute acetic acid. Sufficient water must be added to decompose the excess anhydride and adjust the water content of the solution to 5 10 % so that, aside from hydrolysis, no further decomposition of the molecular mass occurs, but at t he same time the bound sulfuric acid is almost completely split off. The speed o f hydrolysis depends on the temperature, which depending on the process ranges b etween 40 and 80 ?C, and on the amounts of sulfuric acid and water. The course of hydrolysis is constantly monitored by checking the solubility of t he secondary acetate. The reaction is terminated at the desired degree of substi tution by neutralizing the catalyst, preferably with sodium acetate or magnesium acetate. The proportion of free hydroxyl groups in the ester should be maintain ed as reproducibly precise as possible because it determines the properties and the utilization of the ester. 2.1.3.4. Precipitation and Processing The product precipitates in the form of flakes or powder during intense stirring after water or dilute acetic acid has been gradually added. The methylene chlor ide process requires that the methylene chloride be completely distilled before precipitation occurs. A part of the precipitating acid is added to the solution to just before the point of precipitation when the main portion of the acid is a dded. The process must be carefully monitored to achieve a product with an open structure which can be easily rinsed out. The precipitate can be broken down and thoroughly rinsed, whereby the dilute acid is brought back into the cycle. Rins ing is done primarily by using continuous methods based on the countercurrent pr inciple (Fig. (9)). High-quality products for plastic masses are stabilized and bleached. Bound sulf uric acid remnants are removed by either boiling under pressure or heating in 1 % mineral acids during stabilization. After further rinsing and removal of excess water by suctioning or by thrust ext raction, the product is carefully dried, preferably in a vacuum shovel drier, to 3 %. a water content of < 1 The cellulose acetate yield from a good process is at least 95 % of the theoreti cal yield. Major manufacturers of cellulose acetate are the following [103]: Bayer AG, Leve rkusen; British Celanese Ltd., London; Celanese Corp. of America, New York; Cour taulds Ltd., Manchester; Daicel Ltd., Osaka, Japan; E. I. DuPont de Nemours & Co ., Inc., Wilmington; Eastman Kodak Comp., Kingsport; UCB Fabelta, Tubize, Belgiu m; Gevaert-Agfa, Antwerp; Hercules Powder Comp. Ltd., London; Rhodiaceta, Lyon; Soc. Rhodiatoce SpA, Milan; Rh?ne-Poulenc, Paris; VEB Orbitaplast, Eilenburg, GD R. A number of products are further processed to fibers, films, or injection-moldin g compounds in the manufacturers' own facilities and never reach the market as a raw material. [83] L. P. Clermont, F. Bender, J. Polym. Sci. Part A-1 10 (1972) 1669. 2.1.4. Recovery of Reactants The recovery of the incurred large amounts of acetic acid is a decisive factor f or the profitability of a process. Recovery of Acetic Acid. Depending on the process, 2 6 parts of 15 25 % dilute a cetic acid per part of cellulose accumulate. They must be reprocessed to glacial acetic acid and acetic acid anhydride. Only continuous processes consisting of a combination of extraction and azeotrop ic distillation are of current practical importance. The dilute acid is, for exa

mple, extracted with ethyl acetate in a countercurrent and is subsequently disti lled, so that 99.8 % pure glacial acetic acid can be removed from the bottom of the column while the azeotropic ethyl acetate water is removed from the top. Recovery of Acetic Acid Anhydride. Since only a portion of the accumulated glaci al acetic acid is required for the acetylation process, the remainder must be co nverted to glacial acetic acid anhydride. The ketene process developed by the Wacker Co. (? Acetic Anhydride - 1.3.1.1. Pr oduction of Ketene) is currently in general use [97]: Pure, almost anhydrous gla cial acetic acid is continuously vaporized under a vacuum and is split to ketene in the presence of small amounts of the catalyst triethyl phosphate; ketene the n reacts with glacial acetic acid to form the anhydride (? Acetic Anhydride - 1. 3.1.2. Reaction of Ketene with Acetic Acid). Recovery of Methylene Chloride. Methylene chloride can be recovered inexpensivel y because of its insolubility in water, which alllows its recovery from the raw solution without further processing steps in almost pure form. 2.1.5. Properties of Cellulose Acetate Cellulose acetate and the other fatty acid esters are white, amorphous products that are commercially available as a powder or flakes. They are nontoxic, odorle ss, tasteless, and less flammable than nitrocellulose. They are resistant to wea k acids and are largely stable to mineral and fatty oils as well as petroleum. Some physical characteristics are given in Table (11). Properties and applications of cellulose acetates are primarily determined by th e following: 1) viscosity of their solution 2) degree of esterification or the amount of bound acetic acid Viscosityas an indicator for the degree of polymerization influences to a great extent the mechanical properties of the resulting fibers, films, or plastic mass es, as well as their workability. The degree of esterification primarily determines the solubility and compatibili ty with softeners, resin, varnish, etc., and ultimately also influences the mech anical properties. The wide span of solubility properties of hydrolyzed cellulose acetate is shown in Table (12). The compatibility of the plasticizer and the solubility in polar solvents increa se with decreasing acetic acid content while the solubility in nonpolar solvents decreases. Moreover, a correlation between the incompatibility with nonsolvents such as water, alcohol, benzene, or toluene and a decreasing degree of esterifi cation exists. Furthermore, a number of solvent combinations are known which are able to dissolve the cellulose acetate although each of the components is a non solvent. Figure (11) shows a selection of solvents for the industrially interesting range 62 % bound acetic acid). Detailed information on solubili of esterification (52 ty and softener selection can be found in the literature and the manufacturers' information brochures. 2.1.6. Analysis and Quality Control The viscosity is determined in practice by the usual methods. Along with the rel ative viscosity, the measurement of 15 20 % solutions according to the ball drop method corresponding to ASTM 871-56 has been generally accepted. The acetic acid content is generally determined by saponification of the ester w ith 0.5 N-potassium hydroxide and back-titration of the excess. The free acids f rom mixed esters are separated from the residue after saponification by means of distillation or extraction and by extraction or azeotropic distillation isolate d and titrated. Recently, gas-chromatographic methods have found increasing popu larity. A comprehensive presentation can be found in [100], [101].

Determination of the free hydroxyl groups in pure cellulose acetate is not neces sary, since a precise analysis of bound acetic acid is possible. It is primarily used to characterize the mixed esters and can be carried out according to vario us methods. Complete esterification with acetic acid anhydride in pyridine and b ack-titration of the excess is a proven method [102]. The value is mostly given as a percentage of the hydroxyl or as the hydroxyl value (mg of KOH/g). Additional quality control methods for unprocessed cellulose esters are the foll owing: determination of temperature stability by heating to 220 240 ?C and evalu ation of discoloration and melting behavior, the determination of free acid as a n indicator for the efficacy of the rinsing process, and determination of the as h content as well as clarity, color, and filterability of the solution. [97] Cons. f. Elektrochem. Ind., DE 687065, 1933; US 2108829, 1934. 3. References [1] V. Stannet: Cellulose Acetate Plastics, Temple Press Ltd., London 19 50. [2] K. Thinius: Analytische Chemie der Plaste, Springer Verlag, Berlin-G ?ttingen-Heidelberg 1952. [3] Kirk-Othmer, vol. 3, pp. 357 ff. ? [4] E. Ott, H. M. Spurlin, M. W. Grafflin: Cellulose and Cellulose Deriv atives, 2nd ed., vol. V, part II, Interscience Publ., New York-London 1954. [5] R. Houwink, A. J. Staverman: Chemie und Technologie der Kunststoffe, 4th ed., vol. II/2, Akademische Verlagsgesellschaft Geest & Porting KG, Leipzig 1963. ? [6] K. Thinius: Chemie, Physik und Technologie der Weichmacher, VEB Deut scher Verlag f?r Grundstoffindustrie, Leipzig 1963. [7] V. E. Yarsley, W. Flarell, P. S. Adamson, N. G. Perkins: Cellulose P lastics, Iliffe Book Ltd., London 1964. [8] Encyclopedia of Polymer Science and Technology, vol. 3, J. Wiley & S ons, New York 1965. [9] R. Vieweg, E. Becker: Kunstoff-Handbuch, vol. III: "Abgewandelte Nat urstoffe," Hanser Verlag, M?nchen 1965. [10] P. B. Koslov, G. I. Braginski: Chemistry and Technology of Polymers , Iskustvo, Moscow 1965 (Russ.). [11] H. Temming, H. Grunert: Temming-Linters, 2nd ed., P. Temming, Gl?ck stadt 1972. ? [12] J. Barsha: "Inorganic Esters," in E. Ott, H. M. Spurlin, M. W. Graf flin (eds.): Cellulose and Cellulose Derivatives, 2nd ed., part II, Interscience Publ., New York-London 1954, pp. 713 762. ? [13] E. D. Klug: "Cellulose Derivatives," in Kirk-Othmer, 2nd ed., vol. 4, J. Wiley & Sons, New York-London-Sydney-Toronto 1964, pp. 616 652. ? [14] G. D. Hiatt, W. J. Rebell: "Esters," in N. M. Bikales, L. Segal (ed s.): Cellulose and Cellulose Derivatives, part V, Wiley-Interscience, New York-L ondon-Sydney-Toronto 1971, pp. 741 777. ? [15] J. Honeyman: Recent Advances in the Chemistry of Cellulose and Star ch, Heywood & Comp., London 1959. ? [16] E. Sj?str?m: Wood Chemistry, Fundamentals and Applications, Academi c Press, New York-London 1981. ? [17] D. Fengel, G. Wegener: Wood Chemistry, Ultrastructure, Reactions, D e Gruyter, Berlin-New York 1983. ? [18] K. Balser: "Derivate der Cellulose," in W. Burchard (ed.): Polysacc haride, Springer Verlag, Berlin-Heidelberg-New York-Tokyo 1985, pp. 84 110. ? [19] L. C. Wadsworth, D. Daponte: "Cellulose Esters," in T. P. Nevell, S . H. Zeronian (eds.): Cellulose Chemistry and its Applications, Ellis Horwood Lt d., Chichester 1985, pp. 344 362. A. Revely: "A Review of Cellulose Derivatives and their Industrial Applications," in Cellulose Chemistry and its Applications, pp. 211 225.

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