Cellulose triacetate

Cellulose Triacetate. Cellulose triacetate is prepared according to the following reaction ... 

Because cellulose triacetate has a high softening temperature, it must be processed in solution. A mixture of dichloromethane and methanol is a common solvent. 

The predominant cellulose ester fiber is cellulose acetate, a partially acetylated cellulose, also called acetate or secondary acetate. It is widely used in textiles because of its attractive economics, bright color, styling versatiUty, and other favorable aesthetic properties. However, its largest commercial appHcation is as the fibrous material in cigarette filters, where its smoke removal properties and contribution to taste make it the standard for the cigarette industry. Cellulose triacetate fiber, also known as primary cellulose acetate, is an almost completely acetylated cellulose. Although it has fiber properties that are different, and in many ways better than cellulose acetate, it is of lower commercial significance primarily because of environmental considerations in fiber preparation. 

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. 

Processes for Triacetate. There are both batch and continuous process for triacetate. Many of the considerations and support faciUties for producing acetate apply to triacetate however, no acetyl hydrolysis is required. In the batch triacetate sulfuric acid process, however, a sulfate hydrolysis step (or desulfonation) is necessary. This is carried out by slow addition of a dilute aqueous acetic acid solution containing sodium or magnesium acetate (44,45) or triethanolamine (46) to neutrali2e the Hberated sulfuric acid. The cellulose triacetate product has a combined acetic acid content of 61.5%. 

Many ceUulosic derivatives form anisotropic, ie, Hquid crystalline, solutions, and cellulose acetate and triacetate are no exception. Various cellulose acetate anisotropic solutions have been made using a variety of solvents (56,57). The nature of the polymer—solvent interaction determines the concentration at which hquid crystalline behavior is initiated. The better the interaction, the lower the concentration needed to form the anisotropic, birefringent polymer solution. Strong organic acids, eg, trifluoroacetic acid are most effective and can produce an anisotropic phase with concentrations as low as 28% (58). Trifluoroacetic acid has been studied with cellulose triacetate alone or in combination with other solvents (59—64) concentrations of 30—42% (wt vol) triacetate were common. 

Polymer Plasticizer. Nylon, cellulose, and cellulose esters can be plasticized using sulfolane to improve flexibiUty and to increase elongation of the polymer (130,131). More importantly, sulfolane is a preferred plasticizer for the synthesis of cellulose hoUow fibers, which are used as permeabiUty membranes in reverse osmosis (qv) cells (131—133) (see Hollow-FIBERMEMBRANEs). In the preparation of the hoUow fibers, a molten mixture of sulfolane and cellulose triacetate is extmded through a die to form the hoUow fiber. The sulfolane is subsequently extracted from the fiber with water to give a permeable, plasticizer-free, hoUow fiber. 

Cellulose triacetate [9012-09-3] has the highest melting point (ca 300°C) of the triesters melting points generally decrease to a minimum of ca 230°C as the acetyl content decreases to 38—39% (secondary acetate). 

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. 

Table 9. and Nmr Chemical Shifts, ppm, and Coupling Constants, for Cellulose Triacetate, Cellulose Tripropionate, and Cellulose Tributyrate ... 

Fig. 10. Differential scanning calorimetry of cellulose triacetate. Second heating at 20°C/min. glass-transition (T temperature = 177 " C crystallization on heating (T)/j) = 217 C melting temperature (Ta) = 289 C. To convert to cal, divide by 4.184.

Determination of the thermal decomposition temperature by thermal gravimetric analysis (tga) defines the upper limits of processing. The tga for cellulose triacetate is shown in Figure 11. Comparing the melt temperature (289°C) from the dsc in Figure 10 to the onset of decomposition in Figure 11 defines the processing temperature window at which the material can successfully be melt extmded or blended. 

Fig. 11. Thermogravimetric analysis of cellulose triacetate. Method 20°C/min to 700°C, in (N2) at 40 mL/rnin purging rate.

The cellulose esters with the largest commercial consumption are cellulose acetate, including cellulose triacetate, cellulose acetate butyrate, and cellulose acetate propionate. Cellulose acetate is used in textile fibers, plastics, film, sheeting, and lacquers. The cellulose acetate used for photographic film base is almost exclusively triacetate some triacetate is also used for textile fibers because of its crystalline and heat-setting characteristics. The critical properties of cellulose acetate as related to appHcation are given in Table 10. 

It is difficult for dye solutions in water to penetrate synthetic fibers such as polyester, cellulose triacetate, polyamides, and polyacryUcs which are somewhat hydrophobic. The rate of water imbibition differs with each fiber as shown in Table 1 as compared to viscose (see Fibers, regenerated CELLULOSics), which imbibes water at the rate of 100% (1). The low imbibition rate is attributed to the high T obtained when the polymeric fibers are drawn. During this drawing operation the polymer chains become highly oriented and tightly packed, forming a stmcture practically free of voids. 

Cellulose Triacetate. Cellulose acetate having 92% or more of the hydroxyl groups acetylated is referred to as triacetate. This fiber is characteristically more resistant to alkaU than the usual acetate and may be scoured, generally, in openwidth, with aqueous solutions of a synthetic surfactant and soda ash. 

Rejection Rejection is defined in Background and Definitions. The highest-rejection membranes are those designed for single-pass production of potable water from the sea. The generally accepted criterion is 99.4 percent rejection of NaCl. Some membranes, notably cellulose triacetate fibers are rated even higher. A whole range of membranes is available as rejection requirements ease, and membranes with excellent chlorine resistance and hydrolytic stability can be made with salt rejection over 90 percent. 

Cellulose triacetate [9012-09-3] M 72,000-74,000. Extracted with cold EtOH, dried in air, washed with hot distd water, again dried in air, then dried at 50° for 30min. [Madorsky, Hart and Straus J Res Nat Bur Stand 60 343 1958.]... 

Secondary cellulose acetate has also been used for fibres and lacquers whilst cellulose triacetate fibre has been extensively marketed in Great Britain under the trade name Tricel. 

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