Cellulose acetate triacetate

The predominant RO membranes used in water applications include cellulose polymers, thin film oomposites (TFCs) consisting of aromatic polyamides, and crosslinked polyetherurea. Cellulosic membranes are formed by immersion casting of 30 to 40 percent polymer lacquers on a web immersed in water. These lacquers include cellulose acetate, triacetate, and acetate-butyrate. TFCs are formed by interfacial polymerization that involves coating a microporous membrane substrate with an aqueous prepolymer solution and immersing in a water-immiscible solvent containing a reactant [Petersen, J. Memhr. Sol., 83, 81 (1993)]. The Dow FilmTec FT-30 membrane developed by Cadotte uses 1-3 diaminobenzene prepolymer crosslinked with 1-3 and 1-4 benzenedicarboxylic acid chlorides. These membranes have NaCl retention and water permeability claims. 

These dyes have affinity for one or, usually, more types of hydrophobic fibre and they are normally applied by exhaustion from fine aqueous dispersion. Although pure disperse dyes have extremely low solubility in cold water, such dyes nevertheless do dissolve to a limited extent in aqueous surfactant solutions at typical dyeing temperatures. The fibre is believed to sorb dye from this dilute aqueous solution phase, which is continuously replenished by rapid dissolution of particles from suspension. Alternatively, hydrophobic fibres can absorb disperse dyes from the vapour phase. This mechanism is the basis of many continuous dyeing and printing methods of application of these dyes. The requirements and limitations of disperse dyes on cellulose acetate, triacetate, polyester, nylon and other synthetic fibres will be discussed more fully in Chapter 3. Similar products have been employed in the surface coloration of certain thermoplastics, including cellulose acetate, poly(methyl methacrylate) and polystyrene. 

These are the only ranges of precursor products in the Colour Index that are still commercially significant. Azoic dyes have a close formal relationship to those monoazo pigments derived from BON acid or from acetoacetanilides (section 2.3.1) and some are chemically identical with them, although they are used in a totally different way. Azoic components are applied to produce insoluble azo dyes within the textile substrate, which is almost always cotton. Corresponding azoic components for the dyeing of cellulose acetate, triacetate and polyester fibres were once commercially important, but are now obsolete because of environmental hazards and the time-consuming application procedure. 

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. 

Fig. 7. Moisture regains of cellulose acetate (A) and triacetate (T) fibers. Moisture content on a bone-dry basis, measured at 22°C (—...

Secondary Acetate Processes. There is no commercial process to directiy produce secondary cellulose acetate sufficientiy soluble in acetone to produce fiber. Hence, the cellulose is completely acetylated to the triacetate during the dissolution step and then hydrolyzed to the required acetyl value. 

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. 

Cellulose acetate, the second oldest synthetic fiber, is an important factor in the textile and tobacco industries 731,000 metric tons were produced worldwide in 1991 (Fig. 11) (74). Acetate belongs to the group of less expensive fibers triacetate is slightly more expensive. An annual listing of worldwide fiber producers, locations, and fiber types is pubHshed by the Fiber Economics Bureau, Inc. (74). 

Fig. 11. World production of cellulose acetate and triacetate fibers I, cigarette tow B, textile (74).

Triphenyl phosphate [115-86-6] C gH O P, is a colorless soHd, mp 48—49°C, usually produced in the form of flakes or shipped in heated vessels as a hquid. An early appHcation was as a flame retardant for cellulose acetate safety film. It is also used in cellulose nitrate, various coatings, triacetate film and sheet, and rigid urethane foam. It has been used as a flame-retardant additive for engineering thermoplastics such as polyphenylene oxide—high impact polystyrene and ABS—polycarbonate blends. 

Other Cellulosics. Rayon is bleached similarly to cotton but under milder conditions since the fibers are more easily damaged and since there is less colored material to bleach. Cellulose acetate and triacetate are not usually bleached. They can be bleached like rayon, except a slightly lower pH is used to prevent hydrolysis. The above fibers are most commonly bleached with hydrogen peroxide. Linen, dax, and jute requite more bleaching and mil der conditions than cotton, so multiple steps are usually used. Commonly an acidic or neutral hypochlorite solution is followed by alkaline hypochlorite, peroxide, chlorite, or permanganate, or a chlorite step is done between two peroxide steps. A one-step process with sodium chlorite and hydrogen peroxide is also used. 

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. 

The common commercial products are the primary (triacetate) and the secondary (acetone-soluble, ca 39.5% acetyl, 2.45 DS) acetates they are odorless, tasteless, and nontoxic. Their properties depend on the combined acetic acid content (acetyl, see Table 1 and Figure 4) and molecular weight. Solubihty characteristics of cellulose acetates with various acetyl contents are given in Table 4. 

Cellulose Acetate. Almost all cellulose acetate, with the exception of fibrous triacetate, is prepared by a solution process employing sulfuric... 

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. 

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. 

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. 

Acetate—cellulose acetate. When not less than 92% of the hydroxyl groups are acetylated, triacetate may he used as a generic description. 1.2-1.5 G F P G G 1.33 210... 

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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