Secondary cellulose

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. 

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. 

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. 

Large quantities of secondary cellulose acetate are used worldwide in the manufacture of filter material for cigarettes. Because of its excellent clarity and ease of processing, cellulose acetate film is widely used in display packaging and extmded plastic film for decorative signs (see Packaging materials). Injection-molded plastics of cellulose acetate are used in toothbmsh handles, computer bmshes, and a large variety of other appHcations (7). 

The product at this stage is referred to as secondary cellulose acetate. Different degrees of acetylation are required for different end-products and these are indicated in Table 22.3. 

Of these dimethyl phthalate (DMP) is used in most compositions. It is cheap, has a high compatibility with secondary cellulose acetate and is efficient in increasing flexibility, toughness and the ease of flow at a given temperature. Its principal disadvantages are its high volatility and the fact that it increases the flammability of the compound. Similar in compatibility but rather less volatile is diethyl phthalate. This material has less of an influence on flexibility and flow properties than the methyl ester. 

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. 

Hydroxy-containing polymers such as poly(methyl-methacrylate-co-hydroxyethyl methacrylate) [65,66] or secondary cellulose acetate [67,68] were used for this purpose. Vanadium (V) 8-hydroxy quinoline-hydroxy-ethyl methacrylate adduct, prepared by condensation of the latter with a VOQ2OH complex, is polymerized to... 

A similar type of condensation between a hydroxyl-containing polymer (such as secondary cellulose acetate) with VO(BrC6H4N=CHO CfiH4)2 CUVOL2CI] produces photoactive polymers [68]. When irradiated with UV light in the presence of styrene or MMA, grafted and crosslinked polymers were obtained ... 

Table 3.11 Partition coefficient and saturation value of disperse dyes on secondary cellulose acetate [85]...

Table 3.12 Solubility of disubstituted dyes in secondary cellulose acetate [86]...

Bheda et al. ( ) showed that cellulose triacetate forms a mesophase in dichloroacetic acid. Navard and Haudin (18) examined the thermal behavior of liquid crystalline solutions of CTA in TFA. Navard et al. (23) studied the isotropic to anisotropic transitions of solutions of cellulose triacetate in TFA using differential scanning calorimetry. Navard and Haudin (S2) studied the mesophases of cellulose and cellulose triacetate calorimetrically. Navard et al. (83) report similar studies. Meeten and Navard (97) showed the twist of the cholesteric helicoidal structure of CTA and secondary cellulose in TFA is left-handed. 

Which would be more polar—tertiary or secondary cellulose acetate ... 

Secondary-cellulose deposition occurs after cessation of expansion of the primary wall. Layers of the secondary wall, in contrast to the primary wall, display a very orderly, parallel arrangement of the microfibrils. In such plants as flax and hemp,1,2 bamboo,13 sisal,14-16 cotton hairs,2 and pine tracheids,13 three main layers can be detected in the secondary wall, each made up of cellulose microfibrils arranged in a helical fashion around the cell, In each of these secondary walls, the middle layer of cellulose is considerably thicker than the cellulose layers on each side of it, with a helical direction opposed to those of the latter. It is probable that each of these three layers is, in fact, complex, and made from a number of lamellae, each with its own helix of cellulose microfibrils.1 2... 

Significantly, the ordered pattern of fibril deposition in the secondary wall of Micrasterias367 was shown to be derived from the structure of the complexes located in the plasma membrane. The results indicated that the widest fibrils, those in the center of a band, are formed by the longest rows of rosettes, those in the center of arosette array. The shorter rows of rosettes within an array give rise to narrower fibrils. This proportionality between the width of a secondary cellulose fibril and the number of rosettes involved in its formation provides strong evidence that the rosette structure plays a significant role in the synthesis of cellulose fibrils. 

It has already been implied that cellulose triacetate will not produce a thermoplastic, as its softening point cannot be reduced appreciably by plasticizers. It is used in solution processes, however, to produce films and libers. Triacetate films absorb less water than films of secondary cellulose acetate, and they arc therefore more dimensionally stable in environments where the humidity is not controlled. Triacetate fibers, with a similar resistance to water, impart to fabrics wrinkle resistance, dimensional stability, and the ability to dry rapidly. Under United Slates federal regulations, a filler must tic made from a cellulose acetate having... 

Like the triacetate, secondary cellulose acetate (CA) is used in solution processes to produce fibers and films. CA fibers were originally called "rayon." the name that was already in use for regenerated cellulose fibers. In 1951. however, the regulatory authorities formally acknowledged the chemical distinction between CA and cellulose, and the term rayon was reserved for libers of regenerated cellulose. CA fibers are officially called acetate. and they are used in a wide variety of fabrics. They also are used for cigarette filters. However, the majority of CA produced is used for manufacture of plastics. 

Further studies by Badgley and Mark " on relatively homogeneous fractions of a secondary cellulose acetate obtained by controlled precipitation from acetone and methylcellosolve solutions (with methyl alcohol), showed that equations 9, 10 and 11, above, apply over relatively narrow ranges of DP. Above a DP. of about 380, equation 9 gave D.P. values higher than those obtained by osmotic pressure measurements. Modification of equation 11, to the form... 

In the preparation of secondary cellulose acetate rayon cotton linters, waste cotton or high-grade wood pulp is purified by boiling with alkali followed by hypochlorite bleaching. After purification the cellulose is dried... 

Secondary cellulose acetate yarns have a dry strength of T4 g per denier which falls to 0-9 when wet. Although the initial dry breaking-load is less than for viscose, the comparative loss on wetting is not so great because of the more hydrophobic nature of the yarn. The substitution of most of the... 

In cellulose triacetate virtually all the hydroxyl groups in the cellulose have been acetylated and this makes the fibre more hydrophobic and, therefore, less receptive to dye molecules. Triacetate differs from secondary cellulose acetate in that it can be heat set, making it in this respect competitive with the true synthetic fibres. Steam setting is made difficult because tried extends slightly during the process, unlike the synthetic fibres which contract. This adds to the difficulty of fixing dimensions and may cause a ripple effect in the warp direction. For this reason dry-heat setting is preferred because it is not accompanied by extension. 

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