Secondary cellulose acetate

Regenerated cellulose (cellophane) Cellulose acetate (secondary) Cellulose triacetate Cellulose acetate- butyrate Ethyl cellulose... 

Cigarette filter tows are made from cellulose acetate (secondary), which is plasticized by - glyceryl triacetate... 

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. 

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. 

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. 

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 ... 

Pulp mills. These separate the fibers of wood or other materials, such as rags, Enters, waste-paper, and straw, in order to create pulp. Mills may use chemical, semichemical, or mechanical processes, and may create coproducts such as turpentine and tall oil. Most pulp mills bleach the pulp they produce, and, when wastepaper is converted into secondary fiber, it is deinked. The output of some pulp mills is not used to make paper, but to produce cellulose acetate or to be dissolved and regenerated in the form of viscose fibers or cellophane. 

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]...

Various benzimidazolone pigments are heat stable enough to be used in polypropylene spin dyeing. Several types find extensive use in the spin dyeing of other fibers, such as polyacrylonitrile, viscose reyon, and vicose cellulose, or secondary acetate. 

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

The basic cellulose unit contains three hydroxyl groups. The triester cellulose triacetate forms when cellulose is reacted with glacial acetic acid. Hydrolysis removes some of the acetate groups to form a secondary ester, which averages about 2.4 acetyl groups per unit rather than three. The secondary ester is then dissolved in acetone and the solution ejected through a spinneret to form fibers. Cellulose acetate processed in this manner is referred to as acetate rayon, but it may be more commonly known by its trade name Celanese. 

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. 

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 alkali than the usual acetate and may be scoured, generally, in open-width, with aqueous solulions of a synthetic surfactant and soda ash. Triacetate is a hydrophobic liber, as compared to secondary acetate, and consequently does not dye rapidly. It is necessary to increase the rate of diffusion of the disperse dye into the fiber by increasing the dyeing temperature to 110— 130CC or using a dye accelerant or carrier, or both. 

Acetone-soluble cellulose acetate is prepared by deacetylating cellulose triacetate. The product formed directly is unsatisfactory. Thus the distribution of free hydroxyls and acetate groupings is of primary importance. Cramer and Purves118(b) studied the distribution by tosylation and found that the acetyl removal from primary and secondary hydroxyl groups occurs at approximately the same rate, but that the number of... 

Table II. Secondary Hydrolysis of Cellulose Acetate Hydrogensulfate...

Cellulose acetate is usually produced by the so-called solution process with exception of the fully acetylated end product (triacetate). In the solution process the pulp is first pretreated with acetic acid in the presence of a catalyst, usually sulfuric acid. The purpose of this activation step is to swell the fibers and increase their reactivity as well as to decrease the DP to a suitable level. Acetylation is then performed after addition of acetic anhydride and catalytic amounts of sulfuric acid in the presence of acetic acid. After full acetylation the final triacetate obtained is dissolved. This "primary" acetate is usually partially deacetylated in aqueous acetic acid solution to obtain a "secondary" acetate with a lower DS of about 2 to 2.5. 

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