Cellulose acetate compounding

The early 1990s have also seen much interest in biodegradable cellulose acetate compounds. 

A wide range of cellulose acetate compounds are commercially available. The properties of these compounds depend on three major factors ... 

Typical values for the principal properties of cellulose acetate compounds are tabulated in Table 22.2 in comparison with other cellulosic plastics. Since cellulose acetate is seldom used today in applications where detailed knowledge of physical properties are required these are given without further comment. 

As a result of development work between the Battelle Institute in Frankfurt and a German candle-making company, Aetema, biodegradable cellulose acetate compounds have been available since 1991 from the Rhone-Poulenc subsidiary Tubize Plastics. They are marketed under the trade names Bioceta and Biocellat. The system is centred round the use of an additive which acts both as a plasticiser and a biodegrading agent, causing the cellulose ester to decompose within 6-24 months. 

In 1991 Rhone-Poulenc offered biodegradable cellulose acetate compounds in which an additive acts both as plasticiser and biodegrading agent (see Section 22.2.2.1). 

Tetraorganotin compounds with a stereogenic tin atom have been obtained as single enantiomers variously by resolution, asymmetric synthesis or, as in the example of 28, separation of the enantiomers has been achieved by chiral chromatography on cellulose acetate. Compounds such as 28 exhibit no tendency to racemize, in contrast to... 

As solvents, the amyl alcohols are intermediate between hydrocarbon and the more water-miscible lower alcohol and ketone solvents. Eor example, they are good solvents and diluents for lacquers, hydrolytic fluids, dispersing agents in textile printing inks, industrial cleaning compounds, natural oils such as linseed and castor, synthetic resins such as alkyds, phenoHcs, urea —formaldehyde maleics, and adipates, and naturally occurring gums, such as shellac, paraffin waxes, rosin, and manila. In solvent mixtures they dissolve cellulose acetate, nitrocellulose, and ceUulosic ethers. 

Oxidation has also been cited as occurring in the cure of polymethyUiydrosiloxane [9004-73-3] (PMHS) on cellulose acetate fibers. Investigation of the cured, cross-linked siUcone shows no evidence of the Si—H bond. The same compound under an atmosphere of nitrogen does not cure and retains the Si—H bonds (99). 

Zinc chloride is a Lewis acid catalyst that promotes cellulose esterification. However, because of the large quantities required, this type of catalyst would be uneconomical for commercial use. Other compounds such as titanium alkoxides, eg, tetrabutoxytitanium (80), sulfate salts containing cadmium, aluminum, and ammonium ions (81), sulfamic acid, and ammonium sulfate (82) have been reported as catalysts for cellulose acetate production. In general, they require reaction temperatures above 50°C for complete esterification. Relatively small amounts (<0.5%) of sulfuric acid combined with phosphoric acid (83), sulfonic acids, eg, methanesulfonic, or alkyl phosphites (84) have been reported as good acetylation catalysts, especially at reaction temperatures above 90°C. 

The most important of the esters is cellulose acetate. This material has been extensively used in the manufacture of films, moulding and extrusion compounds, fibres and lacquers. As with all the other cellulose polymers it has, however, become of small importance to the plastics industry compared with the polyolefins, PVC and polystyrene. In spite of their higher cost cellulose acetate-butyrate and cellulose propionate appear to have retained their smaller market because of their excellent appearance and toughness. 

Although acetylation thus renders the cellulosic structure soluble, cellulose acetate will still decompose below its softening point. It is thus necessary to compound cellulose acetate with plasticisers in order to obtain plastics materials of suitable flow properties. Other ingredients are also added at the same time. 

Although the prime function of plasticisers in cellulose acetate is to bring the processing temperature of the compound below the polymer decomposition temperature, it has additional values. An increase in the plasticiser content will reduce the melt viscosity at a given temperature and simplify processing. The physical properties of the finished product will be modified, increasing toughness... 

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. 

Triphenyl phosphate is a crystalline solid which has less compatibility with the polymer. This may be expected from solubility parameter data. It is often used in conjunction with dimethyl phthalate and has the added virtues of imparting flame resistance and improved water resistance. It is more permanent than DMP. Triacetin is less important now than at one time since, although it is compatible, it is also highly volatile and lowers the water resistance of the compound. Today it is essential to prepare low-cost compounds to allow cellulose acetate to compete with the synthetic polymers, and plasticisers such as ethyl phthalyl ethyl glycollate, which are superior in some respects, are now rarely used. 

Group of plastics composed of cellulose compounds, for example esters (e.g., cellulose acetate) and ethers (e.g., ethyl cellulose). 

As previously discussed, solvents that dissolve cellulose by derivatization may be employed for further functionahzation, e.g., esterification. Thus, cellulose has been dissolved in paraformaldehyde/DMSO and esterified, e.g., by acetic, butyric, and phthalic anhydride, as well as by unsaturated methacrylic and maleic anhydride, in the presence of pyridine, or an acetate catalyst. DS values from 0.2 to 2.0 were obtained, being higher, 2.5 for cellulose acetate. H and NMR spectroscopy have indicated that the hydroxyl group of the methy-lol chains are preferably esterified with the anhydrides. Treatment of celliflose with this solvent system, at 90 °C, with methylene diacetate or ethylene diacetate, in the presence of potassium acetate, led to cellulose acetate with a DS of 1.5. Interestingly, the reaction with acetyl chloride or activated acid is less convenient DMAc or DMF can be substituted for DMSO [215-219]. In another set of experiments, polymer with high o -celliflose content was esterified with trimethylacetic anhydride, 1,2,4-benzenetricarboylic anhydride, trimellitic anhydride, phthalic anhydride, and a pyridine catalyst. The esters were isolated after 8h of reaction at 80-100°C, or Ih at room temperature (trimellitic anhydride). These are versatile compounds with interesting elastomeric and thermoplastic properties, and can be cast as films and membranes [220]. 

Mineral-basal media may be sterilized by autoclaving, but for almost all organic compounds that are used as sources of C, N, S, or P, it is probably better to prepare concentrated stock solutions and sterilize these by filtration, generally using 0.2 pm cellulose nitrate or cellulose acetate filters. The same applies to solutions of vitamins, and to solutions of bicarbonate and sulfide that are components of many media used for anaerobic bacteria. 

The compound exists normally as the trans or ( )-isomer 21a. This molecule is essentially planar both in the solid state and in solution, although in the gas phase there is evidence that it deviates from planarity. When irradiated with UY light, the ( )-isomer undergoes conversion substantially into the cis or (Z)-isomer 21b which may be isolated as a pure compound. In darkness, the (Z)-isomer reverts thermally to the (F)-isomer which is thermodynamically more stable because of reduced steric congestion. Some early disperse dyes, which were relatively simple azobenzene derivatives introduced commercially initially for application to cellulose acetate fibres, were found to be prone to photochromism (formerly referred to as phototropy), a reversible light-induced colour change. C. I. Disperse Red 1 (22) is an example of a dye which has been observed, under certain circumstances, to give rise to this phenomenon. 

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