Cellulose derivatizing solvents

The basic requirement for cellulose dissolution is that the solvent is capable of interacting with the hydroxyl groups of the AGU, so as to eliminate, at least partially, the strong inter-molecular hydrogen-bonding between the polymer chains. There are two basic schemes for cellulose dissolution (i) Where it results from physical interactions between cellulose and the solvent (ii) where it is achieved via a chemical reaction, leading to covalent bond formation derivatizing solvents . Both routes are addressed in details below. 

Complexatlon principle of cellulose with derivatizing solvent molecules illustrated for the case of cuprammonium hydroxide. Solvent molecules replace the existing hydrogen bonds with solvating Cu-complexes. (After Burchardt et al. [47])... 

The oldest and most widely practiced cellulose regeneration technology of the derivatizing solvent-type is the viscose rayon process. It is based, in part, on the discovery in 1857 by Cross, Bevin, and Beadle of the dissolution of sulfidized cellulose in alkali. Viscose fibers are by far the most important cellulose regenerates, amounting to an annual fiber production of 2.5 X 10 t worldwide [13,74]. 

In recent years cellulose dissolution has been researched quite extensively and new solvents have been discovered that are more environmentally friendly. Several new processes that rely on these solvents have been developed for manufacturing fibers. Furthermore, research has also been focused on cellulose derivatization processes that pollute less and are more economical. 

Functional Cellulose Materials Prepared from Non-derivatizing Solvents... 

Cellulose is very difficult to dissolve in common solvents due to its intramolecular and intermolecular hydrogen bonding networks. Lately, many new non-derivatizing solvents have been developed to dissolve cellulose. 

The utilization of ionic liquids provides a new opportunity for proeessing cellulose while minimizing the energy and environmental concerns, because ionic liquids are chemically and thermally stable, non-flammable and low in volatility [91, 92]. Several ionic liquids that serve as non-derivatizing solvents have been proposed such as 1-ally 1-3-methylimidazolium chloride (AmimCl) [93], 1-butyl-3-methylimidazolium chloride (BmimCl) [94], and 1,3-dialkylimidazolium formate [95]. Manufacturing cellulose fiber using ionic liquids has attracted attention in both academia and industry. For example, regenerated cellulose films... 

The GBR resin works well for nonionic and certain ionic polymers such as various native and derivatized starches, including sodium carboxymethylcel-lulose, methylcellulose, dextrans, carrageenans, hydroxypropyl methylcellu-lose, cellulose sulfate, and pullulans. GBR columns can be used in virtually any solvent or mixture of solvents from hexane to 1 M NaOH as long as they are miscible. Using sulfonated PDVB gels, mixtures of methanol and 0.1 M Na acetate will run many polar ionic-type polymers such as poly-2-acrylamido-2-methyl-l-propanesulfonic acid, polystyrene sulfonic acids, and poly aniline/ polystyrene sulfonic acid. Sulfonated columns can also be used with water glacial acetic acid mixtures, typically 90/10 (v/v). Polyacrylic acids run well on sulfonated gels in 0.2 M NaAc, pH 7.75. 

Several solvent systems dissolve cellulose, a process that may, or may not lead to cellulose derivative formation. Both types of solvent systems will be considered, although the important derivatizing reaction employed in the... 

Another activation treatment, suitable for most celluloses (although with great variation of the time required, 1 to 48 h) is polar solvent displacement at room temperature. The polymer is treated with a series of solvents, ending with the one that will be employed in the derivatization step. Thus, cellulose is treated with the following sequence of solvents, before it is dissolved in LiCl/DMAc water, methanol, and DMAc [37,45-48]. This method, however, is both laborious, needs ca. one day for micro crystalline cellulose, and expensive, since 25 mL of water 64 mb of methanol, and 80 mb of DMAc are required to activate one gram of cellulose. Its use may be reserved for special cases, e.g., where cellulose dissolution with almost no degradation is relatively important [49]. 

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]. 

Regioselective enzymatic acylation of large, insoluble polysaccharides is still a quite difficult task and therefore it is not surprising that only scant data have been reported up to now, most of them describing reaction outcomes which met with limited success. Nevertheless, enzymatic derivatization of polysaccharides has been performed in nonpolar organic solvents using insoluble polysaccharides with soluble [51] or suspended enzymes [52]. Chemically modified celluloses with either enhanced solubility or more readily accessible hydroxyl groups, like cellulose acetate or hydroxypropyl cellulose, were acylated by CalB, as reported by Sereti and coworkers [53]. However, the same authors failed to modify crystalline cellulose under the same reaction conditions. 

---