Of lignin

Conversion of Cyclic to Acyclic Structures. Upon oxidation, the aromatic rings of lignin may be converted direcdy to acycHc stmctures, eg, muconic acid derivatives, or indirectly by oxidative splitting of o-quinoid rings. Further oxidation creates carboxyUc acid fragments attached to the lignin network. 

Substitution Reactions on Side Chains. Because the benzyl carbon is the most reactive site on the propanoid side chain, many substitution reactions occur at this position. Typically, substitution reactions occur by attack of a nucleophilic reagent on a benzyl carbon present in the form of a carbonium ion or a methine group in a quinonemethide stmeture. In a reversal of the ether cleavage reactions described, benzyl alcohols and ethers may be transformed to alkyl or aryl ethers by acid-catalyzed etherifications or transetherifications with alcohol or phenol. The conversion of a benzyl alcohol or ether to a sulfonic acid group is among the most important side chain modification reactions because it is essential to the solubilization of lignin in the sulfite pulping process (17). 

Formation and Elimination of Multiple Bond Functionalities. Reactions that involve the formation and elimination of multiple bond functional groups may significantly effect the color of residual lignin in bleached and unbleached pulps. The ethylenic and carbonyl groups conjugated with phenoHc or quinoid stmctures are possible components of chromophore or leucochromophore systems that contribute to the color of lignin. 

Determination of Lignin Content. Lignin content in plants (wood) is determined by direct or indirect methods (21). The direct method includes measurement of acid-insoluble (ie, Klason) lignin after digesting wood with 72% sulfuric acid to solubilize carbohydrates (22). The Klason lignin contents of representative lignifted materials are shown in Table 2. 

The methods of oxidant consumption are used exclusively in the analysis of residual lignin in unbleached pulps. These procedures are all based on the common principle that lignin consumes the appHed oxidants at a much faster rate than the carbohydrates, and oxidant consumption under carefully specified conditions can be regarded as a measure of lignin concentration in the pulp. 

In solution, lignin is most conveniendy analyzed quaUtatively and quantitatively by uv spectroscopy. Typical absorptivity values, D, at 280 nm for milled wood (MW) lignins and other types of lignins are Hsted ia Table 4. These values are used for quantitative determination of the lignins ia suitable solvents. 

Functional Group Analysis. The total hydroxyl content of lignin is determined by acetylation with an acetic anhydride—pyridine reagent followed by saponification of the acetate, and followed by titration of the resulting acetic acid with a standard 0.05 W sodium hydroxide solution. Either the Kuhn-Roth (35) or the modified Bethge-Liadstrom (36) procedure may be used to determine the total hydroxyl content. The aUphatic hydroxyl content is determined by the difference between the total and phenoHc hydroxyl contents. 

The method of choice for determining carboxyl groups in lignin is based on potentiometric titration in the presence of an internal standard, /)-hydroxybenzoic acid, using tetra- -butylammonium hydroxide as a titrant (42). The carboxyl contents of different lignins are shown in Table 6. In general, the carboxyl content of lignin increases upon oxidation. 

Finally, the sulfonate content of lignin is deterrnined by two main methods one typified by conductometric titration in which sulfonate groups are measured direcdy, and the other which measures the sulfur content and assumes that all of the sulfur is present as sulfonate groups. The method of choice for determining the sulfonate content of lignin samples that contain inorganic or nonsulfonate sulfur, however, is conductometric titration (45). 

Chemical Properties. Lignin is subject to oxidation, reduction, discoloration, hydrolysis, and other chemical and enzymatic reactions. Many ate briefly described elsewhere (51). Key to these reactions is the ability of the phenolic hydroxyl groups of lignin to participate in the formation of reactive intermediates, eg, phenoxy radical (4), quinonemethide (5), and phenoxy anion (6) ... 

The aromatic ring of a phenoxy anion is the site of electrophilic addition, eg, in methylolation with formaldehyde (qv). The phenoxy anion is highly reactive to many oxidants such as oxygen, hydrogen peroxide, ozone, and peroxyacetic acid. Many of the chemical modification reactions of lignin utilizing its aromatic and phenoHc nature have been reviewed elsewhere (53). 

Advances in technology have increased the importance of lignin products in various industrial appHcations. They are derived from an abundant, renewable resource, and they are nontoxic and versatile in performance. 

B. J. Fergus, "The Distribution of Lignin in Wood as Determined by Ultraviolet Microscopy," Ph.D. thesis, McGill University, Montreal, Canada,... 

The aromatic nature of lignin contrasts with the aliphatic stmcture of the carbohydrates and permits the selective use of electrophilic substitution reactions, eg, chlorination, sulfonation, or nitration. A portion of the phenoUc hydroxyl units, which are estimated to comprise 30 wt % of softwood lignin, are unsubstituted. In alkaline systems the ionized hydroxyl group is highly susceptible to oxidative reactions. 

The molecular weight of lignin in the wood, ie, of protolignin, is unknown. In addition to difficulties of isolation and purification, the polymer exhibits strong solvent, ionic, and associative effects in solution. An unequivocal method of measurement has not been developed. The polymer properties of lignin and its derivatives have been discussed (10,16). 

Chemistry ofDelig niiic tion. The chemistry of delignification is complex and, despite the extensive Hterature, not completely understood. A variety of lignin model compounds have been studied and the results compared with the observed behavior of lignin during pulping (1,10—12,16). 

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