Acetylation of lignin

Quantitative Acetylation of Lignins. To avoid fractionation of the lignins and loss of low molecular weight components, which occur in the usual acetylation procedures, the quantitative acetylation described by H. Chum et al. (20,21) was employed. 

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. 

Callow, H.J. (1951). Acetylation of cellulose and lignin in jute. Journal of the Indian Chemical Society, 28(11), 605-610. 

This study describes the application of differential vis-cometry as a GPC detector to the problem of determining molecular weight distributions of acetylated hardwood lignins in tetrahydrofuran. Molecular weight distributions of ball-milled, organosolv, alkali-extracted/mild acid hydrolyzed, and alkali-extracted/steam exploded aspen lignins were estimated using universal calibration. 

This study reports the first application of universal calibration via HPSEC-DV to four acetylated hardwood lignins obtained from aspen (Pop-ulus tremuloides) wood meal by ball milling and solvent extraction steam explosion followed by alkaline extraction organosolv pulping followed by water extraction of the associated sugars and dilute sulfuric acid hydrolysis followed by sodium hydroxide extraction. 

Table I. MWD of Acetylated Aspen Lignins and Model Compounds from Universal Calibration with Narrow Standards 1...

In order to overcome the solubility limitation typical of lignin fractions, chemical modifications have been envisaged. Obviously only those methods giving nearly quantitative recovery are adequate for the purpose of measuring Mn- Table V shows results related to the acetylation technique where only a slight increase in M is observed as expected. 

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