Quantitative acetylation, lignins

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. 

Aminolysis is a laborious procedure, e.g., for wood samples, a 6-7-h reaction period may be required for the aminolysis step alone. The accuracy of this method is critically dependent upon both a quantitative acetylation of phenolic hydroxyl groups and a selective deacetylation of phenolic acetyl groups. Although these requirements may not represent a serious concern in the analysis of soluble or reagent-accessible lignin preparations, they could present a problem in the case of lignocellulosic materials. 

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. 

Feedstock material and processed solids were analyzed for glucan, xylan, arabinan, and acetyl groups by quantitative acid hydrolysis according to standard methods (25). The acid-insoluble residue was considered as Klason lignin, after correction for the acid-insoluble ash (determined by igniting the contents at 575°C for 5 h). 

The benzyl acetate (18) is quantitatively determined by capillary column gas chromatography (GC). Benzyl butanoate (20), formed from butanoic acid (19) concurrently with the formation of benzyl acetate (18), serves as the internal standard (Mansson 1983). Since 1 mol of acetic acid (14) is converted to 1 mol of benzyl acetate (18), the total hydroxyl content of the lignin preparation can be determined by quantitative determination of the benzyl acetate (18). The Mansson procedure is a modification of the Bethge-Lindstrom method for determinating O-acetyl groups in acetylated carbohydrates (Bethge and Lindstrom 1973). 

The absorbance at either 205 or 280 nm is the basis of several techniques for the quantitative determination of lignin. The extinction coefficient depends on species and solvent, and varies from 10 to about 26 L g cm. Summaries of extinction coefficients are available in reviews by Dence [18], Lin [2], and Fengel and Wegener [19]. Lin [2] has provided guidelines for measurement of lignin absorption spectra, while Dence [18] provides instructions for determination of acid-soluble lignin and lignin solubilized by the acetyl bromide method. 

---