Effect of Heat Treatment on the Chemical Structure and Thermal Properties of Softwood-Derived Glycol Lignin.

A large-scale glycol lignin (GL) production process (50 kg wood meal per batch) based on acid-catalyzed polyethylene glycol (PEG) solvolysis of Japanese cedar (JC) was developed at the Forestry and Forest Products Research Institute (FFPRI), Tsukuba, Japan. JC wood meal with various particle size distributions (JC-S < JC-M < JC-L) (average meal size, JC-S (0.4 mm) < JC-M (0.8 mm) < JC-L (1.6 mm)) and liquid PEG with various molecular masses are used as starting materials to produce PEG-modified lignin derivatives, namely, GLs, with various physicochemical and thermal properties. Because GLs are considered a potential feedstock for industrial applications, the effect of heat treatment on GL properties is an important issue for GL-based material production. In this study, GLs obtained from PEG400 solvolysis of JC-S, JC-M, and JC-L were subjected to heating in a constant-temperature drying oven at temperatures ranging from 100 to 220 °C for 1 h. All heat-treated GL series were thermally stable, as determined from the Klason lignin content, TMA, and TGA analyses. SEC analysis suggests the possibility of condensation among lignin fragments during heat treatment. ATR-FTIR spectroscopy, thioacidolysis, and 2D HSQC NMR demonstrated that a structural rearrangement occurs in the heat-treated GL400 samples, in which the content of α-PEG-β-O-4 linkages decreases along with the proportional enrichments of β-5 and β-β linkages, particularly at treatment temperatures above 160 °C.