Microwave-enhanced alkali treatment of Pinus yunnanensis: Physiochemical characterization of the dissolved lignins

Pinus yunnanensis was subjected to water-bath and microwave treatments in 1% NaOH aqueous solutions at 100 °C with various ratios of bath heating time to microwave heating time (0/120, 20/100, 40/80, 60/60, 80/40, 100/20 and 120/0 min). The lignins dissolved in the alkali liquors were separated and purified, and their physicochemical features were comparatively characterized by sugar analysis, GPC, FT-IR, ¹³C and HSQC NMR, as well as thermogravimetric analysis (TGA). The results showed that the lignin fractions extracted with microwave heating (20-120 min) had high molecular weights and polydispersities (M_w 3150-5710 g/mol, M_n 2130-3020 g/mol, M_w/M_n 1.48-2.00) as compared to those prepared without microwave heating (M_w 3080 g/mol, M_n 2080 g/mol, M_w/M_n 1.48). The most striking characteristic of all lignin fractions was the almost absence of associated sugars (0.16-3.25%). The TGA results indicated that the thermal stability of the lignin fraction increased with the increment of the molecular weight. FT-IR and NMR spectra suggested that the lignin fractions showed similar structures which were mainly composed of guaiacyl (G) and minor amounts of p-hydroxyphenyl (H) units. Moreover, HSQC NMR spectrum of a typical lignin fraction (prepared with microwave heating for 120 min) revealed that it contained dominant amounts of β-O-4′ linkages (64.6%) and phenylcoumaran (β-5′) substructures (25.8%) together with small amounts of resinol (β-β′) substructures (6.7%) and coniferyl alcohol end groups (2.9%).