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 (Mw 3150–5710 g/mol, Mn 2130–3020 g/mol, Mw/Mn 1.48–2.00) as compared to those prepared without microwave heating (Mw 3080 g/mol, Mn 2080 g/mol, Mw/Mn 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%).

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► Pinus yunnanensis was subjected to alkaline water-bath and microwave treatments.
► Microwave heating released lignins with high molecular weights and polydispersities.
► Microwave heating did not result in structural changes of lignins.
► All lignins were mainly composed of β-O-4′ inter-unit linkages.