Chemical characterization of kraft lignin (KL) from mixed hardwoods (Acacia spp. from Vietnam and mixed hardwoods (mainly Quercus spp.) from Korea) was conducted for its future applications. To compare the structural changes that occurred in KL, two milled wood lignins (MWLs) were prepared from the same hardwood samples used in the production of KL. Elemental analysis showed that the MWL from acacia (MWL-aca) and mixed hardwood (MWL-mhw) had almost similar carbon content, methoxyl content, and C₉ formula. KL had high carbon content but low oxygen and methoxyl contents compared to MWLs. The C₉ formula of KL was determined to be C₉H_7.29O_2.26N_0.07S_0.12(OCH₃)_1.24. The M_w of KL and MWLs was about 3000 Da and 12,000–13,000 Da, respectively. The structural features of KL and MWLs were investigated by Fourier transform infrared spectroscopy (FT-IR) and nuclear magnetic resonance spectrometry (¹H, ¹³C NMR). The analyses indicated that KL underwent severe structural modifications, such as γ-carbon cleavage, demethylation, and polycondensation reactions during kraft pulping, which resulted in increased aromatic content and decreased aliphatic content. The main linkages in lignin, β-O-4 moieties, were hardly detected in the analysis as these linkages were extensively cleaved by nucleophilic attack of SH^- and OH^- during pulping.

The structural and thermal characterization of milled wood lignin (MWL) prepared from bamboo (Phyllostachys pubescens) grown in Korea was investigated, and the results were compared with bamboo MWLs from other studies. The C₉ formula of the bamboo MWL was C₉H_7.76O_3.23N_0.02 (OCH₃)_1.41. The Mw and Mn of MWL were 13,000 and 4400 Da, respectively, which resulted in a polydispersity index (PDI) of 3.0. The PDI of the prepared MWL was higher than other bamboo MWLs (1.3–2.2), suggesting a broader molecular weight distribution. The structural features of MWL were elucidated using FT-IR spectroscopy and NMR techniques (¹H, ¹³C, HSQC, ³¹P NMR), which indicate that MWL is of the HGS-type lignin. The major lignin linkages (β-O-4, β-β, β-5) were not different from other bamboo MWLs. The syringyl/guaiacyl ratio, determined from ¹H NMR, was calculated as 0.89. ³¹P NMR revealed variations in hydroxyl content, with a higher aliphatic hydroxyl content in MWL compared to other bamboo MWLs. Thermal properties were investigated through TGA, DSC, and pyrolysis-GC/MS spectrometry (Py-GC/MS). The DTG_max of MWL under inert conditions was 287 °C, and the T_g of MWL was 159 °C. Py-GC/MS at 675 °C revealed a syringyl, guaiacyl, p-hydroxyphenyl composition of 17:37:47.