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Pinus radiata bark is a rich source of polyphenols, which are mainly composed of proanthocyanidins. This study aimed to utilize P. radiata bark as a polyol source for bio-foam production in the future. Polyphenol-rich alkaline extracts (AEs) from P. radiata bark were prepared by mild alkaline treatment and then derivatized with propylene oxide (PO). Hydroxypropylated alkaline extracts (HAEs) with varying molar substitutions (MS 0.4–8.0) were characterized by FT-IR, NMR, GPC, TGA, and DSC. The hydroxyl value and solubility in commercial polyols were also determined. The molecular weights of the acetylated HAEs (Ac-HAEs) were found to be 4000 to 4900 Da. Analyses of FT-IR of HAEs and 1H NMR of Ac-HAEs indicated that the aromatic hydroxyl groups were hydroxypropylated and showed an increase in aliphatic hydroxyl group content. The glass transition temperature (Tg) of AE and HAEs were 58 to 60 °C, showing little difference. The hydroxyl value increased as the hydroxypropylation proceeded. Although salts were produced upon neutralization after hydroxypropylation, HAEs still showed suitable solubility in polyether and polyester polyols; HAEs dissolved well in polyether polyol, PEG#400, and solubility reached about 50% (w/w). This indicated that neutralized HAEs could be directly applied to bio-foam production even without removing salts.

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 C9H7.76O3.23N0.02 (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 DTGmax of MWL under inert conditions was 287 °C, and the Tg of MWL was 159 °C. Py-GC/MS at 675 °C revealed a syringyl, guaiacyl, p-hydroxyphenyl composition of 17:37:47.

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 C9H7.29O2.26N0.07S0.12(OCH3)1.24. The Mw 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.