Hydroxypropylation of Polyphenol-Rich Alkaline Extracts from Pinus radiata Bark and Their Physicochemical Properties

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 (1)H 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 (T(g)) 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.