Engineering plastics from lignin II. Characterization of hydroxyalkyl lignin derivatives

Several types of hydroxyalkyl lignin derivatives were synthesized from milled wood, organosolv, steam explosion, acid (H₂SO₄) hydrolysis, and kraft lignin with ethylene oxide, propylene oxide, and butylene oxide by either batch reaction in toluene at 180°C using KOH as catalyst, or in aqueous alkali at room temperature. The isolated derivatives were characterized in terms of their chemical structures by H-NMR and FT-IR spectroscopy. Thermal properties were determined by differential scanning calorimetry. Molecular weights were measured by gel permeation chromatography on polystyrene/lignin model compound calibrated high pressure μ-spherogel columns. Solubilities in various organic solvents spanning a solubility parameter (δ) range from 9.3 to 14.5 and a hydrogen bonding index (γ) range from 1.5 to 18.7 were tested using UV₂₈₀ absorption of solutions of up to with degrees of substitution of between 1 and 2.6 (except for ethylene oxide derivatives which were higher) and with lignin contents of around 60%. The drastic reduction of glass transition temperature of between 50° and 100° is explained with increased free volume of the copolymer and with disruption of hydrogen bonds involving especially phenolic hydroxy groups. The greatly enhanced solubility in organic solvents indicates absence of the gel structure typical of network polymers. No molecular breakdown was observed as a consequence of oxyalkylation. The derivatives had molecular weights (M_w) of between 2000 and 50,000 at dispersity factors of between 2.5 and 25. The derivatives seem to constitute useful prepolymers for thermosetting engineering plastics.