Vanillin based polymers: V. Poly(hydrovanilloin–urethane)

Abstract

Renewable resources based hydrovanilloin [1,2-bis(4-hydroxy-3-methoxyphenyl)-1,2-ethanediol] was synthesized in 86% yield by electrochemical dimerization of vanillin in aqueous NaOH. This symmetrical bis-phenol monomer was then used for the preparation of urethane polymers by two different methods. In the first method a 1:2 mole ratio mixture of hydrovanilloin and diisocyanate was polymerized in DMF using 1,4-diazabicyclo[2,2,2]octane as the catalyst at 60°C, for 1 h to give poly(hydrovanilloin–urethane)s. In the second method diisocyanates were first reacted with polyethylene glycol-400 to give pre-polymers. Then prepolymers were reacted with equivalent amount of hydrovanilloin at 60°C for 4 days to produce poly(hydrovanilloin-ethylene glycol-urethane)s. The first method resulted hard poly(hydrovanilloin–urethane)s showing Tg values in the range of 121–172°C. The second method yielded softer poly(hydrovanilloin-ethylene glycol-urethane)s and these polymers failed to show distinct glass transition temperatures in the DSC analysis. However, poly(hydrovanilloin-ethylene glycol-urethane)s showed better thermal stabilities than polymers without polyethylene glycol units.