Modulating the Tg of Poly(alkylene succinate)s by Inserting Bio-Based Aromatic Units via Ring-Opening Copolymerization

Abstract

Two series of aliphatic-aromatic copolyesters derived from succinic and 2,5-furandicarboxylic acids, and di-O-2-(hydroxyethyl) resorcinol as diol substituent of either 1,4-butanediol or ethylene glycol, respectively, were obtained by ring opening polymerization(ROP) performed in bulk and catalyzed by Sn(Oct)2. Cyclic oligomers of furandicarboxylate of di-O-2-(hydroxyethyl) resorcinol were successfully synthesized by high-dilution condensation, and then copolymerized with cyclic oligomers of either butylene or ethylene succinate. The synthesized resorcinol-containing succinate-furanoatecopolyesters had Mw oscillating between 50,000 and 30,000 g·mol−1 depending on composition, and they all displayed a nearly random microstructure. They showed an excellent thermal stability with onset decomposition temperatures near 300 °C. They are amorphous with Tg increasing monotonically with the content in resorcinol in both series with values ranging from −30 or −13 °C for butylene and ethylene-based copolyesters, respectively, up to around 45 °C. The resorcinol-containing succinate-furanoate copolyesters showed appreciable hydrolytic degradation when incubated for a few weeks in water under physiological conditions, a behavior that was notably enhanced in the presence of lipases.

Keywords

• bio-based copolyesters
• poly(alkylene succinate)s
• resorcinol
• 2,5-furandicarboxylic acid
• ED-ROP
• furane-based polyesters