Bio-Based Polyesters with High Glass-Transition Temperatures and Gas Barrier Properties Derived from Renewable Rigid Tricyclic Diacid or Tetracyclic Anhydride
Haiyan Zhang, Guangyuan Zhou, Min Jiang, Houyu Zhang, Honghua Wang, Yuanpeng Wu, Rui Wang
Abstract
Novel tricyclic diacid (TCDA) and tetracyclic anhydride (TCAH) were synthesized from renewable furan to generate a series of bio-based polyesters via melt polymerization (MP) of TCDA with seven linear α,ω-diols and ring-opening polymerization (ROP) of TCAH with three different epoxides. NMR and single-crystal X-ray revealed a unique rigid W-shaped skeleton of TCDA and TCAH, which was readily converted in diester units to the stable configuration during polymerization. The multicyclic rigid structure imparts high glass-transition temperature (Tg) comparable to petrochemical polymers with the MP polyesters reaching up to 109 °C and ROP polyesters reaching up to 174 °C. In addition, the rigid tricyclic moiety attributes to superior gas barrier properties of the 2,5-furandicarboxylic acid-based polyester, which are significantly better than that of current bio-based polyester poly(butylene succinate) and polylactide. The outstanding heat tolerance and gas barrier properties of these multicyclic polyesters appear to be promising as substitutes for common industrial petrochemical-based polyesters.