Bio-Based Polyesters with High Glass-Transition Temperatures and Gas Barrier Properties Derived from Renewable Rigid Tricyclic Diacid or Tetracyclic Anhydride

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 (T g ) 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.

Recent Progress on Bio-Based Polyesters Derived from 2,5-Furandicarbonxylic Acid (FDCA)

“…However, considering that sometimes the melting point of the product is too high, solution polymerization is an option. ROP have been reported more recently to obtain polyesters from cyclic esters or anhydrides [ 29 , 30 ]. Additionally, ROP is the mainstream in the industrial production of PLA.…”

Development of High-Molecular-Weight Fully Renewable Biopolyesters Based on Oxabicyclic Diacid and 2,5-Furandicarboxylic Acid: Promising as Packaging and Medical Materials

“…Renewable linear polyesters with oxabicyclic units synthesized through the ring-opening polymerization (ROP) of bio-based cyclic anhydrides and epoxides comprise a growing class of polymers with impressive properties, such as high glass-transition temperature ( T g ) and excellent biodegradation behavior. − Thus, these linear polyesters with oxabicyclic units appear to be the next generation of commercial biodegradable materials and are the promising competition to poly­(butylene succinate) (PBS) and polylactide (PLA). , Despite the many positive hallmarks, the scope of applicable anhydride comonomers is limited. While the majority of linear polyesters with oxabicyclic units or copolyesters synthesized via ROP are full-aliphatic materials, the lack of sufficient thermal stability and satisfactory mechanical properties of these aliphatic polyesters with oxabicyclic units poses a great challenge to their large-scale commercial application . In addressing these limitations, the incorporation of aromatic building blocks allows for the facile improvement of the thermal and mechanical properties of polyesters.…”

“…However, the unsatisfactory yields and the low molecular weight result in disappointing T g values and mechanical strength of linear polyesters with oxabicyclic units, often due to the readily volatilizable anhydrides during the MP process. In our recent work, we reported the MP of bulky tricyclic diacid and linear α,ω-diols to obtain high-molecular-weight polyesters, due to the reduction of the outflow of components and increase in the degree of repeat units of oligomers in the esterification step …”

Malononitrile‐involved Michael addition polymerization: An efficient and facile route for cyano‐rich polyesters with programmable thermal and mechanical properties

“…Polycondensation of diol and diacid successfully solve the problems of monomer-universality, oxygen-sensitivity, and water-sensitivity. [12][13][14][15][16][17] Nevertheless, the polycondensation technology has been waned, because of the lower molecular weight, tedious operation and harsh conditions, such as high temperature and high vacuum. 18 Therefore, it is of great significance to explore an efficient and facile route for the polymerization of polyesters.…”