Copolymerization of Natural Camphor-Derived Rigid Diol with Various Dicarboxylic Acids: Access to Biobased Polyesters with Various Properties

Abstract

In this work, alicyclic (1R,3S)-1,2,2-trimethylcyclopentane-1,3-dimethanol (TCDM), derived from natural camphor, was copolymerized with linear α,ω-diacids, terephthalic acid (TPA), and 2,5-furandicarboxylic acid (FDCA), affording a series of polyesters with functional properties. 2D NMR spectroscopy revealed that the stereoconfiguration of TCDM was preserved after polymerization. The TCDM polyester based on TPA showed high thermostability, high Tg value (115 °C), high modulus (1.3 GPa), and high ultimate strength (29.8 MPa). The TCDM polyester based on 1,4-succinic acid exhibited excellent ductility and resilience. Lastly, the rigidity analysis based on van Krevelen’s group contribution method, coupled with the comparisons between TCDM- and sugar-based polyesters, confirmed that TCDM is a highly reactive and rigid diol. Results indicate that TCDM polyesters are suitable for a wide range of applications, including hot-filled containers and transparent packaging materials. This work addresses some critical needs for high performance biopolymers such as achieving high Tg values, high thermostability, and high transparency.