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 T g 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 T g values, high thermostability, and high transparency.

Chemical Modification of Poly(butylene trans-1,4-cyclohexanedicarboxylate) by Camphor: A New Example of Bio-Based Polyesters for Sustainable Food Packaging

“…TCDM has been employed together with linear α,ω-diacids or terephthalic acid (TPA) or 2,5-furandicarboxylic acid (FDCA) for the synthesis of a series of novel bio-based polyesters with interesting functional properties. The polyester based on TCDM and TPA was characterized by high thermostability, a high T g value (over 100 °C), a high elastic modulus, and stress at break; the polyester based on TCDM and 1,4-succinic acid exhibited excellent ductility and resilience [ 36 ].…”

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

“…The polyesters obtained showed a satisfied T g (36.7 °C) and tensile strength (46.9 MPa) with excellent ductility (elongation at break of 830%) [ 84 ]. Gao et al [ 85 ] employed alicyclic (1R,3S)-1,2,2-trimethylcyclopentane-1,3-dimethanol (TCDM), which was derived from camphor in the polyester synthesis with linear or aromatic diacids. Polyesters based on FDCA showed a high T g of 98 °C.…”

Bio-Degradable Polyesters with Rigid Cyclic Diester from Camphor and Tartaric Acid

“…Tartaric acid occurs naturally in many fruits including grapes, bananas, tamarinds, and citrus fruits. As for the molecular structure, it is characterized by accessibility and relative simplicity [ 17 – 25 ]. New bio-monocyclic dimethyl 2,3-O-methylene-L-threarate (Thx-diester) monomer are tartaric acid-derived monomers and are introduced to improve the chain’s stiffness in polyesters [ 10 , 21 , 26 ].…”