Pang Chengcai, Jiang Xueshuang, Yu Yan, Chen Li, Ma Jianbiao, Gao Hui
School of Chemistry and Chemical Engineering, School of Material Science and Engineering, Tianjin Key Laboratory of Organic Solar Cells and Photochemical Conversion, Tianjin University of Technology, Binshui West Road 391, Tianjin 300384, China.
ACS Macro Lett. 2019 Nov 19;8(11):1442-1448. doi: 10.1021/acsmacrolett.9b00570. Epub 2019 Oct 11.
In this work, alicyclic (1,3)-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 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 values, high thermostability, and high transparency.
在本研究中，由天然樟脑衍生而来的脂环族（1,3）-1,2,2-三甲基环戊烷-1,3-二甲醇（TCDM）与线性α,ω-二酸、对苯二甲酸（TPA）和2,5-呋喃二甲酸（FDCA）共聚，得到了一系列具有功能特性的聚酯。二维核磁共振光谱表明，TCDM的立体构型在聚合后得以保留。基于TPA的TCDM聚酯表现出高热稳定性、高玻璃化转变温度（115℃）、高模量（1.3 GPa）和高极限强度（29.8 MPa）。基于1,4-琥珀酸的TCDM聚酯表现出优异的延展性和回弹性。最后，基于范克雷维伦基团贡献法的刚性分析，以及TCDM基聚酯和糖基聚酯之间的比较，证实了TCDM是一种高反应性和刚性的二醇。结果表明，TCDM聚酯适用于广泛的应用，包括热灌装容器和透明包装材料。这项工作满足了对高性能生物聚合物的一些关键需求，如实现高玻璃化转变温度、高热稳定性和高透明度。
