Wang Weiliang, Qu Rui, Suo Hongyi, Gu Yanan, Qin Yusheng
College of Chemistry and Chemical Engineering, Yantai University, Yantai, China.
Front Chem. 2023 May 4;11:1202735. doi: 10.3389/fchem.2023.1202735. eCollection 2023.
The production of biodegradable polycarbonate by copolymerizing CO with epoxides has emerged as an effective method to utilize CO in response to growing concerns about CO emissions and plastic pollution. Previous studies have mainly focused on the preparation of CO-based polycarbonates from petrochemical-derived propylene oxide (PO) or cyclohexene oxide (CHO). However, to reduce dependence on fossil fuels, the development of 100% bio-based polymers has gained attention in polymer synthesis. Herein, we reported the synthesis of glycidyl 4-pentenoate (GPA) from lignocellulose based 4-pentenoic acid (4-PA), which was further copolymerized with CO using a binary catalyst SalenCoCl/PPNCl to produce bio-based polycarbonates with vinyl side chains and molecular weights up to 17.1 kg/mol. Introducing a third monomer, PO, allows for the synthesis of the GPA/PO/CO terpolymer, and the glass transition temperature ( ) of the terpolymer can be adjusted from 2°C to 19°C by controlling the molar feeding ratio of GPA to PO from 7:3 to 3:7. Additionally, post-modification of the vinyl side chains enables the production of functional polycarbonates, providing a novel approach to the preparation of bio-based materials with diverse side chains and functions.
通过将CO与环氧化物共聚来生产可生物降解的聚碳酸酯，已成为一种有效利用CO的方法，以应对人们对CO排放和塑料污染日益增长的担忧。先前的研究主要集中于由石化衍生的环氧丙烷（PO）或环氧环己烷（CHO）制备基于CO的聚碳酸酯。然而，为了减少对化石燃料的依赖，100%生物基聚合物的开发在聚合物合成中受到了关注。在此，我们报道了由木质纤维素基4-戊烯酸（4-PA）合成4-戊烯酸缩水甘油酯（GPA），其进一步与CO使用二元催化剂SalenCoCl/PPNCl进行共聚，以生产具有乙烯基侧链且分子量高达17.1 kg/mol的生物基聚碳酸酯。引入第三种单体PO，可以合成GPA/PO/CO三元共聚物，并且通过将GPA与PO的摩尔进料比从7:3控制到3:7，三元共聚物的玻璃化转变温度（ ）可以从2°C调节到19°C。此外，乙烯基侧链的后修饰能够生产功能性聚碳酸酯，为制备具有不同侧链和功能的生物基材料提供了一种新方法。
