Rondon Brayan, Ungolan Poom, Wu Lianqian, Niu Jia
Department of Chemistry, Boston College, Chestnut Hill, Massachusetts 02467, United States.
J Am Chem Soc. 2024 Aug 7;146(31):21868-21876. doi: 10.1021/jacs.4c06431. Epub 2024 Jul 25.
Recent advances in synthetic methods and monomer design have given access to precision carbohydrate polymers that extend beyond native polysaccharides. In this article, we present the synthesis of a class of chemically recyclable ester-linked pseudo-polysaccharides via the living anionic ring-opening polymerization of glucurono-1,6-lactones. Notably, the pseudo-polysaccharides exhibited defined chain-end groups, well-controlled molecular weights, and narrow molecular weight distributions, all hallmarks of living polymerization. Furthermore, we demonstrate that our approach is modular, as evidenced by tunable glass transition temperatures () and the ability to produce both amorphous and semicrystalline polymers by adjusting the monomer side chain structure. Lastly, we showcased the complete catalytic chemical recycling of these pseudo-polysaccharides back to the monomers. The flexibility of the polymerization and the recyclability of these pseudo-polysaccharides promote a sustainable circular economy while offering the potential to access polysaccharide-like materials with tunable thermal and mechanical properties.
合成方法和单体设计方面的最新进展使得人们能够获得超越天然多糖的精密碳水化合物聚合物。在本文中，我们通过葡糖醛酸-1,6-内酯的活性阴离子开环聚合反应，介绍了一类可化学循环的酯键连接的假多糖的合成。值得注意的是，这些假多糖表现出明确的链端基团、良好控制的分子量和窄的分子量分布，这些都是活性聚合的特征。此外，我们证明了我们的方法具有模块化特点，可调节的玻璃化转变温度以及通过调整单体侧链结构来制备无定形和半结晶聚合物的能力就是证明。最后，我们展示了这些假多糖完全催化化学循环回单体的过程。这种聚合反应的灵活性以及这些假多糖的可回收性促进了可持续的循环经济，同时提供了获得具有可调热性能和机械性能的类多糖材料的潜力。
