College of Materials Science and Engineering, Chongqing University of Technology, Chongqing, 400054, China.
Division of Applied Chemistry, Faculty of Engineering, Hokkaido University, Sapporo, 060-8628, Japan.
Nat Commun. 2022 Jan 10;13(1):163. doi: 10.1038/s41467-021-27830-3.
Switchable polymerization holds considerable potential for the synthesis of highly sequence-controlled multiblock. To date, this method has been limited to three-component systems, which enables the straightforward synthesis of multiblock polymers with less than five blocks. Herein, we report a self-switchable polymerization enabled by simple alkali metal carboxylate catalysts that directly polymerize six-component mixtures into multiblock polymers consisting of up to 11 blocks. Without an external trigger, the catalyst polymerization spontaneously connects five catalytic cycles in an orderly manner, involving four anhydride/epoxide ring-opening copolymerizations and one L-lactide ring-opening polymerization, creating a one-step synthetic pathway. Following this autotandem catalysis, reasonable combinations of different catalytic cycles allow the direct preparation of diverse, sequence-controlled, multiblock copolymers even containing various hyperbranched architectures. This method shows considerable promise in the synthesis of sequentially and architecturally complex polymers, with high monomer sequence control that provides the potential for designing materials.
可切换聚合在合成高度序列可控的多嵌段聚合物方面具有巨大的潜力。迄今为止，这种方法仅限于三组分体系，这使得可以直接合成少于五个嵌段的多嵌段聚合物。在此，我们报告了一种由简单的碱金属羧酸盐催化剂引发的自切换聚合，该催化剂可直接将六组分混合物聚合成长达 11 嵌段的多嵌段聚合物。在没有外部触发的情况下，催化剂聚合会自动有序地连接五个催化循环，涉及四个酸酐/环氧化物开环共聚和一个 L-丙交酯开环聚合，从而形成一步合成途径。在这种自动串联催化之后，不同催化循环的合理组合可以直接制备各种序列可控的多嵌段共聚物，甚至包含各种超支化结构。该方法在合成顺序和结构复杂的聚合物方面具有广阔的前景，其单体序列控制程度高，为设计材料提供了可能性。
