Lee Seul Woo, Kim Kyoung Taek
Department of Chemistry, Seoul National University Seoul 08826 Korea
RSC Adv. 2024 Jan 10;14(4):2285-2292. doi: 10.1039/d3ra07536b.
In this work, we present the synthesis of uniform PMAs, where the number of repeat units and their stereochemical arrangement are precisely defined. Utilizing an iterative convergent approach with orthogonally protected dimandelic acid building blocks, we achieved high molecular weight PMAs with the desired number of repeat units, extending up to 144 mandelic acids. Additionally, stereochemically defined poly(l-mandelic acid)s with up to 32 repeat units were successfully synthesized. These uniform PMAs were subsequently coupled with uniform branched poly(ethylene glycol) blocks to create uniform dendritic-linear block copolymers. The self-assembly of these block copolymers in solution was systematically investigated. In solution self-assembly, the synthesized block copolymers showed multiple phases from cylinder to inverse cubic as the molecular weight of PMA increased. In the case of solvent diffusion-evaporation-mediated self-assembly, the block copolymers underwent a phase transition as the rate of water addition decreased.
在本工作中，我们展示了均一聚扁桃酸（PMA）的合成，其中重复单元的数量及其立体化学排列是精确确定的。利用带有正交保护的二扁桃酸结构单元的迭代收敛方法，我们获得了具有所需重复单元数量的高分子量PMA，其重复单元数量扩展至多达144个扁桃酸。此外，成功合成了具有多达32个重复单元的立体化学定义的聚（L-扁桃酸）。这些均一的PMA随后与均一的支化聚乙二醇嵌段偶联，以制备均一的树枝状-线性嵌段共聚物。对这些嵌段共聚物在溶液中的自组装进行了系统研究。在溶液自组装中，随着PMA分子量增加合成的嵌段共聚物显示出从圆柱相到反立方相的多个相。在溶剂扩散-蒸发介导的自组装情况下，随着水添加速率降低，嵌段共聚物发生相转变。
