Department of Chemistry, Seoul National University , Seoul 151-747, Korea.
J Am Chem Soc. 2016 Jul 13;138(27):8612-22. doi: 10.1021/jacs.6b04695. Epub 2016 Jun 29.
Graft and dendronized polymers have attracted much attention in the polymer community, and there have been significant efforts to develop better synthetic methods. Herein, we report the highly efficient synthesis of graft and dendronized polymers by using Cu-catalyzed multicomponent polymerization (MCP). Based on diversity-oriented synthesis, we prepared a library of various graft and dendronized polymers from combinations of three types of monomers (mono-functionalized alkynes, bis-sulfonyl azides, and diamines/diols) that are bench stable and readily accessible. After reaction optimization, 54 samples of high-molecular-weight graft and dendronized polymers were prepared, the MCP method allowing simultaneous manipulation of the structures of both the main chains and the side chains. Moreover, because of the severe steric hindrance of the side chains, these polymers adopted extended conformations, as shown by the large shape parameter in solution. Also, the extended morphology of the single polymer chains was directly visualized by atomic force microscopy and transmission electron microscopy in the solid state. Most importantly, this diversity-oriented polymerization became possible because of highly step-economical and efficient one-step MCP, paving the way toward the easily tunable synthesis of graft and dendronized polymers.
接枝和树枝状聚合物在聚合物领域引起了广泛关注，并且已经做出了很大的努力来开发更好的合成方法。在此，我们报告了使用铜催化的多组分聚合（MCP）高效合成接枝和树枝状聚合物。基于多样性导向合成，我们从三种类型的单体（单官能化炔烃、双磺酰叠氮化物和二胺/二醇）的组合中制备了各种接枝和树枝状聚合物的文库，这些单体是稳定且易于获得的。经过反应优化，制备了 54 种高分子量的接枝和树枝状聚合物，MCP 方法可以同时操纵主链和侧链的结构。此外，由于侧链的严重空间位阻，这些聚合物在溶液中呈现出伸展构象，如较大的形状参数所示。此外，原子力显微镜和透射电子显微镜在固态下直接观察到单聚合物链的伸展形态。最重要的是，由于高度经济高效的一步 MCP，这种多样性导向聚合成为可能，为接枝和树枝状聚合物的可轻松调节合成铺平了道路。
