Mandal Ankita, Mandal Indradip, Kilbinger Andreas F M
Department of Chemistry, University of Fribourg, Chemin du Musée 9, 1700 Fribourg, Switzerland.
ACS Macro Lett. 2021 Dec 21;10(12):1487-1492. doi: 10.1021/acsmacrolett.1c00613. Epub 2021 Nov 12.
Single chain transfer agents are used to synthesize narrowly distributed heterotelechelic ROMP polymers in one pot, exploiting a new mechanistic and synthetic approach. The chain transfer agents carrying different functional groups are synthesized in a few straightforward steps. Prefunctionalization of commercially available Grubbs' third-generation catalyst is realized in situ using regioselective chain transfer agents within a short reaction period. After monomer consumption, the excess chain transfer agent in the reaction medium automatically end-functionalizes the polymer chain, yielding a heterotelechelic polymer via a ring-opening-ring-closing sequence. H NMR, MALDI-ToF, and SEC analyses confirmed end-group functionalization as well as excellent control over molecular weight and dispersity. This strategy highlights a new way of synthesizing one-pot heterotelechelic ROMP polymers straightforwardly and efficiently.
单链转移剂用于一锅法合成窄分布的杂臂端基开环易位聚合（ROMP）聚合物，采用了一种新的机理和合成方法。通过几个简单步骤合成了带有不同官能团的链转移剂。使用区域选择性链转移剂在短反应时间内原位实现市售第三代格拉布催化剂的预官能化。单体消耗后，反应介质中过量的链转移剂自动使聚合物链端基官能化，通过开环-闭环序列生成杂臂端基聚合物。1H NMR、基质辅助激光解吸电离飞行时间质谱（MALDI-ToF）和尺寸排阻色谱（SEC）分析证实了端基官能化以及对分子量和分散度的出色控制。该策略突出了一种直接且高效地合成一锅法杂臂端基ROMP聚合物的新方法。
