The single‐unit monomer insertion (SUMI), derived from living/controlled polymerization, can be directly functionalized at the end or within the chain of polymers prepared by living/controlled polymerization, offering potential applications in the preparation of polymers with complex architectures. Many scenarios demand the simultaneous incorporation of monomers suitable for different polymerization methods into complex polymers. Therefore, it becomes imperative to utilize SUMI technologies with diverse mechanisms, especially those that are compatible with each other. Here, we reported the orthogonal SUMI technique, seamlessly combining radical and cationic SUMI approaches. Through the careful optimization of monomer and chain transfer agent pairs and adjustments to reaction conditions, we can efficiently execute both radical and cationic SUMI processes in one pot without mutual interference. The utilization of orthogonal SUMI pairs facilitates the integration of radical and cationic reversible addition‐fragmentation chain transfer (RAFT) polymerization in various configurations. This flexibility enables the synthesis of diblock, triblock, and star polymers that incorporate both cationically and radically polymerizable monomers. Moreover, we have successfully implemented a mixing mechanism of free radicals and cations in RAFT step‐growth polymerization, resulting in the creation of a side‐chain sequence‐controlled polymer brushes.

中文翻译：

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用于工程聚合物结构的正交自由基和阳离子单单元单体插入


来自活性/受控聚合的单单元单体插入（SUMI）可以直接在活性/受控聚合制备的聚合物的末端或链内官能化，为制备具有复杂结构的聚合物提供了潜在的应用。许多情况需要将适合不同聚合方法的单体同时掺入复杂的聚合物中。因此，利用具有多种机制的 SUMI 技术，特别是那些相互兼容的技术就变得势在必行。在这里，我们报道了正交 SUMI 技术，无缝结合了自由基和阳离子 SUMI 方法。通过仔细优化单体和链转移剂对以及调整反应条件，我们可以一锅高效地执行自由基和阳离子 SUMI 过程，而不会相互干扰。正交SUMI对的利用促进了自由基和阳离子可逆加成断裂链转移（RAFT）聚合在各种构型中的整合。这种灵活性使得能够合成包含阳离子和自由基聚合单体的二嵌段、三嵌段和星形聚合物。此外，我们在 RAFT 逐步增长聚合中成功实现了自由基和阳离子的混合机制，从而创建了侧链序列控制的聚合物刷。