Schwarz Rony, Diesendruck Charles E
Schulich Faculty of Chemistry and the Resnick Sustainability Center for Catalysis, Technion - Israel Institute of Technology, Haifa, 3200008, Israel.
Adv Sci (Weinh). 2023 Dec;10(34):e2304571. doi: 10.1002/advs.202304571. Epub 2023 Oct 23.
Unstrained C─C bond activation is attained in homopolymers through mechanochemical bond scission followed by functionalization to yield mostly semi-telechelic polymer chains. Ball milling poly(ethylene oxide) (PEO) in the presence of 1-(bromoacetyl)pyrene (BAPy) yields the pyrene terminated PEO. Similarly, milling with 2,4'-dibromoacetophenone followed by Suzuki coupling allows the introduction of various aryl end groups. PEOs with a molecular weight below 20 kDa show no functionalization, supporting a mechanochemical mechanism. The protocol is also tested with doxorubicin, yielding the drug-polymer conjugate. PEO halogenation is also demonstrated by milling PEO with iodine, N-bromosuccinimide, or N-iodosuccinimide, which can then be reacted with an amine substituted anthracene. Grinding additional carbon polymers with BAPy indicates that this functionalization method is general for different polymer chemistries.
通过机械化学断键然后官能团化，在均聚物中实现了未受应变的C─C键活化，从而主要生成半遥爪聚合物链。在1-(溴乙酰基)芘(BAPy)存在下球磨聚环氧乙烷(PEO)，得到芘封端的PEO。类似地，用2,4'-二溴苯乙酮球磨然后进行铃木偶联，可以引入各种芳基端基。分子量低于20 kDa的PEO没有官能团化，这支持了机械化学机理。该方案也用阿霉素进行了测试，得到了药物-聚合物缀合物。通过将PEO与碘、N-溴代琥珀酰亚胺或N-碘代琥珀酰亚胺球磨也证明了PEO卤化，然后它可以与胺取代的蒽反应。用BAPy研磨其他碳聚合物表明，这种官能团化方法对不同的聚合物化学体系是通用的。
