The displacement of an activated leaving group in polymeric repeat units is a powerful method of postpolymerization modification. This strategy enables the synthesis of polymers otherwise unobtainable by direct polymerization as well as the preparation of a diverse array of macromolecular structures. We demonstrate that the activation of acrylamide through the introduction of two tert-butyloxycarbamate (Boc) groups followed by radical polymerization leads to a new class of activated polyacrylamides analogous to well-known activated polyacrylates. Transamidation of poly(di(Boc)-acrylamide) utilizing primary amines proceeds to high conversion under mild conditions, and the products can be readily purified. Less nucleophilic secondary amines and alcohols require more forcing conditions. We demonstrate the utility of this approach by preparing copolymers capable of on-demand gel formation and the synthesis of block polymers using controlled radical polymerization.

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活化聚丙烯酰胺作为聚合后改性的多功能底物

聚合物重复单元中活化离去基团的置换是聚合后改性的有效方法。这种策略能够合成聚合物，否则无法通过直接聚合获得，以及制备各种大分子结构。我们证明了通过引入两个叔胺活化丙烯酰胺-丁氧基氨基甲酸酯 (Boc) 基团随后自由基聚合产生一类新的活化聚丙烯酰胺，类似于众所周知的活化聚丙烯酸酯。利用伯胺对聚(二(Boc)-丙烯酰胺)进行转酰胺反应，在温和条件下转化率高，产物易于纯化。较少亲核的仲胺和醇需要更多的强制条件。我们通过制备能够按需凝胶形成的共聚物和使用受控自由基聚合合成嵌段聚合物来证明这种方法的实用性。