Living anionic polymerization—the most common living polymerization and the one with the longest history—generally requires stringent, water-free conditions and one metal initiator per polymer chain. Here we present the proton transfer anionic polymerization of methacrylates using acidic C–H bonds as the dormant species that are activated by base catalysts. The polymerization mechanism involves reversible chain transfer or termination of the growing enolate species. A weakly acidic compound, such as an alkyl isobutyrate, serves as the initiator or chain-transfer agent in the presence of a bulky potassium base catalyst to produce a polymer chain and, thereby, diminishes the metal compound per chain ratio. An added alcohol serves as a reversible terminator to tame the propagation. End-functionalized, star, block and graft polymers are easily accessible from compounds with C–H bonds.

活性阴离子聚合是最常见的活性聚合，也是历史最悠久的聚合，通常需要严格的无水条件和每个聚合物链一种金属引发剂。在这里，我们提出了甲基丙烯酸酯的质子转移阴离子聚合，使用酸性 C-H 键作为由碱催化剂激活的休眠物质。聚合机制涉及可逆链转移或终止生长的烯醇类物质。弱酸性化合物，例如异丁酸烷基酯，在大体积钾碱催化剂存在下充当引发剂或链转移剂以产生聚合物链，从而减少每条链的金属化合物比率。添加的酒精可作为可逆终止剂来抑制传播。末端官能化、星形、嵌段和接枝聚合物很容易从具有 C-H 键的化合物中获得。