Incorporation of reactive functionalities is often indispensable for achieving optimal polymer properties but heavily challenged by the stringent chemoselectivity requirements on polymerization techniques. Here, polymers bearing multiple acrylate functionalities are synthesized directly by ring-opening (co)polymerization of epoxides comprising mono- or bisubstituted acrylate moieties. The acid-excess Lewis pair type organocatalyst, together with a refined monomer purification protocol, allows alcohol-initiated homopolymerization of glycidyl methacrylate (GMA), glycidyl sorbate (GS), and glycidyl cinnamate (GC) to occur in a perfectly epoxy-selective fashion, affording polyethers with 100% pendant-group fidelity, controlled molar mass (up to 63.9 kg mol^–1), and low dispersity. The control and chemoselectivity are readily extended to statistical copolymerization with propylene oxide, “n + m” or “n + 1” type block copolymerization with ethylene oxide, and alternating copolymerization with cyclic anhydrides, generating a rich array of (multi)acrylate copolyethers and polyesters. Our results have underscored the potency of this catalytic method as a versatile platform for expeditious and precision synthesis of functionalized polymers.

中文翻译：

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有机催化丙烯酸缩水甘油酯衍生物的环氧选择性聚合

反应性官能团的掺入对于实现最佳聚合物性能通常是必不可少的，但聚合技术的严格化学选择性要求却面临着严峻的挑战。这里，带有多个丙烯酸酯官能团的聚合物是通过包含单或双取代的丙烯酸酯部分的环氧化物的开环(共)聚合直接合成的。酸过量的路易斯对型有机催化剂与精炼的单体纯化方案一起，允许醇引发的甲基丙烯酸缩水甘油酯（GMA）、山梨酸缩水甘油酯（GS）和肉桂酸缩水甘油酯（GC）以完美的环氧选择性方式发生均聚，提供具有 100% 侧基保真度、受控摩尔质量（高达 63.9 kg mol ^–1）和低分散性的聚醚。控制和化学选择性很容易扩展到与环氧丙烷的统计共聚、与环氧乙烷的“ n + m ”或“ n +1”型嵌段共聚以及与环酸酐的交替共聚，生成丰富的（多）丙烯酸酯共聚醚和聚酯。我们的结果强调了这种催化方法作为快速、精确合成功能化聚合物的多功能平台的潜力。