Solution radical homopolymerization of isobornyl acrylate (iBoA) under starved‐feed higher temperature conditions unexpectedly leads to polymer product with low dispersity (<1.3) compared to the polymerization of butyl acrylate (BA) under identical conditions. Both backbiting and β‐scission reactions occur, as the poly(iBoA) product contains close to 100% terminal double bond (TDB) functionality. However, the addition of monomer to the midchain radicals formed by backbiting is sterically hindered, greatly reducing both short and long‐chain branching. The poly(iBoA) macromonomer functions as an excellent addition–fragmentation agent, not only lowering dispersity but also providing a means to efficiently produce blocky acrylate copolymers through sequential monomer feeding in the starved‐feed semibatch process.

中文翻译：

---

利用加成-断裂反应通过半间歇自由基聚合生产低分散度的聚丙烯酸异冰片酯和嵌段共聚物。

与在相同条件下丙烯酸丁酯（BA）的聚合相比，在饥饿进料的较高温度条件下，丙烯酸异冰片酯（iBoA）的溶液自由基均聚意外地导致了聚合物分散度低（<1.3）的聚合物产品。由于poly（iBoA）产品包含接近100％的末端双键（TDB）功能，因此会发生反咬和β断裂反应。但是，在位点上阻碍了将单体添加到由反向咬合形成的中链自由基中，大大减少了短链和长链支化。聚（iBoA）大分子单体是一种出色的加成碎片剂，不仅降低了分散性，而且还提供了一种通过在饥饿的半分批进料过程中依次进料单体有效生产嵌段丙烯酸酯共聚物的方法。