Ring-opening polymerization (ROP) of cyclic monomers is a prevalent and convenient method for the synthesis of well-defined polymers with initiators/catalysts that promote a nucleophilic or electrophilic attack on the monomers. Selective activation of functional groups or linkages of the monomer without those carried out in the polymer chains, especially at high conversion, is one of the challenges faced by ROP catalysts. H-bonding organocatalysts can offer precise selectivity for ROP in a wide range of monomers. The firstly reported neutral H-bonding organocatalysts are characterized by high selectivity but long reaction time and low reactivity. In contrast, ionic H-bonding organocatalysts, which have extensively developed over the last ten years, exhibit fast polymerization rates and high selectivity. Besides, some ionic H-bonding organocatalysts with good thermal stability and high reactivity can be used in a wide range of ROP temperatures (-60 °C to over 200 °C). Furthermore, ionic H-bonding organocatalysts comply with biosafety principles promoted by green chemistry. This review covers the mechanistic insights (monomer activation, initiator/chain-end activation, synergistic activation, and bifunctional activation) of ionic H-bonding organocatalytic ROP, as well as the strategies for monomer and initiator/chain-end activation.

环状单体的开环聚合 (ROP) 是一种普遍且方便的方法，用于合成定义明确的聚合物，引发剂/催化剂促进对单体的亲核或亲电攻击。ROP 催化剂面临的挑战之一是选择性活化单体的官能团或键，而不是在聚合物链中进行，尤其是在高转化率时。氢键有机催化剂可以为各种单体中的 ROP 提供精确的选择性。首次报道的中性氢键有机催化剂具有选择性高但反应时间长和反应活性低的特点。相比之下，在过去十年中得到广泛发展的离子氢键有机催化剂表现出快速聚合速率和高选择性。除了，一些具有良好热稳定性和高反应性的离子氢键有机催化剂可用于较宽的 ROP 温度范围（-60 °C 至 200 °C 以上）。此外，离子氢键有机催化剂符合绿色化学促进的生物安全原则。本综述涵盖了离子 H 键有机催化 ROP 的机理见解（单体活化、引发剂/链端活化、协同活化和双功能活化），以及单体和引发剂/链端活化的策略。