The copolymerization of CO₂ and epoxides presents a transformative approach to converting greenhouse gases into aliphatic polycarbonates (CO₂-PCs), thereby reducing the polymer industry’s dependence on fossil resources. Over the past 50 years, a wide array of metallic catalysts, both heterogeneous and homogeneous, have been developed to achieve precise control over polymer selectivity, sequence, regio-, and stereoselectivity. This review details the evolution of metal-based catalysts, with a particular focus on the emergence of organoborane catalysts, and explores how these catalysts effectively address kinetic and thermodynamic challenges in CO₂/epoxides copoly₂merization. Advances in the synthesis of CO₂-PCs with varied sequence and chain architectures through diverse polymerization protocols are examined, alongside the applications of functional CO₂-PCs produced by incorporating different epoxides. The review also underscores the contributions of computational techniques to our understanding of copolymerization mechanisms and highlights recent advances in the closed-loop chemical recycling of CO₂-sourced polycarbonates. Finally, the industrialization efforts of CO₂-PCs are discussed, offering readers a comprehensive understanding of the evolution and future potential of epoxide copolymerization with CO₂.

中文翻译：

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环氧化物和 CO2 共聚物的演变：催化剂、单体、结构和应用


CO₂ 和环氧化物的共聚提供了一种将温室气体转化为脂肪族聚碳酸酯 （CO_2-PC） 的变革性方法，从而减少了聚合物行业对化石资源的依赖。在过去的 50 年里，已经开发了各种非均相和均相金属催化剂，以实现对聚合物选择性、序列、区域和立体选择性的精确控制。本文详细介绍了金属基催化剂的演变，特别关注有机硼烷催化剂的出现，并探讨了这些催化剂如何有效解决 CO₂/环氧化物共聚₂汞化过程中的动力学和热力学挑战。研究了通过不同的聚合方案合成具有不同序列和链结构的 CO_2-PC 的进展，以及通过掺入不同环氧化物生产的功能性 CO_2-PC 的应用。该综述还强调了计算技术对我们理解共聚机制的贡献，并强调了 CO₂ 来源聚碳酸酯的闭环化学回收的最新进展。最后，讨论了 CO_2-PC 的工业化工作，让读者全面了解环氧化物与 CO₂ 共聚的演变和未来潜力。