Synthetic polymer chemistry is a fundamental part of polymer science, and highly efficient polymerization reactions are essential for the synthesis of high-performance polymers. Development of new synthetic methods for emerging polymer science is of great importance in this regard. Bergman cyclization is a chemical process in which highly reactive aryl diradicals form from enediyne precursors, having a strong impact in a number of fields including pharmaceutics, synthetic chemistry, and materials science. Diradical intermediates stemming from enediynes can cause DNA cleavage under physiological conditions, leading to the strong cytotoxicity of many naturally occurring enediyne antibiotics. Meanwhile, diradical intermediates can quickly couple with each other to construct polyarylenes, providing a novel method to synthesize these conjugated polymers with the advantages of facile and catalyst-free operation, high efficiency, and tailored structure. Moreover, conjugated polymers generated by Bergman cyclization exhibit many remarkable properties, such as excellent thermal stability and good solubility and processability, enabling their further processing into carbon-rich materials. This review presents a brief overview of the trajectory of Bergman cyclization in polymer science, followed by an introduction to research advances, mainly from our group, in developing polymerization methods based on Bergman cyclization, taking advantages of its catalyst-free, byproduct-free, in situ polymerization mechanism to synthesize new polymeric materials with various structures and morphologies. These synthetic strategies include fabrication of rod-like polymers with polyester, dendrimer, and chiral imide side chains, functionalization of carbon nanomaterials by surface-grafting conjugated polymers, formation of nanoparticles by intramolecular collapse of single polymer chains, and construction of carbon nanomembranes on the external and internal surface of inorganic nanomaterials. These polymers with novel structural features have been used in a variety of fields, such as energy transformation, energy storage, catalyst support, and fluorescent detection. Finally, the outlook for future developments of Bergman cyclization in polymer science is presented.

合成聚合物化学是聚合物科学的基础部分，高效聚合反应对于合成高性能聚合物至关重要。在这方面，为新兴的聚合物科学开发新的合成方法非常重要。Bergman环化反应是一种化学过程，在该过程中，由二烯炔前体形成高反应性的芳基双自由基，这在包括制药，合成化学和材料科学在内的许多领域中均具有重要影响。烯二炔产生的双自由基中间体可在生理条件下引起DNA裂解，从而导致许多天然存在的烯二炔抗生素具有很强的细胞毒性。同时，双自由基中间体可以快速相互偶联，从而形成聚亚芳基，本发明提供了一种合成这些共轭聚合物的新颖方法，其具有操作简便，无需催化剂，高效和定制结构的优点。此外，通过伯格曼环化生成的共轭聚合物表现出许多卓越的性能，例如出色的热稳定性以及良好的溶解性和可加工性，使其能够进一步加工成富碳材料。这篇评论简要概述了聚合物科学中的Bergman环化的轨迹，然后主要介绍了我们小组在开发基于Bergman环化的聚合方法方面的研究进展，并利用了其无催化剂，无副产物，原位聚合机制合成具有各种结构和形态的新型聚合材料。这些合成策略包括使用聚酯，树枝状聚合物和手性酰亚胺侧链制备棒状聚合物，通过表面接枝共轭聚合物功能化碳纳米材料，通过单个聚合物链的分子内塌陷形成纳米颗粒，以及在碳纳米管上构建碳纳米膜。无机纳米材料的内外表面。这些具有新颖结构特征的聚合物已用于各种领域，例如能量转化，能量存储，催化剂载体和荧光检测。最后，介绍了高分子科学中Bergman环化的未来发展前景。通过单个聚合物链的分子内塌陷形成纳米颗粒，以及在无机纳米材料的内外表面上构建碳纳米膜。这些具有新颖结构特征的聚合物已用于各种领域，例如能量转化，能量存储，催化剂载体和荧光检测。最后，介绍了高分子科学中Bergman环化的未来发展前景。通过单个聚合物链的分子内塌陷形成纳米颗粒，以及在无机纳米材料的内外表面上构建碳纳米膜。这些具有新颖结构特征的聚合物已用于各种领域，例如能量转化，能量存储，催化剂载体和荧光检测。最后，介绍了高分子科学中Bergman环化的未来发展前景。