Multicomponent reactions (MCRs) are remarkable one-pot combinatorial synthetic tools involving at least three reactants whose nearly all atoms are incorporated in the final product. The development of these high atom-efficient reactions considerably raised the level of molecular complexity and diversity in the last decades. Nowadays, MCRs are no longer confined to organic synthesis and have seen their use extended to polymer science. The latter tend to occupy an increasingly important place in polymer synthesis and sustain the eager demand for innovative and structurally diverse macromolecules involved in highly valued applications. While MRCs can serve for monomer synthesis and post-polymerization modification, they offer their full potential in one-pot step-growth polymerizations, namely multicomponent polymerizations (MCPs). This review provides a comprehensive and up to date overview of the imine-based MCPs and highlights their great potential for the design of advanced linear, hyperbranched and crosslinked polymers. The focus is placed on MCPs involving imines, the most common and valuable MCRs’ intermediates which are prone to various nucleophilic attacks and give access to a great variety of products. The efficiency, combinatorial feature, substrates versatility and limitations of these imine-based MCPs as well as the polymer diversity they offer are discussed in detail. Some MCPs can also be combined in one-pot to afford unique and highly complex structures. At this stage, several multicomponent step-growth polymerizations are already mature enough to sustain cutting-edge applications in biomedicine, energy, environment and catalysis amongst others. The existing challenges to be addressed are identified and the future research directions are discussed accordingly. MCPs, in particular imine-based ones, will undoubtedly further grow and confirm their status of essential macromolecular engineering tools in the future.

多组分反应 (MCR) 是一种非凡的一锅法组合合成工具，涉及至少三种反应物，其几乎所有原子都包含在最终产物中。在过去的几十年中，这些高原子效率反应的发展大大提高了分子复杂性和多样性的水平。如今，MCR 不再局限于有机合成，并且已经将其应用扩展到聚合物科学。后者往往在聚合物合成中占据越来越重要的位置，并维持对涉及高价值应用的创新和结构多样化的大分子的迫切需求。虽然 MRC 可用于单体合成和聚合后改性，但它们在单锅逐步增长聚合即多组分聚合 (MCP) 中发挥了全部潜力。本综述对基于亚胺的 MCP 进行了全面和最新的概述，并强调了它们在设计先进的线性、超支化和交联聚合物方面的巨大潜力。重点放在涉及亚胺的 MCP 上，亚胺是最常见和最有价值的 MCR 中间体，容易受到各种亲核攻击并可以得到多种产品。详细讨论了这些基于亚胺的 MCP 的效率、组合特征、底物多功能性和局限性以及它们提供的聚合物多样性。一些 MCP 也可以在一锅中组合，以提供独特且高度复杂的结构。在这个阶段，几种多组分逐步增长聚合已经足够成熟，可以维持在生物医学、能源、环境和催化等领域的前沿应用。确定了要解决的现有挑战，并相应地讨论了未来的研究方向。MCP，尤其是基于亚胺的 MCP，无疑将进一步发展并确认它们在未来成为重要的大分子工程工具的地位。