Carbene polymerization from the catalyzed decomposition of diazo compounds: Mechanism and modern development

[Display omitted] •The non-petroleum-based carbene polymerization toward functional polyolefins.•The stereoselective polymerization, controlled polymerization, and copolymerization.•The carbene insertion polymerization versus carbene radical polymerization.•The tertiary structures, properties, and applications of polycarbene. Carbene polymerization from the catalyzed decomposition of diazo compounds is a unique non-petroleum-based C1 polymerization pathway toward high-density functional polyolefins. The last 20 years have seen vigorous development in carbene polymerization, such as various efficient initiating systems, high molecular weight and stereoregular polycarbene, controlled carbene polymerization, and the combined copolymerization approaches with other polymerization methodologies. This review highlights the recent advancements in developing the new/old disciplines of carbene polymerization, i.e., carbene insertion polymerization and carbene radical polymerization. The representative copolymerization methodologies, aggregation structures, properties, and applications of polycarbene are also summarized. Finally, the future trends in expanding carbene polymerization potentials are discussed.