Polyethylene (PE) is one of the most widely used materials in the world, but it is virtually undegradable and quickly accumulates in nature, which may contaminate the environment. We utilized the cobalt-mediated radical copolymerization (CMRP) of ethylene and cyclic ketene acetals (CKAs) to effectively incorporate ester groups into PE backbone as cleavable structures to make PE-based copolymer degradable under mild conditions. The content of ethylene and ester units in the produced copolymer could be finely regulated by CKA concentration or ethylene pressure. Also, the copolymerization of ethylene and CKA with other functional vinyl monomers can produce functional and degradable PE-based copolymer. All the formed PE-based copolymers could degrade in the presence of trimethylamine (Et₃N).

Cyclic polymers have a number of unique physical properties compared with those of their linear counterparts. However, the methods for the synthesis of cyclic polymers are very limited, and some multicyclic polymers are still not accessible now. Here, we found that the five˗membered cyclic structure and electron withdrawing groups make methylene in rhodanine highly active to aldehyde via highly efficient Knoevenagel reaction. Also, rhodanine can act as an initiator for anionic ring-opening polymerization of thiirane to produce cyclic polythioethers. Therefore, rhodanine can serve as both an initiator for ring-opening polymerization and a monomer in Knoevenagel polymerization. Via rhodanine-based Knoevenagel reaction, we can easily incorporate rhodanine moieties in the backbone, side chain, branched chain, etc, and correspondingly could produce cyclic structures in the backbone, side chain, branched chain, etc, via rhodanine˗based anionic ring-opening polymerization. This rhodanine chemistry would provide easy access to a wide variety of complex multicyclic polymers.

Visible light‐driving syntheses have emerged as a powerful tool for organic synthesis and for the preparation of macromolecules under mild and environmentally benign conditions. However, precious but nonreusable photosensitizers or photocatalysts are often required to activate the reaction, limiting its practicality. Here, it is reported that poly(1,4‐diphenylbutadiyne) (PDPB) nanofibers exhibit remarkable activity in driving the living free radical polymerization under visible light. Moreover, PDPB nanofibers are very stable under irradiation of visible light and can be reused without appreciable loss of activity even after repeated cycling. The nanofiber will be a promising photocatalyst with excellent reusability and stability for the reactions driven by visible light.

The construction of artificial polymers with a comparative degree of structural and compositional diversity/complexity similar to the biomacromolecules created by nature is a great challenge, especially for those prepared by chain-growth polymerizations. Since the development of some novel catalysts and polymerization technologies in the past decade, one-pot chain-growth polymerization strategies have been developed to polymerize structurally distinct monomers, as a result, producing block, multiblock, random, and gradient chain structures with diverse compositions. In this minireview, the recent progress on the synthesis of polymers with advanced chain structures via chain-growth polymerization has been summarized. The main part of this article is divided into three sections according to the different polymerization strategies: hybrid copolymerization, switchable polymerization, and cascade polymerization. It is anticipated that this minireview will provide a unique view for the fabrication of polymers with a high degree of structural and compositional diversity/complexity.