{"database":"biostudies-literature","file_versions":[],"scores":null,"additional":{"submitter":["Xu M"],"funding":["National Natural Science Foundation of China (National Science Foundation of China)"],"pagination":["265"],"full_dataset_link":["https://www.ebi.ac.uk/biostudies/studies/S-EPMC12783137"],"repository":["biostudies-literature"],"omics_type":["Unknown"],"volume":["17(1)"],"pubmed_abstract":["Ethylene-based crystalline copolymers are important materials across broad applications. However, precise control over their primary structures remains a critical challenge in advancing functional materials, limited by the intrinsic reactivity difference between ethylene and comonomers. In this work, we report the development of a light-driven organocatalyzed reversible-deactivation radical copolymerization to access well-defined ethylene-chlorotrifluoroethylene copolymer (ECTFE) under mild conditions (<5 atm, 25 °C). The rational design of a three-armed phenothiazine catalyst in combination with a fluorinated dithiocarbamate furnishes good chain-growth control in the photoredox-mediated copolymerization, yielding ECTFE of excellent alternating sequence with minimized chain defects, which resulted in high crystallinity and superior melting points (up to 263.8 °C). Importantly, the obtained ECTFE exhibits outstanding chain-end activity/fidelity, enabling chain-extension (co)polymerization to access a variety of unprecedented ECTFE-based block copolymers upon visible-light exposure, which has successfully integrated rigid and soft blocks in single chains. The ease of synthesizing such block copolymers creates a versatile and convenient platform to largely tune mechanical properties, affording polymeric materials spanning from thermoplastics to elastomers via structural tailoring."],"journal":["Nature communications"],"pubmed_title":["Photoredox-controlled alternating copolymerization enables highly crystalline structures and block copolymers from thermoplastic to elastomer."],"pmcid":["PMC12783137"],"funding_grant_id":["no. 22425103","no. 22171051"],"pubmed_authors":["Chen Q","Xu M","Chen K","Guo X","Chen M","Han S"],"additional_accession":[]},"is_claimable":false,"name":"Photoredox-controlled alternating copolymerization enables highly crystalline structures and block copolymers from thermoplastic to elastomer.","description":"Ethylene-based crystalline copolymers are important materials across broad applications. However, precise control over their primary structures remains a critical challenge in advancing functional materials, limited by the intrinsic reactivity difference between ethylene and comonomers. In this work, we report the development of a light-driven organocatalyzed reversible-deactivation radical copolymerization to access well-defined ethylene-chlorotrifluoroethylene copolymer (ECTFE) under mild conditions (<5 atm, 25 °C). The rational design of a three-armed phenothiazine catalyst in combination with a fluorinated dithiocarbamate furnishes good chain-growth control in the photoredox-mediated copolymerization, yielding ECTFE of excellent alternating sequence with minimized chain defects, which resulted in high crystallinity and superior melting points (up to 263.8 °C). Importantly, the obtained ECTFE exhibits outstanding chain-end activity/fidelity, enabling chain-extension (co)polymerization to access a variety of unprecedented ECTFE-based block copolymers upon visible-light exposure, which has successfully integrated rigid and soft blocks in single chains. The ease of synthesizing such block copolymers creates a versatile and convenient platform to largely tune mechanical properties, affording polymeric materials spanning from thermoplastics to elastomers via structural tailoring.","dates":{"release":"2025-01-01T00:00:00Z","publication":"2025 Dec","modification":"2026-06-06T13:08:43.512Z","creation":"2026-05-30T03:11:42.278Z"},"accession":"S-EPMC12783137","cross_references":{"pubmed":["41388027"],"doi":["10.1038/s41467-025-66962-8"]}}