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By harnessing rationally designed distal sulfone-substituted aliphatic alkynes as monomers, here we report an efficient radical homopolymerization of aliphatic alkynes via 1,4-group transfer, affording a series of new polymers with defined ABC-type sequence. DFT calculations reveal that the 1,4-group transfer plays a critical role in facilitating chain propagation. The resulting polymers further exhibit outstanding performance as binders for high-temperature proton-exchange membrane fuel cells. Furthermore, the polymers can be chemically degraded to yield a diversity of valuable crotylamines. This work achieves the elusive radical polymerization of aliphatic alkynes that is inaccessible by traditional methods, providing a promising platform for the development of functional polymers.<\/jats:p>","DOI":"10.1021\/jacs.6c16074","type":"journal-article","created":{"date-parts":[[2026,9,3]],"date-time":"2026-09-03T11:41:17Z","timestamp":1788435677000},"page":"39348-39356","source":"Crossref","is-referenced-by-count":0,"title":["Group Transfer Radical\nPolymerization of Sulfone-Substituted\nAliphatic Alkynes"],"prefix":"10.1021","volume":"148","author":[{"given":"Silin","family":"Song","sequence":"first","affiliation":[{"name":"Shanghai Jiao Tong University , , 800 Dongchuan Road , ,","place":["Shanghai, China, 200240"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Guodan","family":"Lu","sequence":"additional","affiliation":[{"name":"Shanghai Jiao Tong University , , 800 Dongchuan Road , ,","place":["Shanghai, China, 200240"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Xianjin","family":"Wang","sequence":"additional","affiliation":[{"name":"Qingdao University of Science and Technology , , ,","place":["Qingdao, China, 266042"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-4548-047X","authenticated-orcid":true,"given":"Chen","family":"Zhu","sequence":"additional","affiliation":[{"name":"Shanghai Jiao Tong University , , 800 Dongchuan Road , ,","place":["Shanghai, China, 200240"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,9,1]]},"reference":[{"key":"2026091609124085500_cit1","doi-asserted-by":"crossref","DOI":"10.1002\/9781118480793","volume-title":"Handbook\nof Polymer Synthesis, Characterization, and Processing","author":"Saldi\u0301var-Guerra","year":"2013"},{"key":"2026091609124085500_cit2","volume-title":"Polymer Synthesis: Modern Methods\nand Technologies","author":"Wang","year":"2021"},{"key":"2026091609124085500_cit3","doi-asserted-by":"crossref","DOI":"10.1007\/978-3-642-28980-4","volume-title":"Polymer Synthesis: Theory and Practice:\nFundamentals, Methods, Experiments","author":"Braun","year":"2013"},{"issue":"4","key":"2026091609124085500_cit4","doi-asserted-by":"publisher","first-page":"493","DOI":"10.1093\/nsr\/nwv047","article-title":"Conjugated\nPolymers Developed from\nAlkynes","volume":"2","author":"Liu","year":"2015","journal-title":"Natl. 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