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Here, we develop a series of water\u2010degradable polymers from the first reported fast and selective cationic copolymerization of formaldehyde (<jats:bold>B<\/jats:bold>) with cyclic anhydrides (<jats:bold>A<\/jats:bold>). In addition to readily accessible monomers, the method is performed at industrially relevant temperatures (~100\u2009\u00b0C), takes tens or even minutes, and uses common acid as the catalyst. Interestingly, such polymers possess tunable <jats:bold>AB<\/jats:bold>\/<jats:bold>ABB<\/jats:bold>\u2010type repeating units, which are considered to be thermodynamic and kinetic products, respectively, resulting in low carbon content ([O]\u2009:\u2009[C] up to 1\u2009:\u20091). Notably, the polymers can completely degrade to valuable diacids within 150\u2005days in water at ambient temperature owing to the incorporation of carboxyl terminals and acid\u2010responsive acetal units. By washing with aqueous sodium carbonate, the polymers are relatively stable over several months.<\/jats:p>","DOI":"10.1002\/anie.202315524","type":"journal-article","created":{"date-parts":[[2024,1,27]],"date-time":"2024-01-27T12:03:35Z","timestamp":1706357015000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":14,"title":["Water\u2010Degradable Oxygen\u2010Rich Polymers with AB\/ABB Units from Fast and Selective Copolymerization"],"prefix":"10.1002","volume":"63","author":[{"given":"Xun","family":"Zhang","sequence":"first","affiliation":[{"name":"National Key Laboratory of Biobased Transportation Fuel Technology International Research Center for X Polymers Department of Polymer Science and Engineering Zhejiang University  310027 Hangzhou China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Yanni","family":"Xia","sequence":"additional","affiliation":[{"name":"National Key Laboratory of Biobased 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