[en] Conjugated vinyl lactones commonly serve as precursors of polymers with pendant cyclic esters, which can undergo several chemical modifications. They have notably been copolymerized with
“more activated monomers” like (meth)acrylates. By contrast, the radical polymerization of nonconjugated methylene lactone analogues has been disregarded as well as their copolymerization with “less-activated monomers” such as acyclic vinyl esters. The present work explores the conventional radical polymerization and the reversible deactivation radical polymerization of γ-methylene-γ-butyrolactone (γMγBL) and its copolymerization with vinyl acetate (VAc). Statistical P(γMγBL-co-VAc) copolymers with predictable molar mass, low dispersity, and precise compositions were notably achieved by organometallic-mediated radical polymerization based on cobalt complexes via both reversible termination, also referred to as reversible chain deactivation, and degenerative chain-transfer pathways. Upon hydrolysis, these γMγBL-containing (co)polymers release one alcohol moiety and one carboxylic group per repeating unit, leading to unprecedented carboxylic acid-functionalized poly(vinyl alcohol) derivatives. A preliminary study emphasizes the pH responsiveness of the latter in water.
Research center :
Center for Education and Research on Macromolecules (CERM) Complex and Entangled Systems from Atoms to Materials (CESAM) Research Unit
Disciplines :
Materials science & engineering Chemistry
Author, co-author :
Wang, Zhuoqun ; University of Liège (ULiège), Complex and Entangled Systems from Atoms to Materials (CESAM) Research Unit, Center for Education and Research on Macromolecules (CERM), Belgium
Poli, Rinaldo; University of Toulouse, CNRS, Laboratoire de Chimie de Coordination, France > Institut Universitaire de France, Paris, France
Detrembleur, Christophe ; University of Liège (ULiège), Complex and Entangled Systems from Atoms to Materials (CESAM) Research Unit, Center for Education and Research on Macromolecules (CERM), Belgium
Debuigne, Antoine ; University of Liège (ULiège), Complex and Entangled Systems from Atoms to Materials (CESAM) Research Unit, Center for Education and Research on Macromolecules (CERM), Belgium
Language :
English
Title :
Organometallic-mediated radical (co)polymerization of γ‑methylene-γ-butyrolactone: access to pH-responsive poly(vinyl alcohol) derivatives
Publication date :
26 November 2019
Journal title :
Macromolecules
ISSN :
0024-9297
eISSN :
1520-5835
Publisher :
American Chemical Society (ACS), United States - District of Columbia
Volume :
52
Issue :
22
Pages :
8976-8988
Peer reviewed :
Peer Reviewed verified by ORBi
Name of the research project :
The Excellence of Science (EOS) program; The NECOPOL project
Funders :
F.R.S.-FNRS - Fonds de la Recherche Scientifique [BE] FWO - Fonds Wetenschappelijk Onderzoek Vlaanderen [BE]
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