[en] Polyoxazolidones, i.e. high-performance polymers bearing cyclic carbamate linkages, were recently obtained by a non-isocyanate route under mild conditions. Herein, we report the preparation of polyoxazolidones bearing thioether linkages, which offer multiple opportunities for facile chain functionalization. The process consists in the chemical upcycling of CO2-based poly(oxo-carbonate)s by aminolysis with allylamines. At room temperature, a poly(oxo-carbonate) is completely decomposed into an allyl-functionalized bis(oxazolidone) which is then copolymerized with dithiols by UV-initiated thiol-ene polymerization. The allyl-functionalized bis(oxazolidone) monomer is also quantitatively obtained by reacting an allylamine with a CO2-based bis(alkylidene cyclic carbonate). A library of poly(oxazolidone-co-thioether) copolymers is easily accessible by varying the nature of dithiol and a Mw of up to 101 000 g mol−1 is reached. All polymers are quantitatively dehydrated by simple thermal treatment at a temperature ranging from 120 °C to 140 °C in the solid state, furnishing poly(oxazolidone-co-thioether) copolymers bearing exocyclic vinylene moieties and presenting a high thermal stability (Tdeg10% up to 360 °C) and various glass transition temperatures. Post-polymerization modifications by thiol oxidation to sulfoxides or sulfones, or through S-alkylation of the thioether linkages, are realized to deliver unprecedented functional polyoxazolidones. Notably, the introduction of sulfonium groups enables the production of the first example of water-soluble polyoxazolidones. This work describes a simple platform to produce a large panel of functional polyoxazolidones that are not accessible by the current isocyanate-based methods, moreover under mild operating conditions by exploiting CO2-based monomers.
Research Center/Unit :
CESAM - Complex and Entangled Systems from Atoms to Materials - ULiège [BE] CERM - Center for Education and Research on Macromolecules - ULiège [BE]
Disciplines :
Materials science & engineering Chemistry
Author, co-author :
Razavi-Esfali, Maliheh ; University of Liège [ULiège] - Complex and Entangled Systems from Atoms to Materials [CESAM] Research Unit - Center for Education and Research on Macromolecules [CERM] - Belgium ; University of the Basque Country - POLYMAT- Donostia/SanSebastian - Spain
Habets, Thomas ; University of Liège [ULiège] - Complex and Entangled Systems from Atoms to Materials [CESAM] Research Unit - Center for Education and Research on Macromolecules [CERM] - Belgium
Siragusa, Fabiana ; Université de Liège - ULiège > Complex and Entangled Systems from Atoms to Materials (CESAM)
Grignard, Bruno ; University of Liège [ULiège] - Complex and Entangled Systems from Atoms to Materials [CESAM] Research Unit - Center for Education and Research on Macromolecules [CERM] - Belgium ; University of Liège [ULiège] - FRITCO2T Platform - Belgium
Sardon, Haritz ; University of the Basque Country - POLYMAT- Donostia/SanSebastian - Spain
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
Language :
English
Title :
Design of functional isocyanate-free poly(oxazolidone)s under mild conditions
Publication date :
21 May 2024
Journal title :
Polymer Chemistry
ISSN :
1759-9954
eISSN :
1759-9962
Publisher :
Royal Society of Chemistry
Volume :
15
Issue :
19
Pages :
1962-1974
Peer reviewed :
Peer Reviewed verified by ORBi
Funders :
EC - European Commission [BE] F.R.S.-FNRS - Fund for Scientific Research [BE] FWO - Research Foundation Flanders [BE] MICINN - Ministerio de Ciencia e Innovacion [ES]
Funding text :
The authors acknowledge the financial support provided by the NIPU-EJD project; this project has received funding from the European Union's Horizon 2020 research and innovation program under the Marie Sk\u0142odowska-Curie grant agreement no 955700. The authors of Liege thank FNRS for financial support in the frame of the CO Switch project under grant T.0075.20. They also thank FNRS and FWO for funding the EOS project \u201CBIOFACT\u201D no O019618F (ID EOS: 30902231). C. D. is a F.R.S.-FNRS Research Director. H. S. acknowledges the financial support from el Ministerio de Ciencia e Innovaci\u00F3n from TED2021-129852B-C22 funded by MCIU/AEI/10.13039/501100011033 and by the European Union NextGeneration EU/PRTR and the grant PID2022-138199NB-I00 funded by MCIU/AEI/10.13039/501100011033. 2
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