Issue 19, 2024

Design of functional isocyanate-free poly(oxazolidone)s under mild conditions

Abstract

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.

Graphical abstract: Design of functional isocyanate-free poly(oxazolidone)s under mild conditions

Supplementary files

Article information

Article type
Paper
Submitted
26 জানু. 2024
Accepted
13 এপ্রিল 2024
First published
15 এপ্রিল 2024

Polym. Chem., 2024,15, 1962-1974

Design of functional isocyanate-free poly(oxazolidone)s under mild conditions

M. Razavi-Esfali, T. Habets, F. Siragusa, B. Grignard, H. Sardon and C. Detrembleur, Polym. Chem., 2024, 15, 1962 DOI: 10.1039/D4PY00101J

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements