vignette image représentant la thématique "Polymérisation radicalaire pour des polymères dégradables" de l'équipe P3R - Polymères de Précision par Procédés Radicalaires - ©Olivier Coutelier

Radical polymerisation for degradable polymers

While polymers derived from radical polymerisation are ubiquitous in today’s society, their indestructibility has caused increasing environmental concern. In order to tackle this isssue, many strategies have been developed to introduce degradable functionalities into the backbone of vinyl polymers.

One of them is radical ring-opening copolymerisation of cyclic ketene acetals (CKAs) with vinyl monomers to produce polymers with degradable ester groups in the polymer backbone.
Recently, thiocarbonyl addition-radical opening (TARO) polymerisation has a emerged as a very promising means to insert thioester degradable moities in polymer chains by copolymerising a vinyl monomer with a thionolactone. Our group developed a series of unsubstituted thionolactones of different ring sizes to prepare copolymers by TARO copolymerisation with vinyl pivalate. One of the specific features of this polymerisation is that thionolactone units coexist both in ring-opened (thioester) and ring-closed (thioketal) forms. Their relative proportion strongly depends on the ring size of the thionolactone and polymerisation conditions.

image illustrant l'introduction de fonctionnalités dégradables dans les polymères vinyliques de la thématique "Polymérisation radicalaire pour des polymères dégradables" de l'équipe P3R - Polymères de Précision par Procédés Radicalaires - ©Oleksandr Sasha Ivanchenko

We revealed an orthogonal reactivity of thioester and thioketal links, with thioesters being selectively cleaved by aminolysis and thioketals by peroxides.
Bleach was identified as a universal agent for accelerated degradation.

 

More recently, we identified rac-thionolactide as a reactive comonomer for TARO copolymerization with styrene and acrylates, and to a lesser extent with MMA. Styrene-thionolactide and t-butyl acrylate-thionolactide copolymers are degraded much slower by bleach than vinyl pivalate-thionolactone counterparts

This project Holygrail is funded by ANR and Toulouse Tech Transfer, SATT Occitanie Ouest.

 

image illustrant le rac-thionolactide comme co-monomère réactif pour la copolymérisation TARO avec le styrène et les acrylates de la thématique "Polymérisation radicalaire pour des polymères dégradables" de l'équipe P3R - Polymères de Précision par Procédés Radicalaires

Laboratory members involved in this topic

Mathias Destarac

Faculty staff

1045
P3R team leader
mathias.destarac[at]univ-tlse3.fr
Stéphane Mazières

Faculty staff

1033
stephane.mazieres[at]univ-tlse3.fr
Sasha Ivanchenko

Post-doctoral fellow

1040
oleksandr.ivanchenko[at]univ-tlse3.fr
Maksym Odnoroh

Post-doctoral fellow

1040
maksym.odnoroh[at]univ-tlse3.fr
Alexandre Wodrinski

Technician

1052
organic synthesis
alexandre.wodrinski[at]univ-tlse3.fr