Bio-based poly(ester-alt-thioether)s synthesized by organo-catalyzed ring-opening copolymerizations of eugenol-based epoxides and N-acetyl homocysteine thiolactone

Simon Le Luyer (1) , Baptiste Quienne (2) , Matthieu Bouzaid (1) , Philippe Guégan (1) , Sylvain Caillol (2) , Nicolas Illy (1)

1 LCP - Chimie des polymères
2 ICGM - Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier

The anionic alternating ring-opening copolymerizations of three bio-based aromatic monomers, eugenol glycidyl ether (EGE), dihydroeugenol glycidyl ether (DEGE) and vanilin glycidyl ether (VGE), were carried out with renewable N-acetyl homocysteine thiolactone (NHTL) using benzyl alcohol and 2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorine (BEMP) as initiating system. This polymerization is a rare example of eugenol-based monomers used to synthesize linear polyesters. Alternating poly(ester-alt-thioether)s are obtained with number-average molar masses M n ranging from 1.1 to 10.8 kg mol-1 and dispersities as low as 1.20. The copolymer structures were carefully characterized by 1 H, 13 C, COSY, HSQC, 1 H-15 N NMR. It was found that the alternate copolymers were obtained selectively under different monomer feed ratios. In addition, the use of EGE and VGE monomers allows the preparation of multi-functional poly(ester-alt-thioether) respectively bearing allyl or aldehyde groups in each repeating unit. The copolymers display only clear glass transition temperatures higher than ambient temperature. This alternating copolymerization method offers a new chemical pathway for the valorization of bio-based aromatic compounds and expand the scope of renewable polyesters.

Mots clés: biobased polymers

Domaines: Polymères

Simon Le Luyer, Baptiste Quienne, Matthieu Bouzaid, Philippe Guégan, Sylvain Caillol, et al.. Bio-based poly(ester-alt-thioether)s synthesized by organo-catalyzed ring-opening copolymerizations of eugenol-based epoxides and N-acetyl homocysteine thiolactone. Green Chemistry, 2021, 23 (19), pp.7743-7750. ⟨10.1039/d1gc02138a⟩. ⟨hal-03359482v1⟩