Self-Photopolymerization of Poly(disulfide) Oligomers - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue ACS Omega Année : 2019

Self-Photopolymerization of Poly(disulfide) Oligomers

Résumé

Base catalyst and oxidant are usually necessary to promote the polymerization of poly(disulfide) oligomers through oxidative coupling of the terminal SH groups into S− S bonds. In this study, we prove that self-polymerization of bifunctional (disulfide) oligomer films can take place in a matter of minutes under UVC irradiation (254 nm, 10.5 mW cm −2). The resulting insoluble polymer is characterized using solid-state NMR, 1 H T 2 NMR relaxation measurements, thermal analysis, and Fourier-transform infrared spectroscopy and proves to have similar composition as a model poly(disulfide) prepared under oxidative conditions, but distinct physical properties. These differences are explained by a change in polymer architecture due to a higher ratio of cyclization relative to linear polymerization. Homolytic photocleavage of internal S−S bonds creates thiyl groups close to each other, driving an increased kinetic feasibility for the cyclization reaction by radical coupling. The subsequent formation of mechanically interlocked macrocycles (polycatenane network) is proposed to account for film properties analogous to those of a cross-linked polymer.

Domaines

Polymères
Fichier principal
Vignette du fichier
acsomega.9b00021.pdf (1.62 Mo) Télécharger le fichier
Origine : Fichiers éditeurs autorisés sur une archive ouverte
Loading...

Dates et versions

hal-02434784 , version 1 (10-01-2020)

Identifiants

Citer

Abraham Chemtob, Noémi Feillée, Cyril Vaulot, Christian Ley, Didier Le Nouen. Self-Photopolymerization of Poly(disulfide) Oligomers. ACS Omega, 2019, 4 (3), pp.5722-5730. ⟨10.1021/acsomega.9b00021⟩. ⟨hal-02434784⟩
37 Consultations
58 Téléchargements

Altmetric

Partager

Gmail Facebook X LinkedIn More