Radiation-induced polymerization of 3-hexylthiophene in oxygen-free and oxygen-saturated dichloromethane solvent

Teseer Bahry (1) , Zhenpeng Cui (1) , Alexandre Dazzi (1) , Matthieu Gervais (2) , Cyrille Sollogoub (2) , Fabrice Goubard (3) , Thanh-Tuân Bui (3) , Samy Remita (1)

1 ICP - Institut de Chimie Physique
2 PIMM - Laboratoire Procédés et Ingénierie en Mécanique et Matériaux
3 LPPI - Laboratoire de Physico-chimie des Polymères et des Interfaces

As alternative radiolytic approach, the synthesis of P3HT was made possible thanks to the oxidation of 3HT monomers by chloromethyl and dichloromethyl radicals or by their corresponding peroxyl radicals in situ produced by dichloromethane solvent radiolysis. Under two different experimental conditions, in oxygen-free solution and in oxygen-saturated solution, two different polymers, “P3HTN2” and “P3HTO2” respectively, were successfully synthesized. Both produced materials were discerned by several analytical and spectroscopic techniques. UV–Vis absorption spectroscopy results showed that the radiolytic yield of 3HT oxidation in dichloromethane solvent is higher under O2 atmosphere. Indeed, a dose of 75 kGy was needed to polymerize 10 mM in 3HT under N2 atmosphere, meanwhile a dose of 35 kGy was sufficient to polymerize the same amount of 3HT under O2. The average molecular weight of P3HTO2was found higher than that of P3HTN2 as revealed by SEC chromatography analysis. Also, P3HTO2exhibits better thermal stability than P3HTN2. ATR-FTIR spectroscopy revealed the specific presence into P3HTO2 polymers of some functional groups such as carbonyl, hydroxyl and carboxyl moieties, which clearly explains the difference between the morphological structures of P3HTN2 and P3HTO2 as highlighted by cryo-TEM, SEM and AFM microscopies. Finally, both radio-synthesized P3HTN2 and P3HTO2 polymers were found characterized by remarkably significant conductive, electronic and optical properties.

Mots clés: Radiolysis; Conducting polymers; Poly(3-hexylthiophene); P3HT

Domaines: Polymères; Radiochimie

Teseer Bahry, Zhenpeng Cui, Alexandre Dazzi, Matthieu Gervais, Cyrille Sollogoub, et al.. Radiation-induced polymerization of 3-hexylthiophene in oxygen-free and oxygen-saturated dichloromethane solvent. Radiation Physics and Chemistry, 2021, 180, pp.109291. ⟨10.1016/j.radphyschem.2020.109291⟩. ⟨hal-03159311⟩