RAFT polymerization of bio-based 1-vinyl-4-dianhydrohexitol-1,2,3-triazole stereoisomers obtained via click chemistry.

Four 1-vinyl-4-dianhydrohexitol-1,2,3-triazole stereoisomers are prepared from isomannide, isoidide, and isosorbide using an alkylation/CuAAC-ligation/elimination three-step strategy. After characterization of the monomers by NMR, differential scanning calorimetry (DSC), and high-resolution mass spectrometry (HRMS), the corresponding stereocontrolled poly(1-vinyl-4-dianhydrohexitol-1,2,3-triazole)s are obtained by RAFT polymerization using a xanthate chain transfer agent. A systematic investigation of the structure-properties relationship of both the monomers and polymers highlights the significant impact of the dianhydrohexitols stereochemistry on their physical properties (1H and 13C NMR chemical shifts, physical state, Tg, thermal stability and solubility). A particularly original and unexpected behavior is highlighted since the two different isosorbide-based poly(1-vinyl-4-dianhydrohexitol-1,2,3-triazole) stereoisomers exhibit contrasting solubility in water.