In this paper, γ-valerolactone (GVL), a bio-based polar solvent, was applied as green solvent for iron(III)-catalyzed AGET ATRP without any external ligand. GVL is a fully degradable, non-toxic green solvent and has complex ability to iron halide complexes through –OCO- group. GVL as the solvent and the ligand for AGET ATRP of MMA in a controlled manner, as proved by kinetic study, the low PDI values and the increase in polymer molecular weight versus monomer conversion. Chain re-initiation experiments and 1HNMR characterization were conducted to further confirm the living feature.

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