The application of bio-based solvents for living radical polymerization has been a hot topic in recent year. In this article, γ-valerolactone (GVL), a bio-based solvent as green media for ARGET atom transfer radical polymerization (ATRP) of styrene (St) were investigated. We first conducted polymerization of St in γ-valerolactone using copper(ii) bromide as the catalyst, tris(2-pyridylmethyl) amine as the ligand, and only sodium ascorbate as reducing agent. The polymerization achieved moderate conversion; however, the controllability of polymerization was not very good, providing a polymer with a broad molecular weight distribution (M w/M n > 1.30). When sodium carbonate is introduced, excellent results were obtained providing high yields and low M w/M n values under very low catalyst usage (∼5 ppm). 1H NMR spectroscopy, chain extension, and MALDI–MS experiments confirmed the final polymer chains with high fidelity. The use of GVL solvent opens a new route for the easy synthesis of PS through ARGET ATRP with low catalyst usage conditions.
