The use of sulfur free reversible addition–fragmentation chain transfer polymerisation (RAFT) as a versatile tool for the controlled synthesis of methacrylic block and comb-like copolymers was demonstrated. Sulfur free RAFT (SF-RAFT) utilises vinyl terminated macromonomers obtained via catalytic chain transfer polymerisation (CCTP) of methacrylates as a chain transfer agent (CTA), and thus precluding adverse aspects of the RAFT such as toxicity of dithioesters. We have synthesised a range of narrow dispersity block copolymers (Đ < 1.2) and comb-like macromolecules by employing emulsion polymerisation allowing for the preparation of relatively large quantities (∼50 g) of the above mentioned copolymers promptly and straightforwardly. Copolymers were characterised using 1H NMR, size exclusion chromatography (SEC), thermogravimetric analysis (TGA) and matrix-assisted laser desorption/ionization time of flight mass spectroscopy (MALDI-TOF-MS) techniques.

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