Methacrylic block copolymers by sulfur free RAFT (SF RAFT) free radical emulsion polymerisation

• Published in: Polymer chemistry Vol. 8; no. 6; pp. 1084 - 1094
• Main Authors: Nurumbetov, Gabit, Engelis, Nikolaos, Godfrey, Jamie, Hand, Rachel, Anastasaki, Athina, Simula, Alexandre, Nikolaou, Vasiliki, Haddleton, David M.
• Format: Journal Article
• Language: English
• Published: 14.02.2017
• Subjects: Block copolymers; Chain transfer; Copolymers; Emulsion polymerization; Polymerization; Rafts; Sulfur; Synthesis (chemistry)
• ISSN: 1759-9954; 1759-9962
• DOI: 10.1039/C6PY02038K

We demonstrate 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. 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 1 H NMR, size exclusion chromatography (SEC), thermogravimetric analysis (TGA) and matrix-assisted laser desorption/ionization time of flight mass spectroscopy (MALDI-TOF-MS) techniques.