RAFT-Mediated ab Initio Emulsion Copolymerization of 1,3-Butadiene with Acrylonitrile

The successful RAFT-mediated ab initio emulsion copolymerization of acrylonitrile and 1,3-butadiene using 2-(((dodecylsulfanyl)carbonothioyl)sulfanyl)propanoic acid (DoPAT) is reported at 45–55 °C. The number-average molecular weight exhibits a linear evolution as a function of monomer conversion (5000 ≤ M n (g mol–1) ≤ 41 000, 1.3 ≤ Đ (−) ≤ 3.3). Relatively good control (e.g., Đ ≈ 1.2 for selected conditions) over the polymerization up to moderate monomer conversion (50–60%) was attained when the employed initial molar ratio of RAFT agent to initiator was 2.5 or higher. Good ω-end-group functionality is evidenced by chain extension of NBR with a polystyrene block, with both 1H NMR and SEC showing the average fraction of the NBR block as ca. 75 mol%. A kinetic model implemented via the PREDICI software package confirms the experimental findings, including a semiempirical approach to account for branch formation. The onset of the loss in control over the copolymerization at conversions >40% was tentatively attributed to branch formation. The current study evidences that RAFT mediated ab initio emulsion polymerization of 1,3-butadiene and acrylonitrile is a viable polymerization protocol for the synthesis of well-defined next generation nitrile–butadiene rubbers including in industrial context.