Block Copolymers Based on Ethylene and Methacrylates Using a Combination of Catalytic Chain Transfer Polymerisation (CCTP) and Radical Polymerisation

Two scalable polymerisation methods are used in combination for the synthesis of ethylene and methacrylate block copolymers. ω‐Unsaturated methacrylic oligomers (MMA(n)) produced by catalytic chain transfer (co)polymerisation (CCTP) of methyl methacrylate (MMA) and methacrylic acid (MAA) are used as reagents in the radical polymerisation of ethylene (E) in dimethyl carbonate solvent under relatively mild conditions (80 bar, 70 °C). Kinetic measurements and analyses of the produced copolymers by size exclusion chromatography (SEC) and a combination of nuclear magnetic resonance (NMR) techniques indicate that MMA(n) is involved in a degradative chain transfer process resulting in the formation of (MMA)(n)‐b‐PE block copolymers. Molecular modelling performed by DFT supports the overall reactivity scheme and observed selectivities. The effect of MMA(n) molar mass and composition is also studied. The block copolymers were characterised by differential scanning calorimetry (DSC) and their bulk behaviour studied by SAXS/WAXS analysis.