Polymerization‐Induced Self‐Assembly for the Synthesis of Polyisoprene‐Polystyrene Block and Random Copolymers: Towards High Molecular Weight and Conversion

In this study, reversible addition-fragmentation chain- transfer (RAFT) polymerization combined with the polymerization-induced self-assembly (PISA) technique is used to synthesize polyisoprene (PI)-based block and random copolymers with polystyrene (PS), aiming for high molecular weight and monomer conversion. The focus is to optimize the polymerization conditions to overcome the existing challenge of cross-linking and Diels-Alder reactions during the polymerization of isoprene, which typically constrain the reaction conversion and molecular weight of the final polymers. Using a poly(methacrylic acid) (PMAA) macroRAFT agent synthesized in ethanol at 80 °C, random and block copolymers of PS-PI with a target molecular weight of 50 000 g mole^-1 and a high monomer conversion of ≈80% are achieved under optimized conditions in water-emulsion at 35 °C. ¹H nuclear magnetic resonance (NMR) verified the successful synthesis as well as the high content of 1,4 microstructure in polyisoprene. The thermal analysis via differential scanning calorimetry indicated distinct glass transitions for the microphase-separated PI-PS block copolymer, while a single transition for PI-PS random copolymer, indicating no microphase separation. Furthermore, dynamic light scattering analysis together with transmission electron microscopy provided further insight into the self-assembled emulsion nanoparticles of the polymers indicating a particle size in the range 70 to 130 nm.