Influence of side chain lengths in mechanophore‐containing polyisobutylene‐graft‐polystyrene

Polymer architecture plays an important role in morphology and mechanochemical response. Here, graft copolymers containing mechanophores at the backbone‐arm junction are synthesized through a combination of post‐polymerization modification of butyl rubber and controlled radical polymerization. A series of graft copolymers with 70:30 or 50:50 polyisobutylene:polystyrene (PIB:PS) volume fractions were synthesized by changing the grafting density and arm length to keep the volume fractions constant. The morphologies for these polymers are disordered but show a decreasing domain size with shorter arm lengths, and the samples with a greater number of PS side chains show greater domain mixing. Using pulsed ultrasound experiments, we found greater backbone scission occurs for polymers with a greater number of short grafts per chain than the long grafts with fewer grafting points. Finally, mechanophore activation is greater for samples with arm molecular weights ≥13 kg/mol, attributed to exceeding the cutoff molecular weight for PS.