Linear tetrablock quaterpolymers via triple click reactions, azide‐alkyne, diels–alder, and nitroxide radical coupling in a one‐pot fashion

Azide‐alkyne and Diels–Alder click reactions together with a click‐like nitroxide radical coupling reaction were used in a one‐pot fashion to generate tetrablock quaterpolymer. The various living polymerization generated linear polymers with orthogonal end‐functionalities, maleimide‐terminated poly(ethylene glycol) (PEG‐MI), anthracene‐ and azide‐terminated polystyrene, alkyne‐ and bromide‐terminated poly( tert ‐butyl acrylate) or alkyne‐poly( n ‐butyl acrylate), and tetramethylpiperidine‐1‐oxyl (TEMPO)‐terminated poly(ε‐caprolactone) (PCL‐TEMPO) were clicked together in a one‐pot fashion to generate PEG‐ b ‐PS‐ b ‐P t BA‐ b ‐PCL or PEG‐ b ‐PS‐ b ‐P n BA‐ b ‐PCL quaterpolymer using Cu(0), CuBr, and N , N , N ′, N ″, N ″‐pentamethyldiethylenetriamine as catalyst in dimethyl formamide at 80 °C for 36 h. Linear precursors and target quaterpolymers were analyzed via 1 H NMR and gel permeation chromatography.