Employing transfer-dominated branching radical telomerisation (TBRT) and atom transfer radical polymerisation (ATRP) to form complex polyester-polymethacrylate branched-linear star copolymer hybrids orthogonal initiation

TBRT and ATRP are orthogonal initiation chemistries used in vinyl polymerisations. Here, we present the first combination of these techniques to readily create high molecular weight branched polyester macroinitiators capable of forming star copolymers from a range of methacrylate monomers. Consecutive free radical telomerisation and reversible-deactivation radical polymerisation reactions allow formation of branched polyester macroinitiators followed by arm growth leading to high molecular weight polyester-methacrylate star copolymers.