Synthesis of Five‐Arm Star Polymers with an Inositol Core by Atom Transfer Radical Polymerisation at Ambient Temperature

Summary: A novel hydroxyl‐functionalised initiator for atom transfer radical polymerisation (ATRP) was synthesised by esterification reaction of a non‐reducing sugar, meso‐inositol. Due to steric hindrance, one of the six hydroxyl groups present in the sugar was not derivatised to the corresponding 2‐bromoisobutyrate. The macroinitiator was used in ambient temperature ATRP of a hydrophobic monomer, methyl methacrylate (MMA) and a hydrophilic monomer, oligoethylene glycol methacrylate (OEGMA) using tri(ethylene glycol) monomethyl ether (TEGMME) as the polymerisation solvent and CuCl/CuCl₂/PMDETA as the catalytic system. Under these conditions, polymerisation proceeded on to high conversion while maintaining low polydispersity giving well‐defined five‐arm star polymers. Hydrolysis under basic conditions was carried out to deduce the number of linear chains that were attached to the sugar.

Five‐arm star polymer.