Facile Synthesis of Well‐Defined Polystyrene Through Microwave Assisted ARGET‐ATRP

ABSTRACT Well defined polystyrene in varied sizes with polydispersity indices < 1.2 were obtained in reduced time using Microwave Assisted Activator Re‐Generated by Electron Transfer Atom Transfer Radical Polymerization Reactions. The use of pre‐synthetized Cu(II)Br/Me 6 TREN catalyst allows for rapid set‐up of the reaction and addition of an excess of stannous octoate allows for oxygen tolerant conditions during the reaction set‐up. The reaction mixture is stable for several days at room temperature, allowing for a series of polymerizations to be set up using an automatized polymerization reaction process. The reaction conditions were optimized in regards of the temperature (80°C–100°C), catalyst loading (0.15 equiv) and reaction times at 85°C (≤ 7 h). Well‐controlled polymerizations are achieved for sizes up to 15 kDa, while maintaining polydispersity index values below 1.05. Kinetic comparisons between microwave irradiation and conventional heating methods show a higher apparent propagation rate constant while obtaining well‐defined polymers. A norbornene‐functionalized initiator allows us to obtain α, ω‐end‐chain functionalized polystyrene, providing potential expansion of applications in fields such as the synthesis of nanoparticles and polymer design.