Synthesis of high molecular weight polystyrene using AGET ATRP under high pressure

High molecular weight polystyrene (PS) was synthesized by ATRP. Under atmospheric pressure (1 bar), PS with Mn up to 200,000 was prepared using either ARGET or ICAR ATRP. Under high pressure (6 kbar), higher molecular weight PS could be obtained due to accelerated radical propagation and diminished radical termination in polymerization of styrene. Therefore, it was possible to synthesize PS with Mn > 1,000,000 and Mw/Mn < 1.25 using AGET ATRP under a pressure of 6 kbar at room temperature. This is the highest molecular weight linear PS prepared by a controlled radical polymerization.