Effect of Polystyrene Synthesis Method on Water Sorption and Glass Transition

Commodity PS is synthesized via free radical polymerization, whereas PS in block copolymers (BCPs) is typically synthesized via living anionic polymerization. The purpose of this work is to investigate how the synthesis method impacts important properties such as water sorption and glass transition temperature (T_g). Water sorption is important because the performance of nanostructured polymer membranes in various applications is known to be affected by environmental conditions such as humidity. T_g is important because it dictates processing conditions, both for commodity PS as well as BCPs such as thermoplastic elastomers. Water sorption in commercial PS was found to be 0.5 mg_water/g_polymer at the highest humidities investigated (about 80%), in agreement with literature. On the other hand, syndiotactic PS synthesized anionically at low temperature absorbed more water, up to 1.5 mg_water/g_polymer, due to higher free volume. The greatest impact on water sorption was due to addition of hydrophilic hydroxyl chain ends to atactic PS, which resulted in water sorption of up to 2.3 mg_water/g_polymer. In addition to measuring water sorption and dry T_g separately, the impact of relative humidity on PS T_g was examined. Combined differential scanning calorimetry and dynamic mechanical analysis show that on going from the dry state to high humidity, the T_g of PS decreases by 5 °C. Moreover, the tensile storage modulus of PS decreases from 1.58 GPa at 0% RH to 0.53 GPa at 40% RH. In addition to the practical relevance of this study, this report fills a gap in experimental literature by using a poor solvent system, PS/water, to examine plasticization in the pure polymer limit.