Polymer chain sequence effects on the glass transition

Progress in synthetic chemistry over the last 20 years has opened the door to synthesis of polymers with an increasing spectrum of monomer sequence control, ranging from gradient copolymers to peptoids. In many of these polymers as in sequence non-controlled polymers, the glass transition plays a central role in dynamic, mechanical, and transport properties. However, the effect of sequence on the glass transition remains poorly understood. Here we employ molecular dynamics simulations of sequence controlled glass-forming liquids to quantify the effect of sequence on glass transition behavior. Results indicate that sequence can have a profound impact on Tg. Ultimately, we explore the transition from sequence effects to interface effects on Tg as monomer block size increases to the phase-separating limit.