Collapse Transition of Branched Polymers in Dilute Solutions: Telechelic Star vs. H‐Polymer

Abstract

SummarySelf‐assembly in polymeric material is facilitated by the presence of active hetero‐atoms either along the backbone or as pendant groups. Self‐assembly leads to a rich variety of morphological pattern influencing various properties of polymeric materials. Presence of branching along the backbone chain also imparts remarkable change in polymeric properties. We report dynamic Monte Carlo (DMC) simulation study on solution behavior of branched polymers. We take multi‐arm telechelic star polymers (TSP, one branch point with terminal active groups) and H‐shaped branched polymers (homopolymers with two branch points), elucidating the driving mechanisms of collapse transition and morphological development. The presence of terminal active groups in TSP drives the collapse transition producing segregated and compact globule structure, on deteriorating solvent quality. On the other hand, presence of two branch points in H‐shaped polymers incorporates conformational heterogeneity (viz., entropically originated) and produces segregated globule structures. The terminal functional groups in TSP form aggregate, resembles to “watermelons” (WM) and double watermelon (DWM) depending on the number of arms and mode of cooling. In H‐polymers, conformational heterogeneity leads to the formation of segregated backbone and branch units (resembles to “Sandwich” or “Janus” morphology) rather an evenly distributed structure consisting of all the units, accompanying with a larger size of branches compared to the backbone.