Self-Assembly Behavior of Hem-Telechelic Polymer System

Self-assembly of hemi-telechelic polymers exhibits behaviors fundamentally distinct from conventional block copolymer systems. Computational studies suggest that long-range ordered morphologies emerge only when electrostatic interactions and segregation strength are carefully balanced. The ratio of functional groups plays a crucial role in mediating association and microphase separation. Despite the promise of such systems, several challenges remain: (1) synthesis and purification are difficult because high end-group purity is required, (2) maintaining low dispersity and high end-group functionality is complicated by side reactions, (3) incompatibility between strong acidic/basic end-groups and backbones such as PDMS can cause degradation, (4) the junction stability must withstand acidic/basic and high-temperature environments to probe thermal effects on structure, and (5) preparation method strongly influences morphology. Here, we report a new synthetic route to Pip–PDMS with high functionality and low dispersity using living anionic polymerization with a functionalized initiator. Polystyrene with 100% –SO₃H end-group functionality and PDMS with piperidine end-groups were employed to systematically study the effects of molecular weight, composition ratio, and temperature on self-assembly.