Phase diagrams, mechanisms and unique characteristics of alternating-structured polymer self-assembly via simulations

Abstract

Alternating-structured polymers (ASPs), like alternating copolymers, regular multiblock copolymers and polycondensates, are very important polymer structures with broad applications in photoelectric materials. However, their self-assembly behaviors, especially the self-assembly of alternating copolymers, have not been clearly studied up to now. Meanwhile, the unique characteristics therein have not been systematically disclosed yet by both experiments and theories. Herein, we have performed a systematic simulation study on the self-assembly of ASPs with two coil alternating segments in solution through dissipative particle dynamics (DPD) simulations. Several morphological phase diagrams were constructed as functions of different impact parameters. Diverse self-assemblies were observed, including spherical micelles, micelle networks, worm-like micelles, disk-like micelles, multimicelle aggregates, bicontinuous micelles, vesicles, nanotubes and channelized micelles. Furthermore, a morphological evolutionary roadmap for all these self-assemblies was constructed, along with which the detailed molecular packing models and self-assembly mechanisms for each aggregate were disclosed. The ASPs were found to adopt a folded-chain mechanism in the self-assemblies. Finally, the unique characteristics for the self-assembly of alternating copolymers were revealed especially, including (1) ultra-fine and uniform feature sizes of the aggregates; (2) independence of self-assembled structures from molecular weight and molecular weight distribution; (3) ultra-small unimolecular aggregates. We believe the current work is beneficial for understanding the self-assembly of alternating structured polymers in solution and can serve as a guide for the further experiments.