Tuning the critical solution temperature of polymers by copolymerization

TL;DR

This study investigates how copolymerization influences the critical solution temperature of polymers using simulations and theory, revealing that CST can vary non-monotonically depending on monomer interactions, aiding in polymer design.

Contribution

It combines computer simulations and mean-field theory to explain how copolymerization affects the CST, providing a framework for tuning polymer phase behavior.

Findings

CST can change monotonically or non-monotonically with copolymerization.

Simulation results are supported by a two-component Flory-de Gennes model.

Insights help in designing polymers with desired thermal properties.

Abstract

We study statistical copolymerization effects on the upper critical solution temperature (CST) of generic homopolymers by means of coarse-grained Langevin dynamics computer simulations and mean-field theory. Our systematic investigation reveals that the CST can change monotonically or non-monotonically with copolymerization, as observed in experimental studies, depending on the degree of non-additivity of the monomer (A-B) cross-interactions. The simulation findings are confirmed and qualitatively explained by a combination of a two-component Flory-de Gennes model for polymer collapse and a simple thermodynamic expansion approach. Our findings provide some rationale behind the effects of copolymerization and may be helpful for tuning CST behavior of polymers in soft material design.