A novel microscopic origin of co-nonsolvency.

Abstract

Co-nonsolvency presents a fundamental paradox in polymer physics where macromolecules undergo collapse or precipitation in mixed good solvents. Through investigations combining simulations of various binary good solvent systems of polymers, including single-chain and multi-chain of homopolymers and block copolymers, and ternary Flory-Huggins theoretical validation, we reveal that the competition between the enthalpy of the system and the mixing entropy of binary solvents results in the liquid-liquid phase separation (LLPS) of the better solvent (S-solvent) and the co-nonsolvency phenomenon. To reduce the enthalpy, the polymer and S-solvent tend to mix together to maximize their contact, which, however, is entropically unfavorable due to the localization of the S-solvent in the polymer domain. The LLPS of the S-solvent, where different chain segments share the localized S-solvent molecules, simultaneously lowers the enthalpy and reduces the loss of the mixing entropy. This sharing leads the chain in single-chain systems to be in a locally folding conformation with a size being much smaller than that of the ideal chain. In multi-chain systems, however, the sharing can be among segments from different chains, which causes chain condensation and hence an average chain size larger than its ideal value. Our study provides a novel mechanism for co-nonsolvency and may provide insights into the LLPS in other soft matter systems.