Effect of distribution of stickers along backbone on temperature-dependent structural properties in associative polymer solutions

TL;DR

This study uses a self-consistent field lattice model to analyze how the distribution of stickers along polymer backbones influences temperature-dependent structural properties, revealing distinct behaviors in different morphologies.

Contribution

It introduces a detailed analysis of how sticker spacing affects aggregation and transition behaviors in associating polymer solutions, highlighting differences between microfluctuation and micelle morphologies.

Findings

Increased sticker spacing broadens the aggregation temperature range in MFH morphology.

The symmetry of the specific heat peak decreases with increased sticker spacing.

Structural transitions are linked to solvent replacement within aggregates.

Abstract

Effect of distribution of stickers along the backbone on structural properties in associating polymer solutions is studied using self-consistent field lattice model. Only two inhomogeneous morphologies, i.e., microfluctuation homogenous (MFH) and micelle morphologies, are observed. If the system is cooled, the solvent content within the aggregates decreases. When the spacing of stickers along the backbone is increased the temperature-dependent range of aggregation in MFH morphology and half-width of specific heat peak for homogenous solutions-MFH transition increase, and the symmetry of the peak decreases. However, with increasing spacing of stickers, the above three corresponding quantities related to micelles behave differently. It is demonstrated that the broad nature of the observed transitions can be ascribed to the structural changes which accompany the replacement of solvents in aggregates by polymer, which is consistent with the experimental conclusion. It is found that different effect of spacing of stickers on the two transitions can be interpreted in terms of intrachain and interchain associations.