Effect of polymer architecture on the adsorption behaviour of amphiphilic copolymers: A theoretical study

Mingduo Mu; Frans A M Leermakers; Jianshe Chen; Melvin Holmes; Rammile Ettelaie

doi:10.1016/j.jcis.2023.04.051

Effect of polymer architecture on the adsorption behaviour of amphiphilic copolymers: A theoretical study

J Colloid Interface Sci. 2023 Aug 15:644:333-345. doi: 10.1016/j.jcis.2023.04.051. Epub 2023 Apr 18.

Authors

Mingduo Mu¹, Frans A M Leermakers², Jianshe Chen³, Melvin Holmes⁴, Rammile Ettelaie⁵

Affiliations

¹ Food Colloids Group, School of Food Science and Nutrition, University of Leeds, Woodhouse Lane, Leeds LS2 9JT, UK. Electronic address: mingduo.mu@mail.mcgill.ca.
² Wageningen Univ & Res, Phys Chem & Soft Matter, Stippeneng 4, 6708 WE Wageningen, Netherlands.
³ School of Food Science and Biotechnology, Zhejiang Gongshang University, Hangzhou, Zhejiang 310018, China.
⁴ Food Colloids Group, School of Food Science and Nutrition, University of Leeds, Woodhouse Lane, Leeds LS2 9JT, UK.
⁵ Food Colloids Group, School of Food Science and Nutrition, University of Leeds, Woodhouse Lane, Leeds LS2 9JT, UK. Electronic address: r.ettelaie@leeds.ac.uk.

PMID: 37120882
DOI: 10.1016/j.jcis.2023.04.051

Abstract

Hypothesis: Polymer architecture is known to have significant impact on its adsorption behaviour. Most studies have been concerned with the more concentrated, "close to surface saturation" regime of the isotherm, where complications such as lateral interactions and crowding also additionally affect the adsorption. We compare a variety of amphiphilic polymer architectures by determining their Henry's adsorption constant (k_H), which, as with other surface active molecules, is the proportionality constant between surface coverage and bulk polymer concentration in a sufficiently dilute regime. It is speculated that not only the number of arms or branches, but also the position of adsorbing hydrophobes influence the adsorption, and that by controlling the latter the two can counteract each other.

Methodology: The Self-consistent field calculation of Scheutjens and Fleer was implemented to calculate the adsorbed amount of polymer for many different polymer architectures including linear, star and dendritic. Using the adsorption isotherms at very low bulk concentrations, we determined the value of k_H for these.

Findings: It is found that the branched structures (star polymers and dendrimers) can be viewed as analogues of linear block polymers based on the location of their adsorbing units. Polymers containing consecutive trains of adsorbing hydrophobes in all cases showed higher level of adsorption compared to their counterparts, where the hydrophobes were more uniformly distributed on the chains. While increasing the number of branches (or arms for star polymers) also confirmed the known result that the adsorption decreased with the number of arms, this trend can be partially offset by the appropriate choice of the location of anchoring groups.

Keywords: Amphiphilic copolymers; Colloidal dispersions; Henry’s constant; Polymer architecture; Polymer surface adsorption; Self-Consistent field (SCF).