Amphiphilic Block–Random Copolymers: Mapping the Boundaries of Aqueous Self-Assembly

IF 5.1 1区化学 Q1 POLYMER SCIENCE

Macromolecules Pub Date : 2024-11-29 DOI:10.1021/acs.macromol.4c02341

Sandra E. Smeltzer, Connor A. Sanders, Arthur Werner, Sean R. George, Andreas Gernandt, Bernd Reck, Michael F. Cunningham

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Abstract

The structure–property relationships of polystyrene-b-poly(styrene-r-(acrylic acid)) block–random copolymers in aqueous media have been investigated. A library of copolymers with varied degree of polymerization of the hydrophobic polystyrene block, varied mol % acrylic acid (AA) in the hydrophilic block, and varied volumetric block ratios was designed. Rather counterintuitively, it was discovered that PS-b-(PS-r-PAA) block–random copolymers containing relatively low amounts of AA in the hydrophilic block disperse much more readily than those containing higher amounts of AA, despite the decrease in the hydrophilic monomer content. Dispersible copolymers were examined in terms of their critical aggregation concentration, aggregation number, and particle size of aggregates in relation to their structure. A change in interblock interaction parameters is proposed for the differences in dispersion behavior between copolymers containing relatively low and high amounts of AA in the stabilizing block. The findings of this study will not only inform their use as stabilizers in emulsion polymerization but shed light on using highly hydrophobic block copolymers to make small aggregates of a tunable size.

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来源期刊

Macromolecules 工程技术-高分子科学

CiteScore

9.30

自引率

16.40%

发文量

942

审稿时长

2 months

期刊介绍： Macromolecules publishes original, fundamental, and impactful research on all aspects of polymer science. Topics of interest include synthesis (e.g., controlled polymerizations, polymerization catalysis, post polymerization modification, new monomer structures and polymer architectures, and polymerization mechanisms/kinetics analysis); phase behavior, thermodynamics, dynamic, and ordering/disordering phenomena (e.g., self-assembly, gelation, crystallization, solution/melt/solid-state characteristics); structure and properties (e.g., mechanical and rheological properties, surface/interfacial characteristics, electronic and transport properties); new state of the art characterization (e.g., spectroscopy, scattering, microscopy, rheology), simulation (e.g., Monte Carlo, molecular dynamics, multi-scale/coarse-grained modeling), and theoretical methods. Renewable/sustainable polymers, polymer networks, responsive polymers, electro-, magneto- and opto-active macromolecules, inorganic polymers, charge-transporting polymers (ion-containing, semiconducting, and conducting), nanostructured polymers, and polymer composites are also of interest. Typical papers published in Macromolecules showcase important and innovative concepts, experimental methods/observations, and theoretical/computational approaches that demonstrate a fundamental advance in the understanding of polymers.