Effect of Surfactant Selectivity on Shape and Inner Morphology of Triblock Terpolymer Microparticles

Abstract

The confined assembly of block copolymers (BCPs) has become a useful tool to prepare microparticles with controlled anisotropy and inner structure. While a solid understanding of the behavior of AB diblock copolymers exists, knowledge on the parameters affecting ABC triblock terpolymer assembly is much more limited. In this work, the effect of block‐selective surfactants, sodium‐4‐vinylbenzenesulfonate (VBS) and sodium dodecylsulfate (SDS), is analyzed in the evaporation‐induced confined assembly (EICA) of a polystyrene‐block‐polybutadiene‐block‐poly(methyl methacrylate) triblock terpolymer (SBM). Despite using the same terpolymer and emulsification process, SDS results in ellipsoidal microparticles with axially stacked lamellae, while VBS results in spherical microparticles with concentric lamellae or 3D spiral morphology. This change in morphology upon switching the surfactant is further substantiated by molecular simulations and enhances the understanding of terpolymer microphase separation in confinement.

Fabrication of poly(4-vinylpyridine)-b-polystyrene-b-poly(4-vinylpyridine) triblock copolymer particles via three-dimensional soft confined self-assembly

“…, ABA, ABC) and more complex polymer architectures. 23,37,38 For example, Qiang et al 39 prepared ellipsoidal particles with stacked PS/PB/PMMA layers using triblock terpolymers of polystyrene- b -polybutadiene- b -poly(methyl methacrylate) (PS- b -PB- b -PMMA) with 10 mg mL −1 CTAB. The surface of such ellipsoidal particles would show a patchy topography during solvent annealing in CHCl 3 with PVA as a surfactant due to the preferential interaction between PMMA and PVA.…”

Impact of channel nanostructures of porous carbon particles on their catalytic performance

“…19–27 This method allows for the synthesis of particles with diverse particle shapes and internal structures, such as spherical particles with lamellar and coiled cylinder structures, football-like particles, and lens-shaped particles. 21,25,28,29 Particularly, continuous channel structures within the particles can be achieved by controlling the BCP structures and selectively etching one of the BCP domains. 30–34 Among the various methods for controlling the orientation of the BCP and channel nanostructure, modulation of the solvent-evaporation rate is an effective technique to achieve continuous channels exposed to the particle surface.…”

Dynamic Electrostatic Interfacial Engineering for Block Copolymer Microparticles with Reversible Structures

“…The interfacial interaction between incompatible components is critical for manufacturing functional nanomaterials with designable structures and high performance, which plays a decisive role in areas such as Pickering emulsions, fluorescence imaging, and block copolymer (BCP) self-assembly. − In particular, in the emulsion-templated soft confined assembly of BCPs, the soft emulsion interface allows spontaneous deformation by facilely modulating the oil/water interfacial interactions. − Previous reports have shown that the interfacial interaction mainly depends on the interfacial affinity between surfactants and BCPs, which determines the interfacial selectivity of oil/water interface and ultimately the shape and internal nanostructure of the BCP microparticles. − However, surfactants with specific responsive behavior (e.g., light-, pH-, and temperature-responsiveness) often involve complicated chemical synthesis. ,, …”