Please use this identifier to cite or link to this item:
Authors: Koch, Lukas
Title: Emulsion templating: unexpected morphology of monodisperse macroporous polymers
Issue Date: 2021 Dissertation X, 135
Abstract: The polymerization and drying of monodisperse water-in-styrene/divinylbenzene (DVB) high internal phase emulsions (HIPEs) leads to monodisperse macroporous polystyrene (PS)/polydivinylbenzene (polyDVB). When the monomer-soluble azobisisobutyronitrile (AIBN) is used as initiator, spherical and interconnected pores and porous pore walls are obtained. In contrast, when the water-soluble potassium peroxodisulfate (KPS) is used, polyhedral and closed pores are obtained and the pore walls are comprised of two similar looking outer layers and one different inner layer. The aim of this work was to identify the mechanism (1) that transforms spherical droplets into polyhedral pores and (2) that creates a three-layered pore wall when the polymerization is initiated from the water/monomer interface with KPS. The styrene/DVB mass ratio and the KPS mass fraction were varied to test the existing hypothesis, i.e. an osmotic transport of DVB. Scanning electron microscopy (SEM) pictures revealed that the morphology of the samples does not change in the way it is expected if osmotic transport of DVB was the acting mechanism. Therefore, the existing hypothesis was rejected and a new explanation had to be found. Experiments in which the surfactant mass fraction βsurfactant was varied revealed that the relative size of the inner layer increases and the relative size of the outer layers decreases when βsurfactant is increased. Moreover, it was found that the outer layers are non-porous and that the inner layer is porous. With the help of a model ternary phase diagram consisting of styrene, surfactant, and PS, it was shown that the surfactant is not soluble in partially polymerized styrene/PS mixtures. The experimental results allow suggesting a mechanism that is based on surfactant diffusion. Since the polymerization starts at the water/monomer interface with KPS, a partially polymerized layer forms close to the interface. From this layer, surfactant molecules that are dissolved in the continuous phase diffuse either (1) to the water/monomer interface or (2) to the interior of the continuous phase. (1) Surfactant diffusion to the interface induces an overpopulation of surfactant. This enables the interface to increase its area, which, in turn, transforms the spherical droplets to polyhedral pores. (2) Surfactant diffusion to the interior of the continuous phase leads to an accumulation of surfactant, while the regions close to the interface become surfactant-free. When the surfactant is washed out during purification, a porous inner and two non-porous outer layers are obtained. Additionally, the mechanical properties of monodisperse macroporous PS/polyDVB were investigated. It was found that the samples are only elastomeric when the amount of DVB is low, while they are elastic-brittle for all other monomer compositions.
Appears in Collections:03 Fakultät Chemie

Files in This Item:
File Description SizeFormat 
Dissertation Lukas Koch 20210506.pdf7,95 MBAdobe PDFView/Open

Items in OPUS are protected by copyright, with all rights reserved, unless otherwise indicated.