Surfactant-free microemulsions (SFMEs) as a template for porous polymer synthesis

Hypothesis: Surfactant-free microemulsions (SFMEs) were recently reported to be an interesting medium for freeradical polymerizations. The aim of this study is to investigate the link between the morphology of PMMA monopolymers as well as PMMA-PHEMA-copolymers with the expected nature of the SFME before polymerization. A surfactant-based microemulsion with nonionic surfactants was investigated as a reference system. It is expected that the kind of mesostructuring of the SFME (oil-in-water-like, bicontinuous, inverse) corresponds with the latter polymer morphology, just like it is the case in surfactant-based systems. Experiments: Simple SFME systems composed of water, a hydrotrope (isopropanol or tert-butyl alcohol), and methyl methacrylate (MMA) as polymerizable oil as well as the more complex system comprising 2-hydroxyethyl methacrylate (HEMA) as an additional amphiphilic co-monomer, were investigated. A surfactant-based system using a mixture of Tergitol 15-S-12 and Synperonic A11-LQ-(TH) as surfactants, water, and MMA in the presence and absence of HEMA as polymerizable co-surfactant was investigated as a reference system. Structural analysis was done by recording (pseudo-)ternary phase diagrams, dynamic light scattering (DLS), and conductivity measurements. Polymerizations were performed using the oil-soluble initiator PEROXAN BCC at 318 K for 24 h with adjacent lyophilization. The morphology of dried polymers was determined by light microscopy, scanning electron microscopy, and BET adsorption isotherms. Findings: Porous polymers of different morphologies (from coagulations of droplet-like aggregates to sponge ones) in the size range of 200 nm up to some mu m can be derived from previously mesostructured, surfactant-free mixtures. Previously unstructured, oil-rich regions lead to solid, transparent polymers without nanostructured morphologies. The surfactant-based reference system comprises remarkably similar phase behavior before lymerizations and similar polymer morphologies as the comparable surfactant-free system. This leads to assumption that the hydrotropic behavior of HEMA and its interplay with MMA and water is the structure-giving factor in this system.

Automated summary

This study investigates the relationship between the morphology of PMMA monopolymers and PMMA-PHEMA copolymers with the expected nature of surfactant-free microemulsions (SFMEs) before polymerization. It is found that previously mesostructured, surfactant-free mixtures can produce porous polymers of different morphologies, while unstructured, oil-rich regions lead to solid, transparent polymers without nanostructured morphologies. Additionally, a surfactant-based reference system shows similar phase behavior and polymer morphologies as the comparable surfactant-free system, indicating the importance of the hydrotropic behavior of HEMA in this system.