Emulsion Templated Porous Poly(thiol-enes): Influence of Photopolymerisation, Emulsion Composition, and Phase Behaviour on the Porous Structure and Morphology.

1,6-hexanediol diacrylate (HDDA) or divinyl adipate (DVA) and pentaerythritol tetrakis(3-mercaptopropionate) (TT) were polymerised via a thiol-ene radical initiated photopolymerisation using emulsions with a high volume fraction of internal droplet phase and monomers in the continuous phase as precursors. The porous structure derived from the high internal phase emulsions (HIPEs) followed the precursor emulsion setup resulting in an open porous cellularly structured polymer. Changing the emulsion composition and polymerisation conditions influenced the resulting morphological structure significantly. The investigated factors influencing the polymer monolith morphology were the emulsion phase ratio and surfactant concentration, leading to either interconnected cellular type morphology, bicontinuous porous morphology or a hollow sphere inverted structure of the polymerised monoliths. The samples with interconnected cellular morphology had pore diameters between 4 µm and 10 µm with approx. 1 µm sized interconnecting channels while samples with bicontinuous morphology featured approx. 5 µm wide pores between the polymer domains. The appropriate choice of emulsion composition enabled the preparation of highly porous poly(thiol-enes) with either polyHIPE or bicontinuous morphology. The porosities of the prepared samples followed the emulsion droplet phase share and could reach up to 88%.

Thiol-Ene Cross-linking of Poly(ethylene glycol) within High Internal Phase Emulsions: Degradable Hydrophilic PolyHIPEs for Controlled Drug Release.

Macroporous polymer monoliths prepared from high internal phase emulsions (HIPEs) can be found in various biomedical applications. While typically water-in-oil HIPEs are applied for polyHIPE preparation, they are not suitable for hydrophilic polyHIPE preparation. Herein, direct oil-in-water emulsions based on water-soluble poly(ethylene glycol)diacrylate or poly(ethylene glycol)dimethacrylate were developed. Furthermore, the incorporation of a hydrophilic water-miscible thiol, ethoxylated trimethylolpropane tris(3-mercaptopropionate) (ETTMP) was reported for the first time within thiol-ene polyHIPEs. Due to the transparency of the emulsions, rapid curing via photopolymerization was feasible. The average pore diameters of the resulting polyHIPEs ranged between 1.2 and 3.6 µm, and porosity of up to 90% was achieved. The water uptake of the materials reached up to 1000% by weight. Drug loading and release were demonstrated, employing salicylic acid as a model drug. Porous profile and biodegradability add to the usefulness of the material for biomedical applications.