Multicomponent Radziszewski Emulsion Polymerization toward Macroporous Poly(ionic liquid) Catalysts

Abstract

Interconnected macroporous imidazolium-based monoliths are produced via the modified Radziszewski multicomponent reaction (MCR) applied to triamines under high internal phase emulsion (HIPE) conditions. This straightforward one-pot synthesis combines the efficiency and versatility of MCRs with the ease of implementation of the emulsion templating polymerization process. The characterization of the chemical structure and morphology of the resulting materials confirms the formation of the expected macroporous poly­(ionic liquid)­s (PILs) networks. The promising catalytic activity and recyclability of these porous PIL monoliths are illustrated for the transesterification reaction and the decarboxylation of caffeic acid. In these cases, almost complete conversion is reached while benefiting from the advantages associated with a heterogeneous catalyst.

Catalyst‐Free Four‐Component Polymerization of Propiolic Acids, Benzylamines, Organoboronic Acids, and Formaldehyde toward Functional Poly(propargylamine)s

“…[ 1,2 ] Compared with classic polymerization approaches, MCPs enjoy great structural diversity of products, strong designability of reaction procedure and product structure, mild reaction condition, simple monomer structures, environmental benefits, and so on. [ 3–6 ] Besides the most widely explored isocyanide‐based MCPs including Passerini three‐component polymerization (3CP) of isocyanide, carboxylic acid and oxo‐component (ketone or aldehyde), [ 7–10 ] and Ugi four‐component polymerization (4CP) of isocyanide, carboxylic acid, oxo‐component (ketone or aldehyde) and amine, [ 11–13 ] alkyne‐based MCPs were extensively reported in the past few years, [ 14–16 ] owing to the rich chemistry of alkynes and the unsaturated product structures with potential optoelectronic properties from alkyne chemistry, [ 17 ] which could be applied in optoelectronic devices, [ 18,19 ] or as luminescent materials, [ 14,20 ] and antibacterial materials. [ 21 ]…”

Fundamentals and Design‐Led Synthesis of Emulsion‐Templated Porous Materials for Environmental Applications

“…In addition to the environmental applications described above, emulsion‐templated porous materials have also been widely used in other applications such as heterogeneous catalysis, [ 132 , 152 , 203 , 211 , 220 , 226 , 249 ] biomedical applications, [ 26 , 50 , 161 , 170 ] energy storage, [ 234 , 236 , 241 , 251 , 258 ] and chromatography, [ 111 , 123 ] to name a few. All these applications have explored the highly interconnected hierarchical porosity, chemical functionality and desired physical properties presented by emulsion‐templated porous materials.…”

“…The resulting materials possessed connected cavities and were demonstrated as a high-performance heterogeneous catalyst for decarboxylation of caffeic acid and transesterification reactions. [152] Considering their uses in biomedical applications, [26,29] Pickering HIPEs are also good platforms for the preparation of biocompatible polyHIPEs. [153] This is because a wide variety of particles with natural origin are available to form Pickering emulsions.…”

“…The resulting materials possessed connected cavities and were demonstrated as a high‐performance heterogeneous catalyst for decarboxylation of caffeic acid and transesterification reactions. [ 152 ]…”

Creation of adjacent monolithic and self‐forming porous fragments in a polymerizing layer by optical scanning stereolithography

“…The possibility to produce materials with the structure, which combines adjacent monolithic and porous fragments, in one technological process opens up a new potential for optical printing of various skeletons for tissue engineering, 1–8 nano‐ and macro‐porous filters, 9,10 flowing nano‐ and micro‐reactors with enhanced operating surface area 11–13 . Stereolithography is a modern high‐resolution method to make polymeric 2D‐ and 3D‐objects of complex geometry 3,14–17 .…”