High-throughput polymer screening in microreactors: boosting the Passerini three component reaction
| Autor: | Jonathan Claes, Tanja Junkers, Joke Vandenbergh, Evelien Baeten, Joris J. Haven |
|---|---|
| Rok vydání: | 2017 |
| Předmět: |
chemistry.chemical_classification
Ketone Polymers and Plastics Isocyanide Carboxylic acid Organic Chemistry Size-exclusion chromatography Bioengineering 02 engineering and technology 010402 general chemistry 021001 nanoscience & nanotechnology 01 natural sciences Biochemistry Aldehyde 0104 chemical sciences Acetic acid chemistry.chemical_compound chemistry Reagent Polymer chemistry Microreactor 0210 nano-technology |
| Zdroj: | Polymer Chemistry. 8:2972-2978 |
| ISSN: | 1759-9962 1759-9954 |
| Popis: | The Passerini three-component reaction (Passerini-3CR) has been studied via on-line microreactor/electrospray ionisation mass spectrometry (MRT/ESI-MS) reaction monitoring to demonstrate the high-throughput screening potential of continuous microreactors for macromolecular design. The Passerini-3CR is an efficient reaction, but generally requires some reagents in excess and comparatively long reaction times to complete. Herein, a reaction protocol is proposed for high yields within minutes of reaction time at equimolar reactant concentrations. The Passerini-3CR allows for the synthesis of α-acyloxy carboxamides by combining an aldehyde (or ketone), an isocyanide and a carboxylic acid moiety. A carboxylic acid (i, 1300 g mol−1) and aldehyde (ii, 1150 g mol−1) endgroup functionalized low molecular weight poly(n-butyl acrylate) were separately screened with their corresponding components as follows: (i) with dodecylaldehyde and ethylisocyano acetate and (ii) with acetic acid and ethylisocyano acetate. Screened parameters were molarity ratios, residence times, absolute reagent concentrations and reactor temperatures. Equimolar carboxylic acid/aldehyde concentrations give excellent Passerini product yields (>95%) within 10 minutes of reaction time. The established reaction protocol is then transferred to a conventional batch process for the synthesis of diblock copolymers P(nBA)-b-P(nBA), P(nBA)-b-P(MMA) and P(nBA)-b-P(EGMEA) with variable block lengths. All diblock copolymers are synthesized by using equimolar carboxylic acid/aldehyde polymer mixtures, showing excellent coupling efficiencies in size exclusion chromatography analysis. The isocyanide component, being ethylisocyano acetate, is consistently utilized in excess in agreement with the literature. |
| Databáze: | OpenAIRE |
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