High-throughput polymer screening in microreactors boosting the Passerini three component reaction

Joris J. Haven, Evelien Baeten, Jonathan Claes, Joke Vandenbergh, Tanja Junkers

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20 Citations (Scopus)


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.

Original languageEnglish
Pages (from-to)2972-2978
Number of pages7
JournalPolymer Chemistry
Issue number19
Publication statusPublished - 21 May 2017
Externally publishedYes

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