Issue 17, 2022

Design rules for performing water-sensitive ring-opening polymerizations in an aqueous dispersion

Abstract

The water sensitivity of ring-opening polymerizations (ROP) prevents any polymerization technique using water as a solvent which ultimately sets a limit on the polymeric material accessible. We implement a droplet microfluidic encapsulation strategy to create polyester and polyether particles dispersed in water. In this work, we systematically investigated the process and formulation parameters that govern the stability of the micro-droplets during generation, flow, and collection. More specifically, we tune droplet viscosity, surface tension, and hydrophobicity through the addition of amphiphilic block copolymers (ABC) and hydrophobes to further shield the ROP catalyst in the aqueous dispersion. The increased catalyst stability ultimately results in higher monomer conversion and higher molecular weight polymer. We subsequently show that by changing the ABC composition, we can further tune the ROP reaction time. Finally, we applied the encapsulation technique and formulation optimization to perform another water-sensitive ROP in an aqueous dispersion. Utilizing our design rules to tune the viscosity and surface tension of the droplets, we successfully synthesized polyether particles dispersed in water. Overall, we demonstrate the power and versatility of the encapsulation methodology and establish the fundamental guiding principles to encapsulate water-sensitive polymerization catalysts to yield spherical polymer particles dispersed in water.

Graphical abstract: Design rules for performing water-sensitive ring-opening polymerizations in an aqueous dispersion

Supplementary files

Article information

Article type
Paper
Submitted
17 Jan 2022
Accepted
04 Mar 2022
First published
16 Mar 2022

Polym. Chem., 2022,13, 2459-2468

Design rules for performing water-sensitive ring-opening polymerizations in an aqueous dispersion

D. D. Harrier and D. Guironnet, Polym. Chem., 2022, 13, 2459 DOI: 10.1039/D2PY00069E

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