Synthesis of Poly(<i>N</i>‑vinylcaprolactam)-Based Microgels by Precipitation Polymerization: Process Modeling and Experimental Validation

The successful application of poly­(<i>N</i>-vinylcaprolactam)-based microgels requires a profound understanding of their synthesis. For this purpose, a validated process model for the microgels synthesis by precipitation copolymerization with the cross-linker <i>N</i>,<i>N</i>′-methylenebis­(acrylamide) is formulated. Unknown reaction rate constants, reaction enthalpies, and partition coefficients are obtained by quantum mechanical calculations. The remaining parameter values are estimated from reaction calorimetry and Raman spectroscopy measurements of experiments with different monomer/cross-linker compositions. Because of high cross-propagation reaction rate constants, simulations predict a fast incorporation of the cross-linker. This agrees with reaction calorimetry measurements. Furthermore, the gel phase is predicted as the major reaction locus. The model is utilized for a prediction of the internal particle structure regarding its cross-link distribution. The highly cross-linked core reported in the literature corresponds to the predictions of the model