Kinetic prediction of functional group distributions in thermosensitive microgels.

A kinetic model accounting for the copolymerization of up to four comonomers is applied to predict both chain and radial functional group distributions in carboxylic-acid-functionalized poly(N-isopropylacrylamide) (NIPAM)-based microgels. The model can accurately predict the experimentally observed radial distributions of functional monomers in microgels prepared using a variety of different carboxylic-acid-functionalized monomers with significantly different hydrophobicities, copolymerization kinetics, and reactivities, without requiring the use of adjustable parameters. Multimodal distributions can both be predicted and experimentally generated by copolymerizing two -COOH-containing monomers with widely different reactivities. Chain distributions and monomer block formation can also be probed using the kinetic model, allowing for qualitative predictions of the potentiometric titration behavior of the microgels. The kinetic model reported herein therefore provides the first available analytical method for semiquantitatively predicting and controlling functional group distributions in bulk-polymerized microgel systems.