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Semi-batch control over functional group distributions in thermoresponsive microgels

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Abstract

Thermosensitive poly(N-isopropylacrylamide-co-methacrylic acid) (poly(NIPAM-co-MAA)) microgels were prepared via semi-batch free radical copolymerization in which the functional monomer (methacrylic acid) was continuously fed into the reaction vessel at various speeds. Microgels with the same bulk MAA contents (and thus the same overall compositions) but different radial functional group distributions were produced, with batch copolymerizations resulting in core-localized functional groups, fast-feed semi-batch copolymerizations resulting in near-uniform functional group distributions, and slow-feed semi-batch copolymerizations resulting in shell-localized functional groups. Functional group distributions in the microgels were probed using titration analysis, electrophoresis, and transmission electron microscopy. The induced functional group distributions have particularly significant impacts on the pH-induced swelling and cationic drug binding behavior of the microgels; slower monomer feeds result in increased pH-induced swelling but lower drug binding. This work suggests that continuous semi-batch feed regimes can be used to synthesize thermoresponsive microgels with well-defined internal morphologies if an understanding of the relative copolymerization kinetics of each comonomer relative to NIPAM is achieved.

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Acknowledgments

The Natural Sciences and Engineering Research Council of Canada (NSERC) is acknowledged for funding. Kevin DeFrance is acknowledged for his assistance in synthesizing the semi-batch microgels.

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Authors and Affiliations

  1. Department of Chemical Engineering, McMaster University, 1280 Main St. W., Hamilton, ON, L8S 4L7, Canada

    Paniz Sheikholeslami, Christopher M. Ewaschuk, Syed Usman Ahmed, Benjamin A. Greenlay & Todd Hoare

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  1. Paniz Sheikholeslami
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  2. Christopher M. Ewaschuk
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  3. Syed Usman Ahmed
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  4. Benjamin A. Greenlay
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  5. Todd Hoare
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Correspondence to Todd Hoare.

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Supplementary Information

Excess Gibbs free energy of ionization and degree of ionization versus pH plots are provided for the batch and semi-batch microgels studied as well as gel permeation chromatography traces of supernatant polymers for fast and slow-feed microgels. (PDF 84 kb)

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Sheikholeslami, P., Ewaschuk, C.M., Ahmed, S.U. et al. Semi-batch control over functional group distributions in thermoresponsive microgels. Colloid Polym Sci 290, 1181–1192 (2012). https://doi.org/10.1007/s00396-012-2642-x

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  • DOI: https://doi.org/10.1007/s00396-012-2642-x

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