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Copolymer microgels by precipitation polymerisation of N-vinylcaprolactam and N-isopropylacrylamides in aqueous medium

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Abstract

In this work, we designed copolymer microgels by the copolymerisation of N-vinylcaprolactam (VCL) and two acrylamides (N-isopropylacrylamide (NIPAAm) and N-isopropylmethacrylamide (NIPMAAm)) under precipitation conditions in aqueous phase. In synthesis protocols, the ratio between monomers was varied from 1:5 to 5:1 mol/mol. By NMR and Raman spectroscopy, we determined the chemical composition of PVCL/NIPAAm and PVCL/NIPMAAm copolymer microgels reflecting the initial monomer ratio in the reaction mixture. The hydrodynamic radii of PVCL/NIPAAm microgels are around 375 nm (at 25 °C) and do not vary with the copolymer composition. On the contrary, for PVCL/NIPMAAm microgels, the size decreases from 450 to 250 nm with an increase of the VCL amount in copolymer structure. The heterogeneity of the microgel structure in terms of the distribution of the monomer units was probed by 1H transverse magnetization relaxation NMR, showing that the VCL, NIPAAm and NIPMAAm units are unorderly distributed in the colloidal networks. The investigation of volume phase transition temperature (VPTT) for copolymer microgels was performed using dynamic light scattering, NMR and differential scanning calorimetry. It has been found that PVCL/NIPAAm microgels show VPTT around 35 °C independently from the copolymer composition; however, PVCL/NIPMAAm particles exhibit a nonlinear increase of VPTT from 34 to 45 °C as the NIPMAAm fraction in copolymer structure increases.

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Acknowledgement

AB and AP thank VolkswagenStiftung for financial support of this research.

Supporting Information

1H NMR spectra of PVCL/NIPMAAm microgels; determination of the chemical composition of PVCL/NIPMAAm microgels by Raman Spectroscopy.

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Authors and Affiliations

  1. Functional and Interactive Polymers, Technical and Macromolecular Chemistry, RWTH Aachen University, Forckenbeckstraße 50, 52056, Aachen, Germany

    Andreea Balaceanu, Veronica Mayorga, Dan E. Demco & Andrij Pich

  2. Lehrstuhl für Makromolekulare Materialien und Oberflächen, RWTH Aachen University, Forckenbeckstraße 50, 52056, Aachen, Germany

    Marco-Philipp Schürings & Alexander Böker

  3. Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, ON, Canada, M5S 3H6

    Wanjuan Lin & Mitchell A. Winnik

Authors
  1. Andreea Balaceanu
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  2. Veronica Mayorga
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  3. Wanjuan Lin
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  4. Marco-Philipp Schürings
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  5. Dan E. Demco
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  6. Alexander Böker
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  7. Mitchell A. Winnik
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  8. Andrij Pich
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Correspondence to Andrij Pich.

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Balaceanu, A., Mayorga, V., Lin, W. et al. Copolymer microgels by precipitation polymerisation of N-vinylcaprolactam and N-isopropylacrylamides in aqueous medium. Colloid Polym Sci 291, 21–31 (2013). https://doi.org/10.1007/s00396-012-2659-1

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  • DOI: https://doi.org/10.1007/s00396-012-2659-1

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