Responsive Polyphenol‐Crosslinked Supramacromolecular Microgels with pH‐Triggered Disassembly in Aqueous Solution

Macromolecular Chemistry and Physics, vol. 224

Abstract

Abstract This work focuses on the pH‐triggered disassembly of supramacromolecular microgels, which are composed of the temperature‐responsive poly(N‐vinylcaprolactam) (PVCL) and the natural polyphenol tannic acid (TA). A systematic investigation of the microgel formation demonstrates that a retarded addition of tannic acid during semi‐batch precipitation polymerization influences the yield, chemical composition, and properties of the microgels to a great extent. Microgel properties, such as size, deformability, and chemical stability, can be easily tuned by varying the ratio between both building blocks PVCL and TA. Finally, the pH‐triggered disassembly of supramacromolecular microgels at different pH and temperatures demonstrates that their chemical structure can precisely control the degradation profile. Temperatures lower than the volume phase transition temperature (VPTT) of PVCL (T < 32 °C) and a pH > 10 result in a complete disassembly of the microgels into PVCL chains and TA due to the destruction of the hydrogen bonds responsible for the formation of a colloidal microgel. Interestingly, at temperatures above VPTT, the microgels keep their integrity due to enhanced hydrophobic interactions between the polymer chains of the microgel and are no longer affected by pH changes.

Authors 6

1. Catalina Molano López Aachen Functional and Interactive Polymers Institute of Technical and Macromolecular Chemistry Functional and Interactive Polymers Institute of Technical and Macromolecular Chemistry

   DWI – Leibniz Institute for Interactive Materials · RWTH Aachen University

   Affiliation as printed

   DWI‐Leibniz Institute for Interactive Materials Forckenbeckstraße 50 D‐52074 Aachen Germany

   Functional and Interactive Polymers Institute of Technical and Macromolecular Chemistry RWTH Aachen University Worringerweg 2 D‐52074 Aachen Germany

   Functional and Interactive Polymers, Institute of Technical and Macromolecular Chemistry, RWTH Aachen University, Worringerweg 2, D-52074 Aachen, Germany

2. Susanne Braun Aachen Functional and Interactive Polymers Institute of Technical and Macromolecular Chemistry Functional and Interactive Polymers Institute of Technical and Macromolecular Chemistry

   DWI – Leibniz Institute for Interactive Materials · RWTH Aachen University

   Affiliation as printed

   DWI‐Leibniz Institute for Interactive Materials Forckenbeckstraße 50 D‐52074 Aachen Germany

   Functional and Interactive Polymers Institute of Technical and Macromolecular Chemistry RWTH Aachen University Worringerweg 2 D‐52074 Aachen Germany

   Functional and Interactive Polymers, Institute of Technical and Macromolecular Chemistry, RWTH Aachen University, Worringerweg 2, D-52074 Aachen, Germany

3. Michael Kather Aachen Functional and Interactive Polymers Institute of Technical and Macromolecular Chemistry Functional and Interactive Polymers Institute of Technical and Macromolecular Chemistry

   DWI – Leibniz Institute for Interactive Materials · RWTH Aachen University

   Affiliation as printed

   DWI‐Leibniz Institute for Interactive Materials Forckenbeckstraße 50 D‐52074 Aachen Germany

   Functional and Interactive Polymers Institute of Technical and Macromolecular Chemistry RWTH Aachen University Worringerweg 2 D‐52074 Aachen Germany

   Functional and Interactive Polymers, Institute of Technical and Macromolecular Chemistry, RWTH Aachen University, Worringerweg 2, D-52074 Aachen, Germany

4. Alexander Töpel Aachen Functional and Interactive Polymers Institute of Technical and Macromolecular Chemistry Functional and Interactive Polymers Institute of Technical and Macromolecular Chemistry

   DWI – Leibniz Institute for Interactive Materials · RWTH Aachen University

   Affiliation as printed

   DWI‐Leibniz Institute for Interactive Materials Forckenbeckstraße 50 D‐52074 Aachen Germany

   Functional and Interactive Polymers Institute of Technical and Macromolecular Chemistry RWTH Aachen University Worringerweg 2 D‐52074 Aachen Germany

   Functional and Interactive Polymers, Institute of Technical and Macromolecular Chemistry, RWTH Aachen University, Worringerweg 2, D-52074 Aachen, Germany

5. Gil van Wissen Aachen Functional and Interactive Polymers Institute of Technical and Macromolecular Chemistry Functional and Interactive Polymers Institute of Technical and Macromolecular Chemistry

   DWI – Leibniz Institute for Interactive Materials · RWTH Aachen University

   Affiliation as printed

   DWI‐Leibniz Institute for Interactive Materials Forckenbeckstraße 50 D‐52074 Aachen Germany

   Functional and Interactive Polymers Institute of Technical and Macromolecular Chemistry RWTH Aachen University Worringerweg 2 D‐52074 Aachen Germany

   Functional and Interactive Polymers, Institute of Technical and Macromolecular Chemistry, RWTH Aachen University, Worringerweg 2, D-52074 Aachen, Germany

6. Andrij Pich corresponding Aachen Functional and Interactive Polymers Institute of Technical and Macromolecular Chemistry Functional and Interactive Polymers Institute of Technical and Macromolecular Chemistry

   Maastricht University · DWI – Leibniz Institute for Interactive Materials · RWTH Aachen University

   Affiliation as printed

   Aachen Maastricht Institute for Biobased Materials (AMIBM) Maastricht University Brightlands Chemelot Campus Geleen 6167 RD The Netherlands

   DWI‐Leibniz Institute for Interactive Materials Forckenbeckstraße 50 D‐52074 Aachen Germany

   Functional and Interactive Polymers Institute of Technical and Macromolecular Chemistry RWTH Aachen University Worringerweg 2 D‐52074 Aachen Germany

   Functional and Interactive Polymers Institute of Technical and Macromolecular Chemistry RWTH Aachen University Worringerweg 2 D‐52074 Aachen Germany

   Functional and Interactive Polymers, Institute of Technical and Macromolecular Chemistry, RWTH Aachen University, Worringerweg 2, D-52074 Aachen, Germany