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Synthesis of Cyclic Polymers and Characterization of Their Diffusive Motion in the Melt State at the Single Molecule Level
Published on: September 26, 2016
Acyclic Diene Metathesis (ADMET) Polymerization of 2,2,6,6-Tetramethylpiperidine-1-sulfanyl (TEMPS) Dimers
Jan Hobich1, Birgit Huber1, Patrick Theato1,2
1Soft Matter Synthesis Laboratory, Institute for Biological Interfaces 3 (IBG 3), Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1, Eggenstein-Leopoldshafen, D-76344, Germany.
Abstract:
The preparation of polymers containing sulfur-nitrogen bond derivatives, particularly 2,2,6,6-tetramethylpiperidine-1-sulfanyl (TEMPS) dimers (i.e., BiTEMPS), has been limited to free-radical or conventional step-growth polymerization as result of the inherent thermal lability of the BiTEMPS unit. Accordingly, a novel poly(diaminodisulfide) possessing the BiTEMPS functional group is synthesized via acyclic diene metathesis (ADMET) polymerization at 65-75 °C within 3 h with precise control over the primary polymer structure. Polymer is isolated with an Mn of 20 400 g mol-1 and Ð of 1.9. Importantly, detailed nuclear magnetic resonance (NMR), size exclusion chromatography, attenuated total reflectance Fourier transform infrared (ATR-IR) in addition to elemental analysis studies of the BiTEMPS polymer confirm the successful polymerization, and show that the BiTEMPS unit remains intact during the polymerization process. Furthermore, the previously unexplored UV-responsiveness of the BiTEMPS decorated polymer backbone is investigated for the very first time.
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