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Accelerated Post-Polymerization Amidation of Polymers with Side-Chain Ester Groups by Intramolecular Activation
Joachim F R Van Guyse1,2, Meike N Leiske1, Jente Verjans1
1Supramolecular Chemistry Group, Centre of Macromolecular Chemistry (CMaC), Department of Organic and Macromolecular Chemistry, Ghent University, Krijgslaan 281 S4, 9000, Ghent, Belgium.
Angewandte Chemie (International Ed. in English)
|May 4, 2022
Summary
This study accelerates polymer amidation using functionalized amines, enabling efficient synthesis of amide-containing polymers. The method enhances polymer upcycling and diversification through faster catalytic conversion of esters to amides.
Area of Science:
- Polymer Chemistry
- Organic Synthesis
- Materials Science
Background:
- Esters are common in polymers, but their direct catalytic conversion to amides is slow.
- Understanding how polymer structure affects amidation reactivity is crucial for polymer modification.
- Existing methods face challenges with reaction kinetics and structural influences.
Purpose of the Study:
- To develop an accelerated method for the catalytic conversion of esters to amides in polymers.
- To investigate the role of amine structure in facilitating polymer amidation.
- To elucidate the influence of polymer architecture on amidation efficiency.
Main Methods:
- Utilized amines with hydrogen bond donating or accepting groups for accelerated amidation.
- Investigated reactivity differences between polymers with pendant ester groups versus main-chain esters.
- Employed FT-IR spectroscopy and molecular mechanics modeling to confirm reaction mechanisms.
Main Results:
- Achieved a >400-fold increase in reactivity for polymers with pendant ester groups compared to main-chain esters.
- Demonstrated accelerated (co)amidation of polymers using specifically designed amines.
- Observed a positive correlation between reactivity and degree of polymerization for poly(methyl acrylate).
Conclusions:
- Hydrogen-bond mediated intramolecular activation of esters enhances amidation rates.
- The developed method allows for the synthesis of diverse (co)polymers with amide side chains.
- This approach offers a pathway for efficient polymer diversification and upcycling from accessible precursors.
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