Anilinium Salts in Polymer Networks for Materials with Mechanical Stability and Mild Thermally Induced Dynamic Properties

Progyateg Chakma; Zachary A Digby; Max P Shulman; Leah R Kuhn; Colleen N Morley; Jessica L Sparks; Dominik Konkolewicz

doi:10.1021/acsmacrolett.8b00819

Anilinium Salts in Polymer Networks for Materials with Mechanical Stability and Mild Thermally Induced Dynamic Properties

ACS Macro Lett. 2019 Feb 19;8(2):95-100. doi: 10.1021/acsmacrolett.8b00819. Epub 2019 Jan 7.

Authors

Progyateg Chakma¹, Zachary A Digby¹, Max P Shulman¹, Leah R Kuhn¹, Colleen N Morley¹, Jessica L Sparks², Dominik Konkolewicz¹

Affiliations

¹ Department of Chemistry and Biochemistry, Miami University, Oxford, Ohio 45056, United States.
² Department of Chemical, Paper and Biomedical Engineering, Miami University, Oxford, Ohio 45056, United States.

PMID: 35619436
DOI: 10.1021/acsmacrolett.8b00819

Abstract

Dynamic nucleophilic exchange of quaternary anilinium salts has been incorporated into rehealable and malleable polymeric materials that can be activated under mild (60 °C) thermal stimulus. The mechanism of dynamic exchange between quaternary anilinium salt and free aniline was assessed in small-molecule model experiments. The dynamic exchange was found to be dissociative in nature, due to the indirect S_N2 mechanism, where initially the bromide anion attacks the anilinium salt to generate an alkyl bromide which undergoes subsequent attack by a free aniline group. A quaternary anilinium-based cross-linker was synthesized to act as dynamic linkages in the polymer network. Cross-linked polymeric materials showed thermoresponsive rehealing and malleability properties at 60 °C along with being resistant to irreversible creep under ambient conditions. The use of anilinium salts enables dynamic exchange to occur with significantly milder thermal stimulus than other comparable materials, while maintaining mechanical stability.