Jump to main content
Jump to site search

Issue 34, 2017
Previous Article Next Article

Computational design of pH-switchable control agents for nitroxide mediated polymerization

Author affiliations

Abstract

In the present work we use accurate quantum chemistry to evaluate several known and novel nitroxides bearing acid–base groups as pH-switchable control agents for room temperature NMP. Based on G3(MP2,CC)(+)//M06-2X/6-31+G(d) calculations with UAKS-CPCM/M06-2X/6-31+G(d) solvation corrections, a number of novel nitroxides are predicted to be suitable for controlled polymerization of bulk styrene at room temperature when deprotonated (i.e. negatively charged), while remaining inert when neutral. These include an α-ethyl analogue of 3-carboxy-PROXYL and novel derivatives of 2,2,5-trimethyl-4-phenyl-3-azahexane-3-nitroxide (TIPNO) that have been modified to include acidic groups. Among the other species evaluated, 3,4-dicarboxy-PROXYL, α-carboxylated PROXYL and the phosphoric acid derivative of N-(2-methylpropyl)-N-(1-diethylphosphono-2,2-dimethylpropyl)-N-oxyl (SG1) are predicted to undergo suitable pH-switching at around 60 °C, and may also be fitting for some applications.

Graphical abstract: Computational design of pH-switchable control agents for nitroxide mediated polymerization

Back to tab navigation

Supplementary files

Publication details

The article was received on 28 Jun 2017, accepted on 08 Aug 2017 and first published on 09 Aug 2017


Article type: Paper
DOI: 10.1039/C7CP04337F
Citation: Phys. Chem. Chem. Phys., 2017,19, 22678-22683
  •   Request permissions

    Computational design of pH-switchable control agents for nitroxide mediated polymerization

    G. Gryn’ova, L. M. Smith and M. L. Coote, Phys. Chem. Chem. Phys., 2017, 19, 22678
    DOI: 10.1039/C7CP04337F

Search articles by author

Spotlight

Advertisements