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Issue 19, 2014
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Synthesis of fluorinated alkoxyamines and alkoxyamine-initiated nitroxide-mediated precipitation polymerizations of styrene in supercritical carbon dioxide

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Abstract

TIPNO (2,2,5-trimethyl-4-phenyl-3-azahexane-3-nitroxide)-alkoxyamine was found to give reasonably controlled/living nitroxide-mediated (NMP) precipitation polymerizations of styrene in supercritical carbon dioxide (scCO2). In contrast under the same conditions, the analogous SG1 (N-tert-butyl-N-(1-diethylphosphono-2,2-dimethylpropyl)nitroxide)-alkoxyamine gave higher rates of polymerization and inferior controlled/living character. The circumvention of the requirement for excess free [nitroxide]0 allowed the study of nitroxide partitioning effects in scCO2 for three newly synthesized fluorinated alkoxyamines. Two alkoxyamines dissociated into scCO2-philic fluorinated TIPNO-nitroxide derivatives, while another contains a similar sized fluorinated “foot”. Despite the increased steric bulk about the N–O bond for the novel fluorinated alkoxyamines, all polymerizations proceeded at a similar rate and level of control to the TIPNO system in solution (toluene). PREDICI simulations for the styrene/TIPNO system are used to support extensive partitioning effects observed in scCO2 for the fluorinated alkoxyamines.

Graphical abstract: Synthesis of fluorinated alkoxyamines and alkoxyamine-initiated nitroxide-mediated precipitation polymerizations of styrene in supercritical carbon dioxide

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Supplementary files

Article information


Submitted
29 May 2014
Accepted
18 Jun 2014
First published
20 Jun 2014

Polym. Chem., 2014,5, 5725-5733
Article type
Paper
Author version available

Synthesis of fluorinated alkoxyamines and alkoxyamine-initiated nitroxide-mediated precipitation polymerizations of styrene in supercritical carbon dioxide

C. Magee, A. Earla, J. Petraitis, C. Higa, R. Braslau, P. B. Zetterlund and F. Aldabbagh, Polym. Chem., 2014, 5, 5725
DOI: 10.1039/C4PY00757C

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