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

Magee, Christopher
; 
Earla, Aruna
; 
Petraitis, Jennifer
; 
Higa, Chad
; 
Braslau, Rebecca
; 
Zetterlund, Per B.
; 
Aldabbagh, Fawaz
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Identifiers
http://hdl.handle.net/10379/5727
https://doi.org/10.13025/14858
Repository DOI
10.1039/C4PY00757C
Publication Date
2014-06-20
Keywords
Chemistry, Transfer radical polymerization, Controlled dispersion polymerization, Methy methacrylate, Chain transfer, Block copolymers, Vinyl monomers, Raft, CO2, Stabilizer, ATRP
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Article
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Citation
Christopher Magee, Aruna Earla, Jennifer Petraitis, Chad Higa, Rebecca Braslau, Per B. Zetterlund and Fawaz Aldabbagh (2014) 'Synthesis of fluorinated alkoxyamines and alkoxyamine-initiated nitroxide-mediated precipitation polymerizations of styrene in supercritical carbon dioxide'. Polymer Chemistry, 5 :5725-5733.
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 (scCO(2)). 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 scCO(2) for three newly synthesized fluorinated alkoxyamines. Two alkoxyamines dissociated into scCO(2)-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 scCO(2) for the fluorinated alkoxyamines.
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Publisher
Royal Society of Chemistry
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Attribution-NonCommercial-NoDerivs 3.0 Ireland
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School of Biological and Chemical Sciences (Scholarly Articles)