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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
Repository DOI
Publication Date
2014-01-01
Keywords
transfer radical polymerization, controlled dispersion polymerization, methyl-methacrylate, chain transfer, block-copolymers, vinyl monomers, raft, co2, stabilizer, atrp
Type
Article
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Citation
Magee, Christopher; Earla, Aruna; Petraitis, Jennifer; Higa, Chad; Braslau, Rebecca; Zetterlund, Per B. Aldabbagh, Fawaz (2014). Synthesis of fluorinated alkoxyamines and alkoxyamine-initiated nitroxide-mediated precipitation polymerizations of styrene in supercritical carbon dioxide. Polym. Chem. 5 (19), 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.
Funder
Publisher
Royal Society of Chemistry (RSC)
Publisher DOI
10.1039/c4py00757c
Rights
Attribution-NonCommercial-NoDerivs 3.0 Ireland
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Externally hosted open access publications with University of Galway authors (2)