Low-temperature preparations of unimolecular nitroxide initiators for "living" free radical polymerizations

Rebecca Braslau, Leland C. Burrill, Michael Siano, Neeta Naik, Rodney K. Howden, Lara Mahal

Research output: Contribution to journalArticle

Abstract

Low-temperature methods for the preparation of monomeric initiators for use in "living" free radical olefin polymerizations have been developed. Oxidative methods for generating carbon radicals in the presence of nitroxide traps such as TEMPO utilize PbO2 with benzylic, alkyl, or phenylhydrazines or CuCl2 with lithium enolates. Photolytic methods employ [Cp(CO)2Fe]2 with a benzylic bromide, diphenyl disulfide with styrene, or di-tert-butyl peroxide with ethers. The use of di-tert-butyl hyponitrite with ethers generates carbon radicals at 50 °C that are trapped by TEMPO.

Original languageEnglish (US)
Pages (from-to)6445-6450
Number of pages6
JournalMacromolecules
Volume30
Issue number21
StatePublished - Oct 20 1997

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Ethers
Free radical polymerization
Phenylhydrazines
Carbon
Styrene
Alkenes
Carbon Monoxide
Peroxides
Bromides
Free radicals
Lithium
Olefins
Free Radicals
Polymerization
Temperature
TEMPO
cupric chloride
hyponitrite
diphenyl disulfide
di-tert-butyl peroxide

ASJC Scopus subject areas

  • Materials Chemistry

Cite this

Braslau, R., Burrill, L. C., Siano, M., Naik, N., Howden, R. K., & Mahal, L. (1997). Low-temperature preparations of unimolecular nitroxide initiators for "living" free radical polymerizations. Macromolecules, 30(21), 6445-6450.

Low-temperature preparations of unimolecular nitroxide initiators for "living" free radical polymerizations. / Braslau, Rebecca; Burrill, Leland C.; Siano, Michael; Naik, Neeta; Howden, Rodney K.; Mahal, Lara.

In: Macromolecules, Vol. 30, No. 21, 20.10.1997, p. 6445-6450.

Research output: Contribution to journalArticle

Braslau, R, Burrill, LC, Siano, M, Naik, N, Howden, RK & Mahal, L 1997, 'Low-temperature preparations of unimolecular nitroxide initiators for "living" free radical polymerizations', Macromolecules, vol. 30, no. 21, pp. 6445-6450.
Braslau, Rebecca ; Burrill, Leland C. ; Siano, Michael ; Naik, Neeta ; Howden, Rodney K. ; Mahal, Lara. / Low-temperature preparations of unimolecular nitroxide initiators for "living" free radical polymerizations. In: Macromolecules. 1997 ; Vol. 30, No. 21. pp. 6445-6450.
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