Novel Dinitroxide Mediating Agent for Stable Free-Radical Polymerization

Jeremy R. Lizotte, Sara G. Anderson, Timothy Edward Long

Research output: Contribution to journalArticle

18 Citations (Scopus)

Abstract

A novel dinitroxide mediating agent that was suitable for stable free-radical polymerization was synthesized and used in the block copolymerization of styrene and t-butyl styrene. Quantitative yields of a novel dinitroxide based on 1,6-hexamethylene diisocyanate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinyloxy were obtained. Various experimental parameters, including the nitroxide-to-initiator molar ratio, were examined, and it was determined that the polymerization was most controlled under conditions similar to those of conventional 2,2,6,6-tetramethyl-1-piperidi-nyloxy-mediated stable free-radical polymerization. Moreover, the dinitroxide mediator proved to be a viable route for the facile two-step synthesis of triblock copolymers of styrene and t-butyl styrene. However, the dinitroxide mediation process resulted in a higher than expected level of nitroxide decomposition, which resulted in polymers possessing a terminal alkoxyamine and an adjacent hydroxylamine rather than a preferred internal bisalkoxyamine. This decomposition resulted in the formation of diblock copolymer species during the triblock copolymer synthesis. Gel permeation chromatography was used to monitor the chain-end decomposition kinetics, and the determined observed rate constant (5.89 × 10 -5s-1) for decomposition agreed well with previous studies for other dinitroxide mediating agents.

Original languageEnglish
Pages (from-to)1547-1556
Number of pages10
JournalJournal of Polymer Science, Part A: Polymer Chemistry
Volume42
Issue number7
DOIs
Publication statusPublished - 2004 Apr 1
Externally publishedYes

Fingerprint

Free radical polymerization
Styrene
Block copolymers
Decomposition
Hydroxylamine
Gel permeation chromatography
Copolymerization
Rate constants
Polymers
Polymerization
Kinetics

Keywords

  • Block copolymers
  • Gel permeation chromatography (GPC)
  • Radical polymerization

ASJC Scopus subject areas

  • Polymers and Plastics
  • Organic Chemistry
  • Materials Chemistry

Cite this

Novel Dinitroxide Mediating Agent for Stable Free-Radical Polymerization. / Lizotte, Jeremy R.; Anderson, Sara G.; Long, Timothy Edward.

In: Journal of Polymer Science, Part A: Polymer Chemistry, Vol. 42, No. 7, 01.04.2004, p. 1547-1556.

Research output: Contribution to journalArticle

Lizotte, Jeremy R. ; Anderson, Sara G. ; Long, Timothy Edward. / Novel Dinitroxide Mediating Agent for Stable Free-Radical Polymerization. In: Journal of Polymer Science, Part A: Polymer Chemistry. 2004 ; Vol. 42, No. 7. pp. 1547-1556.
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