Article

Anionic Polymerization Chemistry of Epoxides: Electron-Transfer Processes

  1. Roderic P. Quirk,
  2. Deanna L. Pickel,
  3. Hiroaki Hasegawa

Article first published online: 20 JUN 2005

DOI: 10.1002/masy.200550807

Issue

Macromolecular Symposia

Macromolecular Symposia

Special Issue: Polymer Chemistry, Reactions and Processes

Volume 226, Issue 1, pages 69–78, May 2005

Additional Information

How to Cite

Quirk, R. P., Pickel, D. L. and Hasegawa, H. (2005), Anionic Polymerization Chemistry of Epoxides: Electron-Transfer Processes. Macromol. Symp., 226: 69–78. doi: 10.1002/masy.200550807

Author Information

  1. Maurice Morton Institute of Polymer Science, The University of Akron, Akron, Ohio 44325-3909, USA, Fax: (+1) 330-972-7510

Publication History

  1. Issue published online: 20 JUN 2005
  2. Article first published online: 20 JUN 2005

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Keywords:

  • anionic polymerization;
  • 1,1-diphenylethylene oxide;
  • electron-transfer;
  • functionalization of polymers;
  • poly(styryl)lithium;
  • styrene oxide

Abstract

The reaction of poly(styryl)lithium (PSLi) with styrene oxide (SO) in benzene solution has been investigated. In addition to the functionalized polymer (83.5 wt %) the product mixture consisted of unfunctionalized polymer (9 wt %) and a dimeric product (5.6 wt %). The structure of the dimeric product was determined to be the head-to-head dimer. The regiochemistry of the addition reaction was unselective: 53 mol % addition to the methylene carbon and 47 mol % corresponding to addition to the hindered, methine carbon. Based on the formation of the dimer and the lack of regioselectivity, a pathway involving electron transfer from PSLi to SO was proposed. To further investigate the propensity to react via this electron-transfer mechanism, the SO functionalization of the adduct of PSLi with 1,1-diphenylethylene was investigated as well as the functionalization of PSLi with 1,1-diphenylethylene oxide.

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