A Novel Redox Process for the Construction of Germanium-Containing Polymers by Utilizing Germylenes and p-Benzoquinone Derivatives: First Clear-Cut Evidence for a Biradical Propagation Mechanism in Polymerization Chemistry

Shiro Kobayashi, Satoru Iwata, Mitsunori Abe, Shinichiro Shoda

Research output: Contribution to journalArticlepeer-review

38 Citations (Scopus)

Abstract

Germylenes bearing bulky amide groups have been copolymerized with various p-benzoquinone derivatives without any added catalyst to give a novel class of germanium-containing polymers having a tetravalent germanium unit and a p-hydroquinone unit altematingly in the main chain. During the copolymerization, the germylene (reductant monomer) is oxidized and the p-benzoquinone derivative (oxidant monomer) is reduced (“oxidation—reduction copolymerization”). The resulting copolymers have high molecular weight (Mw; from 2.0 x 104up to 1.4 x 106) and most of them are soluble in common organic solvents. ESR studies of the copolymerization system and of the model reactions including the structural elucidation of the products gave the first clear-cut evidence for a biradical mechanism involving a germyl radical and a semiquinone radical Trapping experiments using a disulfide, tetramethylpiperidinyloxy (TEMPO) radical, and a sterically hindered p-benzoquinone derivative further supported the biradical structure of the propagating polymer ends.

Original languageEnglish
Pages (from-to)2187-2200
Number of pages14
JournalJournal of the American Chemical Society
Volume117
Issue number8
DOIs
Publication statusPublished - 1995 Jan 1

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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