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Novel polymerizations of germylenes and their reaction mechanisms
Author(s) -
Kobayashi Shiro,
Shoda ShinIchiro,
Iwata Satoru,
Hiraishi Masafumi,
Cao Shaokui
Publication year - 1995
Publication title -
macromolecular symposia
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.257
H-Index - 76
eISSN - 1521-3900
pISSN - 1022-1360
DOI - 10.1002/masy.19950980108
Subject(s) - polymerization , chemistry , germanium , copolymer , polymer chemistry , photochemistry , semiquinone , monomer , polymer , benzoquinone , redox , divalent , organic chemistry , silicon
Novel copolymerizations for the synthesis of germanium‐containing polymers using a divalent germanium species, germylene, have been developed. The copolymerization involves a redox process between a germylene ( M red ) and an oxidant monomer ( M ox ) such as p ‐benzoquinones, cyclic α,β‐unsaturated ketones, and substituted acetylenes. A new germanium‐containing polymer having a germanium‐sulfur bond unit in the main chain has been synthesized by the oxidative addition of a poly(dithioalkylene) toward the germylene. A ligand exchange polymerization has been developed as a new polymerization reaction affording a polygermane. The reaction mechanism of the copolymerization between germylene and p ‐benzoquinone derivatives has definitely been established as a biradical polymerization system involving a germyl radical and a semiquinone radical, providing the first clear‐cut evidence for a biradical mechanism in the polymerization chemistry.