TY - JOUR
T1 - New Polymerization Reactions Using Germylenes
AU - Kobayashi, Shiro
AU - Shoda, Shin Ichiro
PY - 1994
Y1 - 1994
N2 - 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 (Mred) and an oxidant monomer (Mox). Oxidant monomers employed are p-benzo-quinones, N-phenyl-P~benzoquinone monoimines, cyclic α, β-unsaturated ketones, cyclic sulfides, and substituted acetylenes. During the copolymerization, the germylene is oxidized and an oxidant monomer is reduced (“oxidation-reduction copolymerization”). A new germanium-containing polymer having a dithiol unit in the main chain has been synthesized by the oxidative addition of poly (dithioalky-lene) toward the germylene. The reaction mechanism for the copolymerization between germylenes and p-benzoquinone derivatives has been definitely established as a biradical polymerization system involving a germyl radical and a semiquinone radical. This provides the first clear-cut evidence for a biradical mechanism in the polymerization chemistry. In addition, a ligand exchange polymerization has been found as a new concept in polymerization chemistry, which affords a polygermane of higher molecular weight.
AB - 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 (Mred) and an oxidant monomer (Mox). Oxidant monomers employed are p-benzo-quinones, N-phenyl-P~benzoquinone monoimines, cyclic α, β-unsaturated ketones, cyclic sulfides, and substituted acetylenes. During the copolymerization, the germylene is oxidized and an oxidant monomer is reduced (“oxidation-reduction copolymerization”). A new germanium-containing polymer having a dithiol unit in the main chain has been synthesized by the oxidative addition of poly (dithioalky-lene) toward the germylene. The reaction mechanism for the copolymerization between germylenes and p-benzoquinone derivatives has been definitely established as a biradical polymerization system involving a germyl radical and a semiquinone radical. This provides the first clear-cut evidence for a biradical mechanism in the polymerization chemistry. In addition, a ligand exchange polymerization has been found as a new concept in polymerization chemistry, which affords a polygermane of higher molecular weight.
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U2 - 10.1246/nikkashi.1994.280
DO - 10.1246/nikkashi.1994.280
M3 - Article
AN - SCOPUS:85016525274
VL - 1994
SP - 280
EP - 285
JO - Nippon Kagaku Kaishi / Chemical Society of Japan - Chemistry and Industrial Chemistry Journal
JF - Nippon Kagaku Kaishi / Chemical Society of Japan - Chemistry and Industrial Chemistry Journal
SN - 0369-4577
IS - 3
ER -