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Precise architecture of 1:1 alternating copolymers between germylenes and p ‐benzoquinone derivatives: First clear‐ cut evidence of biradical mechanism in polymerization chemistry
Author(s) -
Kobayashi Shiro,
Iwata Satoru,
Shoda ShinIchiro
Publication year - 1994
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.19940770126
Subject(s) - copolymer , benzoquinone , semiquinone , polymer chemistry , chemistry , hydroquinone , substituent , amide , polymerization , polymer , photochemistry , side chain , quinone , organic chemistry
Germylenes bearing a bulky amide substituent have been copolymerized with various p ‐benzoquinone derivatives without any added catalyst to give novel class of germanium‐containing polymers having a tetravalent germanium unit and a p ‐hydroquinone unit alternatingly in the main chain (“oxidation‐reduction alternating copolymerization”). The resulting copolymers have high molecular weight (Mw>5.5×10 4 ) and are soluble in common organic solvents. A novel biradical mechanism involving a germyl radical and a semiquinone radical is proposed on the basis of ESR analysis of the propagating polymer end as well as trapping experiments using a disulfide or TEMPO radical.