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Polyarylene Networks via Bergman Cyclopolymerization of Bis‐ ortho ‐diynyl Arenes
Author(s) -
Smith D. W.,
Shah H. V.,
Perera K. P. U.,
Perpall M. W.,
Babb D. A.,
Martin S. J.
Publication year - 2007
Publication title -
advanced functional materials
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 6.069
H-Index - 322
eISSN - 1616-3028
pISSN - 1616-301X
DOI - 10.1002/adfm.200600450
Subject(s) - materials science , monomer , glass transition , polymer chemistry , thermal stability , polymerization , polymer , curing (chemistry) , isothermal process , thin film , yield (engineering) , chemical engineering , composite material , nanotechnology , physics , engineering , thermodynamics
Bis‐ ortho ‐diynylarene (BODA) monomers, prepared from common bisphenols in three high yielding steps, undergo free‐radical‐mediated thermal polymerization via an initial Bergman cyclo‐rearrangement. Polymerization is carried out at 210 °C in solution or neat with large pre‐vitrification melt windows (4–5 h) to form branched oligomers containing reactive pendant and terminal aryldiynes. Melt‐ and solution‐processable oligomers with weight‐average molecular weight M w = 3000–24 000 g mol –1 can be coated as a thin film or molded using soft lithography techniques. Subsequent curing to 450 °C affords network polymers with no detectable glass transition temperatures below 400 °C and thermal stability ranging from 0.5–1.5 % h –1 isothermal weight loss measured at 450 °C under nitrogen. Heating to 900–1000 °C gives semiconductive glassy carbon in high yield. BODA monomer synthesis, network characterization and kinetics, processability, thin‐film photoluminescence, and thermal properties are described.