Polyarylene Networks via Bergman Cyclopolymerization of Bis‐ortho‐diynyl Arenes
Abstract
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 Mw = 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.
Document Details
- Document Type
- Pub Defense Publication
- Publication Date
- Apr 18, 2007
- Source ID
- 10.1002/adfm.200600450
Entities
People
- D. A. Babb
- D. W. Smith Jr.
- H. V. Shah
- K. P. U. Perera
- M. W. Perpall
- S. J. Martin
Organizations
- American Chemical Society
- American Chemical Society Petroleum Research Fund
- Army Research Office
- National Science Foundation