Abstract
Three hexayne derivatives with different end groups—that is, 10,12,14,16,18,20-triacontahexayne-1,30-diol (1) and its diphenylurethane (2) and diphenylester (3)—were synthesized, and their solid-state polymerization behaviors were investigated. All three monomers were thermally polymerizable. Polymers from 1 and 2 showed an absorption maximum at about 730 nm, indicating that linear polydiacetylenes (PDAs) with octatetraynyl substituents were synthesized. However, broad absorption bands in the near-infrared region were only observed for 2 at 980 and 860 nm, indicating that regular polymerization occurred in 2 to give ladder-type PDA. On the other hand, a polymer from 3 showed a visible absorption increase but no clear absorption maximum. It was estimated that intermolecular hydrogen bonding between hexayne monomers helps to form polymerizable stacks in 1 and 2. In particular, urethane groups are more effective, and 2 showed the highest reactivity in this study with an ordered interlayer structure even after a two-step solid-state polymerization to give ladder-type PDA.
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Acknowledgements
We thank Prof Akihiko Kanazawa and his laboratory members for their cooperation with powder XRD measurements. This study was partially supported by a Grant-in-Aid for Scientific Research on Priority Areas (no. 446) from the Ministry of Education, Culture, Sports, Science and Technology.
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Inayama, S., Tatewaki, Y. & Okada, S. Solid-state polymerization of conjugated hexayne derivatives with different end groups. Polym J 42, 201–207 (2010). https://doi.org/10.1038/pj.2009.326
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DOI: https://doi.org/10.1038/pj.2009.326
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