“Contribution to the Proceedings of the 22nd International Symposium on Chirality [ISCD 22]”
Regular Article/Contribution to the Proceedings of the 22nd International Symposium on Chirality [ISCD 22]
Asymmetric anionic polymerization of 2,7-bis(4-t-butylphenyl)fluoren-9-ylmethyl methacrylate and photoinduced structural transition of the obtained polymer†
Article first published online: 28 APR 2011
Copyright © 2011 Wiley Periodicals, Inc.
Special Issue: Proceedings from the 22nd International Symposium on Chirality, Sapporo, Japan, 2010
Volume 23, Issue 1E, pages E28–E34, 2011
How to Cite
Watanabe, K., Sakamoto, T. and Nakano, T. (2011), Asymmetric anionic polymerization of 2,7-bis(4-t-butylphenyl)fluoren-9-ylmethyl methacrylate and photoinduced structural transition of the obtained polymer. Chirality, 23: E28–E34. doi: 10.1002/chir.20953
- Issue published online: 24 OCT 2011
- Article first published online: 28 APR 2011
- Manuscript Accepted: 20 JAN 2011
- Manuscript Received: 29 NOV 2010
- MEXT. Grant Numbers: 21655037, 22350047
- The Global COE Program (MEXT). Grant Number: B01
- The Asahi Glass Foundation
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- π-stacked structure;
- CD spectrum;
- isomerization polymerization
2,7-Bis(4-t-butylphenyl)fluoren-9-ylmethyl methacrylate (BBPFMMA) was synthesized as a new candidate of a bulky monomer suitable for asymmetric anionic polymerization (IUPAC nomenclature: asymmetric helix-chirogenic polymerization) leading to a preferred-handed helical, optically active polymer. The new monomer was polymerized using the complex of 9-fluorenyllithium and (S)-(+)-1-(2-pyrrolidinylmethyl)pyrrolidine in toluene at −78°C. As opposed to the original intention to obtain a polymethacrylate, the monomer seemed to undergo structural transition (decomposition) giving 2,7-bis(4-t-butylphenyl)dibenzofulvene and the obtained polymer was most probably a terpolymer of BBPFMMA, 2,7-bis(4-t-butylphenyl)dibenzofulvene, and methacrylic acid. The obtained polymer showed circular dichroism (CD) spectra, indicating that chirality had been introduced to the copolymer chain during the course of polymerization. On photo irradiation, the polymer underwent a structural transition involving a remarkable decrease in apparent molecular weight measured by size-exclusion chromatography (SEC) and changes in FT-IR spectral patterns. However, the CD spectrum of the polymer was not obviously altered by irradiation, indicating that polymer chirality is not affected by light. Chirality, 2011. © 2011 Wiley Periodicals, Inc.