Synthesis and Application of Chiral Polymer ・ Supramolecule by Metathesis Polymerization

2005 Fiscal Year Final Research Report Summary

• Project/Area Number: 16550111
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Polymer chemistry
• Research Institution: Yamaguchi University
• Principal Investigator: ONIMURA Kenjiro Yamaguchi University, Faculty of Engineering, Associate Professor, 工学部, 助教授 (90284265)
• Co-Investigator(Kenkyū-buntansha): OISHI Tsutomu Yamaguchi University, Faculty of Engineering, Professor, 工学部, 教授 (30091169)
• Project Period (FY): 2004 – 2005
• Keywords: Metathesis Polymerization / Chiral / Polymer / Supramolecule / Transition Metal Catalyst

Research Abstract

Ring opening metathesis polymerizations (ROMP) of optically active (1R,2R)-N-substituted 1,2,3,6-tetrahydrophthalimide ((1R,2R)-RTPI) (R=benzyl (BnTPI), phenyl (PhTPI), 1-naphthyl (1-NTPI) were carried out using 1st Grubbs' ruthenium catalysts to obtain optically active polymers ([α]_<435>=-338.0°〜+52.0°). The improvement of polymeizability was attributed to the increase of strain on cyclohexene due to the neighboring rigid plane structure of a trans-imide ring. Poly((1R,2R)-BnTPI)s obtained with the 1st Grubbs catalyst (2.0,4.0 mol%) had much higher yield (〜82%) than polymers obtained with the Grubbs catalysts (1.0mol%). The number-average molecular weights (Mn) tended to decrease with increase in the 1st Grubbs catalyst. The GPC curves of poly((1R,2R)-BnTPI) monitored by polarimetric detection almost corresponded to those by UV detector. This suggests that chiroptical properties of the polymers are independent of the molecular weights. The circular dichroism (CD) spectrum of (1R,2R)-BnTPI exhibited a positive Cotton effect at 225〜250nm. On the other hand, the CD spectra of poly((1R,2R)-BnTPI)s showed a negative Cotton effect at 220〜235nm and a positive one at 235〜275nm.