Synthesis and Application of Chiral Polymer ・ Supramolecule by Metathesis Polymerization

Research Project

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
Project Status	Completed (Fiscal Year 2005)
Budget Amount *help	¥3,200,000 (Direct Cost: ¥3,200,000) Fiscal Year 2005: ¥800,000 (Direct Cost: ¥800,000) Fiscal Year 2004: ¥2,400,000 (Direct Cost: ¥2,400,000)
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.