Characteristics of Ring-Opening Isomerization Polymerization of [4.3.0] Cyclic Pseudoureas

The ring-opening isomerization polymerization behavior of 2,5,6,7-tetrahydro-3H-imidazo[2,1-b] [1,3] oxazine(TII) has been studied under various conditions. The present study aimed at improving the low polymerizability of the above monomer (six-membered ring) up to a level comparable to that of 2,5,6-tetrahydroimidazo[2,1-b] [l,3] oxazole(TIO) (five-membered ring). The optimum result could be observed when methyl trifluoromethanesulfonate(MeOTf) and nitrobenzene were used as an initiator and a solvent in the polymerization at $60^{\circ}C$ for 24 h. Polymers were confirmed by$^1H$ NMR과$^{13}C$ NMR, and m measurements. The molecular weight obtained by gel permeation chromatography (GPC) corresponded to the molecular weight theoretically calculated from the feed ratio. The melting temperature ($T_m$) of TII was conspicuously different from that of TIO, because of the difference in the alkyl group.

[4.3.0] 환상 유사 우레아의 이성화 개환중합과 특성평가

5원환의 2,3,5,6-tetrahydroimidazo[2,1-b] [1,3] oxazole(TIO)와 비교하여 6원환인 2,5,6,7-tetrahydro-3H-imidazo[2,1-b] [1,3] oxazine(TII)가 중합반응성이 낮은 결점을 개선하고자 각종의 조건하에서 중합을 실시한 결과, 최적의 중합조건으로 methyl trifluoromethanesulfonate(MeOTf)을 개시제로 사용한, 극성이 높은 니트로벤젠 용매의 $60^{\circ}C$에서 24시간 반응시킴에 의해 고수율의 중합체를 얻었다. 생성된 중합체를 $^1H$ NMR과$^{13}C$ NMR, IR 스펙트럼으로 분석하였으며, GPC로부터 구한 분자량과 이론분자량이 거의 일치함도 확인하였으며, 융점($T_m$)은 알킬 그룹의 길이에 따라 큰 차이를 나타내었다.