Polymer(Korea), Vol.16, No.5, 597-603, September, 1992
전이금속촉매에 의한 2-프로핀-1-올의 중합
Polymerization of 2-Propyn-1-ol by Transition Metal Catalysts
초록
Mo- 및 W-계 촉매를 사용하여 히드록기 관능기가 있는 프로파길유도체인 2-프로핀-1-올의 중합에 대해서 연구하였다. MoCl5계 촉매의 활성이 WCl6계의 그것보다 훨씬 큰 것으로 밝혀졌으며, MoCl5-EtAlCl2 촉매 System의 경우 거의 정량적인 수율을 보였다. 본 중합은 클로로벤젠, 사염화 탄소, 1,1,2-트리클로로에틸렌과 같은 방향족 및 할로겐화 탄화수소용매에서 잘 진행되었으며 중합수율은 중합온도가 증가할수록 철저히 증가하였다. 전이금속알콜사이드인 Mo(OEt)5 및 Mo(OEt)5-EtAlCl2 촉매계를 본 중합에 사용해 본 결과 약 50% 내외의 중합수율을 보여주었다. 합성한 폴리(2-프로핀-1-올)의 적외선분광스펙트럼에서는 아세틸렌의 ≡C-H 및 C≡C 신축띠를 보여주지 않는 대신 1650cm-1 부근에서의 탄소-탄소 이중결합의 특성 피이크가 관찰되었다. 폴리(2-프로핀-1-올)은 사용한 촉매나 조건에 관계없이 유기용매에 녹지 않았으며 대부분 검은색의 분말상이였다.
The polymerization of 2-propyn-1-ol, a propargyl derivative having hydroxy functional group was carried out by various Mo-and W-based catalysts. The catalytic activities of MoCl5-based catalysts were found to be greater than those of WCl6-based catalysts. MoCl5-EtAlCl2 catalyst system gave a quantitative yield of polymer. The polymerization was well proceeded in aromatic and halogenated hydrocarbon solvents such as chlorobenzene, CCl4, 1,1,2-trichloroethylene etc. The polymer yield was increased as the polymerization temperature is increased. Mo(OEt)5 and Mo(OEt)5-EtAlCl2 catalyst systems gave some moderate polymer yields. The infrared spectra of the resulting poly(2-propyn-1-ol) showed neither the acetylenic hydrogen stretching nor the carbon-carbon triple bond stretching frequency. Instead, a new carbon-carbon double bond stretching frequency at about 1650cm-1 appeared, which indicates that the highly conjugated polymer was formed. The resulting poly (2-propyn-1-ol)s were black powder and mostly insoluble in any organic solvents regardless of the catalysts and the polymerization conditions used.
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