화학공학소재연구정보센터
Polymer(Korea), Vol.8, No.6, 425-429, December, 1984
폴리비닐아민유도체-구리(II)착물에 의한 비닐중합
Vinyl Polymerization by Polyvinylamine Derivative-Copper(II) Complexes
초록
사염화탄소존재하에 폴리비닐아민유도체-구리(II)합물에 의해 개시되는 메틸메타크릴레이트 및 아크릴로니트릴의 중합을 검토하였다. 폴리비닐아민유도체는 메틸화도 45%(I) 및 62%(II)정도가 되는 부분적으로 N-메틸화된 폴리비닐아민을 사용하였고 또한 폴리비닐아민도 비교를 위해 사용하였다. 두 종류의 단량체의 중합에 대한 폴리비닐아민유도체합물의 활성은 폴리비닐아민합물의 활성보다 컸다. 또한 메틸메타크릴레이트 중합의 활성화에너지는 폴리비닐아민합물보다 폴리비닐아민유도체합물이 컸다. 이들 결과는 메틸기의 입체장애로 인해 폴리비닐아민유도체합물과 폴리비닐아민합물사이에 불안정성의 차이에 기인될 수 있다. 메틸메타크릴레이트의 중합에 대한 폴리비닐아민유도체(II)합물의 활성은 폴리비닐아민유도체(I)합물의 활성보다 작았다. 이것은 폴리비닐아민유도체의 아미노기의 수소에 관계될지 모른다.
The polymerization of methylmethacrylate and acrylonitrile initiated by copper(II) complexes was studied in the presence of carbon tetrachloride. The polyvinylamine derivative(I) and (II) which have about 45 and 62 percent degree of the N-methylation were used as ligands and also polyvinylamine itself was used for comparison. The activity of the substituted amino complexes for the polymerizations of the monomers was found to be higher than that of the amine complex. The apparent activation energy of the polymerization of methylmethacrylate initiated by the substituted amine complexes was higher than that of the polymerization of methylmethacrylate initiated by the amine complex. These results can be attributed to the difference in instability between the complexes formed with different amines due to the steric hindrance extended by methyl group. The activity of the methylated amino(II) complex for the polymerization of methylmethacrylate was rather lower than that of the methylated amine(I) complex. This result may be due to the presence of hydrogen of amino groups.