(NH4)2S2O8수용액과 toluene 용액의 2상에서 유기상에 용해하는 Hexadecyltrimethylammonium bromide 상이동촉매를 사용하여 단량체인 acrylonitrile(AN)의 라디칼 중합반응에서 초기중합속도와 상이동촉매의 분배계수 및 평형상수를 측정하여, 액-액 불균일계 접촉계면을 통한 중합반응기구를 해석하였다. AN의 중합속도는 수용액상에 존재하는 4급암모니움 이온의 농도와 S2O8-2 이온의 농도가 결합된 항에 정비례하고, AN의 농도에 정비례하였다. 재래적인 개시제를 사용한 라디칼 중합반응기구에 상이동촉매에 의한 반응기구를 적용하여 액-액 불균일 2상계에서 AN의 중합반응속도식을 해석하였다.
The phase-transfer polymerization of acrylonitrile system was investigated in a (NH4)2S2O8 aqueous-organic two-phase system with hexadecyltrimethylammonium bromide. The observed initial rates of polymerization were compared with those obtained from the polymerization mechanism proposed with a cyclic phase-transfer initiation step. The rate of polymerization was found to be proportional to the combined terms of concentrations of quaternary ammonium ion and S2O8-2 in the aqueous solution, and concentration of monomer. The rate of polymerization of acrylonitrile in the liquid-liquid heterogeneous system was interpreted with the polymerization mechanism by phase transfer catalyst applied to that by conventional initiators.
[References]
Weber WP, Gokel GW, "Phase Transfer Catalysis in Organic Synthesis," Springer-Verlag, New York, 1977
Starks CM, Liotta C, "Phase Transfer Catalysis-Principles and Techniques," Academic Press, New York, 1978