The radical polymerization of acrylonitrile was investigated in a Na₂S₂O₄ aqueous and CCl₄-toluene organic two-phase solution system using phase-transfer catalysts such as tricaprylmethylammonium chloride and tetrabutyl-ammonium chloride. 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 term of concentration of Q₊ and of S₂O₄^-2 in the aqueous solution, the square root concentration of CCl₄, and concentration of monomer. The rate of polymerization of acrylonitrile in the liquid-liquid heterogeneous system was presented with the polymerization mechanism by phase- transfer catalysts applied to that by conventional initiators.

Na₂S₂O₄ 수용액과 CCl₄-toluene 용액의 2상에서 유기상에 용해하는 tricaprylmethylammonium chloride 와 tetrabutylammonium chloride 상이동 촉매를 사용하여 단량체인 acrylonitrile (AN) 의 라디칼 중합반응에서 초기중합속도를 측정하여, 액-액 불균일계 접촉계면을 통한 중합반응기구를 해석하였다. AN의 중합속도는 수용액상에 존재하는 Q⁺ 이온의 농도와 S₂O₄^-2 이온의 농도가 결합된 항에 정비례하고, CCl₄ 농도의 제곱근과 AN의 농도에 각각 정비례하였다. 재래적인 개시제를 사용한 라디칼 중합반응기구에 상이동 촉매에 의한 반응기구를 적용한 액-액 불균일 2상계에서 AN의 중합반응속도식을 제시하였다.

Keywords: phase-transfer catalyst; radical polymerization