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Journal of the Korean Chemical Society (JKCS)

ISSN 1017-2548(Print)
ISSN 2234-8530(Online)
Volume 22, Number 6
JKCSEZ 22(6)
December 20, 1978 

The Initiation Mechanism in the Polymerization of Trioxane with Titanium Tetrachloride

TiCl4에 의한 Trioxane의 양이온 중합에 있어서 개시 반응기구
Man Jung Han

트리옥산을 니트로벤젠 용매중에서 TiCl4로서 중합시킬때 개시 반응기구를 연구하였다. 중합반응속도를 측정한결과 미량의 물이나 메탄올을 첨가하면 반응속도가 급격히 감소하였으며 중합을 개시하는 데는 조촉매로서 다른 물질이 필요 없음이 알려졌다. 유전상수 측정결과에 의하면 중합과정중 양성이온이 생기지 않으며 중합제나 개시제 용액의 전기전도도를 측정한 결과 개시 반응은 니트로벤젠 용매중에서 개시제가 동종간 주고 받기반응에 의하여 생긴 TiCl3+ 양이온에 의하여 일어난다는 것이 판명되었다.

The initiation mechanism of trioxane polymerization catalyzed by TiCl4 in nitrobenzene was investigated. The kinetic studies revealed that the rate of polymerization was drastically decreased by the addition of a minute amount of water or methanol. A third substance as cocatalyst was not required for the polymerization. Measurements of dielectric constants gave no evidence for the zwitterionic mechanism of the polymerization. The electric conductivity measurements of polymerization system and the initiator solution showed that the initiation was started by TiCl3+ cation, formed by a disproportionation of the initiator in nitrobenzene.

423 - 430
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