Abstract: A brief study on the effect of addition of cumene hydroperoxide (II, CHP, in text) without or with simultaneous addition of an alkaline additive (sodium carbonate or calcium oxide) on the reduction of the induction period in the autoxidation of cumene (I) showed that the heterogeniety inherent in the latter systems resulted in poor reproducibility. Sodiumsalt of cumene hydroperoxide (III) was introduced as an oilsoluble system in which the initiator and the alkaline additive are in combination. Experiments with various amounts of III at 110° 120°and 130°that the induction period and the autocatalysis were either completely or practically eliminated. The reproducibility of the experiments accompanying the use of III was extremely good. The rate of accumulation of II was 16±0.7% (wt.)/hr. at. 130° at 120° the rate was 8.7%/hr. except when the amount of III was 3.33% (7.3%/hr.); at 110° the rate varies more pronouncedly with the amount of III (3.0-5.0%/hr.). Oxygen-absorption in a closed system was observed in order to examine more closely the phenomena of the elimination of the induction period. It was found that a rapid absorption of oxygen took place in the first minutes, followed by a somewhat slower absorption. Kharaschs conceptions on the alkaline catalyzed decomposition of II and the subsequent, reactions between the resulting dimethylphenylcarbinol and II, yielding free radicals, were considered to be adequate in explaining the instantaneous initiation of the reaction chain. Water of crystallization in II facilitates the ionic reaction. Addition of solid sodium hydroxide also caused a rapid initial oxygen absorption, only that a very brief induction period was observed. This is thought to follow the same course of reaction as outlined above, with traces of II in I participating. The efficiency of the autoxidation of I with respect to II-accumulation when III was used was found to be 92-97%. The use of cobalt stearate in promoting the rate of autoxidation of I was investigated. At 110°, addition of the cobalt-salt indeed increased the initial rate of accumulation of II (11.5-12.5%/hr.), yet the same mechanism that induced the reaction chain and subsequently brought about the faster rate of reaction prevented the accumulation of II (25%) to a higher degree. The destruction of II by cobalt ions was evidenced by the fact that, with the highest concentration of cobalt-salt used, there was actually no accumulation of II.at the beginning of the reaction. Addition of II together with cobalt-salt did not further promote the reaction. It is concluded that traces of II in I was sufficient to be responsible for the chain-initiation processes. The lower accumulation of II with use of cobalt-salt was remedied by simultaneously adding III. The result was that the rate of accumulation of II at 110°?corresponded to that at 130?with addition of II or III alone. The degree of accumulation of II was also high (40%).

摘要： 初步观察了在异丙苯（Ⅰ）自动氧化为异丙苯过氧化氢（Ⅱ）中仅加入异丙苯过氧化氢作为引发剂及同时加入硷性添加剂碳酸钠或氧化钙对缩短或消除诱导期及对Ⅱ累积速率的影响。由于在上述体系中固体硷性剂的悬浮性使反应不易重复,引用了油溶性的异丙苯过氧化氢钠盐（Ⅲ）作为引发剂-硷性剂二者合而为一的体系,用不同加入量,在110°、120°及130℃进行试验,发现诱导期及自动催化期完全或基本上消除,反应极易重复。Ⅱ的累积较在前述情况下的为佳。 在用密闭系统吸氧法进一步研究有Ⅲ存在下的诱导期消失情况时,发现在氧化开始最初几分钟内有快速吸氧现象。认为这是硷与Ⅱ作用引发了氧化链。仅仅加入氢氧化钠也同样产生起始快速吸氧现象,这应是Ⅰ中存在的微量Ⅱ所引起的。在使用Ⅲ情况下的氧化效率求出为92—97%。 迸行了在110°的Ⅰ自动氧化中加入硬酯酸钴的催化效应的研究,消除了诱导期。虽然起始累积速率提高了,但是由于钴盐对Ⅱ的分解,Ⅱ的累积程度不高。同时加入少量Ⅱ并不更加提高起始的累积速率,显然Ⅰ中已有的微量Ⅱ已足够担负与钴盐作用引起反应链。同时加入钴盐和Ⅲ大大提高了Ⅱ的累积速率,相当于仅加Ⅱ或Ⅲ时在130°的累积速率。累积程度亦可达40%。可供工业上考虑采用。