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过氧化月桂酰(1)在苯中50℃分解的主要产物经鉴定为廿二烷、十一烷(烯)、正十二酸十一酯、十二酸及十一烷基苯等。其中廿二烷及酯的生成量不受1的起始浓度的变化及加入的捕获剂galvinoxyl(2)的影响,表明为笼反应产物。十一烷、十二酸及十一烷基苯的生成量随1的起始浓度的变化而有不同程度的变化。加入2后十一烷的量显著减少;十一烷基苯基本消失。有2存在时,1在苯中分解而得到的捕获产物经水解后生成3,5—二叔厂基—4—羟基苯甲醛(3)和2,6—二叔丁基—4—十一烷基苯酚(4)。这些结果表明,诱导分解由十一烷基对溶剂分子加成而形成的十一烷基环己二烯自由基所引起,该自由基的偶合和歧化为主要链终止方式。结合动力学实验结果,提出1在苯中分解反应的机理。
The main products of lauroyl peroxide (1) decomposed at 50 ℃ in benzene have been identified as dodecane, undecane, undecyl undecanoate, dodecanoic acid and undecylbenzene. Among them, the yield of n-dodecane and ester was not affected by the initial concentration of 1 and the effect of added galvinoxyl (2), which was the cage reaction product. The yields of undecane, dodecanoic acid and undecylbenzene varied with the initial concentration of 1. The amount of undecane added after 2 significantly decreased; undecyl benzene disappeared. In the presence of 2, the capture product obtained after the decomposition of 1 in benzene is hydrolyzed to give 3,5-di-tert-butyl-4-hydroxybenzaldehyde (3) and 2,6- Alkylphenols (4). These results indicate that the coupling and disproportionation of the free radical as the main chain termination mode is induced by the induced decomposition of undecylcyclohexadiene radicals formed by the addition of undecane to solvent molecules. Combined with the kinetic experimental results, the mechanism of 1 decomposition reaction in benzene is proposed.