摘要
研制了异丙苯氧化制取二甲基苄醇及过氧化异丙苯的负载型金属卟啉催化剂。其活性及选择性均较高,且易回收。金属卟啉类的活性顺序为:Cu>Co>Mn>Fe>Cr>Pd>Ni。卟啉环的中位苯基上的供电子基团有利于催化活性的提高。铜卟啉负载于不同载体的活性顺序为TiO_2>γ-Al_2O_3>聚苯乙烯(交联)>D261阴离子交换树脂>无载体(均相)。加入有机含氮碱配位体可使铜卟啉活性进一步提高,并降低其他金属卟啉的活性。催化剂经十余次运转后活性下降约20％,此后无进一步明显下降。
Six porphyrins functionalized tetraphenyporphine 5-(4-hydroxyphenyl)-10, 15, 20-tri 4-neth oxyphenyl) porphine, meso-tetra (4-methoxyphenyl) porphine, meso-tetra (sulfophenyl) porphine and its sodium sulfonate, 5-(4-hydroxyphenyl)-10, 15,20—triphenyl porphine and meso-tetra (4-aminophenyl) porphine were synthesized. Metalloporphyrins were prepared by reaction of those porphyrins with acetate or chloride of Cu,Co,Fe,Mn, Cr etc. Metalloporphyrins were supported on titanium dioxide, γ-alumlna, chloromethylated polystyrene and anion exchange resin (D261) respectively.The supported metalloporphyrins efficiently catalyzed the oxidation of eumene to cumyl hydroperoxide and cumyl alcohol at 30℃ under arm pressure of O_2. The initial rates of the catalytic oxidation was found to be of first order with respect to cumene and frist order to dioxygen. A possible mechanism involving activation of dioxygen was proposed. The activity of catalysts on different supporters is TiO_2>γ-Al_2O_3>polystyrene>D261>coresponding homogeneous catalysts, for substituent rings NH_2>OCH_3>H>SO_8^-, for central metal ions Cu>Co>Mn>Fe>Cr>Pd>Ni. Addition of nitrogen base decrease the catalytic activity except supported copper porphyrins
出处
《工业催化》
CAS
1993年第2期37-41,共5页
Industrial Catalysis
基金
湖北省自然科学基金
关键词
金属卟啉
异内苯
氧化
催化剂
metalloporphyrins, supported catalyst, cumene, cumyl hydroperoxide
