高分子担载水杨醛希夫碱钴配合物催化分子氧氧化环己烯性能研究  

Aerobic Oxidation of Cyclohexene Catalyzed by Polymer-bound Schiff-base Cobalt Complex

作　　者：段宗范[1] 王荣民[1] 何玉凤[1] 谢云涛[1] 王云普[1] 夏春谷[2] 

机构地区：[1]甘肃省高分子材料重点实验室西北师范大学高分子研究所,甘肃兰州730070 [2]中国科学院兰州化学物理研究所羰基合成与选择氧化国家重点实验室,甘肃兰州730000

出　　处：《分子催化》2005年第5期383-387,共5页Journal of Molecular Catalysis(China)

基　　金：国家自然科学基金(20274034;29933050);甘肃省中青年自然科学基金(031-A21-006)

摘　　要：合成了聚苯乙烯担载的酪氨酸水杨醛希夫碱钴配合物,并研究了该高分子金属配合物对分子氧氧化环己烯的催化性能.探讨了反应温度、添加剂及反应时间对环己烯转化率和产物选择性的影响.结果表明,70℃时,以微量醋酸为添加剂,在催化剂的催化作用下,以常压氧气氧化环己烯,得到烯丙基位的氧化产物环己烯醇、环己烯酮和中间产物环己烯过氧化氢.催化剂经五次循环使用仍具有较高的催化活性.环己烯在该高分子配合物作用下的催化氧化遵循一个自由基反应历程,与经典的Haber-Weiss历程相一致.The schiff-base cobalt complex derived from tyrosine and salicylaldehyde was successfully supported on the macroporous cross-linked resin of polystyrene and obtained a new polymer-bound salen schiff base complex. This polymer catalyst was used in the aerobic oxidation of cyclohexene under mild conditions. The effects of temperature, additives and reaction time on the catalytic activity and product selectivity had also been investigated. The results indicated the allyl carbon of cyclohexene was catalytically oxidized by molecular oxygen at atmospheric pressure in the presence of the polymer complex and a trace of HOAc at 70℃, which afforded corresponding alcohol, ketone and hydroperoxide acting as intermediate. In addition, the catalytic activity is remained after being recycled 5 times. Mechanism of oxidation is a free radical reaction pathway, which is in accordance with classic Haber-Weiss radical-chain mechanism.

关 键 词：希夫碱配合物 高分子担载催化剂 催化氧化 分子氧 机理 

分 类 号：O643.32[理学—物理化学]