新型负载配位催化剂ZBDPPEDAEPA/TiO_2/Pd催化羰化反应研究  

Carbonylation of Benzyl Chloride Catalysed by a New Type Palladium Catalyst ZBDPPEDAEPA/TiO_2/Pd

作　　者：陈文山[1] 傅相锴[1] 马学兵[1] 李龙芹[1] 陈静蓉[1] 

机构地区：[1]西南师范大学应用化学研究所

出　　处：《分子催化》2001年第6期447-450,共4页Journal of Molecular Catalysis(China)

基　　金：重庆市重点攻关项目

摘　　要：用乙二胺 - N’-乙基膦酸的氨基与季　盐 [Ph2 P+ (CH2 OH) 2 ]Cl- ,经曼尼希反应合成了 N ,N -双二苯膦甲基 -乙二胺 - N’-乙基膦酸 (Ph2 PCH2 ) 2 NCH2 CH2 N+ H2 CH2 CH2 PO3H- (BDPPEDAEPA) ,并制备了相应的 (N,N-双二苯膦甲基 -乙二胺 - N’-乙基膦酸 -磷酸氢 )锆载体 Zr(HPO4) 1 .3 5[(Ph2 PCH2 ) 2 NCH2 CH2 NHCH2 CH2 PO3]0 .6 5· H2 O(ZBDPPEDAEPA)及二氧化钛和二氧化锆微粉表面包膜了 ZBDPPEDAEPA的新型催化剂载体 ZBDPPEDAEPA/Ti O2 、 ZBDPPEDAEPA/Zr O2 和相应的钯催化剂 ZBDPPEDAEPA /Pd、 ZBDPPEDAEPA /Ti O2 /Pd、ZBDPPEDAEPA/Zr O2 /Pd.在常压条件下 ,对该类催化剂催化氯苄羰化反应的活性及产物组成作了初步考察 .对催化剂载体的粒径分析表明 ,ZBDPPEDAEPA/Ti O2 /Pd的高活性归因于 ZBDPPEDAEPA/Ti O2 载体的颗粒均匀、平均粒径小 .ZBDPPEDAEPA以平均 5 0 nm的薄层包膜在 Ti O2 上 。N,N\|bis(diphenylphosphinomethyl)\|ethylenediamine\|N'\|ethylphosphonic\} acid \{(Ph\-2PCH\-2)\-2N\|\}CH\-2CH\-2N\++H\-2CH\-2CH\-2PO\-3H\+-(BDPPEDAEPA) was synthesized with good yield by means of Mannich reaction with ethylenediamine\|N\|ethylphosphonic acid H\-2NCH\-2CH\-2N\++H\-2CH\-2CH\-2PO\-3H\+- and bis\|(hydroxymethyl)diphenylphosphonium chloride [Ph\-2P\++(CH\-2OH)\-2]Cl\+- under mild conditions. The new type of catalyst supports, zirconium [N,N\|bis(diphenylphosphinomethyl)\|ethylenediamine\|N'\|ethylphosphonate\|phosphate] Zr(HPO\-4) 1.35 [(Ph\-2PCH\-2)\-2NCH\-2CH\-2NHCH\-2CH\-2PO\-3] 0.65 ·H\-2O (ZBDPPEDAEPA), ZBDPPEDAEPA/TiO\-2 and ZBDPPEDAEPA/ZrO\-2, in which a layer of ZBDPPEDAEPA is coated on TiO\-2 and ZrO\-2 powder, respectively, and their corresponding palladium catalysts ZBDPPEDAEPA/Pd, ZBDPPEDAEPA/TiO\-2/Pd, ZBDPPEDAEPA/ZrO\-2/Pd were prepared. The carbonylation activities of benzyl chloride catalyzed with these catalysts under atomespheric pressure and the composition of reaction products were studied preliminarily. The results of grading analysis of the prepared catalyst supports demonstrate that the high catalytic activity of ZBDPPEDAEPA / TiO\-2 / Pd can be attributed to the small and relatively even particle sizes of the ZBDPPEDAEPA / TiO\-2 support. The average thickness of the coating layer of ZBDPPEDAEPA on TiO\-2 powder is about 50 nm, which can be considerd as a nanometer catalytic material.

关 键 词：羰化反应 N N-双二苯甲基-乙二胺-N'-乙基膦酸-磷酸氢)锆 钯 负载配位催化剂 二氧化钛 ZBDPPEDAEPA 

分 类 号：O621.251[理学—有机化学] O643.36[理学—化学]