磷钨反应控制相转移催化剂的制备及表征  

Synthesis and Characterization of the Phosphotungstic Reaction-controlled Phase-transfer Catalyst

作　　者：翁志焕[1] 王锦艳[1] 蹇锡高[1] 

机构地区：[1]大连理工大学高分子材料系辽宁省高性能树脂工程技术研究中心,大连116012

出　　处：《化学学报》2008年第3期371-375,共5页Acta Chimica Sinica

基　　金：国家863高技术研究发展计划(No.2003AA33G030)资助项目

摘　　要：制备了三缺位Keggin型反应控制相转移催化剂[C7H7(CH3)3N]9PW9O34(记为Q9PW9),利用FT-IR,31PNMR,XRD和TG对催化剂进行了表征,并确定了反应的催化活性中心.分析结果表明,催化剂Q9PW9在反应后其结构仍然得到了较好的保持,反应中形成的[C7H7(CH3)3N]9PW9O34(O2)x活性中心使催化剂具有反应控制相转移功能.以H2O2水溶液为氧化剂,在氧化苯甲醇制备苯甲醛反应中,发现该催化剂具有良好的催化活性.当H2O2与苯甲醇的物质的量比为0.9时,苯甲醇的转化率为86.2%,H2O2的利用率为95.8%,苯甲醛的选择性≥99%.反应结束后催化剂以沉淀的形式析出,催化剂的回收率保持在86%左右.将催化剂循环使用3次,苯甲醇的转化率和催化剂的回收率均无明显变化,说明Q9PW9具有良好的稳定性.A trilacunary keggin phosphotungstic reaction-controlled phase-transfer catalyst [CTHT（CH3）3N]9PW9O34 （Q9PW9） was synthesized, and characterized by FT-IR, ^31P NMR, XRD and TG, and the catalytic center was confirmed. The results of analysis indicated that the catalyst structure was kept well after the reaction, and the [C7H7（CH3）3N]9PW9034 （O2）x formed during the reaction made the catalyst have the feature of reaction-controlled phase-transfer catalysis. Q9PW9 was applied to the oxidation of benzyl alcohol with hydrogen peroxide as an oxidant and high efficient catalytic performance was achieved. When the molar ratio of H2O2 to benzyl alcohol was 0.9, the conversion of benzyl alcohol was 86.2%, the H2O2 efficiency was 95.8% and the selectivity to benzaldehyde was not less than 99%. After the reaction finished, the catalyst could be recycled from the system easily as deposit, and the catalyst recovery ratio was around 86%. The results of the catalyst recycle indicated that the catalyst exhibited high stability.

关 键 词：磷钨酸盐 反应控制相转移 过氧化氢 苯甲醇 氧化 

分 类 号：O643.36[理学—物理化学] TQ245.12[理学—化学]