两亲聚离子液体-钒掺杂杂多酸离子复合体催化的苯氧化羟化

Hydroxylation of benzene catalyzed by amphiphilic poly(ionic liquid)-phosphovanadomolybdate ionic composites

以N,N-二甲基烯丙基胺、1-氯乙酸、Well-Dawson构型H_(7)[P_(2)Mo_(17)VO_(62)]、,H_(8)[P_(2)Mo_(16)V_(2)O_(62)],、H_(9)[P_(2)Mo_(15)V_(3)O_(62)]为起始原料,经季铵化、自由基聚合、分子自组装构建了三种两亲聚离子液体-钒掺杂杂多酸离子复合体PPIL-1~3,离子复合体集两亲活性、氧化催化活性和多孔性与一体,以其为非均相催化剂,工业级30%过氧化氢为氧化剂,在温和反应条件下,实现了苯一步氧化羟化制备苯酚。当离子复合体用量为0.1g,苯10mmol,过氧化氢20mmol,以15mL乙腈为溶剂,反应温度60℃,反应时间4h,苯酚产率37.3%。离子复合体经离心分离、溶剂洗涤、真空干燥即可再生循环使用,循环使用6次,催化活性基本保持不变。

Three porous amphiphilic poly(ionic liquids)-Well-Dawson type phosphovanadomolybdate ionic composites were synthesized using N,N-dimethylallyamine,chloroacetic,H_(7)[P_(2)Mo_(17)VO_(62)],H_(8)[P_(2)Mo_(16)V_(2)O_(62)],H_(9)[P_(2)Mo_(15)V_(3)O_(62)]as starting materials via quaternization,free-radical polymerization and self-assembly in water.These compounds exhibited surface activity,oxidative catalytic activity and porous property,which acted as efficient recyclable catalyst realized the direct hydroxylation of benzene using 30% H_(2)O_(2) as oxidant.When the dosage of ionic composite,benzene and H_(2)O_(2) was 0.1g,10mmol and 20mmol respectively,CH_(3)CN as solvent,reaction temperature was 60℃,reaction time was 4h,the phenol was obtained with yield of 37.3%.Three ionic composites could be recovered and reused by simply treatment,there were no significant decline in yield after recycling for six times.