树状功能高分子负载锡配合物的合成及其催化酮的Baeyer-Villiger氧化反应性能研究  

SYNTHESIS AND CATALYTIC PROPERTIES OF FUNCTIONAL DENDRITIC TIN COMPLEXES FOR BAEYER-VILLIGER OXIDATION OF KETONES

作　　者：李翠林[1] 雷自强[2] 马恒昌[2] 

机构地区：[1]甘肃联合大学化工学院,兰州730000 [2]西北师范大学化学化工学院,兰州730070

出　　处：《高分子学报》2013年第4期473-481,共9页Acta Polymerica Sinica

基　　金：国家自然科学基金(基金号20474052)资助项目

摘　　要：通过固相合成方法将聚酰胺-胺树状分子担载于氯球上,对其外围分别用2,4-二羟基苯甲醛和邻羟基苯甲醛进行修饰,再与SnCl2.2H2O反应,形成配体不同的两类树状高分子锡配合物.将此类配合物用作30%的双氧水氧化酮的Baeyer-Villiger反应的非均相催化剂,具有较好的催化活性.2-金刚烷酮、环己酮、3-甲基-2-戊酮等都转化为相应的酯和内酯,底物的转化率和产物选择性均较高.对2-羟基苯甲醛、2,4-二羟基苯甲醛和邻羟基苯甲醛修饰的不同类型催化剂催化下的反应进行比较,发现配体对锡的担载量和催化活性均有不同程度的影响.其中邻羟基苯甲醛修饰的配合物因具有较高的锡担载量而具有了最佳的催化活性.此催化体系使用环境友好的低浓度双氧水为氧化剂,催化剂制备方法简单、催化反应完成时间短、催化剂在多次重复利用后活性没有明显降低,可回收和重复利用.Different generations of polyamidoamine dendrimers were successfully incorporated to chloromethyl polystyrene through solid phase synthesis methodology. The peripheral amino groups on these dendrimers have been modified by 2,4-dihydroxybenzaldehyde and salicylaldehyde, respectively. Then the ligands reacted with SnC12＂2H20 to obtained chloromethyl polystyrene supported dendritic Sn complexes. The ligands and complexes were well characterized by IR, ICP and XPS. The complexes as heterogeneous catalysts show promising catalytic activities for the Baeyer-Villiger oxidation of cyclic and acyclic ketones with 30% hydrogen peroxide. 2-Adamantanone, cyclopentanone, 4-methylcyclohexanone, 4-tert-butylcyclohexanone, 3-methyl-2- pentanone and 4-methyl-2-pentanone have all been oxidized in a reaction catalyzed by these complexes at 70 90℃ in different organic solvents, affording the corresponding lactones or esters with high conversion （ 〉 87% ） and selectivity （ 〉 99% ）. Compared to the Baeyer-Villiger oxidation of ketones using complexes with different ligands （4-hydroxybenzaldehyde, 2, 4-dihydroxybenzaldehyde and salicylaldehyde）, it was discovered that ligands played a vital role in metal loadings and the catalytic activity of the complexes. Among them,salicylaldehyde modified complexes were found to be the optimum catalysts as they had the highest tin content. The catalysts could be obtained in a simple and efficient manner using environmentally friendly oxidant under mild reaction condition. Moreover, the catalysts can be recycled for several times without losing significantly the catalytic activity.

关 键 词：树状高分子 锡配合物 Baeyer—Villiger氧化 双氧水 

分 类 号：O643.32[理学—物理化学]