聚酰胺-胺树状分子锡配合物催化性能  

Catalytic Properties of Polyamidoamine Dendritic Tin Complexes

作　　者：李翠林[1] 牛腾[1] 师海雄[1] 姜立萍[1] 马恒昌[2] 

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

出　　处：《精细化工》2013年第6期618-623,668,共7页Fine Chemicals

基　　金：国家自然科学基金(20474052);甘肃联合大学基本科研业务费高水平成果项目(2012GSP02)~~

摘　　要：通过固相合成的方法将聚酰胺-胺树状大分子PAMAM担载于大孔硅胶上,并对其外围分别用对羟基苯甲醛、2,4-二羟基苯甲醛和邻羟基苯甲醛进行修饰,再与SnCl2.2H2O反应形成三类共计9种不同代数树状高分子锡配合物。将该类配合物用作质量分数30%双氧水氧化酮的Baeyer-Villiger(B-V)反应的催化剂,考察其催化活性,结果表明,在该类配合物作用下,2-金刚烷酮、环戊酮、环己酮、4-甲基环己酮、4-叔丁基环己酮、3-甲基-2-戊酮和4-甲基-2-戊酮都可以发生B-V氧化反应而转化为相应的酯和内酯,底物的转化率(75%～99%)和产物选择性(95%～100%)都较高。比较了不同载体(氯球、纤维素、壳聚糖、硅胶)、不同配体的金属锡配合物对B-V催氧化反应的催化效果,研究发现,载体、配体和金属担载量对配合物的催化活性均有不同程度的影响。其中,硅胶为最好的载体,而邻羟基苯甲醛为最好的配体。Polyamidoamine dendrimers were grafted onto macro-porous silica gel through solid phase synthesis methodology, and the peripheral amino groups on these dendrimers were modified by 4- hydroxybenzaldehyde,2,4-dihydroxybenzaldehyde and salicylaldehyde to obtain ligands, and then the product reacted with SnCl2 · 2H2O to obtain silica supported dendritic Sn complexes. The catalytic performance of the silica supported dendritic Sn complexes was investigated by Baeyer-Villiger oxidation of cyclic and acyclic ketones to obtain their corresponding lactones or esters with 30% hydrogen peroxide. It was shown that all the complexes exhibit promising catalytic activity for the oxidation of ketones （ 2-andamantanone, cyclohexanone, cyclopentanone, 4-methylcyclohexanone, 4- tertbutylcyclohexanone,3-methyl-2-pentanone and 4-methyl-2-pentanone ）. Under the mild condition, all the oxidations gave high conversion（75% -99% ） and selectivity（95% -100% ） of lactones or esters. The effects of the supporter（ ehloromethyl polystyrene, cellulose, chitosan, silica） and ligand on the catalytic activity were also studied;it was discovered that both the supporter and the ligand played a vital role in metal loadings and the catalytic activity of the complexes. Silica was the best supporter and salicylaldehyde was the best ligand.

关 键 词：硅胶 树状大分子 锡 Baeyer—Villiger氧化 双氧水 催化与分离提纯技术 

分 类 号：O631[理学—高分子化学]