聚酰胺-胺树状分子锡配合物催化性能研究
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O631

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国家自然科学基金项目(面上项目,重点项目,重大项目)


Catalytic properties of polyamidoamine dendritic Tin complexes
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    摘要:

    近三十年来树状大分子的应用越来越受到研究者的关注,然而液相合成树状大分子常常面临反应时间长和减压蒸馏的繁杂过程,这大大限制树状大分子的应用。本文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,并对其一到三代的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,对此类配合物的结构用元素分析、IR、ICP和XPS进行了表征。研究发现此类配合物是低浓度双氧水氧化酮的Baeyer–Villiger反应的较好的非均相催化剂。部分的酮和环酮都高选择性的转化为相应的酯和内酯。对不同类型催化剂作用下的氧化反应进行比较发现,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。此类催化剂具有制备方法简单、可重复利用等优点。

    Abstract:

    Dendrimer chemistry is one of the most fascinating and rapidly expanding areas of modern chemistry. However, solution-phase synthesis of dendrimers is often challenging requiring long reaction time and tedious purification process, which dramatically limits the applications of dendrimers. In this work, polyamidoamine dendrimers were grafted to silica surface through solid phase synthesis methodology, the peripheral amino groups on these dendrimers were modified by 4-hydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde and salicylaldehyde to obtain ligands, and then reacted with SnCl2•2H2O to obtained silica supported dendritic Sn complexes. The ligands and complexes were well characterized by elemental analysis, IR, ICP and XPS. The catalytic performance of the silica supported dendritic Sn complexes was investigated by Baeyer–Villiger oxidation of cyclic and acyclic ketones to their corresponding lactones or esters with 30 % hydrogen peroxide. It was shown that all the complexes exhibit promising catalytic activities for the oxidation. Under the mild condition, all the oxidations give high conversion and selectivity of lactones or esters. The effects of the supporter and ligand on the catalytic activity were also studied, it was discovered that both supporter and the ligand played a vital role in metal loadings and the catalytic activity of the complexes. Moreover, the catalysts could be obtained in a simple and efficient manner and can be recycled and reused.

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李翠林,牛腾,师海雄,姜立萍,马恒昌.聚酰胺-胺树状分子锡配合物催化性能研究[J].精细化工,2013,30(6):

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  • 收稿日期:2013-01-05
  • 最后修改日期:2013-02-14
  • 录用日期:2013-03-08
  • 在线发布日期: 2013-05-30
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