负载型磷钨酸催化下芳酮类化合物的绿色合成-应用化学专业论文.docxVIP

摘 摘 要 摘 要 近年来，新型催化剂作用下的绿色有机合成越来越受到人们的关注。本文制备了一 系列负载型磷钨酸（HPW）新型催化剂，并以 Friedel-Crafts 酰基化（F-C 酰基化）反应 为模型研究了其催化活性。 首先，将 HPW 负载到 Hβ 分子筛上，研究了 HPW/Hβ 在苯甲醚与正己酸的 F-C 酰 基化反应中的催化性能。在最佳反应条件下，正己酸转化率为 100 %，目标产物 4-甲氧 基苯己酮的选择性达到 89.2 %。催化剂的 XRD、N2 吸附-脱附、NH3-TPD 和 ICP 等表 征结果显示，负载量和焙烧温度是影响催化剂活性的重要因素，HPW/Hβ 催化剂的高活 性得益于其表面高度分散的 HPW 和大量强酸性活性中心。 其次，利用壳聚糖溶于酸而不溶于碱性溶液的性质，在不使用交联剂的条件下制备 了磁性核壳材料 Fe3O4@CS@HPW，并研究了其在苯甲醚与乙酸酐的 F-C 酰基化反应中 的活性。重点与使用交联剂制备的磁性壳聚糖材料 CR-Fe3O4@CS@HPW 进行了对比， 通过 N2 吸附-脱附、XRD、TEM、FT-IR 和磁性测试等表征结果解释了两种催化剂活性 与结构之间的关系。 最后，制备了以 Fe3O4 为核，核外包覆两层 SiO2 壳后再负载 HPW 的磁性核壳材料 Fe3O4@nSiO2@mSiO2@HPW，研究了其在苯甲醚与乙酸酐的 F-C 酰基化反应中的性能。 发现在这两层 SiO2 壳的共同作用下，Fe3O4@nSiO2@mSiO2@HPW 表现出了比单独具有 致密 SiO2 壳和疏松 SiO2 壳的催化剂 Fe3O4@nSiO2@HPW 和 Fe3O4@mSiO2@HPW 更好 的催化活性。 关键词 磷钨酸 负载型 芳酮类化合物 绿色合成 Friedel-Crafts 酰基化反应 I Abstract Abstract Abstract In recent years，green synthesis of organic compounds catalyzed by new kinds of catalysts has attracted more and more attentions. Thus, a series of supported tungstophosphoric acid (HPW) catalysts were prepared, and their catalytic performances were investigated using the Friedel-Crafts acylation (F-C acylation) as a model reaction. Firstly, the catalytic performance of Hβ zeolite supported tungstophosphoric acid catalyst (HPW/Hβ) was studied via the F-C acylation of anisole with hexanoic acid. The conversion of hexanoic acid was 100 % and the yield of 4-methoxy phenyl hexyl ketone reached 89.2 % under the optimized reaction conditions. The catalysts were characterized by XRD, N2 physisorption measurements, NH3-TPD and ICP. It was found that the highly dispersed HPW and large amounts of strongly acidic sites on HPW/Hβ accounted for its high catalytic activity. Secondly, based on the special nature of chitosan, which is insoluble in acid and insoluble in basic solution, a novel Fe3O4@CS@HPW catalyst was prepared free of crosslinking reagent. Its catalytic performance was then tested by the F-C acylation reaction of anisole with acetic anhydride and compared with that of a t