本文選題：Heck反應(yīng) + 多相催化�。� 參考：《遼寧大學(xué)》2017年碩士論文

【摘要】：Heck偶聯(lián)反應(yīng)一般是指芳基鹵代物與活性烯烴之間的反應(yīng),是構(gòu)建不飽和碳碳雙鍵的重要方法。自1970s以來,通過對(duì)其催化劑的不斷完善和反應(yīng)條件的不斷優(yōu)化、對(duì)反應(yīng)底物的不斷拓展,Heck反應(yīng)的應(yīng)用范圍越來越廣泛,已被廣泛應(yīng)用于眾多有機(jī)合成反應(yīng)中。常應(yīng)用于合成藥物分子、天然產(chǎn)物以及新材料等。對(duì)Heck偶聯(lián)反應(yīng)催化劑的研究經(jīng)歷了均相催化劑到多相催化劑的發(fā)展。均相催化劑經(jīng)歷了需要磷配體和不需要磷配體的發(fā)展過程,催化活性有了一定程度的提高,但是由于均相催化劑固有的缺點(diǎn)-難以從反應(yīng)混合物中分離,不能重復(fù)利用等,造成了環(huán)境污染和資源浪費(fèi)。這些缺點(diǎn)限制了Heck偶聯(lián)反應(yīng)的發(fā)展。為了解決這些問題而發(fā)展起來的多相催化劑,即將活性催化位點(diǎn)通過化學(xué)鍵固載到無機(jī)或者有機(jī)載體中。目前常用的載體有配位聚合物、活性炭、介孔材料、氧化鋁等。雖然傳統(tǒng)載體負(fù)載金屬鈀納米粒子在改善均相催化劑易團(tuán)聚、難分離、難以循環(huán)利用的缺點(diǎn)上取得了一定的成效。但是存在操作復(fù)雜或者催化效率偏低或者在使用過程中催化劑催化效率變低的問題,限制了Heck偶聯(lián)反應(yīng)的工業(yè)化。因此開發(fā)一種操作簡(jiǎn)便、催化活性高的新型復(fù)合材料來實(shí)現(xiàn)Heck反應(yīng)的工業(yè)化是很有必要的。MOFs作為一種新型載體具有一系列的優(yōu)點(diǎn),本實(shí)驗(yàn)合成了Pd@MIL-101和Pd@HKUST-1兩種復(fù)合材料催化Heck偶聯(lián)反應(yīng)。我的實(shí)驗(yàn)開篇介紹了Heck反應(yīng)催化劑目前存在的問題、MOFs材料的特點(diǎn)、合成方法、發(fā)展和應(yīng)用,論證了MOFs材料作為載體催化Heck反應(yīng)的可行性。然后我合成了兩種MOFs材料—MIL-101和HKUST-1,分別制備了Pd@MIL-101和Pd@HKUST-1兩種復(fù)合材料。對(duì)這四種材料分別進(jìn)行了表征,說明兩種MOFs材料被成功的合成出來,制備的Pd@MOFs復(fù)合材料晶體構(gòu)型保持不變,對(duì)催化Heck反應(yīng)具有一定的潛力。接著研究了Pd@MOFs作為催化劑對(duì)Heck反應(yīng)的催化,其中Pd@MIL-101對(duì)Heck反應(yīng)的各類底物具有相對(duì)較高的催化活性,尤其是對(duì)于碘苯和丙烯酸酯類的反應(yīng),其催化速率高于目前同類反應(yīng)的數(shù)倍最后對(duì)本論文的材料合成部分和催化實(shí)驗(yàn)部分進(jìn)行總結(jié),Pd@MIL-101復(fù)合材料對(duì)于Heck偶聯(lián)反應(yīng)的高效催化以及可循環(huán)使用有望應(yīng)用于Heck反應(yīng)的工業(yè)生產(chǎn)。
[Abstract]:Heck coupling reaction usually refers to the reaction between aryl halogenates and active alkenes. It is an important method to construct unsaturated carbon and carbon double bonds. Since 1970, through the continuous improvement of the catalyst and the optimization of reaction conditions, the continuous expansion of the reaction substrate Heck reaction has been widely used in many organic synthesis reactions. It is often used to synthesize drug molecules, natural products and new materials. The study of Heck coupling catalyst has experienced the development of homogeneous catalyst to heterogeneous catalyst. The homogeneous catalyst has experienced the development of phosphorus ligands and does not need phosphorus ligands, and the catalytic activity has been improved to some extent. However, due to the inherent shortcomings of homogeneous catalysts, it is difficult to separate from the reaction mixture and can not be reused, etc. It causes environmental pollution and waste of resources. These shortcomings limit the development of Heck coupling reactions. In order to solve these problems, the active catalytic sites are immobilized into inorganic or organic support by chemical bonding. The commonly used carriers are coordination polymers, activated carbon, mesoporous materials, alumina and so on. Although the traditional supported palladium nanoparticles have achieved some success in improving homogeneous catalyst agglomeration, difficult separation, and difficult to recycle. However, the industrialization of Heck coupling reaction is limited by complex operation, low catalytic efficiency or low catalytic efficiency. Therefore, it is necessary to develop a new composite material with simple operation and high catalytic activity to industrialize the Heck reaction. As a new carrier, MOFs has a series of advantages. In this paper, the Heck coupling reaction catalyzed by PD @ MIL-101 and Pdr HKUST-1 composites was synthesized. At the beginning of my experiment, the problems existing in Heck catalyst are introduced. The characteristics, synthesis method, development and application of MOFs are introduced, and the feasibility of using MOFs as carrier to catalyze Heck reaction is demonstrated. Then I synthesized two kinds of MOFs materials, -MIL-101 and HKUST-1, and prepared two kinds of composite materials, PdBM-MIL-101 and Pd@ HKUST-1, respectively. The results show that the two kinds of MOFs have been successfully synthesized, and the crystal configuration of the prepared PD @ MOFs composites remains unchanged, which has a certain potential for catalytic Heck reaction. Then the catalytic activity of PD @ MOFs for Heck reaction was studied. Pd@ MIL-101 had relatively high catalytic activity for various substrates of Heck reaction, especially for the reaction of iodobenzene with acrylate. Its catalytic rate is several times higher than that of the current similar reactions. Finally, the material synthesis and catalytic experiments of this thesis are summarized. The high efficiency catalysis and recycling of PdR MIL-101 composites for Heck coupling reaction are expected to be applied in Heck reaction. Reactive industrial production
【學(xué)位授予單位】：遼寧大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O643.36;O621.251

【參考文獻(xiàn)】

相關(guān)碩士學(xué)位論文 前1條

1 高志強(qiáng);MOFs負(fù)載鈀（Ⅱ）材料的制備及其Ullmann反應(yīng)性能研究[D];華南理工大學(xué);2012年

，

本文編號(hào)：2061606