本文關(guān)鍵詞：改性硅膠固載席夫堿配合物的制備及其催化性能研究　出處：《北京服裝學(xué)院》2017年碩士論文　論文類型：學(xué)位論文

  更多相關(guān)文章： 改性硅膠 席夫堿配合物 負(fù)載 催化 苯乙烯氧化反應(yīng)

【摘要】：席夫堿金屬配合物是非官能化烯烴環(huán)氧化反應(yīng)中的一種高效催化劑,但它有很多缺點(diǎn),比如催化劑和產(chǎn)物難以分離、無法重復(fù)使用、穩(wěn)定性不高、對(duì)環(huán)境污染、在氧化條件下容易聚合等缺點(diǎn),這些缺點(diǎn)限制了其在工業(yè)上的大規(guī)模使用,近年來,將均相催化劑固載到無機(jī)或有機(jī)載體上制備多相催化劑受到廣泛關(guān)注。本文首先選用了(3-環(huán)氧乙基甲氧基丙基)三甲氧基硅烷和氯丙基三氯硅烷對(duì)羥基化的硅膠進(jìn)行改性,以水楊醛、鄰苯二胺、2,4-二羥基苯甲醛、3,5-二叔丁基水楊醛、3,4-二氨基吡啶及過渡金屬鹽等原料合成共4種席夫堿中間體及salen型配體,簡(jiǎn)化反應(yīng)路線,提高反應(yīng)效率,用核磁共振儀、電噴霧高分辨質(zhì)譜等手段對(duì)所得產(chǎn)品進(jìn)行了結(jié)構(gòu)表征。合成第二種配體時(shí),原料水楊醛室溫下為液體,發(fā)現(xiàn)在超聲條件下,僅用少量的溶劑,室溫反應(yīng)時(shí)間0.5h情況下就能得到較好的產(chǎn)率,達(dá)到75%。通過化學(xué)接枝合成了三類負(fù)載型salen金屬配合物催化劑,通過FT-IR,ICP-AES和XRD等對(duì)其進(jìn)行了結(jié)構(gòu)表征。通過ICP-AES檢測(cè),三種負(fù)載催化劑的金屬錳的上載量分別為:A為0.68mmol/g,B為1.05 mmol/g,C為0.72mmol/g。將制備的三類固載型催化劑應(yīng)用于催化過氧化氫氧化苯乙烯的反應(yīng),通過所有單因素實(shí)驗(yàn)數(shù)據(jù)表明,僅探究苯乙烯的轉(zhuǎn)化率,催化劑性能優(yōu)異順序?yàn)锽AC,僅探究環(huán)氧苯乙烷的選擇性,催化劑性能優(yōu)異順序?yàn)镃AB,若綜合考慮底物轉(zhuǎn)化率和產(chǎn)物的選擇性,對(duì)于催化劑A,B,C,最佳反應(yīng)溫度應(yīng)分別為60℃,60℃,50℃,反應(yīng)時(shí)間應(yīng)分別為4h,5h,5h,氧化劑過氧化氫的量與均為底物苯乙烯的3倍,為后續(xù)正交試驗(yàn)設(shè)計(jì),確定最佳反應(yīng)條件提供依據(jù),同時(shí),三種催化劑均能重復(fù)使用4次以上催化活性和選擇性沒有明顯降低。
[Abstract]:Schiff base metal complexes is an efficient catalyst for the epoxidation of unfunctionalized olefins, but it has many disadvantages, such as the catalyst and the product is difficult to be separated, can not be reused, stability is not high, the environmental pollution, the shortcomings of easy polymerization under oxidizing conditions, these shortcomings limit its large-scale use. In the industry in recent years, the homogeneous catalyst immobilized to the inorganic or organic carrier for preparing heterogeneous catalysts has attracted extensive attention. This paper chooses a (3- epoxy ethyl methoxy propyl trimethoxysilane) and three chloro silane on 3-chloropropyl hydroxylated silica gel was modified by salicylaldehyde two, benzene amine, 2,4- two hydroxy benzaldehyde, 3,5- di Ding Jishui Yang Quan, 3,4- two amino pyridine and transition metal salts such as raw material for the synthesis of 4 kinds of Schiff base intermediates and salen ligands, simplified reaction routes, improve the reaction efficiency, using nuclear magnetic resonance spectrometer, High resolution electrospray mass spectra of the products were characterized. The synthesis of second kinds of ligands, the raw material of salicylaldehyde liquid at room temperature, found under the condition of ultrasound, with only a small amount of solvent, reaction time under the condition of 0.5h at room temperature can get better yield reached 75%. by chemical grafting synthesis of three kinds of load type salen Metal Complexes Catalysts by FT-IR, characterized by ICP-AES and XRD. ICP-AES detection, three kinds of catalyst loading amount of metal manganese were: A 0.68mmol/g, B 1.05 mmol/g, three C 0.72mmol/g. the catalyst used in catalytic oxidation of styrene solid hydrogen peroxide supported by all reaction, single factor experiment data show that only on the conversion of styrene and the excellent performance of the catalyst in the order of BAC, only selective inquiry epoxyethylbenzene, forcing agent performance excellent Shun The order of CAB, if considering the substrate conversion and product selectivity, the catalyst A, B, C, respectively. The optimum reaction temperature 60 C, 60 C, 50 C, reaction time was 4h, 5h, 5h, H2O2 and the amount of substrate are styrene 3 times orthogonal experimental design for the follow-up, the optimum reaction conditions provide the basis, at the same time, three kinds of catalysts can be reused 4 times without significant loss of catalytic activity and selectivity.

【學(xué)位授予單位】：北京服裝學(xué)院
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O641.4;O621.25

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本文編號(hào)：1406929