本文選題：樹(shù)枝狀聚酰胺胺(PAMAM) + 2��； 參考：《河北工業(yè)大學(xué)》2015年碩士論文

【摘要】：醇選擇性的氧化成醛酮是化工領(lǐng)域最重要的反應(yīng)之一。2,2,6,6-四甲基哌啶氮氧自由基(TEMPO)作為一種對(duì)光熱穩(wěn)定的催化劑,具有反應(yīng)條件溫和、選擇性好、轉(zhuǎn)化率高等優(yōu)點(diǎn),但是存在其價(jià)格昂貴,沸點(diǎn)與醛酮等產(chǎn)物接近,產(chǎn)物提純難度大等缺點(diǎn)。因此,研究負(fù)載型TEMPO用以催化醇的選擇性氧化,實(shí)現(xiàn)TEMPO的循環(huán)使用具有重要的理論和實(shí)際意義。本文以乙二胺和丙烯酸甲酯為原料經(jīng)重復(fù)Michael和酯氨解反應(yīng)制備出二代(2.0G)樹(shù)枝狀聚酰胺胺(PAMAM)。以PAMAM為載體,經(jīng)縮合、還原將其與2,2,6,6-四甲基哌啶酮氮氧自由(TEMPO)鍵連,得到PAMAM負(fù)載的TEMPO(PAMAM-TEMPO)。采用~1H NMR、~(13)C NMR以及FT-IR等手段對(duì)中間體及最終產(chǎn)物進(jìn)行了表征。將PAMAM-TEMPO與CuBr_2以及2,2’-聯(lián)吡啶結(jié)合構(gòu)成催化體系,用于催化分子氧為氧化劑的醇的選擇性氧化反應(yīng)。對(duì)該體系的催化性能進(jìn)行了考察,得到PAMAM-TEMPO/CuBr_2/2,2’-聯(lián)吡啶催化苯甲醇選擇性氧化反應(yīng)的最優(yōu)條件,即:苯甲醇2 mmol,PAMAM-TEMPO 1 mol%,2,2’-聯(lián)吡啶1 mol%,CuBr_2 3 mol%,K2CO_32.5 mol%,乙腈1.25 ml,水1.25ml,反應(yīng)溫度25℃。在此條件下該體系對(duì)芐基以及烯丙基伯醇的氧化顯示出良好的催化活性和選擇性。TEMPO的負(fù)載使得氧化產(chǎn)物醛很容易與催化體系分離,而且催化劑可以循環(huán)使用。
[Abstract]:The selective oxidation of alcohols to aldehydes and ketones is one of the most important reactions in chemical industry. However, its price is expensive, boiling point is close to aldehydes and ketones, and it is difficult to purify the products. Therefore, it is of great theoretical and practical significance to study the selective oxidation of alcohols catalyzed by supported TEMPO and to realize the recycling of TEMPO. In this paper, the second generation (2.0 G) dendritic polyamide amine (Pama) was prepared from ethylenediamine and methyl acrylate by repeated Michael and ester ammonolysis. Using PAMAM as the carrier, it was reduced by condensation to connect it with the free tetramethylpiperidinone nitrogen oxygen (TEMPO) bond to obtain the PAMAM loaded TEMPOG PAMAM-TEMPO. The intermediate and its final product were characterized by 1H NMR-13C NMR and FT-IR. The selective oxidation of alcohols with molecular oxygen as oxidant was catalyzed by the combination of PAMAM-TEMPO with CuBr_2 and 2H _ 2O _ 2-bipyridine. The catalytic properties of the system were investigated. The optimum conditions for the selective oxidation of benzyl alcohol catalyzed by PAMAM-TEMPO / CuSP / CuBr2 / 2 / 2 + -bipyridine were obtained, namely: benzyl alcohol 2 mmol-TEMPO 1 mol-dipyridine-2-mol-dipyridine-3-molK2CO32.5 mol-1, acetonitrile 1.25 ml, water 1.25 ml, reaction temperature 25 鈩，

本文編號(hào)：1815724