固載化氨基酚型席夫堿氧釩（Ⅳ）配合物的制備及其催化氧化性能的研究
發(fā)布時(shí)間：2018-07-31 19:45
【摘要】：在催化劑的作用下,以分子氧或空氣為氧化劑實(shí)現(xiàn)醇類(lèi)物質(zhì)向羰基化合物的轉(zhuǎn)變,這是備受關(guān)注的綠色化氧化過(guò)程。固載化席夫堿過(guò)渡金屬配合物催化劑在催化分子氧氧化醇類(lèi)物質(zhì)的過(guò)程中具有優(yōu)良的催化活性、選擇性和良好的重復(fù)使用性能,可以有效地將醇類(lèi)物質(zhì)氧化為相應(yīng)的醛或酮。本研究通過(guò)分子設(shè)計(jì),以交聯(lián)聚苯乙烯微球?yàn)檩d體,經(jīng)過(guò)兩步大分子反應(yīng),制備了鍵合有氨基酚型席夫堿配基的功能微球CPSAGAP,然后使之分別與硫酸氧釩、醋酸鈷、硝酸銅、醋酸錳四種物質(zhì)發(fā)生配位螯合反應(yīng),制備了多種表面固載有氨基酚型席夫堿配合物的固體催化劑微球,并將它們用于催化分子氧氧化環(huán)己醇和1-苯乙醇的反應(yīng)中,探究了這些非均相催化劑的催化活性、選擇性和催化氧化機(jī)理。本文的研究結(jié)果在綠色化的醇類(lèi)物質(zhì)催化氧化領(lǐng)域中,具有重要的科學(xué)意義與潛在的應(yīng)用價(jià)值。使乙醛酸與氯甲基化交聯(lián)聚苯乙烯(CMCPS)微球的氯甲基發(fā)生酯化反應(yīng),從而將醛基(GA)引入交聯(lián)聚苯乙烯(CPS)微球表面,得到改性微球CPS-AG,再以間氨基苯酚(MAP)為試劑,與微球CPS-AG表面的醛基發(fā)生席夫堿反應(yīng),制得了表面鍵合有氨基酚型席夫堿配基的功能微球CPS-AGAP,考察了主要因素對(duì)制備功能微球的影響規(guī)律,優(yōu)化了反應(yīng)條件。最后使微球分別與硫酸氧釩、醋酸鈷、硝酸銅、醋酸錳四種物質(zhì)發(fā)生配位螯合反應(yīng),制得了四種表面固載有氨基酚型席夫堿過(guò)渡金屬配合物的固體催化劑微球CPS-[VO(AGAP)_2]、CPS-[Co(AGAP)_2]和CPS-[Mn(AGAP)_2]、CPS-[Cu(AGAP)_2],采用紅外光譜(FT-IR)、固體紫外(UV)及掃描電子顯微鏡(SEM)對(duì)催化劑微球進(jìn)行了充分表征。經(jīng)研究發(fā)現(xiàn),溶劑的極性有利于乙醛酸與CMCPS微球之間的酯化反應(yīng),極性較強(qiáng)的N,N-二甲基乙酰胺為適宜的反應(yīng)溶劑;90℃為適宜的反應(yīng)溫度。在適宜反應(yīng)條件下,CMCPS微球的氯甲基轉(zhuǎn)化率可以達(dá)到82%。所制得的固體催化劑微球CPS-[VO(AGAP)_2]、CPS-[Co(AGAP)_2]、CPS-[Mn(AGAP)_2]和CPS-[Cu(AGAP)_2],其表面金屬物種的固載量分別達(dá)到0.78 mmol/g、0.75 mmol/g、0.71 mmol/g、0.69mmol/g。將四種固載有氨基酚型席夫堿過(guò)渡金屬配合物微球用于環(huán)己醇和1-苯乙醇的分子氧催化氧化過(guò)程,考察了主要因素對(duì)環(huán)己醇和1-苯乙醇催化氧化的影響規(guī)律,探究了催化氧化的機(jī)理。實(shí)驗(yàn)結(jié)果表明,在環(huán)己醇環(huán)己醇和1-苯乙醇的催化反應(yīng)中,四種催化劑微球均表現(xiàn)出一定的催化活性與優(yōu)良的選擇性。催化氧化反應(yīng)具有高選擇性,環(huán)己酮和苯乙酮為反應(yīng)的唯一產(chǎn)物。四種催化劑微球的催化效果相比,催化效果順序?yàn)镃PS-[VO(AGAP)_2]CPS-[Co(AGAP)_2]CPS-[Mn(AGAP)_2]CPS-[Cu(AGAP)_2],催化劑微球CPS-[VO(AGAP)_2]的催化效果最佳。0.78 mmol催化劑微球CPS-[VO(AGAP)_2],在90℃下,反應(yīng)30 h,催化劑微球CPS-[VO(AGAP)_2]可將環(huán)己醇高效的轉(zhuǎn)化為環(huán)己酮,轉(zhuǎn)化率達(dá)到64%。0.546 mmol催化劑微球CPS-[VO(AGAP)_2],在80℃下,反應(yīng)28h,催化劑微球CPS-[VO(AGAP)_2]可將1-苯乙醇高效的轉(zhuǎn)化為苯乙酮,轉(zhuǎn)化率達(dá)到78%。氧釩催化劑CPS-[VO(AGAP)_2]之所以有高的催化活性,主要原因在于高價(jià)態(tài)釩原子對(duì)分子氧具有高親和性,且具有高配位數(shù)。制備的非均相催化劑CPS-[VO(AGAP)_2]重復(fù)使用7次后,環(huán)己醇的轉(zhuǎn)化率基本保持穩(wěn)定在61%左右,1-苯乙醇的轉(zhuǎn)化率基本保持穩(wěn)定在73%左右。顯然,固載化的催化劑CPS-[VO(AGAP)_2]具有良好的循環(huán)使用性能。
[Abstract]:Under the action of catalyst, the conversion of alcohols to carbonyl compounds is realized with molecular oxygen or air as oxidant. This is a highly concerned green oxidation process. The immobilized Schiff base transition metal complexes have excellent catalytic activity, selectivity and good repetition in the process of catalytic oxidation of alcohols by molecular oxygen. Using properties, the alcohols can be effectively oxidized to corresponding aldehydes or ketones. Through molecular design, a functional microsphere CPSAGAP bonded with aminophenol type Schiff base ligand was prepared through two steps of macromolecular reaction, and then it was made with vanadium sulfate, cobalt acetate, copper nitrate, and manganese acetate, four. A variety of solid catalyst microspheres containing aminophenol type Schiff base complexes have been prepared and used to catalyze the reaction of cyclohexanol and 1- phenolols. The catalytic activity, selectivity and catalytic oxidation mechanism of these heterogeneous catalysts are investigated. The results of this paper are in this paper. In the field of catalytic oxidation of green alcohols, it has important scientific significance and potential application value. The glyoxylic acid is esterified with chloromethyl methylation of chloromethylated polystyrene (CMCPS) microspheres, and aldehyde group (GA) is introduced into the surface of crosslinked polystyrene (CPS) microsphere, and the modified microsphere CPS-AG, and then interaminophenol (MAP), is obtained. A functional microsphere CPS-AGAP was prepared for the surface bonding of Schiff base with aminophenol type Schiff base on the surface of the microsphere CPS-AG. The effect of the main factors on the preparation of functional microspheres was investigated, and the reaction conditions were optimized. Finally, the microspheres were made with four substances, vanadium sulfate, cobalt acetate, copper nitrate, and manganese acetate, respectively. Four kinds of solid catalyst microspheres, CPS-[VO (AGAP) _2], CPS-[Co (AGAP) _2] and CPS-[Mn (AGAP) _2], CPS-[Cu (AGAP) _2], were prepared by the chelating reaction. The catalyst microspheres were fully characterized by infrared spectroscopy, solid UV and scanning electron microscopy. It is found that the polarity of the solvent is beneficial to the esterification between glyoxylic acid and CMCPS microspheres. The very strong N, N- two methyl acetamide is a suitable reaction solvent, and the suitable reaction temperature is 90 C. Under the suitable reaction conditions, the conversion rate of chloromethyl of CMCPS microspheres can reach to the solid catalyst microsphere CPS-[VO (AGAP) _2] produced by 82%.. CPS-[Co (AGAP) _2], CPS-[Mn (AGAP) _2] and CPS-[Cu (AGAP) _2], the solid load of the surface metal species reached 0.78 mmol/g, 0.75 mmol/g, 0.71 mmol/g. Four kinds of solid containing aminophenol type Schiff base transition metal complexes were used in the molecular oxygen catalytic oxidation process of cyclohexanol and ethyl alcohol. The main factors were investigated. The mechanism of catalytic oxidation of hexanol and 1- benzol was investigated. The experimental results showed that in the catalytic reaction of cyclohexanol cyclohexanol and 1- Benzol, the four catalyst microspheres showed a certain catalytic activity and excellent selectivity. The catalytic oxidation reaction had high selectivity, and cyclohexanone and acetophenone were reacted. The catalytic effect of the four catalyst microspheres is CPS-[VO (AGAP) _2]CPS-[Co (AGAP) _2]CPS-[Mn (AGAP) _2]CPS-[Cu (AGAP) _2], and the catalyst microsphere CPS-[VO (AGAP) _2] has the best catalytic effect. At 90, the reaction is 30. The conversion of hexanol to cyclohexanone, the conversion of 64%.0.546 mmol catalyst microsphere CPS-[VO (AGAP) _2], at 80 C, reaction 28h, the catalyst microsphere CPS-[VO (AGAP) _2] can convert 1- benzophenone into acetophenone, the conversion rate reaches the high catalytic activity of 78%. oxygen vanadium catalyst. The main reason is high price. The state vanadium atom has high affinity to molecular oxygen and has high coordination number. After repeated use of the heterogeneous catalyst CPS-[VO (AGAP) _2] for 7 times, the conversion rate of cyclohexanol is basically stable at about 61%, and the conversion rate of 1- benzene ethanol is basically around 73%. Obviously, the immobilized catalyst CPS-[VO (AGAP) _2] has a good cycle. Use performance.
【學(xué)位授予單位】：中北大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類(lèi)號(hào)】：O641.4;O643.36
本文編號(hào)：2156642
[Abstract]:Under the action of catalyst, the conversion of alcohols to carbonyl compounds is realized with molecular oxygen or air as oxidant. This is a highly concerned green oxidation process. The immobilized Schiff base transition metal complexes have excellent catalytic activity, selectivity and good repetition in the process of catalytic oxidation of alcohols by molecular oxygen. Using properties, the alcohols can be effectively oxidized to corresponding aldehydes or ketones. Through molecular design, a functional microsphere CPSAGAP bonded with aminophenol type Schiff base ligand was prepared through two steps of macromolecular reaction, and then it was made with vanadium sulfate, cobalt acetate, copper nitrate, and manganese acetate, four. A variety of solid catalyst microspheres containing aminophenol type Schiff base complexes have been prepared and used to catalyze the reaction of cyclohexanol and 1- phenolols. The catalytic activity, selectivity and catalytic oxidation mechanism of these heterogeneous catalysts are investigated. The results of this paper are in this paper. In the field of catalytic oxidation of green alcohols, it has important scientific significance and potential application value. The glyoxylic acid is esterified with chloromethyl methylation of chloromethylated polystyrene (CMCPS) microspheres, and aldehyde group (GA) is introduced into the surface of crosslinked polystyrene (CPS) microsphere, and the modified microsphere CPS-AG, and then interaminophenol (MAP), is obtained. A functional microsphere CPS-AGAP was prepared for the surface bonding of Schiff base with aminophenol type Schiff base on the surface of the microsphere CPS-AG. The effect of the main factors on the preparation of functional microspheres was investigated, and the reaction conditions were optimized. Finally, the microspheres were made with four substances, vanadium sulfate, cobalt acetate, copper nitrate, and manganese acetate, respectively. Four kinds of solid catalyst microspheres, CPS-[VO (AGAP) _2], CPS-[Co (AGAP) _2] and CPS-[Mn (AGAP) _2], CPS-[Cu (AGAP) _2], were prepared by the chelating reaction. The catalyst microspheres were fully characterized by infrared spectroscopy, solid UV and scanning electron microscopy. It is found that the polarity of the solvent is beneficial to the esterification between glyoxylic acid and CMCPS microspheres. The very strong N, N- two methyl acetamide is a suitable reaction solvent, and the suitable reaction temperature is 90 C. Under the suitable reaction conditions, the conversion rate of chloromethyl of CMCPS microspheres can reach to the solid catalyst microsphere CPS-[VO (AGAP) _2] produced by 82%.. CPS-[Co (AGAP) _2], CPS-[Mn (AGAP) _2] and CPS-[Cu (AGAP) _2], the solid load of the surface metal species reached 0.78 mmol/g, 0.75 mmol/g, 0.71 mmol/g. Four kinds of solid containing aminophenol type Schiff base transition metal complexes were used in the molecular oxygen catalytic oxidation process of cyclohexanol and ethyl alcohol. The main factors were investigated. The mechanism of catalytic oxidation of hexanol and 1- benzol was investigated. The experimental results showed that in the catalytic reaction of cyclohexanol cyclohexanol and 1- Benzol, the four catalyst microspheres showed a certain catalytic activity and excellent selectivity. The catalytic oxidation reaction had high selectivity, and cyclohexanone and acetophenone were reacted. The catalytic effect of the four catalyst microspheres is CPS-[VO (AGAP) _2]CPS-[Co (AGAP) _2]CPS-[Mn (AGAP) _2]CPS-[Cu (AGAP) _2], and the catalyst microsphere CPS-[VO (AGAP) _2] has the best catalytic effect. At 90, the reaction is 30. The conversion of hexanol to cyclohexanone, the conversion of 64%.0.546 mmol catalyst microsphere CPS-[VO (AGAP) _2], at 80 C, reaction 28h, the catalyst microsphere CPS-[VO (AGAP) _2] can convert 1- benzophenone into acetophenone, the conversion rate reaches the high catalytic activity of 78%. oxygen vanadium catalyst. The main reason is high price. The state vanadium atom has high affinity to molecular oxygen and has high coordination number. After repeated use of the heterogeneous catalyst CPS-[VO (AGAP) _2] for 7 times, the conversion rate of cyclohexanol is basically stable at about 61%, and the conversion rate of 1- benzene ethanol is basically around 73%. Obviously, the immobilized catalyst CPS-[VO (AGAP) _2] has a good cycle. Use performance.
【學(xué)位授予單位】：中北大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類(lèi)號(hào)】：O641.4;O643.36
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，本文編號(hào)：2156642
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