本文選題：氮氧自由基聚合物刷 + 醇選擇性氧化��； 參考：《河北科技大學(xué)》2016年碩士論文

【摘要】：2,2,6,6-四甲基哌啶-N-氧自由基(TEMPO)是一種穩(wěn)定的自由基,有很多潛在的應(yīng)用價(jià)值。其中,TEMPO作為催化劑應(yīng)用在醇的選擇性催化氧化過(guò)程中,表現(xiàn)出反應(yīng)條件溫和、活性高和選擇性高等優(yōu)點(diǎn)。另一方面其毒性小,可以作為高效的阻聚劑。但是TEMPO價(jià)格偏高,反應(yīng)后難以回收,是其廣泛應(yīng)用的瓶頸。將TEMPO負(fù)載到載體上,實(shí)現(xiàn)其多次循環(huán)使用,是將其進(jìn)行大規(guī)模應(yīng)用的有效方法。本文首先以交聯(lián)聚苯乙烯微球(PS)為基質(zhì),甲基丙烯酸甲酯(MMA)、甲基丙烯酸縮水甘油酯(GMA)和2,2,6,6-四甲基-4-哌啶基甲基丙烯酸酯(TMPM)為功能單體,利用表面引發(fā)電子轉(zhuǎn)移活化再生催化劑原子轉(zhuǎn)移自由基聚合(ARGET ATRP)法成功制得不同鏈結(jié)構(gòu)聚合物刷,包括均聚物刷PS-PMMA、PS-PGMA和PS-PTMPM;嵌段共聚物刷PS-P(MMA-b-TMPM)和PS-P(MMA-b-GMA);無(wú)規(guī)共聚物刷PS-P(MMA-co-TMPM)。然后利用氧化法和開(kāi)環(huán)法制備含有TEMPO結(jié)構(gòu)單元的聚合物刷。氧化法是通過(guò)3-氯過(guò)氧苯甲酸(mCPBA)將TMPM的哌啶基氧化為氮氧自由基,分別制備了均聚物刷PS-PTMA、嵌段共聚物刷PS-P(MMA-b-TMA)、無(wú)規(guī)共聚物刷PS-P(MMA-co-TMA)。開(kāi)環(huán)法是利用聚合物刷PS-PGMA和PS-P(MMA-b-GMA)上含有大量環(huán)氧基團(tuán)與4-羥基-2,2,6,6-四甲基哌啶氮氧自由基(4-OH-TEMPO)的羥基間的開(kāi)環(huán)成醚反應(yīng),制得含氮氧自由基的PS-PGMA-TEMPO均聚物刷和PS-P(MMA-b-GMA-TEMPO)嵌段共聚物刷。最后將氧化法制得的氮氧自由基聚合物刷作為催化劑應(yīng)用在醇的選擇性催化氧化中,探索了聚合物刷在兩種醇的選擇性催化氧化體系中的催化規(guī)律及催化機(jī)理,發(fā)現(xiàn)氮氧自由基聚合物刷的催化性能優(yōu)于氮氧自由基聚合物鏈,具有催化性能高、循環(huán)使用性能好等優(yōu)點(diǎn)。將開(kāi)環(huán)法制得的氮氧自由基聚合物刷作為阻聚劑應(yīng)用在合成環(huán)氧大豆油丙烯酸酯中,阻聚效果良好,且通過(guò)過(guò)濾即可將其回收。進(jìn)而將聚合物刷阻聚劑與小分子阻聚劑4-OH-TEMPO組成復(fù)合阻聚體系,反應(yīng)后回收出聚合物刷,剩余的小分子阻聚劑留在體系中,滿(mǎn)足了反應(yīng)和貯存過(guò)程中對(duì)阻聚劑的不同需求量。所有類(lèi)型的聚合物刷都進(jìn)行了6次以上循環(huán)測(cè)試,發(fā)現(xiàn)多次循環(huán)使用后酯化率基本不變,循環(huán)使用性能良好。
[Abstract]:Tetramethylpiperidine-N- (TEMPO) is a stable free radical and has many potential applications. The application of tempo as catalyst in the selective catalytic oxidation of alcohols shows the advantages of mild reaction conditions, high activity and high selectivity. On the other hand, its toxicity is small, can be used as an effective inhibitor. However, the high price of TEMPO, which is difficult to recover after reaction, is the bottleneck of its wide application. It is an effective method to load TEMPO on the carrier and to recycle it for many times. Firstly, crosslinked polystyrene microspheres (PS) were used as functional monomers, methyl methacrylate (MMA), glycidyl methacrylate (GMA) and TMPM were used as functional monomers. Atom transfer radical polymerization (ARGET ATRP) was used to prepare different chain structure polymer brushes, including homopolymer brushes PS-PMMA-PS-PGMA and PS-PTMPM; block copolymers PS-P (MMA-b-TMPM) and PS-P (MMA-b-GMA); random copolymers brush PS-P (MMA-co-TMPM). Then polymer brushes containing TEMPO structure units were prepared by oxidation and ring opening methods. PS-PTMA-block copolymers (MMA-b-TMA) and random copolymers (PS-P (MMA-co-TMA) were prepared by oxidation of the piperidinyl group of TMPM to nitroxyl radical by 3-chloro peroxy benzoic acid (mCPBA), and block copolymers PS-P (MMA-b-TMA) and random copolymers PS-P (MMA-co-TMA) were prepared respectively. The ring opening reaction of PS-PGMA and PS-P (MMA-b-GMA) containing a large number of epoxide groups on polymer brushes was used to form ethers between the hydroxyl groups of 4-OH-TEMPO radical (4-OH-TEMPO) and PS-PGMA-TEMPO block copolymers of PS-PGMA-TEMPO (MMA-b-GMA-TEMPO) block copolymers of PS-PGMA-TEMPO (MMA-b-GMA-TEMPO) block brushes. Finally, the nitrogen-oxygen radical polymer brush was used as a catalyst in the selective catalytic oxidation of alcohol, and the catalytic law and mechanism of the polymer brush in the system of selective catalytic oxidation of two alcohols were explored. It is found that the catalytic performance of nitroxyl radical polymer brush is better than that of nitroxyl radical polymer chain, which has the advantages of high catalytic performance and good recycle performance. The nitrogen-oxygen radical polymer brush prepared by ring-opening method was used as an inhibitor in the synthesis of epoxy soybean oil acrylate. The polymerization inhibition effect was good and it could be recovered by filtration. Then the polymer brush inhibitor and the small molecular inhibitor 4-OH-TEMPO were used to form a composite polymer inhibitor system, and the polymer brush was recovered after the reaction. The remaining small molecular inhibitor remained in the system, which satisfied the different demand for the inhibitor in the reaction and storage process. All kinds of polymer brushes were tested for more than 6 cycles. It was found that the esterification rate was basically unchanged and the recycling performance was good.
【學(xué)位授予單位】：河北科技大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2016
【分類(lèi)號(hào)】：O631.3

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