本文關(guān)鍵詞： 聚合物分子刷 有機(jī)微孔納米管 一鍋法串聯(lián)反應(yīng) 酸堿雙功能催化劑 超交聯(lián)　出處：《華東師范大學(xué)》2017年博士論文　論文類型：學(xué)位論文

【摘要】：聚合物分子刷材料因?yàn)榫哂袀?cè)鏈接枝密度高,合成方法多樣,尺寸在納米范圍等優(yōu)點(diǎn),過去二十年間,在有機(jī)納米管、刺激-響應(yīng)性材料、生物醫(yī)藥、溶液自組裝和有機(jī)/無機(jī)雜化材料等研究領(lǐng)域得到了廣泛的應(yīng)用。本論文從聚合物分子刷納米材料的功能性角度出發(fā),對(duì)聚合物分子刷納米材料的結(jié)構(gòu)進(jìn)行多元化設(shè)計(jì),探索合成聚合物分子刷納米材料的新方法,嘗試合成新型的聚合物分子刷納米材料,并研究這些材料在催化領(lǐng)域中的應(yīng)用。論文第二章我們合成了兩種聚合物分子刷(CCBC1和CCBC2)。CCBC1中負(fù)載磺酸,用于酸催化;CCBC2中負(fù)載4-氮-(4-乙烯基芐基)乙氧基-氮-甲氨基吡啶(VEMAP),用于堿催化。在CCBC1中,單體苯乙烯基磺酸苯酯(PVBS)的接枝個(gè)數(shù)為23,交聯(lián)劑4-(3-丁烯基)苯乙烯(BS)的接枝個(gè)數(shù)為10,N-異丙基丙烯酰胺(NIPAAm)的接枝個(gè)數(shù)為220。在CCBC2中,單體VEMAP的接枝個(gè)數(shù)為10,BS的接枝個(gè)數(shù)為4,苯乙烯的接枝個(gè)數(shù)為4,NIPAAm的接枝個(gè)數(shù)為260。經(jīng)過催化"一鍋法"串聯(lián)反應(yīng)的試驗(yàn),我們發(fā)現(xiàn),小分子催化劑對(duì)甲苯磺酸(PTSA)和二甲氨基吡啶(DMAP)可以自由通過聚合物分子刷中的內(nèi)部微環(huán)境,與分子刷中的活性中心反應(yīng),而使催化劑失活;分子內(nèi)的交聯(lián)是聚合物分子刷負(fù)載催化劑在催化"一鍋法"反應(yīng)中不失活的關(guān)鍵。本章內(nèi)容第一次報(bào)道了聚合物分子刷材料在催化"一鍋法"串聯(lián)反應(yīng)方面的應(yīng)用,發(fā)展了聚合物分子刷納米材料的應(yīng)用范圍,具有一定的理論和現(xiàn)實(shí)意義。論文第三章報(bào)道了通過聚合物分子刷軟模板法合成可溶性有機(jī)納米管的新方法。主要合成了三種類型的納米管:Acid-nanotube,Base-nanotube,Pd-nanotube。該有機(jī)納米管可用于催化水溶液中的Knoevenagel反應(yīng),"一鍋法"串聯(lián)反應(yīng)和Suzuki-Miyaura偶聯(lián)反應(yīng)。其中Base-nanotube用于催化水溶液中的Knoevenagel反應(yīng),轉(zhuǎn)化率高達(dá)95%。Acid-nanotube和Base-nanotube聯(lián)合使用,用于催化"一鍋法"串聯(lián)反應(yīng),苯甲醛縮甲醇的轉(zhuǎn)化率和最終產(chǎn)物的收率都達(dá)到了100%。Pd-nanotube催化Suzuki-Miyaura偶聯(lián)反應(yīng),轉(zhuǎn)化率達(dá)97%。我們還對(duì)該催化劑進(jìn)行了回收實(shí)驗(yàn),回收5次結(jié)果顯示,該催化劑的催化活性沒有明顯降低。該有機(jī)納米管的催化活性和穩(wěn)定性都比交聯(lián)聚合物分子刷具有優(yōu)勢(shì),該有機(jī)納米管的合成,開創(chuàng)了聚合物分子刷合成可溶性有機(jī)納米管在催化中的應(yīng)用。論文第四章報(bào)道了酸堿雙功能雙親性有機(jī)納米管(Acid-Base-nanotube)在催化"一鍋法"串聯(lián)反應(yīng)中的應(yīng)用。通過聚合物分子刷軟模板法,在納米管內(nèi)部負(fù)載咪唑,在納米管外部負(fù)載磺酸。通過熒光測(cè)試,我們發(fā)現(xiàn)該納米管空腔內(nèi)環(huán)境與二氯甲烷類似。經(jīng)過在水溶液中催化"一鍋法"串聯(lián)反應(yīng)可知,Acid-Base-nanotube在室溫下反應(yīng)即可實(shí)現(xiàn)原料的轉(zhuǎn)化率和最終產(chǎn)物的收率達(dá)到100%。反應(yīng)完成后,在反應(yīng)體系中加入適量的乙醚,即可將產(chǎn)物分離。該催化劑具有很好的穩(wěn)定性,催化回收6次,催化活性沒有明顯降低。該納米管的合成為酸堿雙功能雙親性納米催化劑的合成提供了一種新途徑,具有一定的理論和現(xiàn)實(shí)意義。論文第五章報(bào)道了超交聯(lián)聚合物分子刷制備有機(jī)微孔納米管在多相催化反應(yīng)中的應(yīng)用。首先,通過聚合物分子刷的超交聯(lián),合成了管內(nèi)負(fù)載氨基的超交聯(lián)有機(jī)微孔納米管Amine-MNNs。然后分成兩部分,一部分負(fù)載鎢酸鹽(TMNNs),用于催化硫醚的選擇性氧化。在30℃時(shí),一個(gè)當(dāng)量的30%H202時(shí),硫醚的轉(zhuǎn)化率和選擇性高達(dá)99%。該催化劑的穩(wěn)定性較好,催化回收使用8次,催化活性沒有明顯降低。另一部分利用有機(jī)微孔納米管中的部分氨基與對(duì)環(huán)境友好的酸性催化劑磷鎢酸反應(yīng),通過調(diào)整合適的比例,合成出酸堿雙功能微孔有機(jī)納米管(PTA-MNNs)。該納米管用于催化"一鍋法"串聯(lián)反應(yīng),原料的轉(zhuǎn)化率達(dá)到了100%,最終產(chǎn)物的收率達(dá)到了99%。該催化劑穩(wěn)定性較好,催化回收使用8次,催化劑的活性沒有明顯降低。該微孔有機(jī)納米管的合成,為合成多相納米催化劑在催化硫醚的選擇性氧化和催化"一鍋法"串聯(lián)反應(yīng)的應(yīng)用提供了新途徑。
[Abstract]:Polymer brushes grafted materials because of its high density, synthesis methods, dimensions in the nanometer range and other advantages, in the past twenty years, in the organic nanotubes, stimuli responsive materials, biological medicine, the solution has been widely used since the field assembly and organic / inorganic hybrid materials. This paper from the functional perspective polymer brushes of nano materials, structure of polymer brushes and nano materials diversified design, explore new methods of synthesis of polymer brushes and nano materials, try to synthesize novel polymer brushes and nano materials, research and application of these materials in catalytic field. In the second chapter, we synthesized two kinds of polymer brushes (CCBC1 and CCBC2.CCBC1) load sulfonic acid, used for acid catalysis; nitrogen load 4- CCBC2 - (4- 3-benyethylene) ethoxy - N - dimethylamino pyridine (VEMAP), for alkali rush . in CCBC1, the monomer styrene sulfonic acid phenyl ester (PVBS) the number of grafting was 23, crosslinking agent 4- (3- Ding Xiji) styrene (BS) the number of grafting was 10, N- isopropylacrylamide (NIPAAm) the number of grafting was 220. in CCBC2, the number of grafting monomer VEMAP the 10, the number of grafting BS is 4, the number of grafted styrene is 4 NIPAAm, the grafting number is 260. after the catalytic one pot tandem reaction test, we found that small molecule catalyst p-toluene sulfonic acid (PTSA) and two methyl amino pyridine (DMAP) can be divided by internal free polymer the brush in the micro environment, and activity center in response to molecular brush, catalyst deactivation; intramolecular crosslinking polymer brushes is supported catalyst deactivation is not key in "one pot" catalytic reaction. This chapter first reported the polymer brush materials catalyzed tandem reaction in one pot method "the With the development of the scope of application of polymer brushes and nano materials, has a certain theoretical and practical significance. The third chapter reported a new method for synthesis of soluble organic nanotubes polymer brushes and soft template method. The synthesis of three types: Acid-nanotube, Base-nanotube, Pd-nanotube. nanotubes of the organic nanotubes can be used for Knoevenagel reaction catalyzed by water in the solution, "one pot" tandem reaction and Suzuki-Miyaura coupling reaction. The Base-nanotube used in Knoevenagel catalytic reaction in aqueous solution, the conversion rate of up to 95%.Acid-nanotube and Base-nanotube, for "one pot" catalyzed tandem reaction, the conversion rate of benzaldehyde methanol and final product yield reached 100%.Pd-nanotube catalyzed by Suzuki-Miyaura the coupling reaction, the conversion rate of 97%. we have the catalyst was recycled 5 times and recovery test. Results showed that the catalytic activity was not significantly reduced. The organic nanotubes catalytic activity and stability has more advantages than crosslinked polymer brushes, the synthesis of organic nanotubes, a synthesis of soluble organic polymer molecular brush nanotubes in catalysis applications. The fourth chapter reports the acid-base bifunctional amphiphilic organic nanotubes (Acid-Base-nanotube) tandem reaction by using catalytic in "one pot". The polymer brush soft template method, imidazole load inside the nanotubes, loaded on the nanotubes. The external sulfonic acid by fluorescence test, we found that the nanotubes in the cavity environment with dichloromethane. After similar catalysis in aqueous solution in one pot tandem reaction shows that the transformation the rate of Acid-Base-nanotube reaction at room temperature can be realized by raw materials and final product yield reached 100%. after the completion of the reaction in the reaction system Adding proper amount of ether can be product separation. The catalyst has good stability, catalytic recycled 6 times without loss of catalytic activity. Provide a new way for the synthesis of nanotubes synthesis for acid-base bifunctional amphiphilic nano catalyst, it has certain theoretical and practical significance. The fifth chapter reports the application of super crosslinked polymer brushes and preparation of microporous organic nanotubes on catalytic reaction. Firstly, by hypercrosslinked polymer brushes, tube load amino hypercrosslinked microporous organic nanotubes Amine-MNNs. then synthesized into two parts, part load tungstate (TMNNs), used for selective catalytic oxidation of sulfide at 30 degrees, an equivalent of 30%H202, the stability of the conversion rate of sulfide and the selectivity of the 99%. catalyst is better catalytic recycling used for 8 times without loss of catalytic activity. Another part of the reaction section in nanotubes and microporous organic amino acid catalyst phosphotungstic acid is friendly to the environment, by adjusting the proper proportion, synthesis of acid base bifunctionalized microporous organic nanotubes (PTA-MNNs). The nanotubes used to catalyze the "one pot" series reaction, the conversion rate of raw materials reached 100%, the final product yield the 99%. of the catalyst stability, catalytic recycling 8 times, the activity of the catalyst was not significantly reduced. The synthesis of microporous organic nanotubes, provides a new way for the application of synthetic multi phase nano catalyst in selective oxidation and catalytic reaction series "sulfides catalyzed by one pot method.

【學(xué)位授予單位】：華東師范大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2017
【分類號(hào)】：O631;O643.36

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