基于聚合物分子刷及其纳米管状材料的合成与催化应用

发布时间：2018-02-28 05:11

本文关键词： 聚合物分子刷有机微孔纳米管一锅法串联反应酸碱双功能催化剂超交联　出处：《华东师范大学》2017年博士论文　论文类型：学位论文

【摘要】：聚合物分子刷材料因为具有侧链接枝密度高,合成方法多样,尺寸在纳米范围等优点,过去二十年间,在有机纳米管、刺激-响应性材料、生物医药、溶液自组装和有机/无机杂化材料等研究领域得到了广泛的应用。本论文从聚合物分子刷纳米材料的功能性角度出发,对聚合物分子刷纳米材料的结构进行多元化设计,探索合成聚合物分子刷纳米材料的新方法,尝试合成新型的聚合物分子刷纳米材料,并研究这些材料在催化领域中的应用。论文第二章我们合成了两种聚合物分子刷(CCBC1和CCBC2)。CCBC1中负载磺酸,用于酸催化;CCBC2中负载4-氮-(4-乙烯基苄基)乙氧基-氮-甲氨基吡啶(VEMAP),用于碱催化。在CCBC1中,单体苯乙烯基磺酸苯酯(PVBS)的接枝个数为23,交联剂4-(3-丁烯基)苯乙烯(BS)的接枝个数为10,N-异丙基丙烯酰胺(NIPAAm)的接枝个数为220。在CCBC2中,单体VEMAP的接枝个数为10,BS的接枝个数为4,苯乙烯的接枝个数为4,NIPAAm的接枝个数为260。经过催化"一锅法"串联反应的试验,我们发现,小分子催化剂对甲苯磺酸(PTSA)和二甲氨基吡啶(DMAP)可以自由通过聚合物分子刷中的内部微环境,与分子刷中的活性中心反应,而使催化剂失活;分子内的交联是聚合物分子刷负载催化剂在催化"一锅法"反应中不失活的关键。本章内容第一次报道了聚合物分子刷材料在催化"一锅法"串联反应方面的应用,发展了聚合物分子刷纳米材料的应用范围,具有一定的理论和现实意义。论文第三章报道了通过聚合物分子刷软模板法合成可溶性有机纳米管的新方法。主要合成了三种类型的纳米管:Acid-nanotube,Base-nanotube,Pd-nanotube。该有机纳米管可用于催化水溶液中的Knoevenagel反应,"一锅法"串联反应和Suzuki-Miyaura偶联反应。其中Base-nanotube用于催化水溶液中的Knoevenagel反应,转化率高达95%。Acid-nanotube和Base-nanotube联合使用,用于催化"一锅法"串联反应,苯甲醛缩甲醇的转化率和最终产物的收率都达到了100%。Pd-nanotube催化Suzuki-Miyaura偶联反应,转化率达97%。我们还对该催化剂进行了回收实验,回收5次结果显示,该催化剂的催化活性没有明显降低。该有机纳米管的催化活性和稳定性都比交联聚合物分子刷具有优势,该有机纳米管的合成,开创了聚合物分子刷合成可溶性有机纳米管在催化中的应用。论文第四章报道了酸碱双功能双亲性有机纳米管(Acid-Base-nanotube)在催化"一锅法"串联反应中的应用。通过聚合物分子刷软模板法,在纳米管内部负载咪唑,在纳米管外部负载磺酸。通过荧光测试,我们发现该纳米管空腔内环境与二氯甲烷类似。经过在水溶液中催化"一锅法"串联反应可知,Acid-Base-nanotube在室温下反应即可实现原料的转化率和最终产物的收率达到100%。反应完成后,在反应体系中加入适量的乙醚,即可将产物分离。该催化剂具有很好的稳定性,催化回收6次,催化活性没有明显降低。该纳米管的合成为酸碱双功能双亲性纳米催化剂的合成提供了一种新途径,具有一定的理论和现实意义。论文第五章报道了超交联聚合物分子刷制备有机微孔纳米管在多相催化反应中的应用。首先,通过聚合物分子刷的超交联,合成了管内负载氨基的超交联有机微孔纳米管Amine-MNNs。然后分成两部分,一部分负载钨酸盐(TMNNs),用于催化硫醚的选择性氧化。在30℃时,一个当量的30%H202时,硫醚的转化率和选择性高达99%。该催化剂的稳定性较好,催化回收使用8次,催化活性没有明显降低。另一部分利用有机微孔纳米管中的部分氨基与对环境友好的酸性催化剂磷钨酸反应,通过调整合适的比例,合成出酸碱双功能微孔有机纳米管(PTA-MNNs)。该纳米管用于催化"一锅法"串联反应,原料的转化率达到了100%,最终产物的收率达到了99%。该催化剂稳定性较好,催化回收使用8次,催化剂的活性没有明显降低。该微孔有机纳米管的合成,为合成多相纳米催化剂在催化硫醚的选择性氧化和催化"一锅法"串联反应的应用提供了新途径。
[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.

【学位授予单位】：华东师范大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：O631;O643.36

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