發(fā)布時間：2018-04-04 02:23

  本文選題：氮修飾高分子材料　切入點：有序介孔結(jié)構(gòu)　出處：《上海師范大學》2017年碩士論文

【摘要】：隨著科學的發(fā)展和科技的進步,人們對環(huán)境問題日益關(guān)注,目前人類正在面臨非常嚴重的資源和環(huán)境危機,日益惡化的環(huán)境使化學家們不得不考慮減少化學對環(huán)境造成的危害。綠色化學的概念應運而生,要考慮如何處理化工行業(yè)產(chǎn)生的各種有毒廢物,更主要的是,在源頭加以解決,即選擇可再生無污染的底物,設(shè)計合理的反應條件和催化劑,減少不必要副產(chǎn)品的出現(xiàn),同時,也可以將均相催化劑固載化,可以通過簡單方式將催化劑回收循環(huán)利用。人們在生產(chǎn)和生活方面對具有新型功能的聚合材料的需求,以及科技水平的進步,近年來人們開發(fā)了眾多的有著特殊物理化學性質(zhì)和功能的高分子材料,其性能和特征大大超出了傳統(tǒng)高分子材料的范疇。尤其是功能化介孔高分子材料受到了廣大科學界學者的極大關(guān)注,其物理、化學、生物、醫(yī)藥、環(huán)境、材料等領(lǐng)域正發(fā)生在巨大變革。如何實現(xiàn)高分子材料功能化,實現(xiàn)工業(yè)化生產(chǎn)又是科學家面臨的巨大挑戰(zhàn)。一方面,介孔高分子材料所具有的大比表面積、有序孔結(jié)構(gòu)使得催化活性組分能夠均勻分散在載體表面;另一方面,采用化學穩(wěn)定性好的介孔聚合物材料將不會破壞活性組分的化學微環(huán)境,相反,載體提供的相對惰性的化學微環(huán)境將對催化活性組分起到一定保護作用。而酚醛樹脂有大量的酚羥基,有利于吸附金屬離子,短孔道的納米小球具有快速吸附平衡的能力,豐富的苯環(huán)結(jié)構(gòu)使電子分布不均勻,從而增大材料的吸附量。在制備固載型催化劑時,采用后嫁接法常常會由于有機基團堵塞孔道而導致催化活性的降低;而采用原位共聚法制備非均相催化劑時,由于有機基團共聚到載體骨架中,可使得活性位高度分散,不易造成孔道的堵塞。同時由于高分子本身具有很強的韌性,通過簡單的浸漬法可以將金屬離子給負載到酚醛樹脂上去�；谶@一思路,本論文主要通過水熱方法制備了不同功能化的介孔高分子材料,并考察了他們在水相或無溶劑的有機反應如Knoevenagel反應和Henry反應中的催化活性,以及負載金屬后的催化劑在Suzuki偶聯(lián)反應和Barbier反應的催化活性,主要分為以下三部分:第一部分,采用3-羥基吡啶和苯酚、甲醛作為原料,以非離子型表面活性劑EO-PO聚醚型F127作為結(jié)構(gòu)導向劑,通過水熱合成的方法得到氮修飾的功能化的納米小球(3HP-MPNs)。該材料具有較短的有序直孔道和規(guī)整的形貌,有助于分子和產(chǎn)物分子的傳質(zhì)和擴散,并通過骨架上的堿性活性位點和苯酚的特殊空間取向進行協(xié)同催化,進行水介質(zhì)的Knoevenagel反應。第二部分,采用2-羥基-5-硝基吡啶和苯酚、甲醛作為原料,以F127作為結(jié)構(gòu)導向劑,通過水熱合成的方法得到氮修飾的功能化的有序直孔道和規(guī)整的形貌的納米小球(2HP-5NG-MPNs),該材料有助于分子和產(chǎn)物分子的傳質(zhì)和擴散的特點。并利用其高溫煅燒后形成的氨基催化無溶劑的Henry反應。第三部分,利用水熱法合成了高度有序的氮修飾的功能化的介孔酚醛樹脂,然后通過浸漬法合成負載型金屬(主要是Pd)納米催化劑,基于該催化劑高分子載體的抗堿性及納米粒子的高度均一分散,應用于Suzuki偶聯(lián)反應和Barbier反應,嘗試將第二部分制得材料與其他金屬進行結(jié)合,并測其反應活性�？傊�,論文的主要目標圍繞發(fā)展氮功能化介孔酚醛樹脂合成技術(shù),優(yōu)化制備工藝和條件(反應溫度、濃度、原料組成和時間),并通過應用揭示材料的孔道形態(tài),立體形貌,以及活性位分布對性能的影響。通過觀察材料學發(fā)展史,發(fā)現(xiàn)酚醛樹脂是在催化領(lǐng)域中被廣泛使用的材料之一。因此,結(jié)構(gòu)和組分可控的功能化介孔酚醛樹脂有著廣泛的應用前景。
[Abstract]:With the development of science and technology, people are increasingly concerned about environmental issues, the mankind is facing very serious resource and environmental crisis, the deteriorating environment enables chemists to consider reducing the harm to the environment caused by chemical. The concept of green chemistry should be born, to consider how to deal with all kinds of toxic waste chemical industry the more important is to solve the problems in the source, choose renewable substrate, reaction conditions and catalyst design, reduce unnecessary by-products, at the same time, can also be immobilization of homogeneous catalyst by simple way catalyst recycling. Demand for polymers the new function in the aspects of production and life, and the progress of science and technology level in recent years, people developed many have special physical and chemical properties and function of high Molecular materials, its performance and features greatly beyond the traditional polymer category. Especially functionalized mesoporous polymer materials have attracted great attention, the majority of the scientific community of scholars in the physical, chemical, biological, pharmaceutical, environmental, materials and other fields are in great changes. How to achieve functional polymer materials, industrialized production it is a huge challenge for scientists. On the one hand, the mesoporous polymer material with high specific surface area, pore structure of the catalysts can be uniformly dispersed on the surface of the carrier; on the other hand, using mesoporous polymer material with good chemical stability will not destroy the chemical active components of the micro environment, on the contrary, the relative chemical inert carrier provides the microenvironment of the catalytic active components play a protective role. And phenolic resin phenolic hydroxyl number, is conducive to the adsorption of metal ions, short channel The nano ball has ability of fast adsorption, benzene ring structure rich electronic distribution is not uniform, so as to increase the adsorption capacity of materials. In the preparation of supported catalysts, often lower catalytic activity due to the blockage of the mesopore by grafting method; and by in situ copolymerization prepared by heterogeneous catalyst when the organic group copolymerized with vector backbone, the activity of a highly dispersed, not easy to cause pore blockage. At the same time as the polymer itself has a strong toughness, by the impregnation method can be simple to load metal ions into the phenolic resin. Based on this idea, this paper mainly by hydrothermal method the preparation of mesoporous materials with different functional polymer, and studied them in aqueous or organic solvent free reactions such as catalytic activity of Knoevenagel reaction and Henry reaction, and the load of gold The catalytic activity of the catalyst is in Suzuki coupling reaction and Barbier reaction, mainly divided into the following three parts: the first part, using 3- hydroxy pyridine and phenol and formaldehyde as raw materials, using nonionic surfactant EO-PO polyether type F127 as structure directing agent, nitrogen modified functionalized nanoparticles by the method of water thermal synthesis (3HP-MPNs). The morphology of the material has short straight channel orderly and regular, contribute to the molecular and molecular mass transfer and diffusion, and through the special space framework on the alkaline active site and phenol in orientation of synergistic catalysis, Knoevenagel reaction in aqueous medium. In the second part, using 2- -5- hydroxy nitro pyridine and phenol and formaldehyde as raw material, using F127 as the structure directing agent, nano ball nitrogen modified functional morphology of ordered straight channels and regular by hydrothermal method (2 HP-5NG-MPNs), the characteristics of the materials contribute to the molecular and molecular mass transfer and diffusion. The Henry reaction and the catalytic amino formed after high-temperature calcination without solvent. In the third part, nitrogen modified highly ordered hydrothermally synthesized functionalized mesoporous phenolic resin prepared by impregnation method, and then load type of metal (Pd) catalysts, the catalyst dispersed polymer carrier anti alkaline and highly homogeneous nanoparticles based on Application in Suzuki coupling reaction and Barbier reaction, try to second parts of prepared materials and other metal binding, and test its reactivity. In short, the main goal of the paper around the development of synthetic technology of nitrogen functionalized mesoporous phenolic resin, process optimization and preparation conditions (reaction temperature, concentration, composition of raw materials and time), and through the application of revealing the material pore morphology, vertical shape, and activity The influence of bit distribution on properties is studied. By observing the development history of materials, it is found that phenolic resin is one of the materials widely used in catalysis field. Therefore, functionalized mesoporous phenolic resin with controllable structure and composition has wide application prospects.

【學位授予單位】：上海師范大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：TB383.4;O643.36

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本文編號：1707951