摘要
淡水资源短缺是人类社会在21世纪所面临的最亟需解决的重大挑战之一。把海水转化成淡水是一种解决水资源匮乏现状的有效途径，但是在工业化海水淡化过程中，在海水中以中性状态存在的硼难以被除去。硼过量会使生物体产生毒理反应，造成农作物减产等后果，严重影响工农业生产和日常生活。无论是饮用水净化还是含硼废水的处理，除硼都是一个亟待解决的问题。随着工业化的发展，越来越多的微量有机污染物进入自然水体中，并进一步在生物圈内富集，极大地影响人类健康和生态系统，针对水中微量有机污染物的快速吸附和再生技术是近年来备受关注的研究领域。
硼酸可以和顺式二羟基发生高亲和力的可逆螯合，而环糊精聚合物是一种优异的吸附材料。本论文基于硼酸和糖类的螯合作用，综合环糊精对水中有机污染物超强的包络吸附能力，设计并制备出一种既能吸附水中微有机污染物又具有硼酸螯合能力的多功能吸附材料，并探究了材料的结构组成与吸附性能之间的构效关系。 首先，通过对β-环糊精（β-Cyclodextrin，β-CD）进行改性，得到叠氮的环糊精，再以对苯二甲酰氯为交联剂，制备表面含叠氮官能团的交联环糊精聚合物。利用“点击化学”（click chemistry）将炔键化的糖单体固载到环糊精聚合物上，得到以交联环糊精聚合物为骨架的含糖聚合物纳米海绵。通过控制环糊精
聚合物中叠氮环糊精的含量来控制固载单糖的量，利用傅里叶红外变换（FTIR）、热失重分析（TGA）、元素分析（EA）、孔结构分析（N2adsorption/desorption）、扫描电镜（SEM）等表征手段对固载单糖前后聚合物的化学组成和表面形态进行表征，证明了单糖的成功固载。在吸附实验中，系统地测试了固载不同单糖的纳米海绵材料对硼酸和有机染料（亚甲基蓝）的吸附容量、速率，研究发现单糖的存在能够赋予聚合物有效吸附硼酸的能力，糖基与亚甲基蓝分子之间的次级键作用能够显著地增大对亚甲基蓝的吸附容量，加快其吸附速率。染料的脱附实验表明含糖聚合物纳米海绵材料具有优异的可重复利用性。
其次，在上述工作的基础上，我们进一步优化了合成路线，发展了不利用金属催化剂的合成路径，制备出具有多孔结构和硼螯合能力的以环糊精为骨架的含糖聚合物。以四氟对苯二腈和对苯二甲酰氯这两种不同的交联剂分别制备交联环糊精聚合物，然后将叠氮官能团还原为氨基，利用其与葡萄萄酸内脂开环反应，最终得到了具有不同表面性质和结构的两类含糖聚合物纳米海绵。通过比较两个系列的糖聚物对硼酸和双酚A（BPA）的吸附情况，发现以四氟对苯二腈为交联剂的糖聚物的吸附速率和吸附容量都优于对苯二甲酰氯交联的糖聚物。两类的糖聚物对BPA都有着超快的吸附速率，在30s内就能达到平衡吸附量，对硼酸的吸附速度明显加快，仅需要市场商业树脂Amberlite IRA743平衡吸附时间的十二分之一。
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2010年广东高考作文摘要硕士学位论文关键词：β-环糊精，含糖聚合物，糖的固定化，硼酸，吸附污染物
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硕士学位论文基于环糊精的新型吸附材料的构建及其应用性能研究
Abstract
The shortage of fresh water resources is one of the most important challenges that human society faces in the 21st century. The conversion of seawater into fresh water is an effective way to solve the current situation of water scarcity, but in the process of industrial desalination, boron exit in neutral state in seawater which is difficult to remove. Excessive boron could cause toxicological reactions in organisms, resulting in the consequences of crop yield reduction, which seriously affects industrial and agricultural production and daily life. Whether drinking water purification or treatment of boron-containing wastewater, boron removal is an urgent problem to be solved. With the development of industrialization, more and more organic pollutants enter natural water and further enrich in the biosphere, which greatly threatens human health and ecosystems. The rapid adsorption and regeneration technology for organic pollutants in water have received much attention in recent years.
Boric acid can reversibly chelate with cis-dihydroxyl with high affinity, and cyclodextrin polymer is an excellent adsorbent material. This paper was based on the chelation of boric acid and sugar, combined with the superior envelope adsorption capacity of cyclodextrin for organic pollutants in water, designed and prepared a kind of multifunctional adsorption material with adsorption of micro-organic pollutants and boric acid sequestration ability. It exploreed the structure-activity relationship between the structural composition of the material and the adsorption performance.
First, the surface of cyclodextrin polymer with azide-containing functional group was prepared by modifying β-cyclodextrin (β-CD) to obtain azide cyclodextrin, and then using terephthaloyl chloride as a crosslinking agent. The acetylenical sugar monomer was immobilized on the cyclodextrin polymer by "click chemistry", the obtained glycopolymer nanosponge which have cross-linked cyclodextrin polymer as a skeleton. The amount of immobilized monosaccharide was controlled by controlling the content of azide cyclodextrin in the cyclodextrin polymer, using Fourier transform infrared (FTIR), thermogravimetric analysis (TGA), elemental analysis (EA), and pore structure analysis,(N2 adsorption/desorption), scanning electron microscopy (SEM) and other characterization tools to characterize the chemical composition and surface morphology of the polymer before and after immobilized monosaccharide, which would prove the successful immobilization of monosaccha
rides. In the adsorption experiments, the adsorption capacity and rate of boric acid and organic dye (methylene blue) supported by glycopolymer nanosponge with different
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土田健次郎Abstract 硕士学位论文
monosaccharides were systematically tested. It was found that the presence of monosaccharides could give polymer ability to adsorb boric acid. The secondary bond between glycosyl and methylene blue molecules could significantly increase the adsorption capacity rate. Dye desorption experiments have shown that nanosponge materials have excellent recyclability.
Secondly, based on the above work, we further optimized the synthetic route and developed a synthetic route that did not utilize metal catalysts, then prepared glycopolymer nanosponge with a cyclodextrin as a skeleton which has a porous structure and boron chelation ability. The cross-linked cyclodextrin polymer was prepared by using two different crosslinking agents, tetrafluoroterephthalonitrile (TFN) and terephthalic chloride (TCL), and then the azide functional group was reduced to an amino group which was used to undergo a ring opening reaction with gluconolactone. The reaction finally producted two types of glycopolymer nanosponges that had diffe
rent surface properties and structures. By comparing the adsorption of boric acid and bisphenol A (BPA) by two series of glycopolymers, it was found that the glycopolymer with TFN as cross-linked agent had better performance in adsorption rate and adsorption capacity than that of TCL. Both types of glycopolymers have an ultra-fast adsorption rate for BPA, and the time that took to equilibrium adsorption state was not exceed 30s, which was only 1/12 of the equilibrium adsorption time of market-based commercial resin Amberlite IRA743.
Keywords: β-cyclodextrin, glycopolymer, immobilization of sugar, boric acid, adsorption of pollutants
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硕士学位论文基于环糊精的新型吸附材料的构建及其应用性能研究
目录
郑州航空工业管理学院学报
摘要.......................................................................................................... I Abstract ..................................................................................................... III 1绪论.. (1)
1.1 环糊精简介 (1)
1.1.1 环糊精的结构与性质 (1)
1.1.2 环糊精衍生物 (1)
1.1.3 环糊精聚合物 (2)
1.1.4 环糊精聚合物在环境领域的应用 (3)
1.2 除硼技术概述 (3)
1.2.1 硼简介 (3)
1.2.2 除硼方法与机理 (4)调度指挥系统
1.3 以环糊精为骨架的含糖聚合物的合成与应用 (6)
1.4 本课题研究的意义和内容 (6)
1.4.1 本论文选题的目的与意义 (6)
1.4.2 本论文的主要研究内容 (7)
2实验材料与表征测试方法 (9)
2.1 实验试剂与设备 (9)
2.1.1 实验试剂 (9)
2.1.2 实验仪器 (10)
2.2 以环糊精为骨架的含糖聚合物的制备与研究方案 (11)
2.2.1 环糊精衍生物的制备 (11)
2.2.2 环糊精聚合物的制备 (12)
喜剧世界2.2.3 炔键化单糖的制备 (13)
2.2.4 通过“点击化学”反应制备以环糊精为骨架的含糖聚合物 (14)
三维度2.2.5 含糖聚合物材料对硼酸的吸附 (15)
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