本文選題：β-環(huán)糊精包合物　切入點(diǎn)：Th(Ⅳ)　出處：《南華大學(xué)》2016年碩士論文

【摘要】：環(huán)糊精(CD)作為一種天然無污染的高分子有機(jī)化合物,目前,在各個領(lǐng)域都有非常重要的應(yīng)用。盡管如此,但是天然的環(huán)糊精也存在一些缺點(diǎn)。因此,對天然環(huán)糊精進(jìn)行改性(化學(xué)修飾)至關(guān)重要。經(jīng)過化學(xué)修飾可以制備出很多種類的環(huán)糊精衍生物,這些衍生物的物理和化學(xué)性質(zhì)都能得到相應(yīng)的改善。β-CD作為常見的環(huán)糊精(α、β和λ三種)中應(yīng)用范圍最廣的一種環(huán)糊精,因?yàn)槠涫杷詢?nèi)腔的尺寸與很多分子尺寸相匹配,加上該內(nèi)腔能通過疏水作用力、靜電作用力、范德華力和氫鍵等作用力選擇性地識別包合結(jié)構(gòu)性能相匹配的客體分子形成包合物,而這些包合物的很多方面的性能都優(yōu)于天然β-CD。因此,對β-CD的研究一直都是國內(nèi)外科研工作者的研究重點(diǎn)。本課題的主要目標(biāo)是制備出一種新型的β-CD包合物,即β-CD-6-OTs/聯(lián)苯甲酰包合物,同時對其吸附性能進(jìn)行考察。論文的主要部分包括以下五個方面:1.對β-CD及其衍生物進(jìn)行簡單概況,同時也對β-CD包合物的常見合成方法及其應(yīng)用進(jìn)行總結(jié),最后提出了本課題的主要研究內(nèi)容。2.采用非均相合成的方法制備出6-對甲苯磺酰酯-β-CD(β-CD-6-OTs),利用紅外光譜,核磁共振氫譜和綜合熱分析等手段進(jìn)行表征。實(shí)驗(yàn)結(jié)果表明,該方法簡單可靠,制備的β-CD-6-OTs可作為合成下一步產(chǎn)物的原料。3.采用共沉淀法合成βOTs-6-CD-/聯(lián)苯甲酰包合物,先利用紅外光譜對其合成進(jìn)行初步表征,再利用紫外可見分光光度計對聯(lián)苯甲酰與β-CD-6-OTs的結(jié)合性能進(jìn)行探究,采用綜合熱分析儀對其熱穩(wěn)定性進(jìn)行分析,最后利用核磁共振氫譜和元素分析對其進(jìn)行表征。結(jié)果表明,該方法科學(xué)合理,β-CD-6-OTs對聯(lián)苯甲酰的包合效果優(yōu)異,且包合常數(shù)高達(dá)95.49%。4.以β-CD-6-OTs/聯(lián)苯甲酰包合物為吸附劑,對Th(Ⅳ)離子進(jìn)行吸附研究。先利用紅外光譜和掃描電鏡等手段對吸附Th(Ⅳ)離子前后的吸附劑進(jìn)行表征,再考察吸附劑在不同反應(yīng)時間t、不同p H值、不同初始濃度的Th(Ⅳ)溶液C_0、不同溫度T以及各種干擾離子存在條件下,對Th(Ⅳ)離子的吸附影響情況。通過一系列的單因素實(shí)驗(yàn)結(jié)果可知,在最佳吸附條件下,即t=20 min,pH=3.0,C_0=20mg/L,吸附劑β-CD-6-OTs/聯(lián)苯甲酰包合物對Th(Ⅳ)離子的吸附情況最好,吸附平衡時的最大吸附容量Q_m=17.83g/mg,吸附率為87.8%。同時,在Mg~(2+),Pb~(2+),Zn~(2+),Fe~(3+),Cd~(2+)等5種干擾離子存在下,吸附劑仍能有效吸附Th(Ⅳ)離子。另外,吸附劑對Th(Ⅳ)離子的吸附過程符合吸附動力學(xué)和熱力學(xué)模型,pH=3的HNO_3能有效脫附Th(Ⅳ)離子,且回收率高達(dá)99.2%。5.除了考察吸附劑對Th(Ⅳ)離子的吸附情況外,還將其應(yīng)用于另一種具有放射性的U(Ⅵ)離子的吸附研究。同樣,先利用紅外光譜和掃描電鏡等手段對吸附U(Ⅵ)離子前后的吸附劑進(jìn)行表征,再考察吸附劑在不同反應(yīng)時間t、不同p H值、不同初始濃度的U(Ⅵ)溶液C0、不同溫度T以及各種干擾離子存在條件下,對U(Ⅵ)離子的吸附影響情況。由吸附實(shí)驗(yàn)結(jié)果可知,當(dāng)=min60t,4.5p H=,mg/L20C0=時,吸附劑β-CD-6-OTs/聯(lián)苯甲酰包合物對U(Ⅵ)離子的最大吸附容量g/mg16.12Qm=,吸附率為91.2%。同時,當(dāng)2+Mg,3+e F,2+Cu,2+n M和2+bP的濃度￡L/mg15C時,吸附劑對U(Ⅵ)離子的吸附不受影響。另外,通過吸附動力學(xué)模型可知,準(zhǔn)二級動力學(xué)速率方程更適合描述吸附過程,即發(fā)生的主要是化學(xué)吸附過程。通過比較Langmuir等溫吸附模型(0.9907=R2)和Freundlich等溫吸附模型(0.9810=R2)的模型參數(shù)可知,吸附劑對U(Ⅵ)離子的吸附過程更適合于用Langmuir等溫吸附模型來描述,即吸附劑對U(Ⅵ)離子是單分子層的吸附,吸附主要發(fā)生在其表面。吸附熱力學(xué)模型表明,吸附劑對U(Ⅵ)離子的吸附是自發(fā)吸熱的過程。同時,8 m L 0.4mol/L的HCl能有效脫附U(Ⅵ)離子,且回收率高達(dá)99.1%。本課題為U(Ⅵ)離子的吸附提供部分參考價值。
[Abstract]:Cyclodextrin (CD) as a kind of natural macromolecule organic compound, no pollution at present, have very important applications in various fields. However, natural cyclodextrins but there are also some disadvantages. Therefore, the natural cyclodextrin modified (chemical modification) is essential. After chemical modification can be prepared out of many kinds of cyclodextrin derivatives, the physical and chemical properties of these derivatives can be improved. As a common -CD beta cyclodextrin (alpha, beta and lambda three) a cyclodextrin in the most widely used, because of its hydrophobic cavity size and many molecular size matched with the cavity through hydrophobic interaction, electrostatic force, van Edward guest molecules and hydrogen bonding force of selective recognition of inclusion structure to match the performance of clathrate formation, and the inclusion of a lot of performance is superior to the natural So the study of beta beta -CD., -CD has always been the research focus of domestic and foreign researchers. The main purpose of this research is to prepare a new type of beta -CD complexes, namely -CD-6-OTs/ beta bibenzoyl inclusion complexes, and to study its adsorption properties. The main part of the thesis includes the following five a: 1. of beta -CD and its derivatives were introduced in brief, and also summarizes the common synthesis method of beta -CD package complexes and its application, and finally put forward the method of non homogeneous synthesized 6- p-toluenesulfonyl ester beta -CD with the main research content of the subject.2. (P -CD-6-OTs). By using IR, 1H NMR and thermal analysis were characterized. The experimental results show that this method is simple and reliable, the preparation of beta -CD-6-OTs can be used as the material of the next product synthesis by.3. clathrate coprecipitation synthesis of OTs-6-CD-/ bibenzoyl, First, the synthesis preliminarily characterized by infrared spectroscopy, using UV spectrophotometer and antithetical couplet benzoyl beta -CD-6-OTs binding properties of the integrated thermal analyzer to analyze the thermal stability, characterized by 1H NMR and elemental analysis. The results show that the method is scientific reasonable, beta -CD-6-OTs antithetical couplet benzoyl inclusion effect is excellent, and the inclusion constants up to 95.49%.4. complexes as adsorbent to -CD-6-OTs/ beta bibenzoyl package of Th (IV) adsorption of ions. By infrared spectroscopy and scanning electron microscopy on the adsorption of Th (IV) before and after ion adsorbent characterization the re inspection, the adsorbent in the different reaction time of T and P in different H value, different initial concentration of Th (IV) C_0 solution, different temperature T and various interfering ions under the condition of Th (IV) adsorption effect of ions through. 涓，

本文編號：1710651