新型杯芳烃—壳聚糖聚合物的合成及其吸附性能研究

发布时间：2019-03-25 11:36

【摘要】：本文利用杯芳烃和壳聚糖两种具有良好吸附性能的原料制备了新型杯芳烃-壳聚糖聚合物,包括三种类型:杯[4]芳烃壳聚糖高聚物(C[4]CSP),杯[6]芳烃壳聚糖高聚物(C[6]CSP),杯[8]芳烃壳聚糖高聚物(C[8]CSP),并研究了三种聚合物对于重金属离子和稀土离子的吸附作用。首先制备新的三氟甲磺酸杯[n]芳烃酯TEC[n](n=4,6,8),再由TEC[n]分别与低分子量壳聚糖(CS)通过Buchwald-Hartwig交叉偶联反应,得到三种新型杯[n]芳烃壳聚糖高聚物C[n]CSP(n=4,6,8)。通过红外光谱、XRD、扫描电镜、元素分析、和13C固体核磁共振等手段对三种C[n]CSP进行了结构表征。结果表明,壳聚糖被成功直接引入到三种杯[n]芳烃(n=4,6,8)的下缘。壳聚糖分子上C[4]CSP,C[6]CSP和C[8]CSP的取代度分别为17.75%,21.08%和54.53%。另外,文中通过正交实验对新型聚合物的制备条件进行了优化,结果表明其最佳制备条件为:TEC[n]与CS的摩尔比为1:2,催化剂为0.05当量,溶剂四氢呋喃(THF)与二甲亚砜(DMSO)的体积比为1:1.5,反应时间为5小时。溶解性测试结果表明所有产物在氯仿中的溶解度均较好。通过Martell双液相法与不同分光光度法结合,以三种C[n]CSP作为吸附剂材料,对重金属离子(Fe3+,Cd2+,Pb3+和Hg2+),重铬酸盐阴离子以及稀土金属阳离子(La3+,Ce3+和Eu3+)进行吸附性能研究。结果表明,由于克服水溶液中pH值变化以及氢键的影响,三种C[n]CSP的吸附性能均比原料壳聚糖和杯芳烃有较大提高。其中,C[6]CSP对Hg2+的吸附率达到98.96%,C[4]CSP对Fe3+的吸附容量为0.67 mmol·g1,C[n]CSP对重铬酸根阴离子的吸附能力达到了杯芳烃的三至四倍。上述结果表明,三种新型高聚物均有优异的吸附性能,具有进一步开发成为新型吸附型材料的潜力。
[Abstract]:In this paper, a novel calixarene-chitosan polymer was prepared by using calixarene and chitosan as raw materials, including three types: calix [4] arene chitosan polymer (C [4] CSP),). Calix [6] arene chitosan polymer (C [6] CSP), calix [8] arene chitosan polymer (C [8] CSP),) was studied. The adsorption of heavy metal ions and rare earth ions by three kinds of polymers was studied. First, a new trifluoromethanesulfonate calix [n] aryl ester TEC [n] (n = 4,6,8) was prepared, and then cross-coupling reaction of TEC [n] with low molecular weight chitosan (CS) via Buchwald-Hartwig was carried out. Three new calix [n] arene chitosan polymers C [n] CSP (n = 4,6,8) were obtained. The structures of three C [n] CSP were characterized by infrared spectroscopy, XRD, scanning electron microscopy, elemental analysis and 13C solid state nuclear magnetic resonance. The results showed that chitosan was successfully introduced directly to the lower edge of three calix [n] arene (n = 4, 6, 8). The substitution degrees of C [4] CSP,C [6] CSP and C [8] CSP on chitosan were 17.75%, 21.08% and 54.53%, respectively. In addition, the preparation conditions of the new polymer were optimized by orthogonal experiment. The results showed that the molar ratio of TEC [n] to CS was 1 / 2, and the catalyst was 0.05 eq. The volume ratio of tetrahydrofuran (THF) to dimethyl sulfoxide (DMSO) was 1? 1.5 and the reaction time was 5 hours. The solubility test results showed that the solubility of all the products in chloroform was good. Using three kinds of C [n] CSP as adsorbents, three kinds of C [n] CSP were combined with different spectrophotometry by Martell two-phase method. The heavy metal ions (Fe3, Cd2, Pb3 and Hg2), anions of dichromate and rare earth metal cations (La3, etc.) were used as adsorbents. The adsorption properties of Ce3 and Eu3 were studied. The results show that the adsorption properties of C [n] CSP are better than that of chitosan and calixarene because of overcoming the influence of pH value and hydrogen bond in aqueous solution. Among them, the adsorption rate of C [6] CSP to Hg2 is 98.96%, the adsorption capacity of C [4] CSP to Fe3 is 0.67 mmol 路g 1, and the adsorption capacity of C [n] CSP to dichromate anion is three to four times as much as that of calixarene. The above results show that the three new polymers all have excellent adsorption properties and have the potential to be further developed into new adsorptive materials.
【学位授予单位】：内蒙古农业大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O636.1;O647.3

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