【摘要】：本文利用杯芳烴和殼聚糖兩種具有良好吸附性能的原料制備了新型杯芳烴-殼聚糖聚合物,包括三種類型:杯[4]芳烴殼聚糖高聚物(C[4]CSP),杯[6]芳烴殼聚糖高聚物(C[6]CSP),杯[8]芳烴殼聚糖高聚物(C[8]CSP),并研究了三種聚合物對于重金屬離子和稀土離子的吸附作用。首先制備新的三氟甲磺酸杯[n]芳烴酯TEC[n](n=4,6,8),再由TEC[n]分別與低分子量殼聚糖(CS)通過Buchwald-Hartwig交叉偶聯(lián)反應(yīng),得到三種新型杯[n]芳烴殼聚糖高聚物C[n]CSP(n=4,6,8)。通過紅外光譜、XRD、掃描電鏡、元素分析、和13C固體核磁共振等手段對三種C[n]CSP進行了結(jié)構(gòu)表征。結(jié)果表明,殼聚糖被成功直接引入到三種杯[n]芳烴(n=4,6,8)的下緣。殼聚糖分子上C[4]CSP,C[6]CSP和C[8]CSP的取代度分別為17.75%,21.08%和54.53%。另外,文中通過正交實驗對新型聚合物的制備條件進行了優(yōu)化,結(jié)果表明其最佳制備條件為:TEC[n]與CS的摩爾比為1:2,催化劑為0.05當(dāng)量,溶劑四氫呋喃(THF)與二甲亞砜(DMSO)的體積比為1:1.5,反應(yīng)時間為5小時。溶解性測試結(jié)果表明所有產(chǎn)物在氯仿中的溶解度均較好。通過Martell雙液相法與不同分光光度法結(jié)合,以三種C[n]CSP作為吸附劑材料,對重金屬離子(Fe3+,Cd2+,Pb3+和Hg2+),重鉻酸鹽陰離子以及稀土金屬陽離子(La3+,Ce3+和Eu3+)進行吸附性能研究。結(jié)果表明,由于克服水溶液中pH值變化以及氫鍵的影響,三種C[n]CSP的吸附性能均比原料殼聚糖和杯芳烴有較大提高。其中,C[6]CSP對Hg2+的吸附率達到98.96%,C[4]CSP對Fe3+的吸附容量為0.67 mmol·g1,C[n]CSP對重鉻酸根陰離子的吸附能力達到了杯芳烴的三至四倍。上述結(jié)果表明,三種新型高聚物均有優(yōu)異的吸附性能,具有進一步開發(fā)成為新型吸附型材料的潛力。
[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.
【學(xué)位授予單位】：內(nèi)蒙古農(nóng)業(yè)大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O636.1;O647.3

【參考文獻】

相關(guān)期刊論文 前10條

1 劉宇寧;鐘志梅;;磺基水楊酸分光光度法測定小鼠肝臟鐵(Ⅲ)含量[J];內(nèi)蒙古農(nóng)業(yè)大學(xué)學(xué)報(自然科學(xué)版);2015年06期

2 趙旭初;閆靜;;偶氮胂Ⅲ褪色分光光度法對多糖鈰復(fù)合物中鈰的測定[J];分子科學(xué)學(xué)報;2015年05期

3 孫銀蕾;劉波;;2-乙酰基-6-三甲基硅基苯基三氟甲磺酸酯的合成[J];合成化學(xué);2014年03期

4 莫江敏;韋文業(yè);施先義;;二苯碳酰二肼分光光度法測定硝酸鐵中微量鉻(Ⅵ)[J];化工技術(shù)與開發(fā);2013年02期

5 楊瑞學(xué);;殼聚糖在食品保鮮中的應(yīng)用[J];農(nóng)業(yè)工程;2012年03期

6 楊宇翔;安潔;楊育兵;林海;;杯芳烴改性殼聚糖對釹離子的吸附性能[J];同濟大學(xué)學(xué)報(自然科學(xué)版);2012年01期

7 謝劍偉;楊發(fā)福;陳文;洪碧瓊;;新型席夫堿基杯[4]芳烴-殼聚糖衍生物的合成及其對金屬離子的吸附性能[J];合成化學(xué);2011年01期

8 段金龍;馮小強;李小芳;盧軍芳;崔錦峰;楊聲;;冠醚、杯芳烴改性殼聚糖對金屬離子吸附性能的研究進展[J];天水師范學(xué)院學(xué)報;2010年05期

9 楊華;;稀土元素的配位化合物及應(yīng)用概述[J];稀土;2010年03期

10 張文軒;尚亞波;袁博;蔣玉祥;盧耀柏;秦祖群;陳愛民;王廣智;錢曉志;楊琥;程昒時;;殼聚糖改性絮凝劑絮凝性能的研究[J];高分子通報;2010年04期

相關(guān)碩士學(xué)位論文 前6條

1 盧靜;杯［4］芳烴衍生化殼聚糖鍵合硅膠固定相的制備及其色譜性能研究[D];鄭州大學(xué);2014年

2 張小軍;對叔丁基杯[4]芳烴衍生物的合成及其對釷的吸附性能[D];南華大學(xué);2013年

3 段金龍;殼聚糖改性及應(yīng)用研究[D];蘭州理工大學(xué);2011年

4 鄭林祿;功能化氮雜杯芳烴衍生物及聚合物的研究[D];福建師范大學(xué);2006年

5 王春;殼聚糖基復(fù)合抗菌劑的研究及應(yīng)用[D];中南大學(xué);2004年

6 毛劍英;前向人工神經(jīng)網(wǎng)絡(luò)—分光光度法同時測定水中的鎘、鉛、汞[D];北京工業(yè)大學(xué);2001年

，

本文編號：2446934