羧酸型接枝淀粉吸附树脂的制备和对染料的去除性能  

Preparation of Carboxylic Acid Grafted Starch Adsorption Resin and Its Dye Removal Performance

作　　者：张昊[1,2] 李帆 常娜[3] 王海涛[4] 程博闻[2] 王攀磊 ZHANG Hao;LI Fan;CHANG Na;WANG Haitao;CHENG Bowen;WANG Panlei(School of Textile Science and Engineering,Tian Gong University,Tianjing 300387,China;Tianjin Municipal Key Laboratory of Advanced Fiber and Energy Storage,Tian Gong University,Tianjing 300387,China;School of Chemical Engineering and Technology,Tian Gong University,Tianjing 300387,China;School of Environmental Science and Engineering,Tian Gong University,Tianjing 300387,China)

机构地区：[1]天津工业大学纺织科学与工程学院,天津300387 [2]天津工业大学天津市先进纤维与储能技术重点实验室,天津300387 [3]天津工业大学化学工程与技术学院,天津300387 [4]天津工业大学环境科学与工程学院,天津300387

出　　处：《材料研究学报》2021年第6期419-432,共14页Chinese Journal of Materials Research

基　　金：国家重点研发计划(2019YFC0408404,2019YFC0408405);国家自然科学基金(51503147);天津市中外联合研究中心项目(19PTZWHZ00030);国家级大学生创新训练计划(201610058024)。

摘　　要：以天然淀粉(RS)为基体、以丙烯酸(AA)和乙酸乙烯酯(VAc)为原料在过硫酸铵(APS)和亚硫酸氢钠(SHS)的引发下用水相合成法制备羧酸型接枝淀粉吸附树脂(CSR),使用SEM、IR、XRD、13C-NMR和GPC等手段表征树脂的结构,研究其对染料的去除性能。结果表明:当引发剂的浓度为0.03 mol/L、单体物质量比n(AA):n(VAc)为3∶1、单体浓度为0.8 mol/L时CSR的羧酸基的含量为19.26%,对孔雀石绿的吸附量为17.35 mg/g。与天然淀粉相比,CSR树脂的耐水性和化学稳定性提高且对酸、碱及酶的耐受性增强,经碱处理后树脂的吸附性进一步提高。GPC分析结果表明,CSR树脂中的线型分子逐渐向分支型转化,使大分子形成复杂的网状结构。CSR的主链分子量随着单体添加量的增加和AA/VAc比例的增大呈下降趋势。CSR对碱性品红(BF)、亚甲基蓝(MB)和孔雀石绿(MG)的吸附量优于001×7强酸性离子交换树脂、D151弱酸性离子交换树脂以及羧甲基纤维素CMC与羧甲基淀粉CMS等合成及天然高分子吸附剂,与活性炭的性能接近,且具有广谱吸附性。CSR的零电荷点pHPZC为3.83,远低于天然淀粉树脂(pHPZC=7.38),是其对阳离子染料吸附量提高的重要原因。CSR在较宽的pH值范围内具有良好的染料吸附性能,当pH值为8.5时吸附量最大值。CSR对混合染料废水的脱色率为87.42%,且具有较强的再生能力,8次再生循环后其脱色率不低于首次吸附的88.6%。Carboxylic acid grafted starch adsorption resin(CSR) was synthesized by using natural starch(RS) as matrix, acrylic acid(AA) and vinyl acetate(VAc) as raw materials in the presence of ammonium persulfate(APS) and sodium bisulfite(SHS). The resulted CSR product was characterized by SEM,IR, XRD,13C-NMR and GPC. The results show that when the initiator concentration was 0.03 mol/L, the monomer mass ratio n(AA): n(VAc) was 3:1 and the monomer concentration was 0.8 mol/l, the prepared CSR product presents the carboxyl group content of 19.26% with adsorption capacity of 17.35 mg/g for malachite green, in other words, the water resistance and chemical stability and the tolerance to acid, alkali and enzyme of CSR resin were enhanced in comparison to those of the natural starch. After alkali treatment the adsorption capacity of the resin can be further improved. Linear molecules in CSR resin gradually transformed into branched type, resulting in complex network structure of macromolecules. The molecular mass of the main chain of CSR decreased with the increase of monomer dosage and AA/VAc ratio. The adsorption capacity of CSR for basic fuchsin(BF), methylene blue(MB) and malachite green(MG) is better than that of 001×7 strong acid ion exchange resin, D151 weak acid ion exchange resin,carboxymethyl cellulose CMC and carboxymethyl starch CMS and other synthetic and natural polymer adsorbents. The CSR has broad-spectrum of adsorption closed to that of active carbon. The zerocharge point pHpzc of CSR was 3.83, which was much lower than that of natural starch resin(pHpzc=7.38), that may be an important reason for the increase of adsorption capacity of cationic dyes. The CSR has good dye adsorption performance in a wide range of pH values, and the adsorption capacity reaches the maximum value when pH=8.5. The decolorization rate of CSR for mixed dye waste water was 87.42%. Finally the CSR had strong regeneration ability. Even after eight regeneration cycles, its decolorization rate was not lower than 88.6% of the initial adsor

关 键 词：有机高分子材料 淀粉 羧酸型 离子交换树脂 染料吸附 水处理技术 

分 类 号：TQ321.2[化学工程—合成树脂塑料工业]