CN104592449B - 一种智能水凝胶及其制备方法与应用 - Google Patents
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Abstract
一种智能水凝胶及其制备方法与应用,涉及一种水凝胶。所述智能水凝胶为P(NIPAM‑co‑CS)/Fe3O4,由四氧化三铁、N‑异丙基丙烯酰胺和壳聚糖组成。制备方法:将FeCl2·4H2O和FeCl3·6H2O溶解于乙醇‑水混合溶剂中反应,氮气保护下,以氨水为沉淀剂,制得亲水性的Fe3O4纳米颗粒;将制得的Fe3O4纳米颗粒超声分散在壳聚糖溶液中,加入温敏单体N‑异丙基丙烯酰胺,在交联剂、引发剂作用下,以四甲基乙二胺为加速剂,进行聚合反应,通过微乳液聚合法制得智能水凝胶P(NIPAM‑co‑CS)/Fe3O4。所述智能水凝胶可在制备用于水体重金属离子吸附与解吸剂中应用,脱除水体中的重金属离子。
Description
技术领域
本发明涉及一种水凝胶,尤其是涉及一种智能水凝胶及其制备方法与应用。
背景技术
近年来,随着工业化和城市化进程的加速,尤其是采矿、冶炼、电镀等行业的发展,水体中重金属离子如铬、铜、汞、铅等逐渐增加。重金属离子的生物富集以及毒性累积对人体健康产生极大的威胁,因而寻求有效的水体重金属脱除技术已成为近来研究的热点话题。在众多水体重金属处理技术(如化学沉淀、离子交换及吸附)中,吸附由于其高效、易处理等得到了最广泛的应用。在吸附应用中,吸附剂的选择至关重要。传统吸附剂(D.;V.;Gorgievski,M.;G.;R.Adsorption of heavymetalions by sawdust of deciduous trees.J.Hazard.Mater.2009,171,684.)由于结合容量低,表面活性位缺乏,再生困难,从溶液中回收目标金属离子的能力差等使其应用受到限制。因此,针对大量溶液开发吸附表面积大、可迅速分离、可再生的新型吸附剂具有重要意义。
含功能基团的水凝胶,尤其是能感知外部环境(磁场、温度及pH等)的微小变化并据此迅速作出相应改变的智能水凝胶(Hua R;Li Z.Sulfhydryl functionalizedhydrogel with magnetism:Synthesis,characterization,and adsorption behaviorstudy for heavy metal removal.Chem.Eng.J.2014,249,189.),由于其具有吸附容量高、环境友好及可再生循环利用等优点,是目前水体重金属处理领域的研究热点之一。大量的研究工作通过制备具有敏感性功能基团的水凝胶来实现对水体重金属离子的脱除,然而,这些工作往往使得吸附剂的制备过程复杂(Vani,J.S.;Rao,K.M.;Reddy,N.S.G.;Rao,K.K.Synthesis and Characterization of Sodium Carboxy Methyl Cellulose/Poly(Acrylamide)Magnetic Nano Composite Semi Ipn’ s for Removal of Heavy MetalIons.World,2013,2,33.),成本高昂并且很难真正实现对重金属离子吸附性能的智能化控制。
发明内容
本发明的目的在于针对现有技术所存在的缺陷,提供一种智能水凝胶及其制备方法与应用。
所述智能水凝胶为P(NIPAM-co-CS)/Fe3O4,由四氧化三铁(Fe3O4)、N-异丙基丙烯酰胺(NIPAM)和壳聚糖(CS)组成。
所述智能水凝胶的制备方法,包括如下步骤:
1)将FeCl2·4H2O和FeCl3·6H2O溶解于乙醇-水混合溶剂中反应,氮气保护下,以氨水为沉淀剂,制得亲水性的Fe3O4纳米颗粒;
2)将制得的亲水性的Fe3O4纳米颗粒超声分散在壳聚糖溶液中,加入温敏单体N-异丙基丙烯酰胺,在交联剂、引发剂作用下,以四甲基乙二胺为加速剂,进行聚合反应,通过微乳液聚合法制得智能水凝胶P(NIPAM-co-CS)/Fe3O4。
在步骤1)中,所述FeCl2·4H2O与FeCl3·6H2O的质量比可为1∶(2~3);所述乙醇-水混合溶剂中乙醇与水的体积比可为1∶1;所述反应的温度可为50~80℃,反应的时间可为3h,所述反应最好在机械搅拌下反应,转速可为200~350r/min,经氨水调节的反应体系pH可为9~12。
在步骤2)中,所述壳聚糖溶液的壳聚糖质量浓度可为1.5~6g/200mL,溶剂是1%~3%的醋酸溶液;所述四氧化三铁、壳聚糖与N-异丙基丙烯酰胺的质量比可为2∶1∶1~1∶2∶2;所述交联剂可采用N,N’─亚甲基双丙烯酰胺等;所述引发剂可采用过硫酸铵等;交联剂与引发剂的用量均可占单体总质量的0.05%~1.5%;四甲基乙二胺的用量可占单体总质量的10%;所述聚合反应的温度可为25~40℃,聚合反应的时间可为5h;
所述微乳液聚合中所用油相为石蜡,水相与油相体积比可为1∶(8~10)。
所述智能水凝胶可在制备用于水体重金属离子吸附与解吸剂中应用,脱除水体中的重金属离子。
所述用于水体重金属离子吸附与解吸剂的使用方法为:通过调控外加交变磁场,使智能水凝胶升温至20~35℃,pH为4.8~6.9下进行吸附;在浓度为0.5~10mmol/L的有机弱酸下进行解吸,所述有机弱酸为EDTA溶液。
本发明提供一种简捷、快速、经济高效的智能水凝胶的制备方法及脱除重金属离子的应用,通过共沉淀法制得单分散的亲水性Fe3O4纳米颗粒,而后将其与NIPAM及壳聚糖混合,低温下通过微乳液聚合法快速合成智能水凝胶P(NIPAM-co-CS)/Fe3O4,经交变磁场加热,可实现对重金属离子吸附性能的智能化控制。智能水凝胶P(NIPAM-co-CS)/Fe3O4集磁敏、温敏及pH敏感性于一体。
本发明具有以下有益效果:用于水体重金属离子脱除的智能水凝胶具有磁敏、温敏及pH敏等多重调控性能,其制备过程为低温引发聚合,聚合条件简单,反应过程所需时间短,产品收率高且绿色环保。该法制得的水凝胶对重金属离子吸附容量大,去除效率高;在外加磁场作用下,可轻松实现重金属离子的分离与输送;经交变磁场加热,可实现对重金属离子吸附性能的智能化控制;低浓度有机弱酸下可解吸已吸附的重金属离子,实现再生利用,有效避免二次污染,具有良好的应用前景。
附图说明
图1为实施例3中粒径均一的P(NIPAM-co-CS)/Fe3O4智能水凝胶的形貌图;图片显示该水凝胶大小均匀,粒径约为300nm,分散性良好。
图2为实施例3中P(NIPAM-co-CS)/Fe3O4智能水凝胶的磁性能图;图片显示该水凝胶具有良好的超顺磁性。
图3为实施例3中P(NIPAM-co-CS)/Fe3O4智能水凝胶温敏性能图;图片显示该水凝胶具有良好的温敏性能。
图4为实施例3中P(NIPAM-co-CS)/Fe3O4智能水凝胶对Cu2+的吸附性能图。
图5为实施例3中P(NIPAM-co-CS)/Fe3O4智能水凝胶循环再生能力表征图。
具体实施方式
为了更清楚地说明本发明,下面结合实施例和附图对本发明做进一步的说明。
实施例1
(1)称取4.2g FeCl2·4H2O及8.5g的FeCl3·6H2O完全溶解于150mL的体积比为1:1的乙醇-水混合溶剂中形成混合溶液,氮气保护下将其置于60℃的恒温水浴槽中以250r/min的转速进行机械搅拌,缓慢滴加氨水至溶液pH为10,此时有黑色沉淀析出,继续反应3h后停止。磁性分离后的黑色沉淀物用水反复洗涤多次至洗涤液呈中性。洗涤后的产物在真空干燥箱中干燥。干燥后即得亲水性Fe3O4纳米颗粒。
(2)将0.5g的四氧化三铁纳米颗粒超声分散在20mL浓度为5g/200mL的壳聚糖溶液中形成水相,然后在其中加入0.5g的N-异丙基丙烯酰胺。再在水相中分别加入0.010g的N,N’-亚甲基双丙烯酰胺及过硫酸铵作为交联剂及引发剂。将8mL司盘80加入到100mL液体石蜡中形成油相。两相混合。氮气保护下将其置于25℃的恒温水浴槽中以200r/min的转速进行机械搅拌。加入0.1g的四甲基乙二胺作为加速剂,反应5h后停止。用乙酸乙酯及去离子水反复洗涤磁性分离后的沉淀物多次。洗涤后的产物进行冷冻干燥。干燥后即得P(NIPAM-co-CS)/Fe3O4智能水凝胶。
(3)本发明选用Cu2+为代表性重金属离子配制一定浓度的水样作为工业模拟废水。将30mg水凝胶分散于20mL浓度为150mg/L的Cu2+溶液中,用HAc-NaAc缓冲液及去离子水调节重金属离子溶液的pH为5.0,通过调控外加交变磁场,使水凝胶温度升至28℃,吸附平衡(约2h)后,对重金属离子溶液磁力分离,测试重金属离子的吸附量。而后将磁力分离后的水凝胶浸入4mmol/L的EDTA溶液中,2h后,磁性分离出沉淀物并用去离子水洗涤,吸附-脱附过程连续进行八次,分别计算每次脱附后,水凝胶对重金属离子的吸附及脱附量,以确定水凝胶的再生循环利用能力。
实施例2
本实施例与实施例1的不同之处在于:所用的N,N’-亚甲基双丙烯酰胺及过硫酸铵的量均为0.022g,其余的与实施例1所述相同。
实施例3
(1)称取3.5g FeCl2·4H2O及7.7g的FeCl3·6H2O完全溶解于200mL的体积比为1:1的乙醇-水混合溶剂中形成混合溶液,氮气保护下将其置于70℃的恒温水浴槽中以300r/min的转速进行机械搅拌,缓慢滴加氨水至溶液pH为11,此时有黑色沉淀析出,继续反应3h后停止。磁性分离后的黑色沉淀物用水反复洗涤多次至洗涤液呈中性。洗涤后的产物在真空干燥箱中干燥。干燥后即得亲水性Fe3O4纳米颗粒。
(2)将0.2g的四氧化三铁纳米颗粒超声分散在20mL浓度为4g/200mL的壳聚糖溶液中形成水相,然后加入0.4g N-异丙基丙烯酰胺。再在水相中分别加入0.015g的N,N’-亚甲基双丙烯酰胺及过硫酸铵作为交联剂及引发剂。将8mL的司盘80加入到120mL液体石蜡中形成油相。两相混合。氮气保护下将其置于35℃的恒温水浴槽中以300r/min的转速进行机械搅拌。加入约0.1g的四甲基乙二胺作为加速剂,反应5h后停止。用乙酸乙酯及去离子水反复洗涤磁性分离后的沉淀物多次。洗涤后的产物进行冷冻干燥。干燥后即得P(NIPAM-co-CS)/Fe3O4智能水凝胶。
(3)本发明选用Cu2+为代表性重金属离子配制一定浓度的水样作为工业模拟废水。将60mg水凝胶分散于30mL浓度为200mg/L的Cu2+溶液中,用HAc-NaAc缓冲液及去离子水调节重金属离子溶液的pH为6.0,通过调控外加交变磁场,使水凝胶温度升至30℃,吸附平衡(约2h)后,对重金属离子溶液磁力分离,分别测试不同温度及pH条件下,重金属离子的吸附量,以确定最佳吸附温度及pH条件。而后将磁力分离后的水凝胶浸入7mmol/L的EDTA溶液中,2h后,磁性分离出沉淀物并用去离子水洗涤,吸附-脱附过程连续进行八次,分别计算每次脱附后,水凝胶对重金属离子的吸附及脱附量,以确定水凝胶的再生循环利用能力。
图1给出实施例3中粒径均一的智能水凝胶P(NIPAM-co-CS)/Fe3O4的形貌图;图片显示该水凝胶大小均匀,粒径约为300nm,分散性良好。图2给出实施例3中智能水凝胶的磁性能图;图片显示该水凝胶具有良好的超顺磁性。图3给出实施例3中智能水凝胶温敏性能图;图片显示该水凝胶具有良好的温敏性能。图4给出实施例3中智能水凝胶对Cu2+的吸附性能图。图5给出实施例3中智能水凝胶循环再生能力表征图。
本发明提供一种智能水凝胶的制备及其脱除水体重金属离子的应用,该水凝胶由四氧化三铁(Fe3O4)、N-异丙基丙烯酰胺(NIPAM)和壳聚糖(CS)组成,具有磁敏、温敏及pH敏多重敏感性能,属于高分子材料及水处理应用相结合的技术领域。首先利用共沉淀法,制备出单分散的亲水性Fe3O4纳米颗粒;再将制得的Fe3O4分散在CS溶液中,加入NIPAM单体,以四甲基乙二胺为加速剂,通过微乳液聚合制备出P(NIPAM-co-CS)/Fe3O4复合水凝胶。该制备过程为低温引发聚合,所需时间短,经济效益高。同时,该法制备出的智能水凝胶对重金属离子吸附容量大,去除效率高;外加磁场作用下,可轻松实现重金属离子的富集与输送;经交变磁场加热,可实现对重金属离子吸附性能的智能化控制;低浓度有机弱酸下可解吸已吸附的重金属离子,实现再生利用,具有良好的应用前景。
Claims (4)
1.一种智能水凝胶的制备方法,其特征在于所述智能水凝胶的分子式为P(NIPAM-co-CS)/Fe3O4,由四氧化三铁、N-异丙基丙烯酰胺和壳聚糖组成;
所述制备方法包括如下步骤:
1)将FeCl2·4H2O和FeCl3·6H2O溶解于乙醇-水混合溶剂中反应,氮气保护下,以氨水为沉淀剂,制得亲水性的Fe3O4纳米颗粒;所述FeCl2·4H2O与FeCl3·6H2O的质量比为1∶(2~3);
2)将制得的亲水性的Fe3O4纳米颗粒超声分散在壳聚糖溶液中,加入温敏单体N-异丙基丙烯酰胺,在交联剂、引发剂作用下,以四甲基乙二胺为加速剂,进行聚合反应,通过微乳液聚合法制得智能水凝胶P(NIPAM-co-CS)/Fe3O4;所述壳聚糖溶液的壳聚糖质量浓度为1.5~6g/200mL,溶剂是1%~3%的醋酸溶液;所述四氧化三铁、壳聚糖与N-异丙基丙烯酰胺的质量比为2∶1∶1~1∶2∶2;
所述交联剂采用N,N’─亚甲基双丙烯酰胺;所述引发剂采用过硫酸铵;交联剂与引发剂的用量均占单体总质量的0.05%~1.5%;四甲基乙二胺的用量占单体总质量的10%;所述聚合反应的温度为25~40℃,聚合反应的时间为5h;
所述微乳液聚合中所用油相为石蜡,水相与油相体积比为1∶(8~10)。
2.如权利要求1所述一种智能水凝胶的制备方法,其特征在于在步骤1)中,所述乙醇-水混合溶剂中乙醇与水的体积比为1∶1。
3.如权利要求1所述一种智能水凝胶的制备方法,其特征在于在步骤1)中,所述反应的温度为50~80℃,反应的时间为3h,所述反应在机械搅拌下反应,转速为200~350r/min,经氨水调节的反应体系pH为9~12。
4.如权利要求1所述一种智能水凝胶的制备方法制备的智能水凝胶在制备用于水体重金属离子吸附与解吸剂中的应用;所述用于水体重金属离子吸附与解吸剂的使用方法为:通过调控外加交变磁场,使智能水凝胶升温至20~35℃,pH为4.8~6.9下进行吸附;在浓度为0.5~10mmol/L的有机弱酸下进行解吸,所述有机弱酸为EDTA溶液。
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