CN108905996B - 一种聚吡咯/核壳纳米球的制备方法及其应用 - Google Patents

一种聚吡咯/核壳纳米球的制备方法及其应用 Download PDF

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CN108905996B
CN108905996B CN201810772873.2A CN201810772873A CN108905996B CN 108905996 B CN108905996 B CN 108905996B CN 201810772873 A CN201810772873 A CN 201810772873A CN 108905996 B CN108905996 B CN 108905996B
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高朋
杜琳琳
余传柏
吴夏倪
刘远立
徐旭
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Guilin University of Technology
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Abstract

本发明公开了一种聚吡咯/核壳纳米球的制备方法及其应用。首先，利用乳液聚合制备出一种单分散核壳纳米球，然后以此单分散核壳纳米球为模板将吡咯单体包裹在单分散核壳纳米球的表面，从而制备出聚吡咯/核壳纳米球，其能够应用于去除废水中的Cr(VI)。本发明具有制备工艺简单，纳米球的粒径与表面基团可控等优势，将吡咯在核壳纳米球表面形成一层厚度可控的功能层，不仅提高了吡咯的分散性，而且也达到了对重金属离子的有效去除。

Description

一种聚吡咯/核壳纳米球的制备方法及其应用
技术领域
本发明涉及一种吸附材料的制备方法及其应用，属于水环境保护领域，具体涉及一种聚吡咯/核壳纳米球的制备方法及其应用。
背景技术
近年来，工业废水的处理日益受到人们的关注，工业废水中存在大量的有毒、有害物质，如染料分子、重金属粒子离子等，对人们的生活造成了一定的影响。目前，对重金属离子的去除方法有化学沉淀、超滤、吸附、离子交换、反渗透、电渗析和生物法等。其中，吸附法由于成本低、效率高、易于操作等优点，被广泛应用于工业中重金属离子的去除。
核壳纳米球具有良好的单分散性、表面易功能化与粒径均一可调等特点，目前在医疗、催化、储能、药物载体等领域占有极其重要的地位。
发明内容
本发明的目的是提供一种聚吡咯/核壳纳米球的制备方法及其应用。
本发明思路：利用乳液聚合制备出一种单分散核壳纳米球，然后以此单分散核壳纳米球为模板将吡咯单体包裹在单分散核壳纳米球的表面，从而制备出聚吡咯/核壳纳米球。
制备聚吡咯/核壳纳米球的具体步骤为：
（1）按照质量比为0.5~5:0.1~2:0.1~2:5~20称取核层单体、壳层单体、表面活性剂和去离子水，将称取的核层单体、壳层单体、表面活性剂分别加入到称取的去离子水中，在60~80℃下搅拌1.0~2.0h，然后将温度调为65~90℃，加入引发剂，引发剂用量为溶液总重量的0.1~2.0%，搅拌反应8~16h，制得单分散核壳纳米球。
（2）将FeCl3·6H2O溶解于0.5mol/L的盐酸溶液中，再加入步骤（1）制得的单分散核壳纳米球，所得混合液置于恒温水浴锅中35℃下搅拌30min，单分散核壳纳米球与FeCl3·6H2O的质量比为4:1~3，然后向混合液中逐滴加入吡咯单体，持续搅拌8~12h，吡咯单体与FeCl3·6H2O的摩尔比为1:1.5~3，反应结束后使用无水乙醇与去离子水体积比为1:1的醇水溶液进行洗涤，所得产物在60~80℃下干燥8~12h，即制得聚吡咯/核壳纳米球，该聚吡咯/核壳纳米球的粒径为80~500nm，且表现出良好的单分散性与球形度。
所述核层单体为苯乙烯和二乙烯苯中的一种或两种。
所述壳层单体为丙烯酸、甲基丙烯酸甲酯、丙烯酸羟乙酯、丙烯酰胺和丙烯酸乙氧基乙氧基乙酯中的一种或多种。
所述表面活性剂为十二烷基苯磺酸钠和十二烷基硫酸钠中的一种或两种。
所述引发剂为偶氮二异丁氰、过硫酸铵和过硫酸钾中的一种或多种。
本发明的聚吡咯/核壳纳米球应用于吸附废水中的Cr(VI)。
本发明的有益效果：
（1）本发明中单分散核壳纳米球的制备过程不需要特殊气氛保护，使用前不需要后处理过程，具有良好的单分散性，粒径均一可控，表面功能基团易调控。
（2）本发明的聚吡咯/核壳纳米球具有制备过程简单、易工业化生产，表面的聚吡咯厚度可控，且对Cr(VI)具有优异的吸附性能，对工业废水中重金属离子的去除提供了帮助。
附图说明
图1为本发明实施例中制得的单分散核壳纳米球的TEM照片。
图2为本发明实施例中制得的聚吡咯/核壳纳米球的TEM照片。
图3为本发明实施例中制得的聚吡咯/核壳纳米球在不同pH值条件下对Cr(VI)的吸附性能曲线。
图4为本发明实施例中制得的聚吡咯/核壳纳米球的吸附动力学曲线。
具体实施方式
为了进一步理解本发明，下面结合技术方案和附图详细叙述本发明的具体实施例，但不意味着对本发明的任何限制。
实施例：
（1）将6.02g苯乙烯、0.334g甲基丙烯酸甲酯、0.334g丙烯酸加入到35mL去离子水中，再加入0.003g十二烷基苯磺酸钠，在70℃下搅拌60min，然后将温度调为80℃，再加入0.161g过硫酸铵，搅拌反应10h，制得单分散核壳纳米球。
（2）将FeCl3·6H2O溶解于50mL浓度为0.5mol/L的盐酸溶液中，再加入步骤（1）制得的单分散核壳纳米球，单分散核壳纳米球的浓度为15.0g/L，所得混合液置于恒温水浴锅中35℃下搅拌30min，然后向混合液中逐滴加入吡咯单体，持续搅拌12h，吡咯单体的用量为0.6g/L，吡咯单体与FeCl3·6H2O 的摩尔比为1:2.3，反应结束后使用无水乙醇与去离子水体积比为1:1的醇水溶液进行洗涤，所得产物在60~80℃下干燥8~12h，即制得聚吡咯/核壳纳米球。
将本实施例制得的聚吡咯/核壳纳米球在不同pH值条件下，对Cr(VI)进行吸附性能测试：首先使用0.1~5mol/L的H2SO4和0.1~5mol/L的NaOH溶液对100mg/L的Cr(VI)进行pH值调节，其中溶液体积为50mL，分别将溶液的pH值调节为2~10，加入本实施例制得的吸附剂，吸附一段时间后对残液中的Cr(VI)进行测试。结果表明，当溶液的pH值为2时，对Cr(VI)的吸附效果最佳，去除率为99.11%。

Claims (2)

1.一种聚吡咯/核壳纳米球的制备方法，其特征在于具体步骤为：
（1）按照质量比为0.5~5:0.1~2:0.1~2:5~20，称取核层单体、壳层单体、表面活性剂和去离子水，将称取的核层单体、壳层单体、表面活性剂分别加入到称取的去离子水中，在60~80℃下搅拌1.0~2.0h，然后将温度调为65~90℃，加入引发剂，引发剂用量为溶液总重量的0.1~2.0%，搅拌反应8~16h，制得单分散核壳纳米球；
（2）将FeCl3·6H2O溶解于0.5mol/L的盐酸溶液中，再加入步骤（1）制得的单分散核壳纳米球，所得混合液置于恒温水浴锅中35℃下搅拌30min，单分散核壳纳米球与FeCl3·6H2O的质量比为4:1~3，然后向混合液中逐滴加入吡咯单体，持续搅拌8~12h，吡咯单体与FeCl3·6H2O的摩尔比为1:1.5~3，反应结束后使用无水乙醇与去离子水体积比为1:1的醇水溶液进行洗涤，所得产物在60~80℃下干燥8~12h，即制得聚吡咯/核壳纳米球，该聚吡咯/核壳纳米球的粒径为80~500nm，且表现出良好的单分散性与球形度；
所述核层单体为苯乙烯和二乙烯苯中的一种或两种；
所述壳层单体为丙烯酸、甲基丙烯酸甲酯、丙烯酸羟乙酯、丙烯酰胺和丙烯酸乙氧基乙氧基乙酯中的一种或多种；
所述表面活性剂为十二烷基苯磺酸钠和十二烷基硫酸钠中的一种或两种；
所述引发剂为偶氮二异丁氰、过硫酸铵和过硫酸钾中的一种或多种。
2.一种如权利要求1所述制备方法制备的聚吡咯/核壳纳米球的应用，其特征在于该聚吡咯/核壳纳米球应用于吸附废水中的六价Cr。
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101381435A (zh) * 2008-10-22 2009-03-11 华东理工大学 一种球形聚电解质刷的制备方法及其应用
CN103554341A (zh) * 2013-10-30 2014-02-05 华南理工大学 核壳结构的低温自交联丙烯酸酯乳液及其制备方法与应用
KR20150064948A (ko) * 2013-12-04 2015-06-12 (주)오렌지파워 다공성코어-쉘 구조의 전기 화학 소자용 음극활물질 및 이의 제조 방법
CN105765415A (zh) * 2013-09-16 2016-07-13 科勒克斯有限责任公司 包含聚合物基体和核壳纳米颗粒的复合材料系统、其制备方法及其应用

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101381435A (zh) * 2008-10-22 2009-03-11 华东理工大学 一种球形聚电解质刷的制备方法及其应用
CN105765415A (zh) * 2013-09-16 2016-07-13 科勒克斯有限责任公司 包含聚合物基体和核壳纳米颗粒的复合材料系统、其制备方法及其应用
CN103554341A (zh) * 2013-10-30 2014-02-05 华南理工大学 核壳结构的低温自交联丙烯酸酯乳液及其制备方法与应用
KR20150064948A (ko) * 2013-12-04 2015-06-12 (주)오렌지파워 다공성코어-쉘 구조의 전기 화학 소자용 음극활물질 및 이의 제조 방법

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
"Polyacrylonitrile/polypyrrole core/shell nanofiber mat for the removal of hexavalent chromium from aqueous solution";Jianqiang Wang et al.;《Journal of Hazardous Materials》;20121120;第244-245卷;第121-129页 *
"Simple Fabrication of Full Color Colloidal Crystal Films with Tough Mechanical Strength";Jingxia Wang et al.;《Macromol. Chem. Phys.》;20060307;第207卷;第596-604页 *
"Synthesis and Characterization of Poly(butyl acrylate–methyl methacrylate)/Polyaniline Core–Shell Latexes";Chia-Fu Chen et al.;《Journal of Applied Polymer Science》;20070126;第823-830页 *

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