CN112457456A - 一种聚苯乙烯-二乙烯基苯修饰的磁性碳纳米管复合材料及其应用 - Google Patents

一种聚苯乙烯-二乙烯基苯修饰的磁性碳纳米管复合材料及其应用 Download PDF

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CN112457456A
CN112457456A CN202011425936.0A CN202011425936A CN112457456A CN 112457456 A CN112457456 A CN 112457456A CN 202011425936 A CN202011425936 A CN 202011425936A CN 112457456 A CN112457456 A CN 112457456A
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carbon nanotube
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李楠
陈潮文
邱静
钱永忠
刘会影
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Abstract

本发明属于固相萃取材料领域，具体涉及聚苯乙烯‑二乙烯基苯修饰的磁性碳纳米管复合材料包括基质层、聚合物网络层；所述聚合物网络层设置在所述基质层表面；所述基质层采用采用磁性多壁碳纳米管，所述聚合物网络层采用聚(苯乙烯‑二乙烯基苯)。其有益效果在于：所述的QuEChERS吸附剂创新性结合了磁性纳米颗粒、多壁碳纳米管以及聚(苯乙烯‑二乙烯基苯)三种功能性材料，富含高密度吸附作用位点，能够高效清除基质干扰物，降低基质效应。根据样品中色素深浅，选择性调控聚(苯乙烯‑二乙烯基苯)的厚度及多壁碳纳米管的投料量，从而使吸附剂能够满足不同样品基质的净化。

Description

一种聚苯乙烯-二乙烯基苯修饰的磁性碳纳米管复合材料及 其应用
技术领域
本发明属于固相萃取材料领域，涉及聚苯乙烯-二乙烯基苯修饰的磁性碳纳米管复合材料及其应用。
背景技术
农药在农产品种植生产过程中扮演中重要的角色，农药的不合理使用，会造成农产品存在农药残留甚至超标。
目前，农药残留检测的方法普遍为酶联免疫吸附法，气相色谱法、液相色谱法、高效液相色谱法、高效液相色谱串联质谱、气相色谱串联质谱等。无论采用何种检测方法，都需要对样品进行前处理，以去除基质中干扰物及富集目标分析物。这种前处理操作，对于获得满意的检测准确性、灵敏度及精密度是必不可少的。
QuEChERS是一种新型快速前处理方法，已被广泛应用于国内外权威的农药残留检测标准方法，包括AOAC official method(Official Methods of Analysis)，欧盟检测方法(EN)、GB23200.113等。
常见的QuEChERS吸附剂包括十八烷基硅烷(C18)，乙二胺基-N-丙基硅烷(PSA)，石墨化炭黑(GCB)。由于QuEChERS材料的制备合成尚处于探索阶段，商品化的QuEChERS吸附剂仍然局限于传统的色谱填料，相比于传统固相萃取柱，QuEChERS方法的净化效果仍不尽如人意。
因此，发明新型QuEChERS吸附剂，提高净化效率，以改善检测灵敏度和准确度具有十分重要的意义。
本发明是提供一种新型QuEChERS吸附剂，以解决现有技术中的问题。
发明内容
本发明所要解决的第一个技术问题是设计、制备得到一种基于聚(苯乙烯-二乙烯基苯)修饰磁性碳纳米管的QuEChERS吸附剂。本发明所要解决的第二个技术问题是提供了所述QuEChERS吸附剂的制备方法及其对多类别农药残留检测的应用。
本发明公开了一种聚苯乙烯-二乙烯基苯修饰的磁性碳纳米管复合材料，包括基质层、聚合物网络层；所述聚合物网络层设置在所述基质层表面；所述基质层采用采用磁性多壁碳纳米管，所述聚合物网络层采用聚(苯乙烯-二乙烯基苯)。
进一步地，所述基质层粒径尺寸为5nm～200nm。
本发明还公开了一种聚苯乙烯-二乙烯基苯修饰的磁性碳纳米管复合材料的合成方法，包括如下步骤：
步骤1，合成磁性多壁碳纳米管基质；
步骤2，在磁性多壁碳纳米管基质表面修饰硅烷化试剂；
步骤3，在步骤2修饰后的产物表面修饰聚(苯乙烯-二乙烯基苯)。
优选地，所述步骤3采用表面引发原子转移自由基聚合(SI-ATRP)方法。
本发明还公开了所述聚苯乙烯-二乙烯基苯修饰的磁性碳纳米管复合材料作为QuEChERS吸附剂在果蔬样品中农残检测的应用。
所述聚苯乙烯-二乙烯基苯修饰的磁性碳纳米管复合材料作为QuEChERS吸附剂在果蔬样品中农残检测的应用，包括如下步骤：
步骤1)，将QuEChERS吸附剂分散于农药残留提取液中，使得吸附剂与提取液中的基质干扰物充分接触，并完成吸附；
步骤2)，将步骤1)的吸附产物从提取液中分离；
步骤3)，对步骤2)分离后的提取液中的农药残留进行定性和/或定量分析。
进一步地，所述步骤2)所述的分离操作，包括磁分离、离心。
进一步地，所述步骤3)所述分析操作包括高效液相色谱、串联质谱。
本发明的有益效果在于：
1、所述的QuEChERS吸附剂创新性结合了磁性纳米颗粒、多壁碳纳米管以及聚(苯乙烯-二乙烯基苯)三种功能性材料，富含高密度吸附作用位点，能够高效清除基质干扰物，降低基质效应。
2、根据样品中色素深浅，选择性调控聚(苯乙烯-二乙烯基苯)的厚度及多壁碳纳米管的投料量，从而使吸附剂能够满足不同样品基质的净化。
附图说明
图1Fe3O4MWCNTs@P(St-co-DVB)复合材料的SEM图；
图2样品净化前后对比图；
图3样品提取液中的丁二酸单离子监测(SIM)色谱图；
图4西红柿样品中添加的60种农药总离子流图。
具体实施方式
下面结合实施例对本发明的具体实施方式作进一步描述，以下实施例仅用于更加清楚地说明本发明的技术实施例，而不能以此来限制本发明的保护范围。
实施例1
一种聚苯乙烯-二乙烯基苯修饰的磁性碳纳米管复合材料的合成方法，包括如下步骤：
步骤1，合成磁性多壁碳纳米管基质；
制备聚(苯乙烯-二乙烯基苯)修饰磁性多壁碳纳米管(Fe3O4MWCNTs@P(St-co-DVB))。
步骤1.1，采用共沉淀法制备磁性多壁碳纳米管：将5g氯化铁和5g硫酸亚铁溶解于100mL去离子水中；
步骤1.2，将2g多壁碳纳米管分散于上述溶液中，逐滴加入120mL28％Wt氨水溶液后，反应液加热至70℃，在搅拌条件下继续反应4h；
步骤1.3，将制备得到的黑色产物依次用去离子水、乙醇清洗产物，以去除未反应的残留物，处理后，将产物Fe3O4MWCNTs置于60℃真空干燥箱12小时烘干备用。
步骤2，在磁性多壁碳纳米管基质表面修饰硅烷化试剂；
步骤2.1，在Fe3O4MWCNTs表面修饰3-氨基丙基三乙氧基硅烷(BPS),以引入-Br基团：将Fe3O4MWCNTs(1.5g)，去离子水(3.8mL)，乙醇(37.8mL)，氨水(0.68mL)搅拌混合均匀；
步骤2.2，加入BPS(1.25mL)于上述反应液中，室温下搅拌24h，依次采用去离子水、乙醇清洗产物Fe3O4MWCNTs@Br，置于60℃烘箱过夜干燥。
步骤3，在步骤2修饰后的产物表面修饰聚(苯乙烯-二乙烯基苯)。
步骤3.1，将Fe3O4MWCNTs@Br作为ATRP引发剂，表面引发苯乙烯与二乙烯基苯共聚：将Fe3O4MWCNTs@Br(0.8g)，苯乙烯(2.3mL，20mmol)，二乙烯基苯(1.4mL,10mmol)，溴化亚铜(30.0mg,0.2mmol)，50mL四氢呋喃混合于反应瓶中，充入氮气除氧30分钟；
步骤3.2，迅速加入五甲基二乙烯三胺(35.0μL,0.2mmol)，在氮气氛围中60℃条件下反应12小时，将反应液暴露于空气中终止反应；
步骤3.3，采用四氢呋喃清洗产物并置于真空干燥箱中烘干，最终得到产物Fe3O4MWCNTs@P(St-co-DVB)。
制备的产物如附图1所示。
表1.不同吸附剂中碳(C)、氢(H)、氧(O)元素分析结果
Figure BDA0002824837530000041
为了进一步说明本发明所获得的产物的有益效果，特设置如下实验：
利用本发明产物对西红柿样品中多类别农药残留检测。
检测步骤如下：
将制备得到的Fe3O4MWCNTs@P(St-co-DVB)作为QuEChERS吸附剂，采用高效液相色谱串联质谱检测西红柿样品中的农药残留。
具体QuEChERS方法步骤如下：
准确称取样品10.0g于50mL离心管中，加入15mL1％乙酸乙腈以及QuEChERS提取包P-QuEChERS-AOAC1202，剧烈振荡1min，涡旋1min，8000rpm/min转速离心2min，取上层清液4mL于15mL离心管中，加入200mg Fe3O4MWCNTs@P(St-co-DVB)，涡旋1min，将磁铁块放置离心管外部，使Fe3O4MWCNTs@P(St-co-DVB)从提取液中分离出来，取上清液过滤膜(0.2μm)，采用高效液相色谱串联质谱进行定性定量分析。
小分子有机酸和色素为西红柿样品中普遍存在的基质干扰物，以丁二酸和色素为典型干扰物，考察QuEChERS净化吸附剂Fe3O4MWCNTs@P(St-co-DVB)对于基质干扰物的去除效果。如附图2所示，净化后的样品提取液由红色变为无色透明，表明吸附剂对色素的去除效果良好。
如附图3所示，在样品中添加5μg/g丁二酸，净化前提取液中检出有有丁二酸，净化后提取液中丁二酸几乎完全被净化剂吸附。
以上结果表明，Fe3O4MWCNTs@P(St-co-DVB)能够有效去除西红柿样品中的典型基质干扰物。
为了进一步说明本发明的有益效果，对西红柿样品中农药残留检测方法的准确度、灵敏度进行考察。
选择有机磷类，氨基甲酸酯类、烟碱类等60种农药为目标分析物，向样品中添加已知浓度的农药标准溶液(各个农药浓度均为100ng/mL)，经QuEChERS方法前处理后，如附图4所示，60种农药的回收率为70.2％-119.4％，符合欧盟标准方法建议的回收率范围。
最后应说明的是：以上各实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述各实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。

Claims (8)

1.一种聚苯乙烯-二乙烯基苯修饰的磁性碳纳米管复合材料，其特征在于，包括基质层、聚合物网络层；所述聚合物网络层设置在所述基质层表面；所述基质层采用采用磁性多壁碳纳米管，所述聚合物网络层采用聚(苯乙烯-二乙烯基苯)。
2.根据权利要求1所述的聚苯乙烯-二乙烯基苯修饰的磁性碳纳米管复合材料，其特征在于，所述基质层粒径尺寸为5nm～200nm。
3.根据权利要求1-2任意一项所述的聚苯乙烯-二乙烯基苯修饰的磁性碳纳米管复合材料的合成方法，其特征在于，包括如下步骤：
步骤1，合成磁性多壁碳纳米管基质；
步骤2，在磁性多壁碳纳米管基质表面修饰硅烷化试剂；
步骤3，在步骤2修饰后的产物表面修饰聚(苯乙烯-二乙烯基苯)。
4.根据权利要求3所述的聚苯乙烯-二乙烯基苯修饰的磁性碳纳米管复合材料的合成方法，其特征在于，所述步骤3采用表面引发原子转移自由基聚合(SI-ATRP)方法。
5.根据权利要求1-2任意一项所述的聚苯乙烯-二乙烯基苯修饰的磁性碳纳米管复合材料作为QuEChERS吸附剂在果蔬样品中农残检测的应用。
6.根据权利要求5所述的聚苯乙烯-二乙烯基苯修饰的磁性碳纳米管复合材料作为QuEChERS吸附剂在果蔬样品中农残检测的应用，其特征在于，包括如下步骤：
步骤1)，将QuEChERS吸附剂分散于农药残留提取液中，使得吸附剂与提取液中的基质干扰物充分接触，并完成吸附；
步骤2)，将步骤1)的吸附产物从提取液中分离；
步骤3)，对步骤2)分离后的提取液中的农药残留进行定性和/或定量分析。
7.根据权利要求6所述的聚苯乙烯-二乙烯基苯修饰的磁性碳纳米管复合材料作为QuEChERS吸附剂在果蔬样品中农残检测的应用，其特征在于，所述步骤2)所述的分离操作，包括磁分离、离心。
8.根据权利要求6所述的聚苯乙烯-二乙烯基苯修饰的磁性碳纳米管复合材料作为QuEChERS吸附剂在果蔬样品中农残检测的应用，其特征在于，所述步骤3)所述分析操作包括高效液相色谱、串联质谱。
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CN101513607A (zh) * 2009-02-19 2009-08-26 浙江大学 聚合物碳纳米管复合色谱填料的制备方法
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