阳离子固相萃取填料微波快速制备及其在胺类有机污染物萃取中的应用

doi:10.16258/j.cnki.1674-5906.2022.11.007

生态环境学报 ›› 2022, Vol. 31 ›› Issue (11): 2161-2168.DOI: 10.16258/j.cnki.1674-5906.2022.11.007

阳离子固相萃取填料微波快速制备及其在胺类有机污染物萃取中的应用

蒙素仟¹^,²(), 刘博¹^,²^,³, 赵嘉辉², 张傲², 赖华杰¹^,²^,³^,^*()

1.中国科学院广州化学研究所，广东广州 510650
2.中科检测技术服务（广州）股份有限公司，广东广州 510650
3.中科广化（重庆）新材料研究院有限公司，重庆 400714

收稿日期:2021-06-25 出版日期:2022-11-18 发布日期:2022-12-22
通讯作者: *赖华杰，E-mail: laihuajie@gic.ac.cn
作者简介:蒙素仟（1992年生），女（壮族），硕士，主要研究方向为环境功能材料的开发与应用。E-mail: mengsq@gic.ac.cn
基金资助:
广东省省级科技计划项目--粤东中科检测技术服务中心(2017A040403030)

Rapid Synthesis of Cationic Solid Phase Extraction Material by Microwave Radiation and Its Application in Extraction of Amine Organic Pollutants

MENG Suqian¹^,²(), LIU Bo¹^,²^,³, ZHAO Jiahui², ZHANG Ao², LAI Huajie¹^,²^,³^,^*()

1. Guangzhou Institute of Chemistry, Chinese Academy of Sciences, Guangzhou 510650, China
2. CAS Testing Technical Services (Guangzhou) Co., Ltd., Guangzhou 510650, China
3. New Materials Research Institute of CASCHEM (Chongqing) Co., Ltd., Chongqing 400714, China

Received:2021-06-25 Online:2022-11-18 Published:2022-12-22

摘要/Abstract

摘要：

联苯胺和三聚氰胺等胺类化合物是用途宽泛的有机化工中间体，在工业上大量使用，导致其在环境中广泛残留。而联苯胺和三聚氰胺在环境中浓度低，因此研究该类有机污染物的富集萃取材料尤为必要。固相萃取技术因具有操作简单、重现性高、有机溶剂使用量少的优点成为实验室常用的前处理手段之一。采用微波辅助加热悬浮聚合法快速制备出聚苯乙烯-二乙烯基苯基质微球，并对微球表面进行修饰引入磺酸基团，制备出具有反相、离子交换一体化的固相萃取材料（MCX），最后将其压制成固相萃取柱。所制备的MCX填料呈单分散的球状形貌，平均直径约为54 μm。FTIR和XPS的数据表明微波辅助加热条件下合成的MCX填料与市售阳离子聚合物固相萃取柱的基质材料结构相同，且均含有磺酸基（-SO₃H）功能基团。将MCX填料压制成与商品柱规格一致的固相萃取柱，以河水中的联苯胺和三聚氰胺作为目标物，评价制备的MCX柱的萃取富集性能。测试结果表明，MCX填料和3种市售固相萃取柱填料具有相似的阳离子交换能力。实验结果表明，MCX填料压制的固相萃取柱对河水中联苯胺的回收率为112.7%±3.5%、三聚氰胺的回收率为102.3%±2.8%，满足监测/检测行业需求，且与市售商品柱回收率相近。不同批次的MCX填料压制的固相萃取柱在萃取水样中的目标物时，联苯胺的回收率在90%-120%、三聚氰胺的回收率在95%-105%。综上所述，利用微波辐射加热悬浮聚合法可以快速制备出强阳离子交换材料，以其为填料压制的固相萃取柱可以达到商品化阳离子固相萃取柱相同的萃取效果，且填料的合成方法重复性强，极大地节省了固相萃取填料的制备时间，提高了生产效率。

关键词: 固相萃取柱, 微波辅助加热, 阳离子交换填料, 联苯胺, 三聚氰胺

Abstract:

Amine compounds such as benzidine and melamine are widely applied in industry, leading to inevitable residues in the environment. Therefore, it is necessary to study the extraction materials and determination methods of these amine compounds. Solid phase extraction has become a common pretreatment method in laboratories owing to its advantages of high reproducibility and low usage of organic solvents. In this paper, the microwave radiation was used to rapidly synthesize polystyrene-divinylbenzene substrate. Its surface was modified by sulfonic acid reaction to obtain mixed cation exchange (MCX) materials with reverse phase and ion exchange. Then cation exchange solid phase extraction column was prepared by these MCX materials. The obtained MCX materials presented monodisperse spherical with average diameter of 54 μm. The FTIR and XPS data showed that the synthesized MCX material had the same matrix as the commercial polymer solid phase extraction column, and all of them contained -SO₃H functional group. The MCX materials had similar cation exchange capacity with three kinds of commercial columns. The enrichment performance of the lab-made cation exchange solid phase extraction column was evaluated by using benzidine and melamine as extraction targets in river water samples. The recovery rate of benzidine was 112.7%±3.5%, and that of melamine was 102.3%±2.8%. In summary, the MCX materials can be rapidly synthesized by microwave radiation. Meanwhile, the lab-made MCX cation exchange solid phase extraction column can achieve the same extraction effect as the commercial solid phase extraction column. This research greatly saves the preparation time and reduces the detection costs.

Key words: solid phase extraction column, microwave radiation heating, mixed cation exchange materials, benzidine, melamine

中图分类号:

X132

蒙素仟, 刘博, 赵嘉辉, 张傲, 赖华杰. 阳离子固相萃取填料微波快速制备及其在胺类有机污染物萃取中的应用[J]. 生态环境学报, 2022, 31(11): 2161-2168.

MENG Suqian, LIU Bo, ZHAO Jiahui, ZHANG Ao, LAI Huajie. Rapid Synthesis of Cationic Solid Phase Extraction Material by Microwave Radiation and Its Application in Extraction of Amine Organic Pollutants[J]. Ecology and Environment, 2022, 31(11): 2161-2168.

图/表 13

图1 MCX（a）、商品1（b）和商品3（c）填料的形貌

Figure 1 Morphology of MCX microspheres (a), commercial 1microspheres (b) and the commercialization of 3 (c) microspheres

图2 MCX的粒径分布图

Figure 2 Particle size distribution of MCX

表1 MCX的粒径分布

Table 1 Particle size distribution of MCX

名称 Name	d₍₁₀₎/μm	d₍₅₀₎/μm	d₍₉₀₎/μm	平均粒径d/μm
MCX填料 MCX material	28.2	48.9	86.9	54.0

图3 MCX及商品固相萃取柱填料的FTIR图

Figure 3 FTIR spectrum of MCX and commercial solid phase extraction materials

图4 MCX及商品柱填料的XPS图

Figure 4 XPS spectrum of MCX and commercial solid phase extraction materials

表2 MCX和商品固相萃取柱填料的离子交换量

Table 2 Cation exchange capacity of MCX and commercial solid phase extraction column

样品 Sample	交换容量/(mmol·g^-1)
MCX	0.74
商品1 Commodity 1	0.84
商品2 Commodity 2	0.83
商品3 Commodity 3	0.90

图5 筛板的SEM图

Figure 5 SEM of sieve-plate composition

图6 联苯胺空白样品液相色谱图和联苯胺的标准曲线图（内附图）

Figure 6 Liquid chromatogram of blank sample and the standard curve of benzidine (inside image)

图7 三聚氰胺空白样品液相色谱图和三聚氰胺标准曲线图（内附图）

Figure 7 Liquid chromatogram of blank sample and the standard curve of melamine (inside image)

图8 联苯胺萃取液的高效液相色谱图

Figure 8 Liquid chromatogram of benzidine

图9 三聚氰胺萃取液的高效液相色谱图

Figure 9 Liquid chromatogram of melamine

表3 河水中联苯胺和三聚氰胺回收率和相对标准偏差

Table 3 Recovery and RSD of benzidine and melamine

名称 Name	填料装载量 Materials capacity/mg	目标物 Analyte	加标质量浓度 Standrad addition concentration/(μg·L^-1)	回收量Recycled/(μg·L^-1)	回收率 Recovery/%	相对标准偏差 RSD/%
MCX柱 MCX column	60	联苯胺	2.67×10^-1	3.11×10^-1	116.48	3.51
				2.92×10^-1	109.36
				3.10×10^-1	116.10
商品1 Commodity 1	60			3.00×10^-1	112.36	5.69
				2.99×10^-1	111.99
				3.30×10^-1	123.60
商品2 Commodity 2	60			2.95×10^-1	110.49	6.04
				2.99×10^-1	111.99
				3.29×10^-1	123.22
商品3 Commodity 3	150			2.54×10^-1	95.13	2.36
				2.66×10^-1	99.63
				2.58×10^-1	96.62
MCX柱 MCX column	60	三聚氰胺	5.00×10⁴	5.24×10⁴	104.80	2.55
				4.98×10⁴	99.60
				5.10×10⁴	102.00
商品1 Commodity 1	60			5.59×10⁴	111.80	4.95
				5.07×10⁴	101.40
				5.42×10⁴	108.40
商品2 Commodity 2	60			4.87×10⁴	97.40	2.58
				4.82×10⁴	96.40
				5.06×10⁴	101.20
商品3 Commodity 3	150			4.89×10⁴	97.78	0.11
				4.88×10⁴	97.60
				4.88×10⁴	97.60

表4 不同批次MCX柱对河水中联苯胺和三聚氰胺回收率

Table 4 The recovery of benzidine and melamine in the river water sample with different batch of MCX

批次 Batch	填料装载量 Materials capacity/mg	目标物 Analyte	加标质量浓度 Standrad addition concentration/(μg·L^-1)	回收量 Recycled/ (μg·L^-1)	回收率 Recovery/%
1	60	联苯胺	2.67×10^-1	3.11×10^-1	116.48
				2.92×10^-1	109.36
				3.10×10^-1	116.10
2				2.47×10^-1	92.51
				3.20×10^-1	119.85
				2.87×10^-1	107.49
3		三聚氰胺	5.00×10⁴	4.84×10⁴	96.80
				4.93×10⁴	98.60
				5.01×10⁴	100.20
4				5.24×10⁴	104.80
				4.98×10⁴	99.60
				5.10×10⁴	102.00

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阳离子固相萃取填料微波快速制备及其在胺类有机污染物萃取中的应用

Rapid Synthesis of Cationic Solid Phase Extraction Material by Microwave Radiation and Its Application in Extraction of Amine Organic Pollutants

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