一种表面共聚氢氧根选择性阴离子色谱固定相

doi:10.3724/SP.J.1123.2019.07031

摘要/Abstract

摘要：

报道了一种基于聚(苯乙烯-二乙烯基苯)微球(PS-DVB)的表面共聚氢氧根选择性阴离子固定相。它以烯丙基缩水甘油醚(AGE)为功能单体、通过自由基引发直接与PS-DVB微球表面残留的悬挂双键共聚,再通过醇胺开环得到。考察了两种醇胺试剂对分离的影响;扫描电镜、红外光谱、元素分析表征结果表明:表面共聚反应成功在微球表面引入季胺基团,且对微球理化性质无显著影响;所得固定相表现氢氧根淋洗液的高选择性,对常规无机阴离子表现出良好的分离性能(分离度>1.5)和运行稳定性(保留时间的相对标准偏差<1.13%),其实用性通过分析茶叶样品中无机阴离子进行了展示。

关键词: 离子色谱, 固定相, 悬挂双键, 表面共聚, 烯丙基缩水甘油醚

Abstract:

A polystyrene-divinylbenzene (PS-DVB) microspheres-based hydroxide-selective anion exchange stationary phase is described. This stationary phase is obtained by the surface polymerization of an allyl glycidyl ether (AGE) and the pendant vinyl groups onto the surface of PS-DVB, followed by open-ring of the epoxy groups using an alkylol amine (abbreviated as P@A-M). Both alkylol amines were compared in terms of separation performance of the stationary phase. Scanning electron microscopy, infrared spectroscopy, and elemental analyses were carried out to characterize the stationary phase. The results indicated that the quaternary amine group was successfully introduced onto the surface of the PS-DVB microspheres, and that there was no obvious change in the physicochemical properties of the resin during the surface polymerization reaction. The P@A-M phase showed high hydroxide-selectivity and good separation performance (resolution>1.5) as well as high running stability (relative standard deviation of retention times<1.13%). The utility of the P@A-M phase was demonstrated by using it for the determination of inorganic anions in the tea.

Key words: ion chromatography (IC), stationary phase, pendant vinyl group, surface polymerization, allyl glycidyl ether

中图分类号:

O658

杨占强, 李宗英, 杨德辉, 章飞芳, 杨丙成. 一种表面共聚氢氧根选择性阴离子色谱固定相[J]. 色谱, 2020, 38(4): 452-457.

YANG Zhanqiang, LI Zongying, YANG Dehui, ZHANG Feifang, YANG Bingcheng. A polymer resin surface polymerization-based hydroxide-selective anion exchange stationary phase[J]. Chinese Journal of Chromatography, 2020, 38(4): 452-457.

图/表 7

图1 P@A-M固定相合成路线示意图

Fig. 1 Schematic diagram of the synthesis route of P@A-M stationary phase PS-DVB: polystyrene-divinylbenzene.

图2 (a和b)PS-DVB微球和(c)P@A-M固定相的扫描电镜图

Fig. 2 Scanning electron microscopy images of (a and b) PS-DVB microspheres and (c) P@A-M stationary phase

图3 固定相(a)氮气吸脱附等温线、(b)孔径分布图和 (c)红外光谱

Fig. 3 (a) Nitrogen adsorption and desorption isotherms, (b) pore size distribution, and (c) IR spectrum of stationary phase

图4 (a) P@A-D和(b) P@A-M固定相所得色谱图

Fig. 4 Chromatograms obtained with (a) P@A-D and (b) P@A-M stationary phase Conditions: eluent, 10 mmol/L KOH; column temperature, 30 ℃; column size, 150 mm×4.6 mm; injection volume, 25 μL; flow rate, 1.0 mL/min; suppressed conductance detection.

图5 梯度模式下P@A-M固定相分离7种常规阴离子的色谱图

Fig. 5 Chromatogram of the seven model anions using P@A-M anion exchange stationary phase in gradient model Conditions: eluent, 0-10.5 min (4 mmol/L KOH), 11-16 min (8 mmol/L KOH), 16.5-20 min (4 mmol/L KOH). Other conditions are the same as those in Fig. 4.

图6 P@A-M固定相长期稳定性考察(n=3)

Fig. 6 Long-term stability of P@A-M anion exchange stationary phase (n=3) Conditions: eluent, 4 mmol/L KOH. Other conditions are the same as those in Fig. 4.

表1 系统定量分析参数

Table 1 Quantification parameters of the system

Anion	Linear range/ (μmol/L)	Correlation equation	R²	LOD/ (μmol/L)
F^-	5-500	P=7.7972C+0.0014	0.9999	0.0319
Cl^-	5-500	P=9.9920C-0.0374	0.9998	0.0688
N $O 2 -$	5-500	P=8.4451C-0.0141	0.9999	0.1863
Br^-	5-500	P=8.8852C-0.0578	0.9994	0.1863
N $O 3 -$	5-500	P=8.1853C-0.0319	0.9998	0.5588
S $O 4 2 -$	5-500	P=18.5879C-0.1200	0.9998	0.1064

表1 系统定量分析参数

Table 1 Quantification parameters of the system

Anion	Linear range/ (μmol/L)	Correlation equation	R²	LOD/ (μmol/L)
F^-	5-500	P=7.7972C+0.0014	0.9999	0.0319
Cl^-	5-500	P=9.9920C-0.0374	0.9998	0.0688
N $O 2 -$	5-500	P=8.4451C-0.0141	0.9999	0.1863
Br^-	5-500	P=8.8852C-0.0578	0.9994	0.1863
N $O 3 -$	5-500	P=8.1853C-0.0319	0.9998	0.5588
S $O 4 2 -$	5-500	P=18.5879C-0.1200	0.9998	0.1064

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