Preparation of difunctional polymer-based cation exchangers and their application in ion chromatography

doi:10.3724/SP.J.1123.2019.07023

Abstract

Abstract:

Ion chromatography (IC) is one of the most important means for the separation and analysis of cationic compounds. Research on high-performance cation exchangers is of great significance for the advancement of modern IC techniques. Herein we proposed a newly developed modification method for polymer-based particles, based on thiol-radical-mediated polymerization. Specifically, acrylic acid and maleic anhydride were used as monomers and sodium 2-mercaptoethanesulfonate was used as the thiol modifier to prepare novel difunctional cation exchangers, functionalized with both carboxylic and sulfonic groups. With simple strong acid eluents, typical cations were well separated with good resolution. The retention behaviors of metal cations and organic amines on the cation exchangers were investigated using multiple chromatographic models. The good performances of the cation exchangers were also demonstrated by the gradient separation of ten cations within 24 min. The new method was easy to perform with high efficiency. Additionally, the cation exchange capacities of the cation exchangers were easily modulated by adjusting the initial content of the thiol modifier.

Key words: thiol-ene, polymer-based, cation exchanger, stationary phase, ion chromatography (IC)

CLC Number:

O658

ZHANG Kai, ZHI Mingyu, HE Yi, ZHU Yan, ZENG Xiuqiong, SHOU Dan. Preparation of difunctional polymer-based cation exchangers and their application in ion chromatography[J]. Chinese Journal of Chromatography, 2020, 38(4): 445-451.

Figures/Tables 8

Fig. 1 Scheme for the preparation of the cation exchangers AIBN: azobisisobutyronitrile.

Table 1 Element contents of the cation exchangers and their estimated capacities

Stationary phase	Element contents/%					Capacities/ (μequiv/g)
Stationary phase	N	C	H	O	S	-COOH	-SO₃H
EVB-DVB	0.00	89.82	7.87	2.31	0.00	n. a.	n. a.
CE-R	0.87	83.63	7.88	7.62	0.00	1659	0
CE-1	0.06	78.19	7.52	13.90	0.34	3542	53
CE-2	0.06	77.61	7.52	13.44	0.37	3389	58
CE-3	0.05	77.94	7.46	14.13	0.42	3600	66

Fig. 2 Scanning electron microscopic images of the stationary phase particles a. EVB/DVB; b. cation exchanger (CE-3).

Fig. 3 Comparison of the chromatograms of the cation exchangers Eluent: 20 mmol/L methanesulfonic acid (MSA).

Fig. 4 Chromatograms of the seven inorganic cations

Fig. 5 Plots of the log k and pH, and the fittings of chromatographic models of the seven inorganic cations on the cation exchangers

Fig. 6 plot of the log k and log P of N H 4 +, alkylamines, and alkanolamines on CE-3 n-PrNH2: n-propylamine; NHEt2: diethylamine; NMe3: trimethylamine; EtNH2: ethylamine; NHMe2: dimethylamine. Eluent: 30 mmol/L MSA.

Fig. 7 Chromatogram of the ten cations on CE-3 in a gradient mode

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