二氧化锆微球表面键合磺化交联聚苯乙烯固相萃取填料的制备及应用

以聚合诱导胶体凝聚法(PICA)制备二氧化锆微球,用钛酸酯偶联剂对其进行表面改性,使其接枝上碳碳双键基团。在溶液体系中,该双键与单体苯乙烯和二乙烯苯在自由基引发下交联聚合,形成的聚合物包覆在二氧化锆微球表面。再通过磺化方法将磺酸基离子连接到苯环上,得到阳离子交换固相萃取填料。通过红外光谱、扫描电镜/X射线能谱等手段对其进行了表征。将装填得到的固相萃取柱与高效液相色谱联用,测定了水中的甲基磺草酮、阿特拉津和乙草胺。3种化合物的色谱峰面积与质量浓度呈良好的线性关系,相关系数(r²)均大于0.99;甲基磺草酮、阿特拉津和乙草胺的检出限分别为5.41、6.72和13.4 μg/L。结果表明,制得的聚合物包覆二氧化锆微球的粒径为6~8 μm,用该填料制成的固相萃取小柱对3种目标物的吸附率高。

Preparation and application of solid phase extraction packing of zirconia microsphere coated with sulfonated crosslinked polystyrene

Zirconia microsphere was prepared by polymerization-induced colloid aggregation (PICA) method and carbon-carbon double bond was grafted onto its surface by titanic acid ester coupling reagent. Poly(styrene-divinylbenzene) was synthesized by free radical polymerization by using styrene, divinylbenzene and carbon-carbon double bond on the microsphere surface in solution system, so the polymer was coated on the microsphere surface. After the benzene ring of the polymer was sulfonated, the cation exchange packing for solid phase extraction (SPE) was obtained. The material was characterized by Fourier transform infrared spectroscopy, scanning electron microscope and X-ray energy dispersive spectroscopy. Three herbicides of mesotrione, atrazine and acetochlor in water were determined by the SPE cartridge coupled with high performance liquid chromatography (HPLC). In the range of 0.5-3.0 mg/L, the relationships between the peak areas and mass concentrations of mesotrione, atrazine and acetochlor were linear with the correlation coefficients of 0.9936, 0.9925, 0.9919, respectively. The limits of detection were 5.41, 6.72 and 13.4 μg/L for mesotrione, atrazine and acetochlor, respectively. The results showed that the zirconium dioxide microspheres coated with polymer have diameters in the range of about 6 to 8 μm, the SPE cartridges of which have high adsorption rate for the targets.