超高效液相色谱-质谱法测定儿童玩具中氯系有机磷酯类阻燃剂

Simultaneous Determination of Organophosphorous Flame Retardants in Children's Toys by High Performance Liquid Chromatography-Mass Spectrometry

建立了超声辅助萃取技术提取,高效液相色谱-质谱联用技术同时测定玩具中三（2-氯乙基）磷酸酯、三（1,3-二氯丙基）磷酸酯和磷酸三氯丙酯3种氯系有机磷酸酯类阻燃剂的分析方法,并考察了萃取溶剂、萃取时间和不同流动相对实验体系的影响。结果表明,以丙酮为萃取溶剂,萃取时间为25 min,水（含0.05%甲酸）-乙腈为流动相,利用SIM模式定量分析时,三（2-氯乙基）磷酸酯、三（1,3-二氯丙基）磷酸酯和磷酸三氯丙酯的浓度分别在1.0~500、10~500、10~500μg/L范围内与峰面积成正比,相关系数大于0.997,其定量下限分别为0.5、8.0、6.0μg/kg。加标回收率为83.4%~98.9%,相对标准偏差为4.0%~7.7%。该方法简单、灵敏、准确,可用于市售塑料和毛绒儿童玩具样品的测定。

An effective method was established for the simultaneous determination of three kinds of organophosphorous flame retardants including tris-（ 2-chloroethyl）-phosphate（ TCEP）,tris-（ 1,3-dichlorepropyl）-phosphate（ TDCP） and tris（ chloro-2-propyl） phosphate（ TCPP） in children＇s toys, based on ultrasonic assisted extraction coupled with high performance liquid chromatography- mass spectrometry. Effects of extraction solvent type,extraction time and mobile phase on extraction efficiencies were investigated. The optimal conditions were as follows： extraction solvent： acetone,ex- traction time： 25 min,mobile phase： water containing 0. 05% formic acid- acetonitrile. Under the optimal conditions,the calibration curves were linear in the ranges of 1. 0- 500 μg / L for TCEP,10- 500 μg / L for TCPP and 10- 500 μg / L for TDCP,respectively,with correlation coefficients more than 0. 997,The quantitation limits for TCEP,TCPP and TDCP were 0. 5,8. 0,6. 0 μg / kg,respectively. The spiked recoveries varied from 83. 4% to 98. 9% with relative standard deviations of 4. 0%- 7. 7%. The proposed method was successfully applied in the determination of organophosphorous flame retardants in commercially available toys including plastic children＇s toys and stuffed children＇s toy. The method developed is simple,rapid,sensitive and accurate,and could satisfy the demand for analysis of banned organpphosphorous flame retardants in children＇s toys.