分散固相萃取-液相色谱-串联质谱法测定聚氨酯制品中25种有机磷阻燃剂  

Determination of 25 Organophosphate Flame Retardants in Polyurethane Products by Dispersive Solid Phase Extraction and Liquid Chromatography-Tandem Mass Spectrometry

作　　者：杨阳 任洁芳 唐纱丽 曹慧 周学军 王瑾 YANG Yang;REN Jie-fang;TANG Sha-li;CAO Hui;ZHOU Xue-jun;WANG Jin(Zhejiang Institute of Product Quality and Safety Science,Hangzhou 310018,China;College of Environment&Resource Science,Zhejiang University,Hangzhou 310058,China)

机构地区：[1]浙江省产品质量安全科学研究院,浙江杭州310018 [2]浙江大学环境与资源学院,浙江杭州310058

出　　处：《质谱学报》2025年第2期206-216,I0004,共12页Journal of Chinese Mass Spectrometry Society

基　　金：国家市场监督管理总局科技计划项目(2022MK047);浙江省市场监督管理局重点科技计划项目(ZD2024003)。

摘　　要：本研究建立了液相色谱-串联质谱法检测聚氨酯制品中25种有机磷阻燃剂(organophosphate flame retardants,OPFRs),并对提取溶剂和固相萃取方式等前处理过程进行优化。结果表明,采用乙腈提取样品后,经柱层层析硅胶(Si)和N-丙基乙二胺吸附剂(PSA)分散固相萃取可有效消除基质效应的影响。净化后的提取液经Kinete^(®)C_(18)色谱柱(2.6μm×3 mm,150 mm),在0.1%甲酸水-甲醇溶液梯度洗脱下分离,电喷雾电离正离子多反应监测模式分析。方法学验证结果表明,25种OPFRs在各自浓度范围呈现良好的线性关系(r>0.999),检出限和定量限分别在0.02~0.50、0.05~1.00 mg/kg之间。3个浓度水平的加标回收率在61.09%~114.89%之间,相对标准偏差(RSD)在0.27%~13.92%之间。该方法的各项指标均能够满足检测要求,同时该净化方式避免了商品化固相萃取小柱的繁琐流程,成本低廉、耗时短、操作简便,可提高批量样品的分析效率。采用该方法检测实际样品,发现OPFRs广泛存在于日用消费品中,应加强对该类产品中OPFRs赋存情况的关注。Organophosphate flame retardants(OPFRs)have widely used in the manufacturing of plastics,textiles,foam products and various building materials because of their dual roles of flame retardants and plasticizers.With in-depth studies of toxicology research,the multiple toxicity of OPFRs to human health has been gradually revealed.It is of great significance to establish accurate detection and quantitative methods of OPFRs in various industrial products and pay attention to the presence of OPFRs for understanding the exposure risk of OPFRs.A method of liquid chromatography tandem mass spectrometry was established for the determination of 25 OPFRs in polyurethane products.A convenient ultrasonic extraction method with organic solvent was used to extract OPFRs from samples.In order to improve the accuracy of the method,the pre-treatment processes such as extraction solvents and solid phase extraction methods were optimized.The experimental results showed that acetonitrile extraction has the highest effectiveness.Subsequently,the extraction solution was further dispersed with silica gel(Si,200 mg)and N-propyl ethylene diamine adsorbent(PSA,200 mg),which can effectively eliminate the matrix effect and improve the accuracy of the method.The purified solution was separated on a Kinete®C_(18) column(2.6μm×3 mm,150 mm)under the gradient elution of 0.1%formic acid water and methanol,and analyzed by electrospray ionization positive ion mode with multi-reaction monitoring.The results of methodological verification indicated that the calibration curves of 25 OPFRs show an excellent linear correlation(r>0.999)in the specific concentration ranges.The limits of detection(LODs)and the limits of quantitation(LOQs)of the method are 0.02-0.50,0.05-1.00 mg/kg,respectively.The recoveries of low,medium and high spiked level are between 61.09%and 114.89%.The relative standard deviations(RSDs)range from 0.27%to 13.92%.All the results of method verification can meet the detection requirement.At the meanwhile,while the efficiency of batch s

关 键 词：有机磷阻燃剂(OPFRs) 液相色谱-串联质谱(LC-MS/MS) 分散固相萃取 聚氨酯材料 

分 类 号：O657.63[理学—分析化学]