气相色谱-质谱法测定电子废品回收件高聚物中的5种十二氯代阻燃剂

Determination of Five Types of Dodecachlorinated Flame Retardants in Polymer of E-waste Recyclables by Gas Chromatography Mass Spectrometry

建立了气相色谱-质谱同时测定电子废品回收件高聚物中灭蚁灵、得克隆602、得克隆603、顺式得克隆以及反式得克隆5种十二氯代阻燃剂的方法。以N-甲基吡咯烷酮(NMP)作为提取液,超声辅助提取方式可使丙烯腈-丁二烯-苯乙烯共聚物(ABS)、聚丙烯(PP)、硅橡胶材质阳性样品溶解,目标物提取率为86.6%~95.3%;聚对苯二甲酸乙二醇酯(PET)材质阳性样品采用微波辅助方式提取,目标物提取率为79.7%~87.0%。提取液经硅胶固相萃取小柱净化,可降低杂质对质谱的干扰。结果表明,5种目标物在0.15~50 mg·L^(-1)浓度范围内与响应值呈较好的线性关系,相关系数均在0.996以上,对4种阳性样品分别重复测定7次,5种目标物的变异系数均在3.1%~7.4%范围内。在空白样品中添加3个浓度水平的标准物质,添加回收率在81.7%~112.2%范围内。该方法灵敏和高效,适用于电子废品高聚物回收件中5种十二氯代阻燃剂含量的测定。

An analytical method was developed for the determination of five types of dodecachlorinated flame retardants in the polymer of e-waste recyclables.The target flame retardants included Mirex,Dechlorane 602,Dechlorane 603,syn-Dechlorane Plus and anti-Dechlorane Plus.After investigation of the effect of five types of solutions on the extraction,ultrasonic extraction with N-Methyl pyrrolidone(NMP)as the extracting solution could effectively dissolve the samples containing the target flame retardants of acrylonitrile butadiene styrene(ABS),polypropylene(PP),and silicone rubber.The extraction rate of the target flame retardants was between 88.6%-95.3%.Polyethylene terephthalate(PET)sample was processed by microwave extraction.The optimal test conditions were obtained by designing orthogonal tests,and the extraction rate of target flame retardants was between 79.7%-87.0%.The extraction solution was purified by silica solid-phase extraction column,which could reduce the interference of impurities on mass spectrometry.The calibration curves were linear within the ranges of 0.15-50 mg·L^(-1) for the target flame retardants and the correlation coefficients were over 0.996.The measurement was repeatedly conducted for 7 times for each of the 4 samples containing the target flame retardants,and the coefficient of variation for the 5 target flame retardants was within the range of 3.1%-7.4%.Three concentration levels of standard solution were added to the blank sample,and the recovery was in the range of 81.7%-112.2%.This method was sensitive and efficient,and was suitable for the determination of 5 types of dodecachlorinated flame retardants in the polymer of e-waste recyclables.