气相色谱-负化学源质谱法测定电子电气产品聚合物材料中的卤代磷酸酯阻燃剂

采用丙酮作为萃取溶剂，对电子电气产品聚合物材料中的卤代磷酸酯阻燃剂超声萃取1.5 h后，浓缩、定容、上机。为提高仪器分析方法的选择性，减少前处理流程，选取负化学电离（NCI）模式，在离子源温度210 ℃、甲烷气流量2.5 mL/min条件下对目标分析物进行定性定量分析。结果表明，磷酸三（2-氯乙基）酯（TCEP）和磷酸三（1-氯-2丙基）酯（TCPP）在0.1~10 mg/L浓度范围内，磷酸三（1,3-二氯异丙基）酯（TDCP）和磷酸三（2,3-二溴丙基）酯（TDBP）在0.010~10 mg/L浓度范围内，均有良好的线性关系，相关系数（R²）大于0.999。TCEP和TCPP的检出限和定量限分别为0.010 mg/kg（S/N=3）和0.10 mg/kg（S/N=10）；TDCP和TDBP的检出限和定量限分别为0.001 mg/kg（S/N=3）和0.010 mg/kg（S/N=10）。本方法对空白样品中目标分析物的加标回收率为85.6%~108.9%，相对标准偏差为8.5%。分析了30批次实际样品，包括丙烯腈-丁二烯-苯乙烯共聚物（ABS）、聚氯乙烯（PVC）、印刷电路板（环氧树脂为主要成分）和聚丙烯（PP）等电子电气产品聚合物材料，有2批次检出TCPP，其含量分别为367.5 mg/kg、695.2 mg/kg。可见，电子电气产品聚合物材料中存在一定的卤代磷酸酯阻燃剂污染风险。

Determination of Halogenated Phosphate Ester Flame Retardants in Polymer Material of Electrical and Electronic Products by GC-NCI-MS

Halogenated phosphate ester flame retardants in polymer material of electrical and electronic products were extracted by ultrasound with acetone solvent for 1.5 h, then the extract was evaporated to almost dryness and dissolved with 1.0 mL n-hexane, and detected by instrument. In order to improve method selectivity and reduce sample preparation procedure, negative chemical ionization (NCI) model was selected. Taget analytes were determined qualitatively and quantitatively at 210 ℃ of ion source temperature with 2.5 mL/min of methane gas flow. The linear range of tris-(2-chloroethyl) phosphate (TCEP) and tris-(1-chloro-2-propyl) phosphate (TCPP) are 0.10-10 mg/L with R²≥0.999, while tris-(1,3-dichloro-2-propanol) phosphate (TDCP) and tris-(2,3-dibromo-1-propanol) phosphate (TDBP) are 0.010-10 mg/L withR²≥0.999. The limit of detection (S/N=3) is 0.010 mg/kg for TCEP and TCPP, and 0.001 mg/kg for TDCP and TDBP. The limit of quantitative (S/N=10) is 0.10 mg/kg for TCEP and TCPP, and 0.010 mg/kg for TDCP and TDBP. The feasibility of this method was demonstrated by determination of halogenated phosphate ester fire retardants in electrical and electronic products with spiked recoveries, which is in the range of 85.6%-108.9%, the relative standard deviation (RSD) is less than 8.5%. 30 actual samples were analyzed, including acrylonitrile-butadiene-styrene (ABS), polyvinyl chloride (PVC), printed circuit board which was mainly made from epoxy resin and polypropylene (PP). Only two samples are detected with TCPP concentration of 367.5 mg/kg and 695.2 mg/kg. Therefore, there is a certain risk of halogenated phosphate ester flame retardants for polymer material of electrical and electronic products.