超高效液相色谱-串联质谱法测定橡胶产品中4种秋兰姆类硫化促进剂含量

Determination of 4 Thiurams Vulcanization Accelerators in Rubber Products by Ultra Performance Liquid Chromatography-Tandem Mass Spectrometry

建立了橡胶产品中4种秋兰姆类硫化促进剂（二硫化四苄基秋兰姆（TBZTD）、二硫化二甲基二苯基秋兰姆（TMD）、福美双-D12（Thiram D12）、二环戊亚甲基二硫化秋兰姆（DPTD））的超高效液相色谱-串联质谱检测方法。橡胶材料中的硫化促进剂经甲醇超声多次提取,提取液离心过滤后以反相C18色谱柱为分离柱,甲醇和水作为流动相进行洗脱,经超高效液相色谱-串联质谱仪测定,外标法定量。研究了不同色谱条件下目标物质的分离情况和不同提取溶剂对提取净化效率的影响。在最优化条件下,TMD和Thiram D12在0.002-1.000 mg/L浓度范围内线性关系良好,其定量下限分别为0.001 0 mg/L和0.001 2 mg/L;TBZTD在0.100-10.000 mg/L浓度范围内线性关系良好,定量下限为0.100 0 mg/L;DPTD在0.020-10.000 mg/L浓度范围内线性关系良好,定量下限为0.020 0 mg/L。空白样品在不同浓度水平的平均加标回收率为82.7%-98.8%,相对标准偏差（RSD）为4.6%-7.0%。该方法简便、快速、灵敏,可满足橡胶产品中TBZTD,TMD,Thiram D12和DPTD的测试要求。

A rapid method was developed for the determnation of 4 thiurams vulcanization accelerators,tetrabenzyl thiuram disulfide（TBZTD）,dimethyldiphenylthiuram disulfide（TMD）,thiram D12 and dicyclopentamethylenethiuram disulfide（DPTD） in rubber products by ultra performance liquid chromatography tandem mass spectrometry（UPLC-MS / MS）.Rubber samples were diluted in methanol and extracted by ultrasonic.After centrifugation and filtration,the target compounds were separated on a reversed-phase C18 column with a mixture of methanol and water as mobile phase,analyzed by UPLC-MS / MS and quantified by the external standard method.Separation of the target substances in different chromatographic conditions was investigated,and effects of different extraction solvents on extraction effienciency were investigated.Under the optimal conditions,the calibration curves for TMD,thiram D12,TBZTD and DPTD were in good linearity in the ranges of 0.002-1.000,0.002-1.000,0.100-10.000,0.020-10.000 mg / L,respectively,with limits of quantitation of0.001 0,0.001 2,0.100 0,0.020 0 mg / L,respectively.Recovery tests were made by the addition of standards to blank sample at different concentrations,and the recoveries were in the range of82.7%-98.8% with relative standard deviations（RSDs,n = 5） of 4.6%-7.0%.The method is simple,rapid and sensitive,and could meet the requirements for detection of TBZTD,TMD,Thi-ram D12 and DPTD in rubber products.