Extractable organic compounds in polyurethane foam with special reference to aromatic amines and derivatives thereof
Extractable organic compounds in polyurethane foam with special reference to aromatic amines and derivatives thereof
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DOI：
10.1016/j.aca.2003.12.063
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发表时间：
2004-05-10
影响因子：
6.2
通讯作者：
Skarping, G
中科院分区：
文献类型：
--
作者：
Marand, A;Karlsson, D;Skarping, G
研究了甲苯二异氰酸酯(TDI)基聚氨酯(PUR)软泡中芳香胺及相关化合物的测定方法。泡沫用0.1%(w/v)的醋酸(HAc)水溶液提取。对萃取液进行了分析，确定了芳香胺为氯甲酸乙酯(ET)和五氟丙酸酐(PFPA)的衍生物。采用电喷雾电离(ESI)或化学电离监测负离子(NCI)的气相色谱-质谱法(GC-MS)进行检测。采用LC-ESI+-MS法测定ET衍生物，检出限为2pg甲苯二胺(TDA)。分别用LC-ESI-MS和GC-NCI-MS测定PFPA衍生物，检出限分别为0.1pg和0.02pg。以氚标记的TDA为内标，线性范围为0.0 1~0.5 0mug ml(-1)(n=7)，相关系数为0.999。将LC-MS测定的TDA-PFPA衍生物与GC-MS测定的TDA-PFPA和LC-MS测定的TDA-ET的校正曲线绘制成线性曲线。相对标准偏差(R.S.D.)测定泡沫提取液中TDA的含量为13%。与ET衍生物的LC-MS相比，LC-MS测定PFPA衍生物具有更高的选择性。在泡沫萃取液中，观察到2，4-和2，6-TDA，亚甲基二苯胺(MDA)的几种异构体和TDA/TDI的二聚体。2，4-TDA和4，4‘-丙二醛可能是人类致癌物质。萃取液的水解液显示出大量的TDA/TDI化合物和低聚物。TDA在泡沫中的浓度受提取介质、温度和时间的影响。衍生化程序的选择也影响了TDA的测定。在6种不同商品软质泡沫的萃取液中，2，4-和2，6-TDA质量分别在0-7和0-6杯(-1)泡沫范围内被发现。当软质泡沫被加热时，观察到相当高的TDA浓度。(C)2004爱思唯尔B.V.保留所有权利。
Methods for determination of aromatic amines and related compounds in flexible toluene diisocyanate (TDI)-based polyurethane (PUR) foam were investigated. The foam was extracted using 0.1% (w/v) aqueous acetic acid (HAc). Extraction solutions were analysed and aromatic amines were determined as ethyl chloroformate (Et) and pentafluoropropionic acid anhydride (PFPA) derivatives. The determinations were performed using liquid chromatography (LC) and mass spectrometry (MS) detection with electrospray ionisation (ESI) or gas chromatography (GC)-MS with chemical ionisation monitoring negative ions (NCI). The Et derivatives were determined using LC-ESI+-MS with detection limit of 2 pg of toluenediamine (TDA). The PFPA derivatives were determined using LC-ESI--MS or GC-NCI-MS with detection limits of 0.1 and 0.02 pg of TDA, respectively. Using trideuterium labelled TDA as internal standard, linear calibration curves were obtained in the range of 0.01-0.50 mug ml(-1) (n = 7), with correlation coefficients >0.999. When plotting calibration curves for TDA-PFPA derivatives determined using LC-MS against TDA-PFPA using GC-MS and TDA-Et using LC-MS, linear curves were obtained. The relative standard deviation (R.S.D.) for determination of TDA in foam extraction solutions were 13%. LC-MS determination of PFPA derivatives was more selective, as compared to LC-MS of Et derivatives.In foam extraction solutions, 2,4- and 2,6-TDA, several isomers of methylenedianiline (MDA) and dimers of TDA/TDI were observed. 2,4-TDA and 4,4'-MDA are possible human carcinogens. Hydrolysis of the extraction solution revealed a large pool of TDA/TDI compounds and oligomers. The concentration of TDA in foam was affected by the extraction media, temperature and duration. The choice of derivatisation procedure also affected the determination of TDA. In extraction solutions from six different commercially available flexible foam qualities 2,4- and 2,6-TDA were found in the range of 0-7 and 0-6 mug g(-1) foam, respectively. When flexible foam was heated, considerable higher concentrations of TDA were observed. (C) 2004 Elsevier B.V. All rights reserved.